JP5506732B2 - High strength aluminum alloy fin material for heat exchanger - Google Patents
High strength aluminum alloy fin material for heat exchanger Download PDFInfo
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- JP5506732B2 JP5506732B2 JP2011087668A JP2011087668A JP5506732B2 JP 5506732 B2 JP5506732 B2 JP 5506732B2 JP 2011087668 A JP2011087668 A JP 2011087668A JP 2011087668 A JP2011087668 A JP 2011087668A JP 5506732 B2 JP5506732 B2 JP 5506732B2
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- 239000000463 material Substances 0.000 title claims description 82
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 23
- 238000005219 brazing Methods 0.000 claims description 80
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000000137 annealing Methods 0.000 description 71
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- 150000001875 compounds Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
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- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Description
本発明は、ろう付け性に優れた熱交換器用アルミニウム合金フィン材およびその製造方法に関し、詳しくは、ラジエータ、カーヒータ、カーエアコンなどのようにフィンと作動流体通路構成材料とがろう付けにより接合される熱交換器に用いられるアルミニウム合金フィン材であって、ろう付け前の強度が適度であるためフィン成形が容易で、つまりろう付け前の強度が高すぎてフィン成形が困難となることが無く、しかも、ろう付け後の強度が高く、且つ伝熱特性、耐エロージョン性、耐サグ性、犠牲陽極効果、自己耐食性に優れた熱交換器用高強度アルミニウム合金フィン材に関する。 TECHNICAL FIELD The present invention relates to an aluminum alloy fin material for a heat exchanger excellent in brazing and a method for manufacturing the same, and more specifically, a fin and a working fluid passage component material are joined by brazing, such as a radiator, a car heater, and a car air conditioner. Aluminum alloy fin material used in heat exchangers that have a moderate strength before brazing, so fin forming is easy, that is, the strength before brazing is too high and fin forming is not difficult. Moreover, the present invention relates to a high-strength aluminum alloy fin material for a heat exchanger that has high strength after brazing and is excellent in heat transfer characteristics, erosion resistance, sag resistance, sacrificial anode effect, and self-corrosion resistance.
自動車のラジエータ、エアコン、インタークーラー、オイルクーラーなどの熱交換器は、Ａｌ−Ｃｕ系合金、Ａｌ−Ｍｎ系合金、Ａｌ−Ｍｎ−Ｃｕ系合金などからなる作動流体通路構成材料と、Ａｌ−Ｍｎ系合金などからなるフィンとをろう付けすることにより組立てられる。フィン材には、作動流体通路構成材料を防食するために犠牲陽極効果が要求されるとともに、ろう付け時の高温加熱により変形したり、ろうが浸透したりしないように優れた耐サグ性、耐エロージョン性が要求される。 Heat exchangers for automobile radiators, air conditioners, intercoolers, oil coolers, etc. are composed of working fluid passage materials composed of Al-Cu alloys, Al-Mn alloys, Al-Mn-Cu alloys, and Al-Mn alloys. It is assembled by brazing a fin made of an alloy or the like. The fin material is required to have a sacrificial anode effect in order to prevent the working fluid passage constituent material from being corroded, and has excellent sag resistance and resistance to prevent deformation due to high temperature heating during brazing and penetration of the braze. Erosion is required.
フィン材としてＪＩＳ ３００３、ＪＩＳ ３２０３などのＡｌ−Ｍｎ系アルミニウム合金が使用されるのは、Ｍｎがろう付け時の変形やろうの浸食を防ぐために有効に作用するためである。Ａｌ−Ｍｎ系合金フィン材に犠牲陽極効果を付与するためには、この合金にＺｎ、Ｓｎ、Ｉｎなどを添加して電気化学的に卑にする方法（特許文献１（特開昭６２−１２０４５５号公報））などがあり、耐高温座屈性（耐サグ性）をさらに向上させるためには、Ａｌ−Ｍｎ系合金にＣｒ、Ｔｉ、Ｚｒなどを含有させる方法（特許文献２（特開昭５０−１１８９１９号公報））などがある。 The reason why Al-Mn aluminum alloys such as JIS 3003 and JIS 3203 are used as the fin material is that Mn acts effectively to prevent deformation during brazing and erosion of the brazing. In order to impart the sacrificial anode effect to the Al—Mn alloy fin material, a method of adding Zn, Sn, In, or the like to this alloy to make it electrochemically base (Patent Document 1 (Japanese Patent Laid-Open No. 62-120455)). In order to further improve the high temperature buckling resistance (sag resistance), a method in which an Al—Mn based alloy contains Cr, Ti, Zr, etc. No. 50-118919))).
しかし、最近では、熱交換器の軽量化、コスト低減がますます強く要求され、作動流体通路構成材料、フィン材などの熱交換器構成材料をさらに薄肉化することが必要となってきている。しかし、例えばフィンを薄肉化すると伝熱断面積が小さくなるために熱交換性能が低下し、製品としての熱交換器の強度、耐久性にも問題が生じるところから、一層高い伝熱性能とろう付け後の強度、耐サグ性、耐エロージョン性、自己耐食性が望まれている。 Recently, however, there is an increasing demand for weight reduction and cost reduction of heat exchangers, and it is necessary to further reduce the thickness of heat exchanger constituent materials such as working fluid passage constituent materials and fin materials. However, for example, if the fins are made thinner, the heat transfer cross-sectional area becomes smaller and the heat exchange performance deteriorates, causing problems with the strength and durability of the heat exchanger as a product. The strength, sag resistance, erosion resistance and self-corrosion resistance after application are desired.
従来のＡｌ−Ｍｎ系合金では、ろう付け時の加熱によりＭｎが固溶するため、熱伝導率が低下するという問題点がある。この難点を解決するフィン材として、Ｍｎ含有量を０．８wt％以下に制限し、Ｚｒ：０．０２〜０．２wt％およびＳｉ：０．１〜０．８wt％を含むアルミニウム合金が提案されている（特許文献３（特公昭６３−２３２６０号公報））。この合金は改善された熱伝導率を有するが、Ｍｎが少ないためろう付け後の強度が不十分で、熱交換器として使用中にフィン倒れや変形が生じ易く、また電位が十分に卑でないために犠牲陽極効果が小さいという欠点がある。 A conventional Al-Mn alloy has a problem that thermal conductivity is lowered because Mn is dissolved by heating during brazing. As a fin material that solves this problem, an aluminum alloy that limits the Mn content to 0.8 wt% or less and contains Zr: 0.02 to 0.2 wt% and Si: 0.1 to 0.8 wt% has been proposed. (Patent Document 3 (Japanese Patent Publication No. 63-23260)). This alloy has improved thermal conductivity, but because Mn is low, the strength after brazing is insufficient, fins are liable to collapse and deform during use as a heat exchanger, and the potential is not sufficiently low. However, the sacrificial anode effect is small.
一方、アルミニウム合金溶湯を注湯してスラブを鋳造する際の冷却速度を速くすることで、Ｓｉ、Ｍｎ含有量などを０．０５〜１．５質量％としてもスラブの段階で晶出している金属間化合物のサイズを最大値５μｍ以下と小さくすることが可能となり、このようなスラブから圧延工程を経ることで、フィン材の疲労特性を向上させる提案もなされている（特許文献４（特開２００１−２２６７３０号公報））。しかし、当該発明は疲労寿命を向上させることが目的であり、又スラブを鋳造する際の冷却速度を速くする手段については鋳造スラブを薄くするなどの記載はあるものの、実操業規模における双ベルト鋳造機による薄スラブ連続鋳造などの具体的な開示は見られない。 On the other hand, by increasing the cooling rate when casting the slab by pouring molten aluminum alloy, the crystallization of the slab crystallizes even if the Si, Mn content, etc. is 0.05-1.5 mass%. It has become possible to reduce the size of the intermetallic compound to a maximum value of 5 μm or less, and a proposal has been made to improve the fatigue characteristics of the fin material by performing a rolling process from such a slab (Patent Document 4 (Japanese Patent Laid-Open No. 2003-32083). 2001-226730 gazette)). However, the present invention is intended to improve the fatigue life, and although there is a description of thinning the casting slab as a means for increasing the cooling rate when casting the slab, it is a twin belt casting on an actual operation scale. There is no specific disclosure of thin slab continuous casting by machine.
