JP2012097320A - Heat exchanger made from aluminum and manufacturing method thereof - Google Patents
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Abstract
【課題】本発明は、ろう付け加熱後に高い耐食性を有するアルミニウム製熱交換器およびその製造方法を提供することを目的とするものである。
【解決手段】ろう付けにより製造されるアルミニウム製熱交換器において、Ｓｉ０．４〜１．６ｍａｓｓ％を含有し、残部Ａｌおよび不可避的不純物からなるアルミニウム合金材を通路部材として用いた熱交換器であって、当該アルミニウム合金材を用いた通路部材の導電率が、当該アルミニウム合金を製造する際のろう付加熱後の導電率よりも２％ＩＡＣＳ以上高いことを特徴とする耐食性に優れたアルミニウム製熱交換器。
【選択図】 なしAn object of the present invention is to provide an aluminum heat exchanger having high corrosion resistance after brazing and a method for producing the same.
In an aluminum heat exchanger manufactured by brazing, an aluminum alloy material containing 0.4 to 1.6 mass% of Si, the balance being Al and unavoidable impurities is used as a passage member. Further, the electrical conductivity of the passage member using the aluminum alloy material is 2% IACS or more higher than the electrical conductivity after brazing addition heat when the aluminum alloy is manufactured. Heat exchanger.
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Description
本発明は、例えばカーエアコン用コンデンサ、エバポレータ、オイルクーラー、ラジエータなどのアルミニウム製熱交換器の耐食性向上方法、特に粒界腐食の発生を低減させる方法に関するものである。 The present invention relates to a method for improving the corrosion resistance of aluminum heat exchangers such as condensers for car air conditioners, evaporators, oil coolers, and radiators, and more particularly to a method for reducing the occurrence of intergranular corrosion.
アルミニウム合金は軽量で熱伝導性に優れること、適切処理により高耐食性が実現できること、およびブレージングシートを利用したろう付けで効率的な接合が可能であることから、自動車用などの熱交換器用材料として重用されている。近年、自動車の高性能化あるいは環境対応として、より軽量で高い耐久性を持つよう熱交換器の性能向上が求められている。 Aluminum alloy is lightweight and has excellent thermal conductivity, high corrosion resistance can be realized by appropriate treatment, and brazing using a brazing sheet enables efficient joining. It is heavily used. In recent years, there has been a demand for improving the performance of heat exchangers so as to have lighter weight and higher durability in order to improve the performance of automobiles or to cope with the environment.
一般に、ろう付に使用される熱交換器用アルミニウム合金の心材には、Ａｌ−Ｍｎ系合金が使用され、ろう材には、Ａｌ−Ｓｉ系合金が使用され、腐食環境になる箇所には、犠牲防食材として、Ａｌ−Ｚｎ系合金もしくは、Ａｌ−Ｓｉ−Ｚｎ系合金が使用されている。
近年の自動車用熱交換器の軽量・薄肉化の要求に応えつつ、強度を向上させる方法として、心材に用いるアルミニウム合金に、材料強度の向上に寄与する元素、すなわち強化元素を添加して、アルミニウム合金の強度を高める試みがなされている。ここで、アルミニウム合金における強化元素としては、Ｓｉ、Ｃｕ、Ｍｎ、Ｓｉ、Ｆｅ、Ｔｉ等種々のものがあるが、固溶強化による強度向上に寄与するＳｉ、Ｃｕ、Ｍｎが用いられることが多い。しかし、これらの元素は、ろう付加熱時の冷却中に粒界に優先析出し、粒界近傍に固溶元素の欠乏領域を形成し、粒界腐食が発生する場合がある。
Generally, an Al-Mn alloy is used for the core material of the aluminum alloy for heat exchangers used for brazing, and an Al-Si alloy is used for the brazing material. As the anticorrosive material, an Al—Zn alloy or an Al—Si—Zn alloy is used.
As a method for improving strength while meeting the demand for lighter and thinner automotive heat exchangers in recent years, an element that contributes to improving material strength, that is, a strengthening element, is added to the aluminum alloy used for the core material, and aluminum Attempts have been made to increase the strength of the alloy. Here, there are various elements such as Si, Cu, Mn, Si, Fe, and Ti as reinforcing elements in the aluminum alloy, but Si, Cu, and Mn that contribute to strength improvement by solid solution strengthening are often used. . However, these elements may preferentially precipitate at the grain boundaries during cooling during brazing addition heat, forming a solid solution element deficient region in the vicinity of the grain boundaries, and intergranular corrosion may occur.
