JP2012067385A - Brazing sheet and method for producing the same - Google Patents
Brazing sheet and method for producing the same Download PDFInfo
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Description
本発明は、板厚４０μｍ〜８０μｍの薄板で、耐高温座屈性に優れ、非腐食性フラックスブレージングに適したブレージングシート及びその製造方法に関するものである。 The present invention relates to a brazing sheet having a thickness of 40 μm to 80 μm, excellent in high temperature buckling resistance and suitable for non-corrosive flux brazing, and a method for producing the same.
従来、車載クーラー用のコンデンサー、エバポレータなどの熱交換器は、アルミニウム合金製の押出多穴チューブ等の冷媒通路構成部材とコルゲートフィン等とから構成されている。
一般にこのような押出多穴チューブにはＪＩＳ Ａ１０５０（９９．５質量％以上のＡｌ（以下、質量％を単に％と記す。））やＡ３００３（Ａｌ−０．１５％Ｃｕ−１．１％Ｍｎ）合金が用いられ、コルゲートフィンにはＡ３００３あるいはＡ３２０３（Ａｌ−１．１％Ｍｎ）を芯材とし、これらの両面にＡｌ−Ｓｉ系合金、例えば４３４３合金（Ａｌ−７．５％Ｓｉ）や４００４（Ａｌ−１０％Ｓｉ−１．５％Ｍｇ）がクラッドされた、いわゆるブレージングシートが用いられる。
そしてこれらのブレージングシートを用いる熱交換器の製造は、押出多穴チューブとブレージングシートとを用いて所望の形状に組み立てた後、雰囲気を調整した炉内で５９０℃〜６２０℃に数分加熱して接合する方法、いわゆるブレージング法により行なわれる。
2. Description of the Related Art Conventionally, heat exchangers such as condensers and evaporators for in-vehicle coolers are composed of refrigerant passage components such as extruded multi-hole tubes made of aluminum alloy, corrugated fins, and the like.
Generally, such an extruded multi-hole tube has JIS A1050 (99.5 mass% or more Al (hereinafter, mass% is simply referred to as%)) or A3003 (Al-0.15% Cu-1.1% Mn). ) Alloy is used, and the corrugated fin is made of A3003 or A3203 (Al-1.1% Mn) as a core material, and an Al-Si alloy such as 4343 alloy (Al-7.5% Si) or A so-called brazing sheet clad with 4004 (Al-10% Si-1.5% Mg) is used.
And the manufacture of the heat exchanger using these brazing sheets is assembled to a desired shape using an extruded multi-hole tube and a brazing sheet, and then heated to 590 ° C. to 620 ° C. for several minutes in a furnace with an adjusted atmosphere. And a so-called brazing method.
ところでブレージング法の中で非腐食性フラックスブレージング法を用いるブレージングシートの場合、コルゲートフィンの芯材（あるいは皮材にも）Ａ３００３合金にＺｎを添加し、犠牲陽極フィンの効果を与え押出しチューブ材を防食する必要がある。しかしながら、Ｚｎを添加すると犠牲陽極効果は向上するものの耐高温座屈性が低下する。
耐高温座屈性を向上させる方法がいくつか提案されている。特許文献１では、このようなブレージング法に用いるアルミニウム合金製フィン材の製造方法として、Ｍｎ、Ｍｇ、Ｚｒなどを所定量含有するアルミニウム合金の芯材に皮材をクラッドしたフィン材の製造方法が提案されている。
特許文献２では、Ｍｎ、Ｚｎ、Ｃｕ、Ｆｅ、Ｓｉを所定量含有したアルミニウム合金を芯材として高強度化、高温座屈性を向上させている。
また特許文献３では、Ｍｎ、Ｚｎ、Ｆｅ、Ｓｉを所定量含有したアルミニウム合金を芯材として、熱間圧延の途中で３００℃〜４５０℃、１分間以上保持することで、フィン材のブレージング加熱の高温加熱時で析出と再結晶の競合が緩和されて耐高温座屈性を向上させている。
さらに特許文献４では、薄肉化させたアルミニウム合金クラッド材において材料中の平均Ｓｉ濃度とクラッド率を調整することで溶融ろうが芯材へ侵食することを防ぎ、高温座屈を防止している。
By the way, in the case of a brazing sheet using a non-corrosive flux brazing method in the brazing method, Zn is added to the core material (or skin material) of the corrugated fin A3003 alloy to give the effect of a sacrificial anode fin, and an extruded tube material is used. It is necessary to prevent corrosion. However, when Zn is added, the sacrificial anode effect is improved, but the high temperature buckling resistance is lowered.
Several methods for improving the high temperature buckling resistance have been proposed. In
In
Moreover, in
Furthermore, in Patent Document 4, by adjusting the average Si concentration in the material and the cladding ratio in the thinned aluminum alloy cladding material, the molten brazing is prevented from eroding into the core material and high temperature buckling is prevented.
近年、熱交換器の軽量化、コスト低減の要求はますます高まり、フィン材はじめ主要部材の薄肉化が進行している。フィン材を薄くする際、熱交換器の特性を維持、向上するためにフィン材の高強度化が必須である。しかし、ブレージングシートのろう溶融加熱時は溶融ろうのＳｉが芯材へ拡散し、芯材のＳｉ濃度が増加する。このとき、Ｓｉ濃度が高くなると、芯材の融点が下がり、ろう溶融時に芯材のろうの侵食及び芯材の溶解が生じやすくなる。この現象は芯材厚さが薄くなるほど顕著になり、強度が低下し、ろう溶融時にフィンの座屈が生じやすくなる。
上記の特許文献１〜３は耐高温座屈性を向上させているが、いずれも板厚１００μｍ未満の薄肉化フィンには対応していない。
また、材料を薄肉化すると皮材や芯材の板厚が薄くなるため、ろう材中のＳｉが芯材へ拡散しやすくなる。Ｓｉが芯材へ拡散すると芯材のＳｉ濃度が高くなり、融点が下がる。これによりろう付け加熱時にフィンが溶融する問題も生じてくる。特許文献４では材料中の平均Ｓｉ濃度とクラッド率とを調整することで溶融ろうが芯材へ侵食することを防ぎ、高温座屈を防止しているが、薄肉化に伴った強度を確保するための製造工程や芯材中に含まれる析出物が占める数密度が規定されていない。
従って、フィン材の薄肉化を進めるに当たり、フィンの耐高温座屈性を向上させるとフィンの溶融を抑えることは必須であり、より適切な合金成分やクラッド率の組合せと強度の確保が求められる。
In recent years, demands for weight reduction and cost reduction of heat exchangers are increasing, and thinning of main members such as fin materials is progressing. When thinning the fin material, it is essential to increase the strength of the fin material in order to maintain and improve the characteristics of the heat exchanger. However, during brazing and heating of the brazing sheet, the molten solder Si diffuses into the core material, and the Si concentration of the core material increases. At this time, when the Si concentration is increased, the melting point of the core material is lowered, and the wax erosion of the core material and the melting of the core material are liable to occur during the melting of the wax. This phenomenon becomes more prominent as the core material becomes thinner, the strength is lowered, and the fins are likely to buckle during brazing.