本発明の目的は、フィン成形が容易な適度のろう付け前強度を有し、しかもろう付け後には高い強度を有し、且つ耐サグ性、耐エロージョン性、自己耐食性、犠牲陽極効果に優れた熱交換器用アルミニウム合金フィン材を提供することである。 The object of the present invention is to have a moderate strength before brazing that allows easy fin molding, and a high strength after brazing, and is excellent in sag resistance, erosion resistance, self-corrosion resistance, and sacrificial anode effect. An aluminum alloy fin material for a heat exchanger is provided.
上記の目的を達成するために、本発明の熱交換器用高強度アルミニウム合金フィン材は、Ｓｉ：０．８〜１．４wt％、Ｆｅ：０．１５〜０．７wt％、Ｍｎ：１．５〜３．０wt％、Ｚｎ：０．５〜２．５wt％を含み、さらに不純物としてのＭｇを０．０５wt％以下に限定し、残部が通常の不純物とＡｌからなる化学組成を有し、ろう付け前の金属組織がファイバーな結晶粒組織であり、ろう付前の抗張力が２４０ＭＰａ以下、ろう付後の抗張力が１５０ＭＰａ以上であり、且つろう付け後の再結晶粒径が５００μｍ以上であることを特徴とする。 In order to achieve the above object, the high-strength aluminum alloy fin material for a heat exchanger of the present invention has Si: 0.8 to 1.4 wt%, Fe: 0.15 to 0.7 wt%, Mn: 1.5 -3.0wt%, Zn: 0.5-2.5wt%, Mg as impurities is limited to 0.05wt% or less, and the balance has a chemical composition consisting of ordinary impurities and Al. The metal structure before brazing is a fiber crystal grain structure, the tensile strength before brazing is 240 MPa or less, the tensile strength after brazing is 150 MPa or more, and the recrystallized grain size after brazing is 500 μm or more. Features.
上記本発明の熱交換器用高強度アルミニウム合金フィン材を製造する第１の方法は、上記フィン材の化学組成を有する溶湯を注湯して、双ベルト式鋳造機により厚さ５〜１０mmの薄スラブを連続的に鋳造してロールに巻き取った後、板厚１．０〜６．０mmに冷間圧延し、２００〜３５０°Ｃで第１次中間焼鈍を施し、更に冷間圧延を行って、板厚０．０５〜０．４ｍｍに冷間圧延し、３６０〜４５０℃での第２次中間焼鈍を施し、最終冷延率１０〜５０％未満の冷間圧延を行って最終板厚４０〜２００μｍとすることを特徴とする。 The first method for producing the high-strength aluminum alloy fin material for a heat exchanger according to the present invention is to pour a molten metal having the chemical composition of the fin material, and to form a thin film having a thickness of 5 to 10 mm by a twin belt casting machine. After the slab is continuously cast and wound on a roll, it is cold-rolled to a thickness of 1.0 to 6.0 mm, subjected to first intermediate annealing at 200 to 350 ° C., and further cold-rolled. The steel sheet is cold-rolled to a thickness of 0.05 to 0.4 mm, subjected to secondary intermediate annealing at 360 to 450 ° C., and subjected to cold rolling with a final cold rolling rate of less than 10 to 50% to obtain a final thickness. It is characterized by being 40-200 μm.
上記本発明の熱交換器用高強度アルミニウム合金フィン材を製造する第２の方法は、上記フィン材の化学組成を有する溶湯を注湯して、双ベルト式鋳造機により厚さ５〜１０mmの薄スラブを連続的に鋳造してロールに巻き取った後、板厚１．０〜６．０mmに冷間圧延し、２００〜４５０°Ｃで第１次中間焼鈍を施し、更に冷間圧延を行って、板厚０．０８〜２．０ｍｍに冷間圧延し、３６０〜４５０℃での第２次中間焼鈍を施し、冷延率５０〜９６％の冷間圧延を行って最終板厚４０〜２００μｍとして２００〜４００℃で最終焼鈍を施すことを特徴とする。 The second method for producing the high-strength aluminum alloy fin material for a heat exchanger according to the present invention is to pour a molten metal having the chemical composition of the fin material, and to form a thin film having a thickness of 5 to 10 mm by a twin belt casting machine. After the slab is continuously cast and wound on a roll, it is cold-rolled to a thickness of 1.0 to 6.0 mm, subjected to first intermediate annealing at 200 to 450 ° C., and further cold-rolled. The steel sheet is cold-rolled to a thickness of 0.08 to 2.0 mm, subjected to secondary intermediate annealing at 360 to 450 ° C., and cold-rolled at a cold rolling rate of 50 to 96% to obtain a final thickness of 40 to The final annealing is performed at 200 to 400 ° C. as 200 μm.
上記第１および第２の方法において、前記第１次中間焼鈍を、連続焼鈍炉により昇温速度１００°Ｃ／ｍｉｎ以上、且つ保持温度４００〜５００℃で保持時間５分以内で行うことが望ましい。 In the first and second methods, it is preferable that the first intermediate annealing is performed by a continuous annealing furnace at a temperature increase rate of 100 ° C./min or more and a holding temperature of 400 to 500 ° C. within a holding time of 5 minutes. .
上記第１および第２の方法において、前記第１次中間焼鈍後、第２次中間焼鈍後、最終焼鈍後（ろう付け前）の何れの段階においても、金属組織がファイバーな結晶粒組織であることが望ましい。 In the first and second methods, the metal structure is a fiber crystal grain structure at any stage after the first intermediate annealing, after the second intermediate annealing, and after the final annealing (before brazing). It is desirable.
本発明によれば、上記のように化学組成と、ろう付け前後の結晶粒組織および抗張力を限定したことにより、高強度で且つ伝熱特性、耐エロージョン性、耐サグ性、犠牲陽極効果および自己耐食性に優れた熱交換器用高強度アルミニウム合金フィン材が得られる。
このアルミニウム合金フィン材は上記第１および第２の方法により製造できる。
According to the present invention, by limiting the chemical composition, the crystal grain structure before and after brazing, and the tensile strength as described above, high strength and heat transfer characteristics, erosion resistance, sag resistance, sacrificial anode effect, and self A high-strength aluminum alloy fin material for heat exchangers excellent in corrosion resistance can be obtained.
This aluminum alloy fin material can be manufactured by the first and second methods.
本発明者は、熱交換器用フィン材に対する薄肉化の要求を満足するアルミニウム合金フィン材を開発するために、強度特性、伝熱性能、耐サグ性、耐エロージョン性、自己耐食性および犠牲陽極効果について、従来のＤＣスラブ鋳造からの圧延材と双ベルト式連続鋳造からの圧延材の比較を行いつつ、その組成、中間焼鈍条件、圧下率、最終焼鈍との関係について種々の検討を行った結果、本発明を完成した。 In order to develop an aluminum alloy fin material that satisfies the requirements for thinning the heat exchanger fin material, the present inventor is concerned with strength characteristics, heat transfer performance, sag resistance, erosion resistance, self-corrosion resistance, and sacrificial anode effect. As a result of performing various studies on the relationship between the composition, intermediate annealing conditions, rolling reduction, and final annealing, while comparing the rolling material from the conventional DC slab casting and the rolling material from the twin belt type continuous casting, The present invention has been completed.