粒界腐食に対する耐食性を向上させるために、ろう付加熱後に熱処理を加える手法が提案されている。特許文献１には、Ｍｎを含むアルミニウム合金からなる芯材の表面に、Ａｌ−Ｓｉ系ろう材が用いられた製品の製造方法として、ろう付け作業の後、１００〜４００℃の温度で１５分以上の熱処理を行なうものであり、この技術によれば、電位を下げるＺｎなどの元素を添加せずに、実質的に犠牲防食が可能となる。 In order to improve the corrosion resistance against intergranular corrosion, a method of applying heat treatment after brazing heat has been proposed. In Patent Document 1, as a method of manufacturing a product in which an Al—Si brazing material is used on the surface of a core material made of an aluminum alloy containing Mn, a brazing operation is performed at a temperature of 100 to 400 ° C. for 15 minutes. The above heat treatment is performed, and according to this technique, sacrificial corrosion can be substantially prevented without adding an element such as Zn that lowers the potential.
また、熱処理によってＭｎ固溶量を制御し、耐食性を向上させる手法も提案されている。特許文献２には、Ｓｉを０．０５〜０．６％、Ｆｅを０．０５〜０．７％、Ｃｕを０．０４〜０．２％、Ｍｎを０．６〜１．０％、Ｍｇを０．０１〜０．１５％、Ｚｎを０．１〜３．０％含有し、残部がＡｌと不可避不純物からなるアルミニウム合金鋳塊に熱間押出および抽伸加工をこの順に施して素管とし、次いで前記素管に４５０〜５５０℃で１〜１０時間の最終焼鈍処理を施すことを特徴とする耐食性に優れる熱交換器用アルミニウム合金配管材の製造方法が開示されている。 In addition, a method for improving the corrosion resistance by controlling the solid solution amount of Mn by heat treatment has been proposed. In Patent Literature 2, Si is 0.05 to 0.6%, Fe is 0.05 to 0.7%, Cu is 0.04 to 0.2%, Mn is 0.6 to 1.0%, An aluminum alloy ingot containing 0.01 to 0.15% Mg and 0.1 to 3.0% Zn, with the balance being Al and inevitable impurities, subjected to hot extrusion and drawing in this order, Then, a method for producing an aluminum alloy piping material for heat exchangers having excellent corrosion resistance is disclosed, in which the base tube is subjected to a final annealing treatment at 450 to 550 ° C. for 1 to 10 hours.
しかし、これらの手法では、特にＳｉに起因する粒界腐食を抑制することはできず、耐食性向上の手法として不十分である。
本発明は、以上の事情を背景としてなされたもので、ろう付け加熱後に高い耐食性を有するアルミニウム製熱交換器およびその製造方法を提供することを目的とするものである。 The present invention has been made against the background described above, and an object of the present invention is to provide an aluminum heat exchanger having high corrosion resistance after brazing heating and a method for manufacturing the same.
前述のような課題を解決すべく本発明者らがアルミニウム製熱交換器の耐食性、導電率および強度と、合金成分組成および熱処理との関係について詳細に実験・検討を重ねた結果、心材合金へのＳｉ、ＭｎおよびＣｕの添加量を適切に調整するとともに、熱処理を制御することによって、十分に耐食性を向上させることができることを見出した。本発明はこの知見に基づきなされた。 In order to solve the problems as described above, the present inventors have conducted detailed experiments and examinations on the relationship between the corrosion resistance, electrical conductivity and strength of the aluminum heat exchanger, the alloy composition and the heat treatment. It was found that the corrosion resistance can be sufficiently improved by appropriately adjusting the amount of Si, Mn and Cu added and controlling the heat treatment. The present invention has been made based on this finding.
すなわち、本発明の第１の発明は、ろう付けにより製造されるアルミニウム製熱交換器において、Ｓｉ０．４〜１．６ｍａｓｓ％を含有し、残部Ａｌおよび不可避的不純物からなるアルミニウム合金材を通路部材として用いた熱交換器であって、当該アルミニウム合金材を用いた通路部材の導電率が、当該アルミニウム合金を製造する際のろう付加熱後の導電率よりも２％ＩＡＣＳ以上高いことを特徴とする耐食性に優れたアルミニウム製熱交換器である。 That is, according to the first aspect of the present invention, in the aluminum heat exchanger manufactured by brazing, an aluminum alloy material containing 0.4 to 1.6 mass% of Si and the balance Al and inevitable impurities is used as a passage member. The electrical conductivity of the passage member using the aluminum alloy material is 2% IACS or more higher than the electrical conductivity after brazing addition heat when the aluminum alloy is manufactured. It is an aluminum heat exchanger with excellent corrosion resistance.