Although
Further, when the material is thinned, the thickness of the skin material and the core material becomes thin, so that Si in the brazing material is easily diffused into the core material. When Si diffuses into the core material, the Si concentration of the core material increases and the melting point decreases. This also causes a problem that the fin melts during brazing heating. In Patent Document 4, by adjusting the average Si concentration in the material and the cladding rate, the molten brazing is prevented from eroding into the core material and high temperature buckling is prevented, but the strength accompanying thinning is ensured. Number density occupied by precipitates contained in the manufacturing process and core material is not specified.
Therefore, in order to reduce the thickness of the fin material, it is indispensable to suppress the melting of the fin if the high temperature buckling resistance of the fin is improved, and it is required to ensure a more appropriate combination of alloy components and cladding ratio and strength. .
本発明の目的は、合金成分、クラッド率、製造条件の組合せを検討することで、これまでのフィン材よりも薄肉化しても耐高温座屈性や強度が高く、優れた犠牲陽極効果を示すフィン材用ブレージングシートの製造方法を提供することである。 The object of the present invention is to examine the combination of alloy components, clad rate, and manufacturing conditions, so that even if the fin material is thinner than the conventional fin material, the high temperature buckling resistance and strength are high, and an excellent sacrificial anode effect is exhibited. It is providing the manufacturing method of the brazing sheet for fin materials.
本発明者らは上記問題点を解決するため、検討を重ねた結果、Ｍｎ、Ｚｎ、Ｆｅ、Ｓｉを所定量含有したアルミニウム合金を芯材とし、Ａｌ−Ｓｉ系ろう材を皮材として膜形成した合せ材に対して、所定の熱処理及び加工を施すことによりその目的を達成しうることを見出し、この知見に基づき本発明を完成するに至った。
本発明によれば、以下の手段が提供される。
（１）Ｍｎを０．６質量％〜１．８質量％（以下、質量％を単に％と記す。）、Ｆｅを０．０５％〜０．６％、Ｓｉを０．０２％〜０．７％、Ｚｎを０．０２％〜３．０％、Ｚｒを０．０５％〜０．３％、Ｔｉを０．０５％〜０．３％含有し、残部がＡｌと不可避的不純物からなるアルミニウム合金を芯材とし、この芯材の片面、又は両面にＳｉを６．０％〜１５．０％含有し、残部がＡｌと不可避的不純物からなるアルミニウム合金を皮材としたブレージングシートの製造方法であって、
前記皮材のクラッド率が片面で５％〜１５％となるように皮材をクラッドしてアルミニウム合金合せ材を形成する工程と、
前記アルミニウム合金合せ材を４２０℃〜５００℃で加熱した後に、熱間圧延、冷間圧延及び中間焼鈍を行う工程と、
前記アルミニウム合金合せ材の圧延率が、２０％〜７０％となるようにして最終冷間圧延を行い、４０μｍ〜８０μｍの板厚のブレージングシートを製造する工程と、
を具えることを特徴とする、ブレージングシートの製造方法（以下、第１の発明という）。
（２）Ｍｎを０．６％〜１．８％、Ｆｅを０．０５％〜０．６％、Ｓｉを０．０２％〜０．７％、Ｃｕを０．０５％〜０．８％、Ｚｎを０．０２％〜３．０％、Ｚｒを０．０５％〜０．３％、Ｔｉを０．０５％〜０．３％含有し、残部がＡｌと不可避的不純物からなるアルミニウム合金を芯材とし、芯材の片面、又は両面にＳｉを６．０％〜１５．０％含有し、残部がＡｌと不可避的不純物からなるアルミニウム合金を皮材としたブレージングシートの製造方法であって、
前記皮材のクラッド率が片面で５％〜１５％となるように皮材をクラッドしてアルミニウム合金合せ材を形成する工程と、
前記アルミニウム合金合せ材を４２０℃〜５００℃で加熱した後に、熱間圧延、冷間圧延及び中間焼鈍を行う工程と、
前記アルミニウム合金合せ材の圧延率が、２０％〜７０％となるようにして最終冷間圧延を行い、４０μｍ〜８０μｍの板厚のブレージングシートを製造する工程と、
を具えることを特徴とする、ブレージングシートの製造方法（以下、第２の発明という）。
（３）最終板厚Ｔ（μｍ）と芯材のＳｉ量ａ（％）と皮材のＳｉ量ｂ（％）、皮材のクラッド率をＣ（％）とした場合、ａ＋｛０．００１ｂ（２Ｃ／１００）＋０．０２４｝／（Ｔ／１０００）＜１．４０の式を満たすことを特徴とする、（１）または（２）に記載の製造方法により製造されたブレージングシート。
（４）芯材中に占めるＡｌ−Ｍｎ−ＦｅやＡｌ−Ｍｎ−Ｓｉ系の粒径０．１μｍ以上３．０μｍ未満の微細な析出物が占める数密度Ａ（個／ｍｍ２）と粒径３．０μｍ以上の粗大な析出物が占める数密度Ｂ（個／ｍｍ２）の比率Ａ／Ｂが５０≦Ａ／Ｂ≦５００を満たすことを特徴とする、（１）または（２）に記載の製造方法により製造されたブレージングシート。
なお、本発明におけるクラッド率とは、全体の板厚に対して皮材が占める厚さの割合で、皮材の厚さ／全体の板厚×１００（％）で表される。
As a result of repeated studies to solve the above problems, the present inventors have formed a film using an aluminum alloy containing a predetermined amount of Mn, Zn, Fe, and Si as a core material and an Al-Si brazing material as a skin material. It has been found that the purpose can be achieved by subjecting the laminated material to predetermined heat treatment and processing, and the present invention has been completed based on this finding.