本発明の熱交換器用アルミニウム合金フィン材における合金成分の意義および限定理由を以下に説明する。 The significance and reasons for limitation of the alloy components in the aluminum alloy fin material for heat exchangers of the present invention will be described below.
〔Ｓｉ：０．８〜１．４wt％〕 Ｓｉは、Ｆｅ、Ｍｎと共存してろう付け時にサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系の化合物を生成し、強度を向上させ、同時にＭｎの固溶量を減少させて熱伝導率を向上させる。Ｓｉの含有量が０．８wt％未満ではその効果が十分でなく、１．４wt％を超えると、ろう付け時にフィン材の溶融を生じるおそれがある。従って、好ましい含有範囲は０．８〜１．４wt％である。Ｓｉのさらに好ましい含有量は０．９〜１．４wt％の範囲である。 [Si: 0.8 to 1.4 wt%] Si coexists with Fe and Mn to produce a sub-micron level Al- (Fe.Mn) -Si based compound at the time of brazing, thereby improving the strength. At the same time, the thermal conductivity is improved by reducing the solid solution amount of Mn. If the Si content is less than 0.8 wt%, the effect is not sufficient. If it exceeds 1.4 wt%, the fin material may be melted during brazing. Therefore, a preferable content range is 0.8 to 1.4 wt%. A more preferable content of Si is in the range of 0.9 to 1.4 wt%.
〔Ｆｅ：０．１５〜０．７wt％〕 Ｆｅは、Ｍｎ、Ｓｉと共存してろう付け時にサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系の化合物を生成し、強度を向上させるとともに、Ｍｎの固溶量を減少させて熱伝導率を向上させる。Ｆｅの含有量が０．１５wt％未満では高純度の地金を必要とするため製造コストが高くなり好ましくない。０．７wt％を超えると合金の鋳造時に粗大なＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系晶出物が生成して板材の製造が困難となる。従って、好ましい含有範囲は０．１５〜０．７wt％である。Ｆｅのさらに好ましい含有量は０．１７〜０．６wt％の範囲である。 [Fe: 0.15 to 0.7 wt%] Fe coexists with Mn and Si to produce submicron-level Al- (Fe.Mn) -Si compounds during brazing and improve strength. The thermal conductivity is improved by reducing the solid solution amount of Mn. If the Fe content is less than 0.15 wt%, a high-purity metal is required, which is not preferable because the production cost increases. If it exceeds 0.7 wt%, coarse Al- (Fe.Mn) -Si-based crystallized products are produced during casting of the alloy, making it difficult to produce a plate material. Therefore, a preferable content range is 0.15-0.7 wt%. A more preferable content of Fe is in the range of 0.17 to 0.6 wt%.
〔Ｍｎ：１．５〜３．０wt％〕 Ｍｎは、Ｆｅ、Ｓｉと共存させることによりろう付け時にサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物として高密度に析出して、ろう付け後の合金材の強度を向上させる。また、サブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系析出物は強い再結晶阻止作用を有するため再結晶粒が５００μｍ以上と粗大になり、耐サグ性と耐エロージョン性が向上する。Ｍｎが１．５wt％未満ではその効果が十分でなく、３．０wt％を超えると合金の鋳造時に粗大なＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系晶出物が生成して板材の製造が困難となるとともに、Ｍｎの固溶量が増加して熱伝導率が低下する。従って、好ましい含有範囲は１．５〜３．０wt％である。Ｍｎのさらに好ましい含有量は１．６−２．８wt％である。 [Mn: 1.5 to 3.0 wt%] Mn precipitates at a high density as a submicron-level Al- (Fe.Mn) -Si compound at the time of brazing by coexisting with Fe and Si. Improves the strength of the alloy material after application. Further, since the submicron level Al- (Fe.Mn) -Si-based precipitate has a strong recrystallization inhibiting action, the recrystallized grains become coarser to 500 μm or more, and the sag resistance and erosion resistance are improved. If Mn is less than 1.5 wt%, the effect is not sufficient, and if it exceeds 3.0 wt%, coarse Al- (Fe · Mn) -Si-based crystallized products are produced during casting of the alloy, making it difficult to produce a plate material. At the same time, the solid solution amount of Mn increases and the thermal conductivity decreases. Therefore, a preferable content range is 1.5 to 3.0 wt%. A more preferable content of Mn is 1.6 to 2.8 wt%.
〔Ｚｎ：０．５〜２．５wt％〕 Ｚｎは、フィン材の電位を卑にし、犠牲陽極効果を与える。含有量が０．５wt％未満ではその効果が十分でなく、２．５wt％を超えると材料の自己耐食性が劣化し、また、Ｚｎの固溶によって熱伝導率が低下する。従って、好ましい含有範囲は０．５〜２．５wt％である。Ｚｎのさらに好ましい含有量は１．０〜２．０wt％の範囲である。 [Zn: 0.5 to 2.5 wt%] Zn lowers the potential of the fin material and provides a sacrificial anode effect. If the content is less than 0.5 wt%, the effect is not sufficient, and if it exceeds 2.5 wt%, the self-corrosion resistance of the material is deteriorated, and the thermal conductivity is lowered by solid solution of Zn. Therefore, a preferable content range is 0.5 to 2.5 wt%. A more preferable content of Zn is in the range of 1.0 to 2.0 wt%.
〔Ｍｇ：０．０５wt％以下〕 Ｍｇは、ろう付け性に影響し、含有量が０．０５wt％を超えるとろう付け性を害するおそれがある。とくにフッ化物系フラックスろう付けの場合、フラックスの成分であるフッ素（Ｆ）と合金中のＭｇとが反応し易くなり、ＭｇＦ2 などの化合物が生成することに起因してろう付け時に有効に作用するフラックスの絶対量が不足し、ろう付け不良が生じ易くなる。従って、不純物としてのＭｇの含有量は０．０５wt％以下に限定する。 [Mg: 0.05 wt% or less] Mg affects the brazing property, and if the content exceeds 0.05 wt%, the brazing property may be impaired. Particularly in the case of fluoride-based flux brazing, fluorine (F), which is a component of the flux, easily reacts with Mg in the alloy, and works effectively during brazing due to the formation of compounds such as MgF 2. The absolute amount of flux to be used is insufficient, and brazing defects are likely to occur. Therefore, the content of Mg as an impurity is limited to 0.05 wt% or less.
Ｍｇ以外の不純物成分については、Ｃｕは材料の電位を貴にするため０．２wt％以下に制限するのが好ましく、Ｃｒ、Ｚｒ、Ｔｉ、Ｖは、微量でも材料の熱伝導率を著しく低下させるので、これらの元素の合計含有量は０．２０wt％以下に限定するのが好ましい。 For impurity components other than Mg, Cu is preferably limited to 0.2 wt% or less in order to make the potential of the material noble, and Cr, Zr, Ti, and V significantly reduce the thermal conductivity of the material even in a small amount. Therefore, the total content of these elements is preferably limited to 0.20 wt% or less.
次に、本発明における薄スラブの鋳造条件、中間焼鈍条件、最終冷延率、最終焼鈍条件の意義および限定理由を以下に説明する。 Next, the significance of the casting conditions, the intermediate annealing conditions, the final cold rolling rate, and the final annealing conditions of the thin slab in the present invention and the reasons for limitation will be described below.