本発明の第２の発明は、請求項１に記載の発明に加えて前記アルミニウム合金材が、さらにＣｕ０．０５〜０．５ｍａｓｓ％、Ｍｎ０．５〜１．５ｍａｓｓ％、Ｍｇ０．０５〜０．５のうち１種または２種以上を含有することを特徴とする耐食性に優れたアルミニウム製熱交換器である。 According to a second aspect of the present invention, in addition to the first aspect of the present invention, the aluminum alloy material further comprises Cu 0.05 to 0.5 mass%, Mn 0.5 to 1.5 mass%, Mg0.05 to 0.00. 5 is an aluminum heat exchanger excellent in corrosion resistance, characterized by containing one or more of five.
本発明の第３の発明は、請求項１及び請求項２に記載のアルミニウム合金材の片面もしくは両面に、Ａｌ−Ｓｉ系合金あるいはＡｌ−Ｚｎ系合金のいずれかがクラッドされていることを特徴とする耐食性に優れたアルミニウム製熱交換器である。 According to a third aspect of the present invention, either one or both surfaces of the aluminum alloy material according to claims 1 and 2 is clad with either an Al-Si alloy or an Al-Zn alloy. It is an aluminum heat exchanger with excellent corrosion resistance.
本発明の第４の発明は、請求項１乃至請求項３記載のアルミニウム製熱交換器の製造方法において、ろう付け加熱後、室温まで冷却した後、２０５〜３０５℃の温度での熱処理を行い、かつ当該熱処理条件と前記Ｓｉ量との関係が（１）の不等式を満たすことを特徴とする耐食性に優れたアルミニウム製熱交換器の製造方法である。
１ ＜ Ｘ ＜ ２ ・・・（１）
ただし、Ｘ＝（ｔ１／３０００＋ｔ２／１５００＋ｔ３／８００＋ｔ４／４２０＋ｔ５／２３０＋ｔ６／１３０＋ｔ７／７２＋ｔ８／４２＋ｔ９／２５＋ｔ１０／１５）×Ｓｉ含有量
ｔ１：加熱処理中に温度が２０５℃以上、２１５℃未満であった時間（ｍｉｎ）
ｔ２：加熱処理中に温度が２１５℃以上、２２５℃未満であった時間（ｍｉｎ）
ｔ３：加熱処理中に温度が２２５℃以上、２３５℃未満であった時間（ｍｉｎ）
ｔ４：加熱処理中に温度が２３５℃以上、２４５℃未満であった時間（ｍｉｎ）
ｔ５：加熱処理中に温度が２４５℃以上、２５５℃未満であった時間（ｍｉｎ）
ｔ６：加熱処理中に温度が２５５℃以上、２６５℃未満であった時間（ｍｉｎ）
ｔ７：加熱処理中に温度が２６５℃以上、２７５℃未満であった時間（ｍｉｎ）
ｔ８：加熱処理中に温度が２７５℃以上、２８５℃未満であった時間（ｍｉｎ）
ｔ９：加熱処理中に温度が２８５℃以上、２９５℃以下であった時間（ｍｉｎ）
ｔ１０：加熱処理中に温度が２９５℃以上、３０５℃以下であった時間（ｍｉｎ）
According to a fourth aspect of the present invention, in the method for manufacturing an aluminum heat exchanger according to any one of the first to third aspects, after brazing and heating, cooling to room temperature, and then performing heat treatment at a temperature of 205 to 305 ° C. And the relationship between the said heat processing conditions and the said Si quantity satisfy | fills the inequality of (1), It is a manufacturing method of the aluminum heat exchanger excellent in corrosion resistance.
1 <X <2 (1)
However, X = (t 1/3000 + t 2/1500 + t 3/800 + t 4/420 + t 5/230 + t 6/130 + t 7/72 + t 8/42 + t 9/25 + t 10/15) × Si content
t 1 : Time during which the temperature was 205 ° C. or higher and lower than 215 ° C. during the heat treatment (min)
t 2 : Time (min) during which the temperature was 215 ° C. or higher and lower than 225 ° C. during the heat treatment
t 3 : Time during which the temperature was 225 ° C. or higher and lower than 235 ° C. during the heat treatment (min)
t 4 : Time during which the temperature was 235 ° C. or higher and lower than 245 ° C. during the heat treatment (min)
t 5 : Time during which the temperature was 245 ° C. or higher and lower than 255 ° C. during the heat treatment (min)
t 6 : Time during which the temperature was not lower than 255 ° C. and lower than 265 ° C. during the heat treatment (min)
t 7 : Time during which the temperature was 265 ° C. or higher and lower than 275 ° C. during the heat treatment (min)
t 8 : Time during which the temperature was 275 ° C. or higher and lower than 285 ° C. during the heat treatment (min)
t 9 : Time during which the temperature was 285 ° C. or higher and 295 ° C. or lower during the heat treatment (min)
t 10 : Time during which the temperature was 295 ° C. or higher and 305 ° C. or lower during the heat treatment (min)
本発明は、アルミニウム製熱交換器の耐食性、特に粒界腐食の発生を抑制する効果がある。 The present invention has an effect of suppressing the corrosion resistance of an aluminum heat exchanger, particularly the occurrence of intergranular corrosion.