According to the present invention, the following means are provided.
(1) Mn is 0.6 mass% to 1.8 mass% (hereinafter, mass% is simply referred to as%), Fe is 0.05% to 0.6%, and Si is 0.02% to 0.00. 7%, Zn is 0.02% to 3.0%, Zr is 0.05% to 0.3%, Ti is 0.05% to 0.3%, and the balance is made of Al and inevitable impurities. Production of brazing sheet using aluminum alloy as core material, and containing 6.0% to 15.0% of Si on one side or both sides of the core material, with the balance being aluminum alloy consisting of Al and inevitable impurities. A method,
A step of clad the skin material so that the cladding rate of the skin material is 5% to 15% on one side to form an aluminum alloy laminated material;
A step of performing hot rolling, cold rolling and intermediate annealing after heating the aluminum alloy laminated material at 420 ° C. to 500 ° C .;
A step of producing a brazing sheet having a thickness of 40 μm to 80 μm by performing final cold rolling so that the rolling ratio of the aluminum alloy laminated material is 20% to 70%;
A method for producing a brazing sheet (hereinafter referred to as the first invention).
(2) Mn: 0.6% to 1.8%, Fe: 0.05% to 0.6%, Si: 0.02% to 0.7%, Cu: 0.05% to 0.8% Aluminum alloy containing 0.02% to 3.0% Zn, 0.05% to 0.3% Zr, 0.05% to 0.3% Ti, the balance being Al and inevitable impurities Is a core material, containing 6.0% to 15.0% of Si on one or both sides of the core material, and a brazing sheet manufacturing method using an aluminum alloy consisting of Al and inevitable impurities as the skin material. And
A step of clad the skin material so that the cladding rate of the skin material is 5% to 15% on one side to form an aluminum alloy laminated material;
A step of performing hot rolling, cold rolling and intermediate annealing after heating the aluminum alloy laminated material at 420 ° C. to 500 ° C .;
A step of producing a brazing sheet having a thickness of 40 μm to 80 μm by performing final cold rolling so that the rolling ratio of the aluminum alloy laminated material is 20% to 70%;
A method for producing a brazing sheet (hereinafter, referred to as a second invention).
(3) When the final thickness T (μm), the Si amount a (%) of the core material, the Si amount b (%) of the skin material, and the cladding rate of the skin material C (%), a + {0.001b The brazing sheet manufactured by the manufacturing method according to (1) or (2), wherein the formula (2C / 100) +0.024} / (T / 1000) <1.40 is satisfied.
(4) Number density A (pieces / mm 2 ) and particle size occupied by fine precipitates of Al—Mn—Fe or Al—Mn—Si based particle size of 0.1 μm to less than 3.0 μm in the core material The ratio A / B of the number density B (pieces / mm 2 ) occupied by coarse precipitates of 3.0 μm or more satisfies 50 ≦ A / B ≦ 500, as described in (1) or (2) The brazing sheet manufactured by the manufacturing method.
The clad rate in the present invention is the ratio of the thickness occupied by the skin material to the overall plate thickness, and is expressed by the thickness of the skin material / total plate thickness × 100 (%).
本発明のブレージングシートは、耐高温座屈性、強度及び耐食性に優れているために薄肉化することができるので、これを用いることにより熱交換器を従来のものに比べ軽量化することが可能である。本発明の製造方法によれば、耐高温座屈性、強度及び耐食性に優れ、薄肉のブレージングシートを提供できる。 Since the brazing sheet of the present invention is excellent in high temperature buckling resistance, strength and corrosion resistance, it can be thinned, so that it is possible to reduce the weight of the heat exchanger compared to the conventional one. It is. According to the production method of the present invention, a thin brazing sheet having excellent high temperature buckling resistance, strength and corrosion resistance can be provided.
以下、本発明の詳細、並びにその他の特徴及び利点について、発明の実施の形態に基づいて説明する。
最初に、本発明のフィン材の芯材に用いられるアルミニウム合金組成における各成分の作用を説明する。なお、以下、質量％を単に％と記す。
Ｍｎは合金の強度を向上させるとともにＡｌ−Ｍｎ−ＦｅあるいはＡｌ−Ｍｎ−Ｓｉ系の化合物が析出し、再結晶粒を粗大化させ、ブレージング時の高温過熱の際の耐高温座屈性を向上させる働きを持つ。その量が少なすぎるとその効果が小さい。また、多すぎる場合はＡｌ−Ｍｎ−Ｆｅ、Ａｌ−Ｍｎ−Ｓｉ系の粗大な化合物が密に析出して成形性を悪化させる。また、巨大晶出物が生じ易く、再結晶が阻害され結晶粒が微細化し、結晶粒界の耐食性を悪化させる。従って、Ｍｎの含有量は０．６％〜１．８％で、更に好ましくは０．９％〜１．４％の範囲である。
Hereinafter, details of the present invention and other features and advantages will be described based on embodiments of the present invention.
First, the action of each component in the aluminum alloy composition used for the core material of the fin material of the present invention will be described. Hereinafter, mass% is simply referred to as%.
Mn improves the strength of the alloy and Al—Mn—Fe or Al—Mn—Si based compounds precipitate, coarsening the recrystallized grains and improving high temperature buckling resistance during high temperature overheating during brazing. It has a function to make it. If the amount is too small, the effect is small. On the other hand, when the amount is too large, coarse Al-Mn-Fe and Al-Mn-Si based compounds are densely deposited, thereby deteriorating the moldability. In addition, giant crystals are easily generated, recrystallization is inhibited, crystal grains are refined, and the corrosion resistance of crystal grain boundaries is deteriorated. Therefore, the Mn content is 0.6% to 1.8%, more preferably 0.9% to 1.4%.