〔薄スラブの鋳造条件〕 双ベルト鋳造法は、上下に対峙し水冷されている回転ベルト間に溶湯を注湯してベルト面からの冷却で溶湯を凝固させてスラブとし、ベルトの反注湯側より該スラブを連続して引き出してコイル状に巻き取る連続鋳造方法である。
本発明においては、鋳造するスラブの厚さは５〜１０mmが好ましい。この厚さであると板厚中央部の凝固速度も速く、均一組織でしかも本発明範囲の組成であると粗大な化合物の少ない、およびろう付け後において結晶粒径の大きい優れた諸性質を有するフィン材とすることができる。
[Casting conditions for thin slabs] In the double belt casting method, the molten metal is poured between rotating belts facing each other up and down, and the molten metal is solidified by cooling from the belt surface to form a slab. This is a continuous casting method in which the slab is continuously drawn out from the side and wound into a coil shape.
In the present invention, the thickness of the cast slab is preferably 5 to 10 mm. With this thickness, the solidification rate in the central part of the plate thickness is fast, and with a uniform structure and with a composition within the range of the present invention, there are few coarse compounds and excellent properties with a large crystal grain size after brazing. It can be a fin material.
双ベルト式鋳造機による薄スラブ厚さが５mm未満であると、単位時間当たりに鋳造機を通過するアルミニウム量が小さくなりすぎて、鋳造が困難になる。逆に厚さが１０mmを超えると、ロールによる巻取りができなくなるため、スラブ厚さの範囲を５〜１０mmとするのが好ましい。 When the thickness of the thin slab by the twin belt type casting machine is less than 5 mm, the amount of aluminum passing through the casting machine per unit time becomes too small and casting becomes difficult. On the other hand, if the thickness exceeds 10 mm, winding with a roll cannot be performed, so the slab thickness range is preferably 5 to 10 mm.
なお、溶湯の凝固時の鋳造速度は５〜１５ｍ／ｍｉｎ であることが好ましく、ベルト内で凝固が完了することが望ましい。鋳造速度が５ｍ／ｍｉｎ 未満の場合、鋳造に時間が掛かりすぎて生産性が低下するため、好ましくない。鋳造速度が１５ｍ／ｍｉｎ を超える場合、アルミニウム溶湯の供給が追いつかず、所定の形状の薄スラブを得ることが困難となる。 In addition, it is preferable that the casting speed at the time of solidification of a molten metal is 5-15 m / min, and it is desirable that solidification is completed within a belt. A casting speed of less than 5 m / min is not preferable because it takes too much time for casting and decreases productivity. When the casting speed exceeds 15 m / min, the supply of the molten aluminum cannot catch up, and it becomes difficult to obtain a thin slab having a predetermined shape.
〔第１次中間焼鈍条件〕 製品の強度を低く抑えるために最終冷延率を１０−５０％未満と低くする場合（第２実施形態）において、第１次中間焼鈍の保持温度は２００〜３５０°Ｃが好ましい。第1次中間焼鈍の保持温度が２００°Ｃ未満の場合、十分な軟化状態を得ることができない。第１次中間焼鈍の保持温度が３５０°Ｃを超えると、マトリックス中の固溶Ｍｎが高温での中間焼鈍時にＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物として析出してしまうため、第２次中間焼鈍時に再結晶してしまい，その後の１０−５０％未満と低い最終冷間圧延率では，ろう付時に未再結晶状態のままとなってしまい、ろう付け時の耐サグ性と耐エロージョン性が低下する。 [First Intermediate Annealing Conditions] In the case where the final cold rolling rate is lowered to less than 10-50% in order to keep the strength of the product low (second embodiment), the holding temperature of the first intermediate annealing is 200 to 350. ° C is preferred. When the holding temperature of the first intermediate annealing is less than 200 ° C., a sufficient softened state cannot be obtained. If the holding temperature of the first intermediate annealing exceeds 350 ° C., the solid solution Mn in the matrix is precipitated as an Al— (Fe · Mn) —Si compound during the intermediate annealing at a high temperature. Recrystallization occurs during the intermediate annealing, and at the subsequent cold rolling reduction of less than 10-50%, it remains in an unrecrystallized state during brazing, and sag and erosion resistance during brazing. Decreases.
最終冷延率が５０〜９６％と高い場合は，最終焼鈍を施すことによって製品の強度を低く抑えることが肝要である。この場合（第３実施形態）において、第１次中間焼鈍の保持温度は２００〜４５０℃が好ましい。第1次中間焼鈍の保持温度が２００°Ｃ未満の場合、十分な軟化状態を得ることができない。第１次中間焼鈍の保持温度が３５０°Ｃを超えると、マトリックス中の固溶Ｍｎが高温での中間焼鈍時にＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物として析出してしまうが、最終冷間圧延率が高いということは、第２次中間焼鈍処理前の冷延率が低いため転位密度が低く、第２次中間焼鈍時に再結晶が起こらない。しかし、第１次中間焼鈍の保持温度が４５０°Ｃを超えると、マトリックス中の固溶Ｍｎが高温での中間焼鈍時にＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物として多量且つ粗大に析出してしまうため、第２次中間焼鈍時に最再結晶するばかりか，ろう付け時の再結晶阻止作用が弱まって、再結晶粒径が５００μｍ未満となり、ろう付け時の耐サグ性と耐エロージョン性が低下する。 When the final cold rolling rate is as high as 50 to 96%, it is important to keep the strength of the product low by performing final annealing. In this case (third embodiment), the holding temperature of the first intermediate annealing is preferably 200 to 450 ° C. When the holding temperature of the first intermediate annealing is less than 200 ° C., a sufficient softened state cannot be obtained. When the holding temperature of the first intermediate annealing exceeds 350 ° C., the solid solution Mn in the matrix is precipitated as an Al— (Fe · Mn) —Si compound during intermediate annealing at a high temperature. A high rolling ratio means that the dislocation density is low because the cold rolling ratio before the second intermediate annealing treatment is low, and recrystallization does not occur during the second intermediate annealing. However, when the holding temperature of the first intermediate annealing exceeds 450 ° C, the solid solution Mn in the matrix precipitates in a large amount and coarsely as an Al- (Fe · Mn) -Si-based compound during the intermediate annealing at a high temperature. Therefore, not only the recrystallization at the second intermediate annealing, but also the recrystallization prevention action at the time of brazing is weakened, the recrystallized grain size becomes less than 500μm, and the sag resistance and erosion resistance at the time of brazing are lowered. To do.
第１次中間焼鈍の保持時間は特に限定する必要はないが、１〜５時間の範囲とすることが好ましい。第１次中間焼鈍の保持時間が１時間未満では、コイル全体の温度が不均一なままで、板中における均一な再結晶組織の得られない可能性があるので好ましくない。第１次中間焼鈍の保持時間が５時間を超えると、固溶Ｍｎの析出が進行してろう付け後の再結晶粒径５００μｍ以上を安定して確保する上で不利になるばかりでなく、処理に時間が掛かりすぎて生産性が低下するため、好ましくない。 The holding time of the first intermediate annealing is not particularly limited, but is preferably in the range of 1 to 5 hours. If the holding time of the first intermediate annealing is less than 1 hour, the temperature of the entire coil remains non-uniform, and a uniform recrystallized structure in the plate may not be obtained. If the holding time of the first intermediate annealing exceeds 5 hours, the precipitation of the solid solution Mn proceeds, which is not only disadvantageous in securing a recrystallized grain size of 500 μm or more after brazing, but also processing. This is not preferable because it takes too much time to reduce productivity.
第1次中間焼鈍処理時の昇温速度および冷却速度は特に限定する必要はないが、３０°Ｃ／時間以上とすることが好ましい。第1次中間焼鈍処理時の昇温速度および冷却速度が３０°Ｃ／時間未満の場合、固溶Ｍｎの析出が進行してろう付け後の再結晶粒径５００μｍ以上を安定して確保する上で不利であるばかりでなく、処理に時間が掛かりすぎて生産性が低下するので、好ましくない。 The temperature increase rate and the cooling rate during the first intermediate annealing treatment are not particularly limited, but are preferably 30 ° C./hour or more. When the heating rate and cooling rate during the first intermediate annealing treatment are less than 30 ° C./hour, precipitation of solute Mn proceeds to stably secure a recrystallized grain size of 500 μm or more after brazing. In addition to being disadvantageous, it takes too much time for processing, and productivity is lowered, which is not preferable.