以下、本発明で数値を限定する理由について説明する。
本発明において、アルミニウム製熱交換器の通路部材の導電率が、ろう付加熱後の導電率よりも２％ＩＡＣＳ以上高いと規定したのは、導電率の変化が２％ＩＡＣＳより小さい場合にはＳｉ系化合物の粒内析出が十分でなく、粒界腐食の起こる可能性があるためである。つまり、ろう付加熱時の冷却過程において、過飽和に固溶したＳｉは、例えば熱交換器の使用サイクルによる熱履歴等の入熱によってＳｉ系化合物として析出する。Ｓｉ系化合物の析出は、拡散係数の大きい粒界に優先的に起こり、粒界近傍にはＳｉの欠乏領域が形成される。Ｓｉ欠乏領域は、周囲の粒内よりも孔食電位が卑であるため、欠乏領域が優先的に溶解することで粒界腐食の発生する可能性がある。このことを抑制するためには、粒界だけでなく、粒内にも十分にＳｉ系化合物を析出させ、粒内のＳｉ固溶量をＳｉ欠乏層と同程度まで低下させ、孔食電位を卑化させることが必要である。Ｓｉ析出量は、導電率と負の相関があり、導電率からＳｉ析出量を推定できる。
Hereinafter, the reason why the numerical values are limited in the present invention will be described.
In the present invention, it is defined that the conductivity of the passage member of the aluminum heat exchanger is 2% IACS or more higher than the conductivity after brazing addition heat when the change in conductivity is smaller than 2% IACS. This is because the intragranular precipitation of the Si-based compound is not sufficient and there is a possibility that intergranular corrosion occurs. That is, in the cooling process at the time of brazing addition heat, Si dissolved in supersaturation is precipitated as a Si-based compound by heat input such as a heat history due to a use cycle of a heat exchanger, for example. Precipitation of Si compounds occurs preferentially at grain boundaries having a large diffusion coefficient, and a Si-deficient region is formed in the vicinity of the grain boundaries. Since the pitting potential is lower in the Si-deficient region than in the surrounding grains, there is a possibility that intergranular corrosion may occur due to the preferential dissolution of the deficient region. In order to suppress this, the Si-based compound is sufficiently precipitated not only at the grain boundaries but also within the grains, the amount of Si solid solution in the grains is reduced to the same level as the Si-deficient layer, and the pitting potential is reduced. It is necessary to deceive. The Si precipitation amount has a negative correlation with the conductivity, and the Si precipitation amount can be estimated from the conductivity.
本発明における、アルミニウム製熱交換器の通路部材のアルミニウム合金中のＳｉは、０．４〜１．６ｍａｓｓ％含有される。Ｓｉは、マトリックスに固溶したり、Ｓｉ系化合物を生成したりすることによって、強度を向上させる元素である。このＳｉ添加の効果を得るためには、０．４ｍａｓｓ％以上のＳｉの含有が必要であり、より好ましくは０．６ｍａｓｓ％以上のＳｉとする。一方、過剰にＳｉが含有されれば、合金の融点を低下させてろう付時に材料の溶融を招いてしまう。この過剰なＳｉの含有による悪影響を回避するためには、Ｓｉ量の上限は１．６ｍａｓｓ％とする必要がある。 In the present invention, Si in the aluminum alloy of the passage member of the aluminum heat exchanger is contained in an amount of 0.4 to 1.6 mass%. Si is an element that improves the strength by forming a solid solution in a matrix or generating a Si-based compound. In order to obtain the effect of this Si addition, it is necessary to contain 0.4 mass% or more of Si, and more preferably 0.6 mass% or more of Si. On the other hand, if Si is contained excessively, the melting point of the alloy is lowered and the material is melted during brazing. In order to avoid the adverse effect due to the excessive Si content, the upper limit of the Si amount needs to be 1.6 mass%.