Ｆｅは、Ａｌ、Ｍｎとの共存によってＡｌ−Ｍｎ−Ｆｅ系の析出物を生じ、再結晶粒を粗大化させ、ブレージング時の高温過熱の際の耐高温座屈性を向上させる働きを持つ。少なすぎると、再結晶粒は十分に粗大化されず、結晶粒が微細になり結晶粒界の腐食が進行し耐食性が悪化する。一方、多すぎるとＡｌ−Ｍｎ−Ｆｅ系の粗大な化合物が密に析出して成形性を悪化させる。また、晶出物の量が増え、再結晶の核サイトとして働くため、再結晶粒が微細化し、結晶粒界の耐食性及び耐高温座屈性を悪化させる。従って、Ｆｅの含有量は０．０５％〜０．６％で、更に好ましくは０．１％〜０．３％の範囲である。 Fe coexists with Al and Mn to produce Al-Mn-Fe-based precipitates, coarsening the recrystallized grains, and improving the high temperature buckling resistance during high temperature overheating during brazing. If the amount is too small, the recrystallized grains are not sufficiently coarsened, the crystal grains become fine, the corrosion of the crystal grain boundaries proceeds, and the corrosion resistance deteriorates. On the other hand, if the amount is too large, coarse Al—Mn—Fe-based compounds are densely deposited to deteriorate the moldability. Moreover, since the amount of crystallized substances increases and works as a nucleus site for recrystallization, the recrystallized grains become finer, and the corrosion resistance and high temperature buckling resistance of the crystal grain boundaries are deteriorated. Therefore, the Fe content is 0.05% to 0.6%, more preferably 0.1% to 0.3%.
ＳｉはＡｌ−Ｍｎ−Ｓｉ系の微細な化合物を析出させて強度を向上させる。また、再結晶粒を粗大化させ、ブレージング時の高温加熱の際の耐高温座屈性を向上させる働きを持つ。少なすぎるとその効果が十分に得られず、多すぎるとＡｌ−Ｍｎ−Ｓｉ系の微細な析出物が密になり、また、晶出物の効果で再結晶粒が微細化し結晶粒界の腐食が進行し耐食性及び耐高温座屈性を悪化させる。また、融点が低下しろう溶融時に芯材が溶融してしまう。従って、Ｓｉの含有量は０．０２％〜０．７％で、更に好ましくは０．４％〜０．６％の範囲である。
Ｚｎはフィン材の電位を卑にし、犠牲陽極効果でチューブなどの作動流体通路の孔食を防ぐ作用がある。少なすぎるとその効果が十分に得られず、多すぎると自己腐食が高くなるとともにろう付性が低下する。従って、Ｚｎの含有量は０．０２％〜３．０％で、更に好ましくは０．５％〜１．５％の範囲である。
Si precipitates an Al—Mn—Si based fine compound to improve the strength. Moreover, it has the function which coarsens a recrystallized grain and improves the high temperature buckling resistance at the time of the high temperature heating at the time of brazing. If the amount is too small, the effect cannot be obtained sufficiently. If the amount is too large, fine precipitates of the Al-Mn-Si system become dense, and the recrystallized grains become fine due to the effect of crystallized matter, and the grain boundary corrosion. Progresses and deteriorates corrosion resistance and high temperature buckling resistance. Further, the core material is melted at the time of melting so that the melting point is lowered. Therefore, the Si content is 0.02% to 0.7%, more preferably 0.4% to 0.6%.
Zn has the effect of lowering the potential of the fin material and preventing pitting corrosion of the working fluid passage such as a tube by the sacrificial anode effect. If the amount is too small, the effect cannot be obtained sufficiently. If the amount is too large, the self-corrosion becomes high and the brazing property decreases. Therefore, the Zn content is 0.02% to 3.0%, more preferably 0.5% to 1.5%.
Ｃｕは合金の強度を上げてブレージング時の高温加熱の際の耐高温座屈性を向上させる働きを持つ。Ｃｕはフィン材の電位を貴にし、犠牲陽極効果を減じるため、従来添加は好ましくない元素と考えられてきた。本願第１の発明は、Ｃｕを特に添加せず、不可避的不純物程度であっても、耐高温座屈性に必要な強度を有するブレージングシートである。本願第２の発明は、Ｃｕを添加することで耐高温座屈性をさらに向上させたブレージングシートを提案している。Ｃｕを添加した場合には、その添加量に応じてＺｎの添加量を０．０２％〜３．０％に調整することでフィン材の犠牲陽極効果を損なわずに、強度及び耐高温座屈性を向上させられることを見出した。多すぎると強度が急増してフィン材としての成形性が悪くなると共にフィンの電位が貴となり犠牲陽極効果が無くなる。従って、Ｃｕの含有量は０．０５％〜０．８％で、更に好ましくは０．１％〜０．５％の範囲である。 Cu has the function of increasing the strength of the alloy and improving the high temperature buckling resistance during high temperature heating during brazing. Since Cu makes the potential of the fin material noble and reduces the sacrificial anode effect, conventionally addition has been considered an undesirable element. 1st invention of this application is a brazing sheet which does not add Cu especially, but has intensity | strength required for high temperature buckling resistance, even if it is an unavoidable impurity grade. The second invention of the present application proposes a brazing sheet in which high temperature buckling resistance is further improved by adding Cu. When Cu is added, the addition amount of Zn is adjusted to 0.02% to 3.0% according to the addition amount, and without sacrificing the sacrificial anode effect of the fin material, strength and high temperature buckling resistance It was found that the property can be improved. If the amount is too large, the strength rapidly increases and the moldability as a fin material deteriorates and the potential of the fin becomes noble and the sacrificial anode effect is lost. Therefore, the Cu content is 0.05% to 0.8%, more preferably 0.1% to 0.5%.
Ｚｒは微細な金属間化合物を形成し合金の強度と耐高温座屈性を向上させる。Ｚｒが少なすぎるとその効果が十分に得られず、多すぎると、成形性が低下し、組付けなどの加工時に割れが生じてしまう。従って、Ｚｒの含有量は０．０５％〜０．３％で、更に好ましくは０．１％〜０．２％の範囲である。
Ｔｉは微細な金属間化合物を形成し合金の強度と耐高温座屈性を向上させる。Ｔｉが少なすぎるとその効果が十分に得られず、多すぎると、鋳塊に粗大な化合物が生じて熱間圧延時に割れが生じてしまう。従って、Ｔｉの含有量は０．０５％〜０．３％で、更に好ましくは０．１％〜０．２％の範囲である。
なお、本発明において、その他の不可避的不純物元素（Ｍｇ、Ｃｒ、Ｃａ等）は各々０．０５％以下、合計で０．１５％以下であれば本発明の効果に影響を与えない。
Zr forms a fine intermetallic compound and improves the strength and high temperature buckling resistance of the alloy. If the amount of Zr is too small, the effect cannot be obtained sufficiently. If the amount is too large, the moldability deteriorates and cracks occur during processing such as assembly. Therefore, the content of Zr is 0.05% to 0.3%, more preferably 0.1% to 0.2%.