連続焼鈍炉による第１次中間焼鈍の温度は４００〜５００℃が好ましい。４００℃未満の場合、十分な軟化状態を得ることができない。しかし、保持温度が５００℃を超えると、マトリックス中の固溶Ｍｎが高温での中間焼鈍時にＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物として粗大に析出してしまうため、第２次中間焼鈍時或いはろう付け時の再結晶阻止作用が弱まって、再結晶粒径が５００μｍ未満となり、ろう付け時の耐サグ性と耐エロージョン性が低下する。 Temperature of the primary intermediate annealing by the continuous annealing furnace is preferably 400 to 500 ° C.. When the temperature is lower than 400 ° C., a sufficient softened state cannot be obtained. However, when the holding temperature exceeds 500 ° C., the solid solution Mn in the matrix is coarsely precipitated as an Al— (Fe · Mn) —Si-based compound during intermediate annealing at a high temperature. Or the recrystallization inhibitory action at the time of brazing becomes weak, the recrystallized grain size becomes less than 500 μm, and the sag resistance and erosion resistance at the time of brazing deteriorate.
連続焼鈍の保持時間は５分以内とすることが好ましい。連続焼鈍の保持時間が５分以内を超えると、固溶Ｍｎの析出が進行してろう付け後の再結晶粒径５００μｍ以上を安定して確保する上で不利になるばかりでなく、処理に時間が掛かりすぎて生産性が低下するため、好ましくない。 The holding time for continuous annealing is preferably within 5 minutes. When the holding time of continuous annealing exceeds 5 minutes, not only is the solid solution Mn precipitating progressing, but it is disadvantageous in securing a recrystallized grain size of 500 μm or more after brazing, and it takes time for processing. This is not preferable because the productivity is lowered due to excessive application.
連続焼鈍処理時の昇温速度および冷却速度は、昇温速度については１００°Ｃ／ｍｉｎ以上とすることが好ましい。連続焼鈍処理時の昇温速度が１００°Ｃ／ｍｉｎ未満の場合、処理に時間が掛かりすぎて生産性が低下するため、好ましくない。 The heating rate and cooling rate during the continuous annealing treatment are preferably 100 ° C./min or higher for the heating rate. When the rate of temperature increase during the continuous annealing process is less than 100 ° C./min, the process takes too much time and productivity is lowered, which is not preferable.
〔第２次中間焼鈍条件〕 第２次中間焼鈍の保持温度は３６０〜４５０°Ｃが好ましい。第２次中間焼鈍の保持温度が３６０°Ｃ未満の場合、十分な軟化状態を得ることができない。しかし、第２次中間焼鈍の保持温度が４５０°Ｃを超えると、マトリックス中の固溶Ｍｎが高温での中間焼鈍時にＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物として粗大に析出してしまうため、および再結晶組織となってしまうため、ろう付け時の再結晶阻止作用が弱まって、再結晶粒径が５００μｍ未満となり、ろう付け時の耐サグ性と耐エロージョン性が低下する。 [Secondary intermediate annealing conditions] The holding temperature of the second intermediate annealing is preferably 360 to 450 ° C. When the holding temperature of the second intermediate annealing is less than 360 ° C., a sufficient softened state cannot be obtained. However, if the holding temperature of the second intermediate annealing exceeds 450 ° C., the solid solution Mn in the matrix is coarsely precipitated as an Al— (Fe · Mn) —Si based compound at the intermediate annealing at a high temperature. And the recrystallized structure weakens the recrystallization inhibiting action during brazing, resulting in a recrystallized grain size of less than 500 μm, which decreases sag resistance and erosion resistance during brazing.
第２次中間焼鈍の保持時間は特に限定する必要はないが、１〜５時間の範囲とすることが好ましい。第２次中間焼鈍の保持時間が１時間未満では、コイル全体の温度が不均一なままで、板中における均一な再結晶組織の得られない可能性があるので好ましくない。第２次中間焼鈍の保持時間が５時間を超えると、固溶Ｍｎの析出が進行してろう付け後の再結晶粒径５００μｍ以上を安定して確保する上で不利になるばかりでなく、処理に時間が掛かりすぎて生産性が低下するため、好ましくない。 The holding time of the second intermediate annealing is not particularly limited, but is preferably in the range of 1 to 5 hours. If the holding time of the second intermediate annealing is less than 1 hour, the temperature of the entire coil remains non-uniform, and a uniform recrystallized structure in the plate may not be obtained. If the holding time of the second intermediate annealing exceeds 5 hours, the precipitation of the solid solution Mn progresses, which is not only disadvantageous in securing a recrystallized grain size of 500 μm or more after brazing but also processing. This is not preferable because it takes too much time to reduce productivity.
第２次中間焼鈍処理時の昇温速度および冷却速度は特に限定する必要はないが、３０°Ｃ／時間以上とすることが好ましい。第２次中間焼鈍処理時の昇温速度および冷却速度が３０°Ｃ／時間未満の場合、固溶Ｍｎの析出が進行してろう付け後の再結晶粒径５００μｍ以上を安定して確保する上で不利であるばかりでなく、処理に時間が掛かりすぎて生産性が低下するので、好ましくない。 The temperature increase rate and the cooling rate during the second intermediate annealing treatment are not particularly limited, but are preferably 30 ° C./hour or more. When the heating rate and cooling rate during the second intermediate annealing treatment are less than 30 ° C./hour, precipitation of solute Mn proceeds to stably secure a recrystallized grain size of 500 μm or more after brazing. In addition to being disadvantageous, it takes too much time for processing, and productivity is lowered, which is not preferable.
〔ファイバーな結晶粒組織〕 前記第１次中間焼鈍後、第２次中間焼鈍後、最終焼鈍後（ろう付け前）の何れの段階においても、金属組織がファイバーな結晶粒組織であるとは、何れの段階においても、金属組織が２００μｍ以上の結晶粒組織を含まないファイバーな結晶粒組織であることを意味する。 [Fiber crystal grain structure] The metal structure is a fiber crystal grain structure at any stage after the first intermediate annealing, after the second intermediate annealing, and after the final annealing (before brazing). In any stage, it means that the metal structure is a fiber crystal grain structure not containing a crystal grain structure of 200 μm or more.
〔最終冷延率〕 最終冷延率は１０〜９６％が好ましい。最終冷延率が１０％未満の場合、冷間圧延で蓄積される歪エネルギーが少なく、ろう付け時の昇温過程で再結晶が完了しないため、耐サグ性と耐エロージョン性が低下する。最終冷延率が９６％を超えると圧延時の耳割れが顕著になり歩留まりが低下する。最終焼鈍を行わない場合，最終冷間圧延率が５０％を超えると，製品強度が高くなりすぎて，フィン材成形において所定のフィン形状を得る事が困難になる。一方、最終冷延率が５０％以上の場合、組成によっては製品強度が高くなり過ぎて、フィン成形において所定のフィン形状を得ることが困難になるが、このときには、最終冷延板に保持温度２００〜４００°Ｃで１〜３時間程度の最終焼鈍（軟化処理）を行っても諸特性を損なうことはない。特に連続焼鈍炉により第１次中間焼鈍を施した後、最終冷間圧延された板に、更に保持温度２００〜４００°Ｃで１〜３時間程度の最終焼鈍（軟化処理）を施したフィン材は、フィン成形性に優れており、しかもろう付け後の強度も高く、耐サグ性に優れている。 [Final cold rolling rate] The final cold rolling rate is preferably 10 to 96%. When the final cold rolling rate is less than 10%, the strain energy accumulated by cold rolling is small, and recrystallization is not completed in the temperature rising process during brazing, so the sag resistance and erosion resistance are lowered. When the final cold rolling rate exceeds 96%, the ear cracks at the time of rolling become remarkable and the yield decreases. When final annealing is not performed, if the final cold rolling rate exceeds 50%, the product strength becomes too high, and it becomes difficult to obtain a predetermined fin shape in fin material molding. On the other hand, when the final cold rolling rate is 50% or more, depending on the composition, the product strength becomes too high, and it becomes difficult to obtain a predetermined fin shape in the fin forming. Even if final annealing (softening treatment) is performed at 200 to 400 ° C. for about 1 to 3 hours, various characteristics are not impaired. In particular, after first intermediate annealing is performed by a continuous annealing furnace, the final cold-rolled plate is further subjected to final annealing (softening treatment) for about 1 to 3 hours at a holding temperature of 200 to 400 ° C. Is excellent in fin moldability, has high strength after brazing, and has excellent sag resistance.