本発明において、アルミニウム製熱交換器の通路部材のアルミニウム合金中のＣｕは、０．０５〜０．５ｍａｓｓ％含有されても良い。Ｃｕは、マトリックスに固溶したり、Ｃｕ系化合物を生成したりすることによって、強度を向上させる元素である。このＣｕ添加の効果を得るためには、０．０５ｍａｓｓ％以上のＣｕの含有が好ましい。一方、Ｃｕ系化合物も粒界に優先析出し、粒界腐食を発生させる可能性があり、Ｃｕ量の上限は０．５ｍａｓｓ％とするのが好ましい。 In the present invention, Cu in the aluminum alloy of the passage member of the aluminum heat exchanger may be contained in an amount of 0.05 to 0.5 mass%. Cu is an element that improves the strength by forming a solid solution in the matrix or forming a Cu-based compound. In order to obtain the effect of Cu addition, it is preferable to contain 0.05 mass% or more of Cu. On the other hand, Cu-based compounds also preferentially precipitate at the grain boundaries and may cause grain boundary corrosion, and the upper limit of the Cu content is preferably 0.5 mass%.
本発明において、アルミニウム製熱交換器の通路部材のアルミニウム合金中のＭｎは、０．５〜１．５ｍａｓｓ％含有されても良い。Ｍｎは、Ａｌ−Ｍｎ系金属間化合物として晶出又は析出して、強度の向上に寄与する。また、Ａｌ−Ｍｎ系金属間化合物は、Ｆｅを取り込むために、不可避不純物であるＦｅによる耐食性阻害効果を抑制する働きもある。これらの効果を得るためには、０．５ｍａｓｓ％以上のＭｎを添加するのが好ましく、より好ましくは０．８ｍａｓｓ％以上のＭｎを添加する。但し、Ｍｎ量が１．５ｍａｓｓ％を超えれば、巨大な金属間化合物が晶出し、製造性を阻害するおそれがあり、したがって、Ｍｎ量の上限は１．５ｍａｓｓ％をとするのが望ましい。 In the present invention, Mn in the aluminum alloy of the passage member of the aluminum heat exchanger may be contained in an amount of 0.5 to 1.5 mass%. Mn crystallizes or precipitates as an Al—Mn intermetallic compound and contributes to the improvement of strength. In addition, since the Al—Mn intermetallic compound takes in Fe, it also has a function of suppressing the corrosion resistance-inhibiting effect by Fe, which is an inevitable impurity. In order to obtain these effects, it is preferable to add 0.5 mass% or more of Mn, and more preferably 0.8 mass% or more of Mn. However, if the amount of Mn exceeds 1.5 mass%, a huge intermetallic compound may be crystallized, which may impair manufacturability. Therefore, the upper limit of the amount of Mn is desirably set to 1.5 mass%.
本発明において、アルミニウム製熱交換器の通路部材のアルミニウム合金中のＭｇは、０．０５〜０．５ｍａｓｓ％含有されても良い。Ｍｇは、Ｓｉ存在下で、Ｍｇ２Ｓｉとして析出し、強度の向上に寄与する。この効果を得るためには、０．０５ｍａｓｓ％以上のＭｇを添加するのが好ましい。Ｍｇ２Ｓｉは、非常に溶解しやすい金属間化合物で、過剰なＭｇ添加で耐食性を劣化させる影響が大きくなる。したがって、Ｍｇ量の上限は０．５ｍａｓｓ％とするのが望ましい。 In the present invention, Mg in the aluminum alloy of the passage member of the aluminum heat exchanger may be contained in an amount of 0.05 to 0.5 mass%. Mg precipitates as Mg 2 Si in the presence of Si and contributes to the improvement of strength. In order to obtain this effect, 0.05 mass% or more of Mg is preferably added. Mg 2 Si is an intermetallic compound that is very easy to dissolve, and the effect of deteriorating the corrosion resistance by adding excessive Mg increases. Therefore, it is desirable that the upper limit of the Mg amount is 0.5 mass%.
本発明において、アルミニウム製熱交換器の通路部材のアルミニウム合金中の不純物としてのＦｅは０．４ｍａｓｓ％以下に制限されるのが望ましい。Ｆｅは、Ｓｉとともに不純物元素として含有される。Ｆｅが含有されると、Ｆｅを含む金属間化合物が晶出する。腐食環境において、表面に露出した金属間化合物は、Ａｌの腐食速度を速めてしまう。この過剰なＦｅの含有による悪影響を回避するためには、不純物としてのＦｅ量は０．４ｍａｓｓ％以下に制限することが望ましい。 In the present invention, Fe as an impurity in the aluminum alloy of the passage member of the aluminum heat exchanger is desirably limited to 0.4 mass% or less. Fe is contained as an impurity element together with Si. When Fe is contained, an intermetallic compound containing Fe is crystallized. In a corrosive environment, intermetallic compounds exposed on the surface increase the corrosion rate of Al. In order to avoid this adverse effect due to the excessive Fe content, it is desirable to limit the amount of Fe as an impurity to 0.4 mass% or less.
本発明における、アルミニウム製熱交換器の通路部材のアルミニウム合金には、それぞれ０．２ｍａｓｓ％以下のＴｉ、Ｃｒ、Ｚｒを含有しても良い。 In the present invention, the aluminum alloy of the passage member of the aluminum heat exchanger may contain 0.2 mass% or less of Ti, Cr, and Zr, respectively.