Ti forms a fine intermetallic compound and improves the strength and high temperature buckling resistance of the alloy. If the amount of Ti is too small, the effect cannot be obtained sufficiently. If the amount is too large, a coarse compound is formed in the ingot, and cracks occur during hot rolling. Therefore, the Ti content is 0.05% to 0.3%, more preferably 0.1% to 0.2%.
In the present invention, other unavoidable impurity elements (Mg, Cr, Ca, etc.) do not affect the effects of the present invention as long as each is 0.05% or less and the total is 0.15% or less.
次に本発明のフィン材の皮材に添加されたＳｉの作用を説明する。皮材中のＳｉは皮材の融点を低下させ、溶融ろうの流動性及び、チューブやサイドプレートの接合性を向上させる効果を有する。Ｓｉの含有量は、少なすぎると上記効果が十分に得られない。多すぎると皮材の融点が高くなり、ろうが溶融され難くなりチューブやサイドプレートの接合性が低下する。従って、皮材のＳｉの含有量は６．０％〜１５．０％が好ましく、更に好ましくは８．０％〜１２．０％の範囲である。
なお、皮材の残部はＡｌと不可避的不純物からなる。不可避的不純物元素Ｃｕ、Ｚｎは０．０１％以下であれば本発明の効果に影響を与えない。Ｆｅは多いと材料の腐食を促進させるが０．８％以内であれば、本発明の効果に影響を与えない。また、ＮａやＳｒは皮材のＳｉ粒子を微細化させて芯材へのＳｉ粒子の侵食を抑える働きがあるので、皮材にＮａもしくはＳｒを添加しても良い。
Next, the action of Si added to the skin of the fin material of the present invention will be described. Si in the skin material has the effect of lowering the melting point of the skin material and improving the flowability of the molten braze and the joining properties of the tube and the side plate. If the Si content is too small, the above effects cannot be obtained sufficiently. If the amount is too large, the melting point of the skin material becomes high, the wax is hardly melted, and the bonding properties of the tube and the side plate are lowered. Therefore, the content of Si in the skin material is preferably 6.0% to 15.0%, and more preferably 8.0% to 12.0%.
The balance of the skin material is made of Al and inevitable impurities. If the inevitable impurity elements Cu and Zn are 0.01% or less, the effects of the present invention are not affected. If the amount of Fe is large, corrosion of the material is promoted, but if it is within 0.8%, the effect of the present invention is not affected. Further, since Na and Sr have a function of minimizing the Si particles of the skin material and suppressing the erosion of the Si particles into the core material, Na or Sr may be added to the skin material.
皮材のクラッド率は５％〜１５％とする。クラッド率が低すぎるとクラッドフィンのろうが不足して、チューブ材との接合性が低下する恐れがある。また、クラッド率が高すぎると溶融ろうが多くなり芯材が溶解されやすくなる。従って、皮材のクラッド率は片面で５％〜１５％が好ましく、更に好ましくは８％〜１２％の範囲である。 The cladding rate of the skin material is 5% to 15%. If the clad rate is too low, the clad fins are insufficiently brazed, and the bondability with the tube material may be reduced. On the other hand, if the cladding ratio is too high, the amount of melting wax increases and the core material is easily dissolved. Therefore, the cladding rate of the skin material is preferably 5% to 15%, more preferably 8% to 12% on one side.
ブレージングシートの板厚Ｔ（μｍ）と芯材のＳｉ量ａ（％）と皮材のＳｉ量ｂ（％）、皮材のクラッド率をＣ（％）とした場合、
ａ＋｛０．００１ｂ（２Ｃ／１００）＋０．０２４｝／
（Ｔ／１０００）＜１．４０ （１）
を満たしていなければならない。この（１）式はろう付け加熱時６００℃の芯材のＳｉ量を表している。通常、熱交換器用ブレージングシートのろう溶融加熱は６００℃前後で行われるが、加熱中は皮材のＳｉが芯材へ拡散して芯材のＳｉ量が増加する。ブレージングシートの板厚が薄いほど、皮材や芯材の板厚が薄くなるため、ろう材中のＳｉが芯材へ拡散しやすくなる。本発明のブレージングシートの芯材のＳｉ量が１．４０％を超えると芯材の溶融が始まる。芯材のＳｉ量が０．０２％〜０．７％、皮材のＳｉ量が６．０％〜１５．０％、皮材のクラッド率が５％〜１５％、フィン材の板厚は４０μｍ〜８０μｍであれば、上記（１）式を満たし、ブレージングシートの特性を向上することができる。更に好ましくは、芯材のＳｉ量が０．４％〜０．６％、皮材のＳｉ量が７．０％〜１０．０％、皮材のクラッド率が８％〜１２％、フィン材の板厚は４０μｍ〜８０μｍの範囲である。
When the thickness T (μm) of the brazing sheet, the Si amount a (%) of the core material, the Si amount b (%) of the skin material, and the cladding ratio of the skin material C (%),
a + {0.001b (2C / 100) +0.024} /
(T / 1000) <1.40 (1)
Must be met. This equation (1) represents the Si content of the core material at 600 ° C. during brazing heating. Usually, brazing and heating of the brazing sheet for heat exchanger is performed at around 600 ° C., but during heating, Si of the skin material diffuses into the core material and the amount of Si of the core material increases. The thinner the brazing sheet, the thinner the skin and core material, so that Si in the brazing material is easily diffused into the core material. When the Si content of the core material of the brazing sheet of the present invention exceeds 1.40%, the core material starts to melt. The Si content of the core material is 0.02% to 0.7%, the Si content of the skin material is 6.0% to 15.0%, the cladding rate of the skin material is 5% to 15%, and the plate thickness of the fin material is If it is 40 micrometers-80 micrometers, the said (1) Formula is satisfy | filled and the characteristic of a brazing sheet can be improved. More preferably, the Si content of the core material is 0.4% to 0.6%, the Si content of the skin material is 7.0% to 10.0%, the cladding ratio of the skin material is 8% to 12%, and the fin material The plate thickness is in the range of 40 μm to 80 μm.