本発明のフィン材は、所定幅にスリッティングした後コルゲート加工して、作動流体通路用材料、例えば、ろう材を被覆した３００３合金などからなるクラッド板からなる偏平管と交互に積層し、ろう付け接合することにより熱交換器ユニットとする。 The fin material of the present invention is subjected to corrugation after slitting to a predetermined width, and alternately laminated with flat tubes made of a clad plate made of a working fluid passage material, for example, a 3003 alloy coated with a brazing material. A heat exchanger unit is obtained by jointing.
本発明の方法によれば、双ベルト式鋳造機による薄スラブ鋳造時、スラブ中にＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物が均一かつ微細に晶出するとともに、母相Ａｌ中に過飽和に固溶したＭｎとＳｉが、ろう付け時の高温加熱によってサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ相として高密度に析出する。これにより熱伝導性を大きく低下させるマトリックス中の固溶Ｍｎ量が少なくなるため、ろう付け後の電気伝導率は高くなり、優れた熱伝導性を示す。また、同様の理由により、微細に晶出したＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物、および高密度に析出したサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ相が塑性変形時の転位の動きを妨げるため、ろう付け後の最終板の抗張力は高い値を示す。また、ろう付け時に析出するサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ相は強い再結晶阻止作用を有するため、ろう付け後の再結晶粒径が５００μｍ以上となるため耐サグ性が良好となり、同様の理由から、ろう付け後にも優れた耐エロージョン性を示すようになる。また、本発明においてＭｎの含有量を１．５wt%以上に限定したことから、ろう付け後の再結晶粒の平均粒径が３０００μｍを超えても抗張力が低下することはない。 According to the method of the present invention, at the time of thin slab casting by a twin belt type casting machine, Al- (Fe · Mn) -Si compound is crystallized uniformly and finely in the slab and supersaturated in the matrix Al. The solid solution Mn and Si are deposited at a high density as a sub-micron level Al- (Fe.Mn) -Si phase by high-temperature heating during brazing. As a result, the amount of solid solution Mn in the matrix that greatly lowers the thermal conductivity is reduced, so that the electrical conductivity after brazing is increased and excellent thermal conductivity is exhibited. For the same reason, the Al- (Fe · Mn) -Si compound finely crystallized and the submicron-level Al- (Fe · Mn) -Si phase precipitated at high density are dislocations during plastic deformation. The tensile strength of the final plate after brazing shows a high value. In addition, the sub-micron-level Al- (Fe.Mn) -Si phase that precipitates during brazing has a strong recrystallization-inhibiting action, so that the recrystallized grain size after brazing is 500 μm or more, thus providing good sag resistance. Thus, for the same reason, it exhibits excellent erosion resistance even after brazing. In the present invention, since the Mn content is limited to 1.5 wt% or more, the tensile strength does not decrease even if the average grain size of the recrystallized grains after brazing exceeds 3000 μm.
さらに、双ベルト式鋳造機は溶湯の凝固速度が速く、薄スラブ中に晶出するＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ系化合物は均一で微細なものとなる。そのため最終のフィン材において、粗大な晶出物起因の円相当径で５μｍ以上の第二相粒子が存在しなくなり、優れた自己耐食性を発現するようになる。 Further, the twin-belt casting machine has a high solidification rate of the molten metal, and the Al— (Fe · Mn) —Si compound crystallized in the thin slab becomes uniform and fine. Therefore, in the final fin material, second phase particles having a circle-equivalent diameter of 5 μm or more due to coarse crystals are not present, and excellent self-corrosion resistance is exhibited.
このように双ベルト式連続鋳造法により薄スラブを鋳造することにより、スラブ鋳塊におけるＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ化合物を均一かつ微細とし、ろう付け後のサブミクロンレベルのＡｌ−（Ｆｅ・Ｍｎ）−Ｓｉ相析出物を高密度にするとともに、ろう付け後の結晶粒径を５００μｍ以上と粗くすることで、ろう付け後の強度、熱伝導率、耐サグ性、耐エロージョン性、自己腐食性を高め、同時にＺｎを含有させることによって材料の電位を卑にして犠牲陽極効果を優れたものとし、耐久性の優れた熱交換器用アルミニウム合金フィン材とすることができる。 Thus, by casting the thin slab by the twin belt type continuous casting method, the Al— (Fe · Mn) —Si compound in the slab ingot is made uniform and fine, and the submicron level Al— (Fe・ Mn) -Si phase precipitates are densified and the grain size after brazing is coarsened to 500 μm or more, so that strength after brazing, thermal conductivity, sag resistance, erosion resistance, self By increasing the corrosivity and simultaneously containing Zn, the potential of the material can be reduced, the sacrificial anode effect can be improved, and the aluminum alloy fin material for a heat exchanger having excellent durability can be obtained.
以下、本発明の実施例を比較例と対比して説明する。
本発明例および比較例として、表１に示した合金番号１から１２の組成の合金溶湯を溶製し、セラミックス製フィルターを通過させて双ベルト鋳造鋳型に注湯し、鋳造速度８ｍ／ｍｉｎ で、厚さ７mmのスラブを連続鋳造した。溶湯の凝固時冷却速度は５０°Ｃ／ｓｅｃ であった。該薄スラブを表２〜４に示す板厚（Ｉ/Ａ１板厚）まで冷間圧延した。その後、試料をアニーラーに挿入し、昇温速度５０°Ｃ／ｈｒで昇温して、表２〜４に示す各温度で２ｈｒ保持した後、冷却速度５０°Ｃ／ｈｒで１００°Ｃまで冷却するか、又は試料を４５０℃のソルト浴に１５ｓｅｃ保持後、水焼入れをする第１次中間焼鈍処理を施した。次いで試料を表２〜４に示す板厚（Ｉ/Ａ２板厚）まで冷間圧延した後、アニーラーに挿入し、昇温速度５０°Ｃ／ｈｒで昇温して、表２〜４に示す各温度で２ｈｒ保持した後、冷却速度５０°Ｃ／ｈｒで１００°Ｃまで冷却する第２中間焼鈍処理を施した。次いで表２〜４に示す最終冷延率で冷間圧延を施し、厚さ６０μｍのフィン材とした。これら試料のうち一部については、更に試料をアニーラーに挿入し、昇温速度５０°Ｃ／ｈｒで昇温して、表４に示す各温度で２ｈｒ保持した後、冷却速度５０°Ｃ／ｈｒで１００°Ｃまで冷却する最終焼鈍処理を施した。
Examples of the present invention will be described below in comparison with comparative examples.