前記アルミニウム合金成分の残部は、Ａｌ及び不可避不純物とすればよく、不可避的不純物はそれぞれが０．０５ｍａｓｓ％以下で、かつ合計で０．１５ｍａｓｓ％以下であることが好ましい。 The balance of the aluminum alloy component may be Al and inevitable impurities, and the inevitable impurities are each preferably 0.05 mass% or less and a total of 0.15 mass% or less.
本発明において、アルミニウム製熱交換器の通路部材のアルミニウム合金材の片面、もしくは両面に、Ａｌ−Ｓｉ系ろう材、もしくはＡｌ−Ｚｎ系皮材のいずれか、もしくは両方がクラッドされても良い。Ａｌ−Ｓｉ系ろう材の成分は任意に決定でき、例えば、Ｓｉを３〜１２ｍａｓｓ％含有し、犠牲防食作用を付与するために１〜４ｍａｓｓ％のＺｎを含有させても良い。Ａｌ−Ｚｎ系皮材も任意に決定でき、例えば、１〜４ｍａｓｓ％のＺｎを含有したものが好適である。 In the present invention, either one or both of an Al—Si brazing material and an Al—Zn base material may be clad on one side or both sides of the aluminum alloy material of the passage member of the aluminum heat exchanger. The component of the Al—Si brazing material can be arbitrarily determined. For example, Si may be contained in an amount of 3 to 12 mass%, and Zn may be contained in an amount of 1 to 4 mass% in order to provide a sacrificial anticorrosive action. An Al—Zn-based skin material can also be arbitrarily determined, and for example, a material containing 1 to 4 mass% of Zn is suitable.
本発明のアルミニウム製熱交換器の通路部材のアルミニウム合金複合材を製造するにあたっては、まず構成要素となる素材をそれぞれ通常の半連続鋳造法で鋳造する。これらは、適宜、面削や予備熱間圧延などで厚さを調整して組み合わせた後、熱間圧延によりクラッド接合される。続いて、冷間圧延および必要に応じて焼鈍を含む工程で所定の板厚および加工調質状態とする。 In manufacturing the aluminum alloy composite material of the passage member of the aluminum heat exchanger according to the present invention, first, the raw materials as the constituent elements are each cast by a normal semi-continuous casting method. These are suitably combined by adjusting the thickness by chamfering or preliminary hot rolling, and then clad-joined by hot rolling. Then, it is set as a predetermined | prescribed plate | board thickness and process tempered state by the process including cold rolling and annealing as needed.
本発明において、アルミニウム製熱交換器を製造する際のろう付に関しての雰囲気や加熱温度、時間等の条件については特に限定されるものではなく、また、ろう付方法も特に限定されない。なお、一般的なろう付け条件としては、フラックスを使用し、窒素ガス雰囲気中で温度６００℃で３ｍｉｎ保持し、その後、５０〜２００℃／ｍｉｎで冷却する条件が挙げられる。ろう付加熱後、２０５〜３０５℃の温度に曝される加熱処理を受け、かつその加熱処理が（１）の不等式を満たす条件で行われて製造されることが望ましい。ろう付加熱の冷却中に、アルミニウム合金中に過飽和にＳｉが固溶する。この後に加熱処理を行うことで、粒内および粒界に十分にＳｉ系化合物を析出させ、粒界腐食の発生しないアルミニウム製熱交換器とすることが狙いである。温度が２０５℃よりも小さい場合には、化合物の析出速度が遅いため、加熱処理時間が長くなってしまい、温度が３０５℃よりも大きい場合には、化合物の成長が速いため、適切な組織状態を得ることが困難になる。
１ ＜ Ｘ ＜ ２ ・・・（１）
ただし、Ｘ＝（ｔ１／３０００＋ｔ２／１５００＋ｔ３／８００＋ｔ４／４２０＋ｔ５／２３０＋ｔ６／１３０＋ｔ７／７２＋ｔ８／４２＋ｔ９／２５＋ｔ１０／１５）×Ｓｉ含有量
ｔ１：加熱処理中に温度が２０５℃以上、２１５℃未満であった時間（ｍｉｎ）
ｔ２：加熱処理中に温度が２１５℃以上、２２５℃未満であった時間（ｍｉｎ）
ｔ３：加熱処理中に温度が２２５℃以上、２３５℃未満であった時間（ｍｉｎ）
ｔ４：加熱処理中に温度が２３５℃以上、２４５℃未満であった時間（ｍｉｎ）
ｔ５：加熱処理中に温度が２４５℃以上、２５５℃未満であった時間（ｍｉｎ）
ｔ６：加熱処理中に温度が２５５℃以上、２６５℃未満であった時間（ｍｉｎ）
ｔ７：加熱処理中に温度が２６５℃以上、２７５℃未満であった時間（ｍｉｎ）
ｔ８：加熱処理中に温度が２７５℃以上、２８５℃未満であった時間（ｍｉｎ）
ｔ９：加熱処理中に温度が２８５℃以上、２９５℃以下であった時間（ｍｉｎ）
ｔ１０：加熱処理中に温度が２９５℃以上、３０５℃以下であった時間（ｍｉｎ）
式（１）のＸはＳｉ系化合物の成長度と正の相関性を持ち、これが１以下では、Ｓｉ系化合物の粒内析出が十分でなく、粒界腐食の起こる可能性があり、２以上では、効果が飽和してしまい不経済なため、式（１）の如く範囲を規定した。式（１）のｔ１〜ｔ９は、加熱処理中に２０５〜３０５℃で１０℃ごとに区切った各温度範囲にアルミニウム合金材があった時間を示している。高温の温度範囲にある場合、短時間でもＸが増加し、すなわちＳｉ系化合物が増えるのに対し、低温の温度範囲では同様の状態になるには長時間を要する。また、アルミニウム合金材のＳｉ添加量が多いほど、Ｘが大きくなり、すなわちＳｉ系化合物の分布が増えることと対応する。式の係数は種々の実験結果をもとに演繹的に決定したものであり、その一部は後の実施例に含まれる。