ブレージングシートの板厚は４０μｍ〜８０μｍである。４０μｍ未満だと溶融ろうによって芯材が溶融されやすい。また、強度が不足して耐高温座屈性が著しく低下する。８０μｍを超えると本発明の目的である薄肉化にならない。 The thickness of the brazing sheet is 40 μm to 80 μm. When the thickness is less than 40 μm, the core material is easily melted by the melting wax. Further, the strength is insufficient and the high temperature buckling resistance is remarkably lowered. If it exceeds 80 μm, the thinning which is the object of the present invention is not achieved.
従来の熱交換器用チューブ材やフィン材は鋳造後に芯材に組成の均質化処理を施すが、本発明方法においては均質化処理をすることなく、芯材に皮材をクラッドして合わせ加熱だけでも組成の均質化を図ることができて十分要求特性を満足することができる。
芯材の均質化処理を施さずに芯材と皮材を４２０℃〜５００℃の温度で加熱した後、熱間圧延を行なう。加熱温度を４２０℃〜５００℃とすることにより、Ａｌ−Ｍｎ−ＦｅやＡｌ−Ｍｎ−Ｓｉ系の金属間化合物を析出させて強度か向上し、薄肉化したフィン材の耐高温座屈性を向上することができる。４２０℃未満では熱間圧延の変形抵抗が大きくなり、圧延が困難になる。また、５００℃を超えると金属間化合物が過剰に析出するため、耐高温座屈性が低下する。また、晶出物の効果で再結晶粒が微細化し結晶粒界の腐食が進行し耐食性を悪化させる。尚、加熱保持時間は１時間〜５時間が望ましい。
熱間圧延終了後、冷間圧延を行なった後に中間焼鈍を行う。中間焼鈍の際に固溶元素の析出を促進するために冷間圧延は必要であり、その圧下率は１０％〜９０％が望ましい。
Conventional heat exchanger tube materials and fin materials are subjected to a homogenization treatment on the core material after casting, but in the method of the present invention, the core material is clad with the skin material and only heated together. However, the composition can be homogenized and the required characteristics can be sufficiently satisfied.
The core material and the skin material are heated at a temperature of 420 ° C. to 500 ° C. without subjecting the core material to homogenization, followed by hot rolling. By setting the heating temperature to 420 ° C. to 500 ° C., Al—Mn—Fe or Al—Mn—Si based intermetallic compounds are precipitated to improve the strength, and the high temperature buckling resistance of the thinned fin material is improved. Can be improved. If it is less than 420 degreeC, the deformation resistance of hot rolling will become large and rolling will become difficult. Moreover, since an intermetallic compound will precipitate excessively when it exceeds 500 degreeC, high temperature buckling resistance falls. Further, the recrystallized grains are refined by the effect of the crystallized substance, and the corrosion of the crystal grain boundaries proceeds to deteriorate the corrosion resistance. The heating and holding time is desirably 1 hour to 5 hours.
After the hot rolling, intermediate annealing is performed after cold rolling. In order to promote precipitation of solid solution elements during intermediate annealing, cold rolling is necessary, and the rolling reduction is preferably 10% to 90%.
中間焼鈍は、固溶しているＭｎ、Ｃｕ、Ｓｉなどの元素が析出し易い３００℃以上で０．５時間〜４時間加熱するのが望ましい。
中間焼鈍の後に最終の冷間圧延を行い製品とするのであるがこの冷間圧延率（最終冷延率）は２０％〜７０％とする。この冷延率が低すぎると薄肉化という要求を満足する強度のフィン材が得られない。一方、冷延率が高すぎると加工量が多いため、変形帯からも再結晶の核発生が起こり、再結晶粒が微細となり、皮材からＳｉが粒界拡散し、粒界の耐食性が低下する。従って、中間焼鈍のあとの冷間圧延率は２０％〜７０％であることが好ましく、更に好ましくは３５％〜５５％の範囲である。
In the intermediate annealing, it is desirable to heat at 300 ° C. or more for 0.5 to 4 hours at which elements such as Mn, Cu, and Si that are dissolved easily precipitate.
Although the final cold rolling is performed after the intermediate annealing to obtain a product, the cold rolling rate (final cold rolling rate) is 20% to 70%. If the cold rolling rate is too low, a fin material having a strength that satisfies the demand for thinning cannot be obtained. On the other hand, if the cold rolling rate is too high, the amount of work is large, so recrystallization nucleation occurs from the deformation zone, the recrystallized grains become fine, Si diffuses from the skin, and the corrosion resistance of the grain boundaries decreases. To do. Therefore, the cold rolling rate after the intermediate annealing is preferably 20% to 70%, and more preferably 35% to 55%.
前述の工程で製造されたブレージングシートにおいて、芯材中に占めるＡｌ−Ｍｎ−ＦｅやＡｌ−Ｍｎ−Ｓｉ系の粒径０．１μｍ以上３．０μｍ未満の微細な析出物が占める数密度Ａ（個／ｍｍ２）と粒径３．０μｍ以上の粗大な析出物が占める数密度Ｂ（個／ｍｍ２）の比率Ａ／Ｂが５０≦Ａ／Ｂ≦５００を満たしていなければならない。前述の比率５０≦Ａ／Ｂ≦５００は芯材の均質化処理を施さずに熱間圧延前に芯材と皮材を４２０℃〜５００℃の温度で加熱することで得られ、ブレージング時の高温過熱の際の耐高温座屈性を向上させる働きを持つ。Ａ／Ｂが小さすぎると粒径０．１μｍ以上３．０μｍ未満の微細な析出物と粒径３．０μｍ以上の粗大な析出物が少なく、十分な強度が得られず耐高温座屈性を低下させる。もしくは、粒径３．０μｍ以上の粗大な析出物が占める数密度Ｂが高く成形性を悪化させる。Ａ／Ｂが大きすぎると再結晶粒が微細化し結晶粒界の腐食が進行し耐食性及び耐高温座屈性を悪化させる。したがって５０≦Ａ／Ｂ≦５００で、さらに好ましくは２００≦Ａ／Ｂ≦３５０である。 In the brazing sheet manufactured in the above-mentioned process, the number density A (occupied by fine precipitates of Al-Mn-Fe or Al-Mn-Si-based particles having a particle size of 0.1 µm to less than 3.0 µm in the core material. pieces / mm 2) and must meet the 50 ≦ a / B ≦ 500 ratio a / B number density B occupied by the particle size 3.0μm or more coarse precipitates (number / mm 2). The above-mentioned ratio 50 ≦ A / B ≦ 500 is obtained by heating the core material and the skin material at a temperature of 420 ° C. to 500 ° C. before hot rolling without subjecting the core material to homogenization. It functions to improve high temperature buckling resistance during high temperature overheating. If A / B is too small, there are few fine precipitates with a particle size of 0.1 μm or more and less than 3.0 μm and coarse precipitates with a particle size of 3.0 μm or more, and sufficient strength cannot be obtained, resulting in high temperature buckling resistance. Reduce. Or the number density B which the coarse precipitate with a particle size of 3.0 micrometers or more occupies is high, and a moldability is deteriorated. If A / B is too large, the recrystallized grains become finer, and the grain boundary corrosion proceeds to deteriorate the corrosion resistance and the high temperature buckling resistance. Therefore, 50 ≦ A / B ≦ 500, and more preferably 200 ≦ A / B ≦ 350.