As an example of the present invention and a comparative example, a molten alloy having the composition of alloy numbers 1 to 12 shown in Table 1 was melted, passed through a ceramic filter, poured into a twin belt casting mold, and cast at a casting speed of 8 m / min. A 7 mm thick slab was continuously cast. The cooling rate during solidification of the molten metal was 50 ° C / sec. The thin slab was cold-rolled to a plate thickness (I / A1 plate thickness) shown in Tables 2-4. Thereafter, the sample was inserted into an annealer, heated at a heating rate of 50 ° C./hr, held at each temperature shown in Tables 2 to 2 for 2 hr, and then cooled to 100 ° C. at a cooling rate of 50 ° C./hr. Alternatively, the sample was kept in a 450 ° C. salt bath for 15 seconds, and then subjected to a first intermediate annealing treatment in which water quenching was performed. Next, the sample was cold-rolled to the thickness shown in Tables 2 to 4 (I / A2 thickness), then inserted into an annealer, heated at a temperature increase rate of 50 ° C./hr, and shown in Tables 2 to 4 After holding at each temperature for 2 hr, a second intermediate annealing treatment was performed to cool to 100 ° C. at a cooling rate of 50 ° C./hr. Subsequently, it cold-rolled with the final cold rolling rate shown in Tables 2-4, and was set as the 60-micrometer-thick fin material. For some of these samples, the sample was further inserted into an annealer, heated at a temperature rising rate of 50 ° C./hr, held at each temperature shown in Table 4 for 2 hr, and then cooled at a rate of 50 ° C./hr. The final annealing process which cools to 100 degreeC was performed.
比較例として、表１に示した合金番号１３、１４の組成の合金溶湯を溶製し、常法のＤＣ鋳造（厚さ５００mm、凝固時冷却速度約１°Ｃ／ｓｅｃ ）、面削、均熱処理、熱間圧延、冷間圧延（厚さ１００μm）、中間焼鈍（４００°Ｃ×２ｈｒ）、冷間圧延により厚さ６０μｍのフィン材を製造した。
得られた本発明例および比較例のフィン材について下記（１）〜（３）の測定を行なった。
As a comparative example, a molten alloy having the composition of Alloy Nos. 13 and 14 shown in Table 1 was melted, and the conventional DC casting (thickness: 500 mm, cooling rate at solidification: about 1 ° C / sec), face grinding, leveling, A fin material having a thickness of 60 μm was manufactured by heat treatment, hot rolling, cold rolling (thickness 100 μm), intermediate annealing (400 ° C. × 2 hr), and cold rolling.
The following measurements (1) to (3) were performed on the fin materials of the present invention examples and comparative examples.
（１）得られたフィン材の抗張力（ＭＰａ ） （２）ろう付け温度を想定して６００〜６０５°Ｃ×３．５ｍｉｎ加熱し、冷却後下記項目を測定した。
[1] 抗張力（ＭＰａ ） [2] 表面を電解研磨してバーカー法で結晶粒組織を現出後、切断法で圧延方向に平行な結晶粒径（μｍ） [3] 銀塩化銀電極を照合電極として、５％食塩水中で６０ｍｉｎ浸漬後の自然電位（ｍV） [4] 銀塩化銀電極を照合電極として、５％食塩水中で電位掃引速度２０mV／ｍｉｎで行ったカソード分極より求めた腐食電流密度（μＡ／cm2 ） [5] ＪＩＳ−Ｈ０５０５記載の導電性試験法で導電率［％ＩＡＣＳ］
(1) Tensile strength (MPa) of the obtained fin material (2) Heating was performed at 600 to 605 ° C. for 3.5 minutes assuming a brazing temperature, and the following items were measured after cooling.
[1] Tensile strength (MPa) [2] Electrolytic polishing of the surface and revealing the grain structure by Barker method, then crystal grain size (μm) parallel to rolling direction by cutting method [3] Silver silver chloride electrode is verified Natural potential (mV) after immersion for 60 min in 5% saline as an electrode [4] Corrosion current obtained from cathodic polarization performed at a potential sweep rate of 20 mV / min in 5% saline using a silver-silver chloride electrode as a reference electrode Density (μA / cm 2 ) [5] Conductivity [% IACS] according to the conductivity test method described in JIS-H0505
（３）ＬＷＳ Ｔ ８８０１記載のサグ試験方法で、突き出し長さ５０mmとしたサグ量（mm） （４）コルゲート状に加工したフィン材を非腐食性弗化物系フラックスを塗布した厚さ０．２５mmのブレージングシート（ろう材４０４５合金クラッド率８％）のろう材面上に載置（負荷荷重３２４ｇ）し、昇温速度５０°Ｃ／ｍｉｎ で６０５°Ｃまで加熱して５ｍｉｎ保持した。冷却後、ろう付け断面を観察し、フィン材結晶粒界のエロージョンが軽微なものを良（○印）とし、エロージョンが激しくフィン材の溶融が顕著なものを不良（×印）とした。なおコルゲート形状は下記のとおりとした。
コルゲート形状：高さ２．３mm×幅２１mm×ピッチ３．４mm、１０山 結果を表５〜７に示す。
(3) Sag amount (mm) with a protruding length of 50 mm by the sag test method described in LWS T 8801 (4) Thickness of 0.25 mm with noncorrosive fluoride flux applied to corrugated fin material Was placed on the brazing material surface of the brazing sheet (brazing material 4045 alloy clad rate 8%) (load load 324 g), heated to 605 ° C. at a heating rate of 50 ° C./min and held for 5 min. After cooling, the brazed cross section was observed, and a slight erosion of the fin material crystal grain boundary was judged as good (◯ mark), and a erosion was severe and the fin material melted markedly as poor (x mark). The corrugated shape was as follows.
Corrugated shape: height 2.3 mm × width 21 mm × pitch 3.4 mm, 10 peaks The results are shown in Tables 5-7.
表５の結果から、本発明によるフィン材（フィン材番号１〜５）は、ろう付け後の抗張力、耐エロージョン性、耐サグ性、犠牲陽極効果および自己耐食性のいずれも良好であることが判る。比較例のフィン材番号６は、Ｍｎ含有量が低く、ろう付け後抗張力が低い。
比較例のフィン材番号７は、Ｍｎ含有量が多く、鋳造時に巨大晶出物が生成し、冷間圧延中に割れを生じフィン材が得られなかった。比較例のフィン材番号８は、Ｓｉ含有量が低く、ろう付け後抗張力が低い。比較例のフィン材番号９は、Ｓｉ含有量が多く、耐エロージョン性が劣った。比較例のフィン材番号１０は、Ｆｅ含有量が多く、鋳造時に巨大晶出物が生成し、冷間圧延中に割れを生じフィン材が得られなかった。
From the results of Table 5, it can be seen that the fin materials (fin material numbers 1 to 5) according to the present invention have good tensile strength, erosion resistance, sag resistance, sacrificial anode effect and self-corrosion resistance after brazing. . Fin material number 6 of the comparative example has a low Mn content and a low tensile strength after brazing.
The fin material No. 7 of the comparative example had a large Mn content, a large crystallized product was generated during casting, cracking occurred during cold rolling, and a fin material was not obtained. Fin material number 8 of the comparative example has a low Si content and a low tensile strength after brazing. Fin material number 9 of the comparative example had a large Si content and was inferior in erosion resistance. The fin material No. 10 of the comparative example had a large Fe content, a large crystallized product was generated during casting, cracks occurred during cold rolling, and a fin material was not obtained.