In the present invention, conditions such as atmosphere, heating temperature, and time for brazing when producing an aluminum heat exchanger are not particularly limited, and the brazing method is not particularly limited. In addition, as general brazing conditions, the conditions which use a flux, hold | maintain for 3 minutes at the temperature of 600 degreeC in nitrogen gas atmosphere, and cool at 50-200 degreeC / min after that are mentioned. After the brazing heat, it is desirable that the heat treatment be performed at a temperature of 205 to 305 ° C., and that the heat treatment be performed under conditions satisfying the inequality (1). During the cooling of the brazing heat, Si is supersaturated in the aluminum alloy. The aim is to obtain an aluminum heat exchanger that does not cause intergranular corrosion by sufficiently heat-treating the Si-based compound in the grains and at the grain boundaries. When the temperature is lower than 205 ° C., the deposition rate of the compound is slow, so that the heat treatment time becomes longer. When the temperature is higher than 305 ° C., the compound grows faster, so that an appropriate structure state is obtained. It becomes difficult to get.
1 <X <2 (1)
However, X = (t 1/3000 + t 2/1500 + t 3/800 + t 4/420 + t 5/230 + t 6/130 + t 7/72 + t 8/42 + t 9/25 + t 10/15) × Si content
t 1 : Time during which the temperature was 205 ° C. or higher and lower than 215 ° C. during the heat treatment (min)
t 2 : Time (min) during which the temperature was 215 ° C. or higher and lower than 225 ° C. during the heat treatment
t 3 : Time during which the temperature was 225 ° C. or higher and lower than 235 ° C. during the heat treatment (min)
t 4 : Time during which the temperature was 235 ° C. or higher and lower than 245 ° C. during the heat treatment (min)
t 5 : Time during which the temperature was 245 ° C. or higher and lower than 255 ° C. during the heat treatment (min)
t 6 : Time during which the temperature was not lower than 255 ° C. and lower than 265 ° C. during the heat treatment (min)
t 7 : Time during which the temperature was 265 ° C. or higher and lower than 275 ° C. during the heat treatment (min)
t 8 : Time during which the temperature was 275 ° C. or higher and lower than 285 ° C. during the heat treatment (min)
t 9 : Time during which the temperature was 285 ° C. or higher and 295 ° C. or lower during the heat treatment (min)
t 10 : Time during which the temperature was 295 ° C. or higher and 305 ° C. or lower during the heat treatment (min)
X in the formula (1) has a positive correlation with the growth degree of the Si-based compound, and when this is 1 or less, the intra-granular precipitation of the Si-based compound is insufficient, and there is a possibility that intergranular corrosion occurs. Then, since the effect is saturated and it is uneconomical, the range is defined as shown in Equation (1). In the formula (1), t 1 to t 9 indicate the time during which the aluminum alloy material was present in each temperature range divided by 10 ° C. at 205 to 305 ° C. during the heat treatment. In the high temperature range, X increases even in a short time, that is, Si-based compounds increase, whereas in the low temperature range, it takes a long time to achieve the same state. Further, as the amount of Si added to the aluminum alloy material increases, X increases, that is, the distribution of Si-based compounds increases. The coefficients of the formula are determined a priori based on various experimental results, and some of them are included in later examples.