次に本発明を実施例に基づき更に詳細に説明する。
表１には、本実施例で用いた芯材の合金組成を示す。Ａ１〜Ａ１５の組成を持つ合金を用いて２５８ｍｍ×７９０ｍｍ×１６００ｍｍサイズの鋳塊を作製し、面削した。次に、表２に示すＢ１〜Ｂ５の合金組成を有する皮材をクラッド率３．５％〜２５％で該芯材合金の両面にクラッドし、表３に示す試作材Ｎｏ．１〜５４の合せ材を準備した。次に３２０℃〜５６０℃の３時間の合せ加熱を行なった後、３．５ｍｍまで熱間圧延を行い、所定の板厚まで冷間圧延した後、３９０℃で２時間の中間焼鈍を行い、更に冷間圧延を行って板厚６０μｍ、４０μｍ、比較例として３０μｍのブレージングシートを作製した。
Next, the present invention will be described in more detail based on examples.
Table 1 shows the alloy composition of the core material used in this example. An ingot having a size of 258 mm × 790 mm × 1600 mm was produced using an alloy having a composition of A1 to A15, and chamfered. Next, a skin material having an alloy composition of B1 to B5 shown in Table 2 was clad on both surfaces of the core material alloy with a clad rate of 3.5% to 25%. 1 to 54 laminated materials were prepared. Next, after performing combined heating at 320 ° C. to 560 ° C. for 3 hours, hot rolling to 3.5 mm, cold rolling to a predetermined plate thickness, and then performing intermediate annealing at 390 ° C. for 2 hours, Further, cold rolling was performed to produce a brazing sheet having a thickness of 60 μm and 40 μm and a comparative example of 30 μm.
上記のように得られたフィン材の引張強度、耐高温座屈性及び耐食試験を行い、結果を表４に示した。
（１）引張強度
引張試験はＪＩＳ５号のサイズに加工した試験片で実施した。結果より引張強度が高いほど耐高温座屈性の垂下量が低い傾向になった。比較例の板厚３０μｍの試作材Ｎｏ．５１、Ｎｏ．５３は板厚が薄いため、強度に関係なく加熱後の垂下量が高くなった。
（２）耐高温座屈性（垂下量）
試作材Ｎｏ．１〜５４から幅１６ｍｍ、長さ６０ｍｍの試料片１を作製し、これを図１（ａ）のように台２上に固定具３を用いて、片持ちで０．０６ｔ×１６ｗ×５０ｌ（ｍｍ）の張り出し部を保持し、６００℃、３分間窒素雰囲気中で加熱した。図１（ａ）は加熱前の模式的な正面図、図１（ｂ）は図１（ａ）の状態での模式的な平面図である。図１（ｃ）は加熱後の垂下した状態を模式的に示す正面図である。図１（ｃ）に示す加熱後の垂下量が１５ｍｍ以下を合格とした。
（３）フィン接合性
図２に示すようにフィン材４をコルゲート加工した後、両側に０．５ｔ×１６ｗ×７０ｌ（ｍｍ）Ａ３００３板５を非腐食性フラックスブレージング法でろう付けした。フィンと板５の接合部にろう溜まり（フィレット）が形成されているかを判断基準とした。
（４）フィン材の耐孔食性試験（耐食性）
図２に示すようにフィン材４をコルゲート加工した後、両側に０．５ｔ×１６ｗ×７０ｌ（ｍｍ）Ａ３００３板５を非腐食性フラックスブレージング法でろう付けした。
この試験片を用いて塩水噴霧（ＪＩＳ２３７１に準じる）４０００時間を行い、Ａ３００３板に生じた孔食を調べた
（５）Ａｌ−Ｍｎ−Ｆｅ、Ａｌ−Ｍｎ−Ｓｉ系金属化合物の数密度
ろう付け加熱前素板の芯材の断面を日本電子（株）社製、走査型電子顕微鏡（ＪＳＭ−６４６０ＬＡ）で×１０００倍率にて撮影し、円相当径０．１μｍ以上のＡｌ−Ｍｎ−Ｆｅ、Ａｌ−Ｍｎ−Ｓｉ系金属化合物個数を旭化成エンジニアリング（株）社製画像解析ソフト（Ａ像くん）にてカウントし、数密度を測定した。表４に「粒径０．１μｍ以上３．０μｍ未満の微細な析出物が占める数密度Ａ（個／ｍｍ２）と粒径３．０μｍ以上の粗大な析出物が占める数密度Ｂ（個／ｍｍ２）の比率Ａ／Ｂ」として示した。
The tensile strength, high-temperature buckling resistance and corrosion resistance test of the fin material obtained as described above were performed, and the results are shown in Table 4.
(1) Tensile strength The tensile test was carried out on a test piece processed to the size of JIS5. The higher the tensile strength, the lower the amount of high temperature buckling resistance drooping. A comparative sample No. 30 having a plate thickness of 30 μm was prepared. 51, no. No. 53 had a small plate thickness, so that the amount of droop after heating was high regardless of the strength.