比較例のフィン材番号１１は、Ｚｎ含有量が低く、自然電位が貴であり、犠牲陽極効果が劣った。比較例のフィン材番号１２は、Ｚｎ含有量が多く、自己耐食性が劣っており、耐エロージョン性も劣った。常法のＤＣ鋳造（厚さ５００mm、凝固時冷却速度約１°Ｃ／ｓｅｃ ）、面削、均熱処理、熱間圧延、冷間圧延（厚さ１００μm）、中間焼鈍（４００°Ｃ×２ｈｒ）、冷間圧延により得られたＭｎ含有量の低い比較例のフィン材番号１３およびＳｉ、Ｍｎ含有量の低い比較例のフィン材番号１４は、ろう付け後の抗張力が低く、ろう付け後の結晶粒径が小さく、耐サグ性、耐エロージョン性ともに劣った。 Fin material number 11 of the comparative example had a low Zn content, a natural potential was noble, and the sacrificial anode effect was inferior. Fin material number 12 of the comparative example had a large Zn content, inferior self-corrosion resistance, and inferior in erosion resistance. Conventional DC casting (thickness: 500 mm, solidification cooling rate: approx. 1 ° C / sec), chamfering, soaking, hot rolling, cold rolling (thickness: 100 μm), intermediate annealing (400 ° C x 2 hr) The fin material number 13 of the comparative example with a low Mn content obtained by cold rolling and the fin material number 14 of the comparative example with a low Mn content are low in tensile strength after brazing and have a crystal after brazing. The particle size was small, and both sag resistance and erosion resistance were poor.
表６の結果から、本発明によるフィン材（フィン材番号１、１５、１６）は、ろう付け前の抗張力が２４０ＭＰａ以下であり成形性に優れ、ろう付け後の抗張力、耐エロージョン性、耐サグ性のいずれも良好であることが判る。比較例のフィン材番号１７は、最終冷延率が６０％であるため、ろう付け前の抗張力が高く成形性が劣った。比較例のフィン材番号１８、１９は、第１次中間焼鈍処理の温度が高いため、ろう付け後の組織が再結晶せず、耐サグ性、耐エロージョン性が劣った。比較例のフィン材番号２０は、最終冷延率が６０％であるため、ろう付け加熱前の抗張力が高く、耐エロージョン性が劣る。比較例のフィン材番号２１、２２は、第２次中間焼鈍処理の温度が低いため、ろう付け加熱前の抗張力が高く成形性が劣った。比較例のフィン材番号２３、２５は、第２次焼鈍処理の温度が低いため、ろう付け加熱前の抗張力が高く成形性が劣った。比較例のフィン材番号２４は、第２中間焼鈍処理の温度が高いため、再結晶が起こってしまい耐エロージョン性が劣った。 From the results shown in Table 6, the fin materials according to the present invention (fin material numbers 1, 15, and 16) have a tensile strength before brazing of 240 MPa or less and excellent moldability, and have a tensile strength, erosion resistance, and sag resistance after brazing. It turns out that all of sex is favorable. The fin material number 17 of the comparative example had a final cold rolling rate of 60%, and therefore had high tensile strength before brazing and poor moldability. Since the fin material numbers 18 and 19 of the comparative examples had a high temperature in the first intermediate annealing treatment, the structure after brazing was not recrystallized, and the sag resistance and the erosion resistance were inferior. The fin material number 20 of the comparative example has a final cold rolling rate of 60%, and thus has a high tensile strength before brazing heating and is inferior in erosion resistance. The fin material numbers 21 and 22 of the comparative examples had a high tensile strength before brazing heating and a poor moldability because the temperature of the second intermediate annealing treatment was low. The fin material numbers 23 and 25 of the comparative examples had a low tensile strength before brazing heating because the temperature of the secondary annealing treatment was low, and the moldability was poor. Since the fin material number 24 of the comparative example had a high temperature for the second intermediate annealing treatment, recrystallization occurred and the erosion resistance was inferior.
表７の結果から、本発明によるフィン材（フィン材番号２６〜２９）は、ろう付け前の抗張力が２４０ＭＰａ以下であり成形性に優れ、ろう付け後の抗張力、耐エロージョン性、耐サグ性のいずれも良好であることが判る。比較例のフィン材番号３０は、最終焼鈍処理の温度が高いため、再結晶が起こってしまい耐エロージョン性が劣った。比較例のフィン材番号３１は、最終焼鈍処理の温度が低いため、ろう付け加熱前の抗張力が高く成形性が劣った。 From the results of Table 7, the fin material according to the present invention (fin material numbers 26 to 29) has a tensile strength before brazing of 240 MPa or less and excellent moldability, and has a high tensile strength, erosion resistance and sag resistance after brazing. It turns out that all are good. The fin material No. 30 of the comparative example was inferior in erosion resistance because recrystallization occurred because the temperature of the final annealing treatment was high. The fin material No. 31 of the comparative example has a low tensile strength before brazing heating because the temperature of the final annealing treatment is low, and the moldability is poor.
本発明によれば、フィン成形が容易な適度なろう付け前の抗張力、およびろう付け後において高い強度を有し、伝熱特性、耐サグ性、耐エロージョン性、自己耐食性、犠牲陽極効果に優れた熱交換器用アルミニウム合金フィン材が提供される。 According to the present invention, it has an appropriate tensile strength before brazing that facilitates fin molding and high strength after brazing, and is excellent in heat transfer characteristics, sag resistance, erosion resistance, self-corrosion resistance, and sacrificial anode effect. An aluminum alloy fin material for a heat exchanger is provided.
Claims (2)
ろう付け前の金属組織が圧延組織であり、ろう付前の抗張力が２４０ＭＰａ以下であり、さらに
加熱温度６００〜６０５℃で３．５分保持し、冷却した後の抗張力が１５０ＭＰａ以上であり、且つ加熱温度６００〜６０５℃で３．５分保持し、冷却した後の圧延方向に平行な平均再結晶粒径が６７００μｍであることを特徴とする熱交換器用高強度アルミニウム合金フィン材。 Si: 0.8-1.4 wt%, Fe: 0.45-0.7 wt%, Mn: 1.5-3.0 wt%, Zn: 0.5-2.5 wt%, and further as impurities High-strength aluminum alloy for heat exchangers with Mg limited to 0.05 wt% or less, Cu as impurities limited to 0.02 wt% or less, and the balance consisting only of an aluminum alloy having a chemical composition of ordinary impurities and Al A fin material,
The metal structure before brazing is a rolled structure, the tensile strength before brazing is 240 MPa or less, and the tensile strength after cooling at a heating temperature of 600 to 605 ° C. for 3.5 minutes is 150 MPa or more, and A high-strength aluminum alloy fin material for heat exchangers characterized in that the average recrystallized grain size parallel to the rolling direction after being held at a heating temperature of 600 to 605 ° C. for 3.5 minutes and cooled is 6700 μm.
ろう付け前の金属組織が圧延組織であり、ろう付前の抗張力が２４０ＭＰａ以下であり、さらに
加熱温度６００〜６０５℃で３．５分保持し、冷却した後の抗張力が１５０ＭＰａ以上であり、且つ加熱温度６００〜６０５℃で３．５分保持し、冷却した後の圧延方向に平行な平均再結晶粒径が６７００μｍであることを特徴とする熱交換器用高強度アルミニウム合金フィン材。 Si: 0.8-1.4 wt%, Fe: 0.45-0.7 wt%, Mn: 2.1-3.0 wt%, Zn: 0.5-2.5 wt%, and further as impurities High-strength aluminum alloy for heat exchangers with Mg limited to 0.05 wt% or less, Cu as impurities limited to 0.2 wt% or less, and the balance consisting only of an aluminum alloy having a chemical composition of ordinary impurities and Al A fin material,
The metal structure before brazing is a rolled structure, the tensile strength before brazing is 240 MPa or less, and the tensile strength after cooling at a heating temperature of 600 to 605 ° C. for 3.5 minutes is 150 MPa or more, and A high-strength aluminum alloy fin material for heat exchangers characterized in that the average recrystallized grain size parallel to the rolling direction after being held at a heating temperature of 600 to 605 ° C. for 3.5 minutes and cooled is 6700 μm.
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