(2) High temperature buckling resistance (hanging amount)
Prototype material No. Width from 1 to 54 16 mm, to prepare a
(3) Fin bondability After corrugating the fin material 4 as shown in FIG. 2, 0.5 t × 16 w × 70 l (mm)
(4) Pitting corrosion resistance test of fin material (corrosion resistance)
After corrugating the fin material 4 as shown in FIG. 2, 0.5 t × 16 w × 70 l (mm)
Using this test piece, salt water spray (according to JIS 2371) was performed for 4000 hours to examine pitting corrosion occurring on the A3003 plate. (5) Number density of Al—Mn—Fe and Al—Mn—Si based metal compounds Brazing A cross section of the core of the base plate before heating was taken with a scanning electron microscope (JSM-6460LA) manufactured by JEOL Ltd. at a magnification of × 1000, Al-Mn-Fe having an equivalent circle diameter of 0.1 μm or more, The number of Al-Mn-Si metal compounds was counted with image analysis software (A image kun) manufactured by Asahi Kasei Engineering Co., Ltd., and the number density was measured. Table 4 shows “number density A (pieces / mm 2 ) occupied by fine precipitates having a particle size of 0.1 μm or more and less than 3.0 μm and number density B (pieces / pieces) occupied by coarse precipitates having a particle size of 3.0 μm or more. mm 2 ) ratio A / B ”.
（本発明の結果）
従来の厚い材料に対して、本発明の薄肉化した材料でも、十分な強度と耐高温座屈性が得られ、よりフィンの薄肉化が可能となる。一方で、耐高温座屈性試験において垂下量が１５ｍｍを超えた試作材は、図２のような形状にフィンを加工してろう付加熱した際、フィンの座屈が確認された。また、板厚が４０μｍの試作材は本発明の特性を得ることができたが、板厚が３０μｍの試作材になると、強度に関係なくろう付加熱後の垂下量が高くなり、フィンの溶解が起こり易く、本発明の特性を得ることが困難であることが確認された。
したがって本発明方法によれば非腐食性フラックスブレージング及びキャリアーガスブレージングに適するフィン用アルミニウム薄板を製造することができる。
(Results of the present invention)
Compared to the conventional thick material, even with the thinned material of the present invention, sufficient strength and high temperature buckling resistance can be obtained, and the fin can be made thinner. On the other hand, in the high temperature buckling resistance test, the prototype material whose drooping amount exceeded 15 mm was confirmed to be buckled when the fin was processed into a shape as shown in FIG. In addition, the prototype material with a thickness of 40 μm was able to obtain the characteristics of the present invention. However, when the thickness of the prototype material was 30 μm, the amount of drooping after brazing heat increased regardless of the strength, and the dissolution of the fins It has been confirmed that it is difficult to obtain the characteristics of the present invention.
Therefore, according to the method of the present invention, an aluminum thin plate for fins suitable for non-corrosive flux brazing and carrier gas brazing can be produced.
本発明品は自動車用熱交換器向のアルミニウム合金フィン材において、高強度かつ、耐食性に優れ、薄肉化により、本発明品を用いた熱交換器は従来のものに比べ軽量化できることが期待され、産業上顕著な効果を有するものである。 The product of the present invention is an aluminum alloy fin material for automotive heat exchangers, and is expected to be lighter than conventional products because of its high strength and excellent corrosion resistance. It has a significant industrial effect.
１ 試料片
２ 台
３ 固定具
４ フィン材
５ 板
1
Claims (4)
前記皮材のクラッド率が片面で５％〜１５％となるように皮材をクラッドしてアルミニウム合金合せ材を形成する工程と、
前記アルミニウム合金合せ材を４２０℃〜５００℃で加熱した後に、熱間圧延、冷間圧延及び中間焼鈍を行う工程と、
前記アルミニウム合金合せ材の圧延率が、２０％〜７０％となるようにして最終冷間圧延を行い、４０μｍ〜８０μｍの板厚のブレージングシートを製造する工程と、
を具えることを特徴とする、ブレージングシートの製造方法。 Mn is 0.6 mass% to 1.8 mass% (hereinafter, mass% is simply referred to as%), Fe is 0.05% to 0.6%, Si is 0.02% to 0.7%, An aluminum alloy containing 0.02% to 3.0% Zn, 0.05% to 0.3% Zr, 0.05% to 0.3% Ti, and the balance being Al and inevitable impurities. This is a method for producing a brazing sheet using a core material and an aluminum alloy containing 6.0% to 15.0% of Si on one side or both sides of the core material and the balance being Al and inevitable impurities. And
A step of clad the skin material so that the cladding rate of the skin material is 5% to 15% on one side to form an aluminum alloy laminated material;
A step of performing hot rolling, cold rolling and intermediate annealing after heating the aluminum alloy laminated material at 420 ° C. to 500 ° C .;
A step of producing a brazing sheet having a thickness of 40 μm to 80 μm by performing final cold rolling so that the rolling ratio of the aluminum alloy laminated material is 20% to 70%;
A method for producing a brazing sheet, comprising:
前記皮材のクラッド率が片面で５％〜１５％となるように皮材をクラッドしてアルミニウム合金合せ材を形成する工程と、
前記アルミニウム合金合せ材を４２０℃〜５００℃で加熱した後に、熱間圧延、冷間圧延及び中間焼鈍を行う工程と、
前記アルミニウム合金合せ材の圧延率が、２０％〜７０％となるようにして最終冷間圧延を行い、４０μｍ〜８０μｍの板厚のブレージングシートを製造する工程と、
を具えることを特徴とする、ブレージングシートの製造方法。 Mn 0.6% to 1.8%, Fe 0.05% to 0.6%, Si 0.02% to 0.7%, Cu 0.05% to 0.8%, Zn An aluminum alloy containing 0.02% to 3.0%, Zr 0.05% to 0.3%, Ti 0.05% to 0.3%, the balance being Al and unavoidable impurities. And a method for producing a brazing sheet using, as a skin material, an aluminum alloy containing 6.0% to 15.0% of Si on one side or both sides of a core material, and the balance being Al and inevitable impurities,
A step of clad the skin material so that the cladding rate of the skin material is 5% to 15% on one side to form an aluminum alloy laminated material;
A step of performing hot rolling, cold rolling and intermediate annealing after heating the aluminum alloy laminated material at 420 ° C. to 500 ° C .;
A step of producing a brazing sheet having a thickness of 40 μm to 80 μm by performing final cold rolling so that the rolling ratio of the aluminum alloy laminated material is 20% to 70%;
A method for producing a brazing sheet, comprising:
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