本発明により得られる熱交換器は、高耐圧特性を有しており、しかも良好な耐食性を有しているから、例えば厳しい腐食環境下で使用される自動車等においても、良好な耐久性を発揮することができる。 The heat exchanger obtained by the present invention has high pressure resistance characteristics and good corrosion resistance. For example, it exhibits good durability even in automobiles used in severe corrosive environments. can do.
以下に、本発明例と比較例に基づいて本発明の実施の形態を具体的に説明する。
（本発明例１〜２１及び比較例１〜９）
表１に示す組成のアルミニウム合金材およびアルミニウム合金複合材の各構成を通常の半連続鋳造により合金のスラブを鋳造した。さらに６００℃、３ｈの均質化処理を施し、熱間圧延で３．５ｍｍまで、冷間圧延で１ｍｍまで圧延し、アルミニウム合金材およびアルミニウム合金複合材を作製した。次いで、５００℃、１０ｈの熱処理を行った後、溶体化処理として、水冷し、導電率を測定した。さらに、表２に示す熱処理を行ない、導電率を測定した。
Embodiments of the present invention will be specifically described below based on the present invention examples and comparative examples.
(Invention Examples 1 to 21 and Comparative Examples 1 to 9)
Alloy slabs were cast by ordinary semi-continuous casting of each of the aluminum alloy materials and aluminum alloy composite materials having the compositions shown in Table 1. Furthermore, the homogenization process of 600 degreeC and 3 h was performed, and it rolled to 3.5 mm by hot rolling and 1 mm by cold rolling, and produced the aluminum alloy material and the aluminum alloy composite material. Next, after heat treatment at 500 ° C. for 10 hours, as a solution treatment, water cooling was performed, and the conductivity was measured. Furthermore, the heat treatment shown in Table 2 was performed, and the conductivity was measured.
評価は、３電極式の導電率計による導電率の測定、ＣＡＳＳ ５００ｈによる腐食深さ、１ｍＡ／ｃｍ２、６ｈの定電流電解試験による断面観察から粒界腐食発生の有無を判断した。結果を表３に示す。判定方法として、ＣＡＳＳによる耐食性では、腐食深さが０．２ｍｍ以下を◎、０．２ｍｍを越え０．７ｍｍ以下を○、０．７ｍｍを越えた場合を×とした。粒界腐食感受性では、粒界腐食が発生しなかった場合を○、発生した場合を×とした。 In the evaluation, the presence or absence of occurrence of intergranular corrosion was determined from the measurement of conductivity using a three-electrode type conductivity meter, the corrosion depth by CASS 500h, and the cross-sectional observation by a constant current electrolysis test of 1 mA / cm 2 , 6h. The results are shown in Table 3. As a judgment method, in the corrosion resistance by CASS, the case where the corrosion depth is 0.2 mm or less is ◎, the case where it exceeds 0.2 mm and 0.7 mm or less is ○, and the case where it exceeds 0.7 mm is ×. In the case of intergranular corrosion susceptibility, the case where no intergranular corrosion occurred was marked with ◯, and the case where it occurred was marked with x.
比較例１では、Ｓｉ量が少ないために、導電率の変化が小さく、粒界腐食感受性はなかったが、腐食深さが深い。
比較例２では、Ｃｕ量が多いために、腐食深さが深く、かつ、粒界腐食も発生した。
比較例３では、Ｓｉ量が多いために、腐食深さが浅かったが、粒界腐食が発生した。
比較例４では、Ｍｎ量が多いために、粒界腐食が発生しなかったが、腐食深さが深い。
比較例５では、Ｍｇ量が多いために、腐食深さが浅かったが、粒界腐食が発生した。
比較例６では、Ｍｎ量が多いために、粒界腐食が発生しなかったが、腐食深さが深い。
比較例７では、Ｍｇ量が多く、Ｃｕ、Ｍｎも含まれているために、腐食深さが深く、かつ、粒界腐食も発生した。
比較例８では、Ｍｇ量が多く、Ｃｕも含まれているために、腐食深さが深く、かつ、粒界腐食も発生した。
比較例９では、Ｍｇ量が多く、Ｍｎも含まれているために、腐食深さが深く、かつ、粒界腐食も発生した。
（本発明例２２〜３３及び比較例１０〜１５）
In Comparative Example 1, since the amount of Si was small, the change in conductivity was small and there was no intergranular corrosion sensitivity, but the corrosion depth was deep.
In Comparative Example 2, since the amount of Cu was large, the corrosion depth was deep and intergranular corrosion also occurred.
In Comparative Example 3, due to the large amount of Si, the corrosion depth was shallow, but intergranular corrosion occurred.
In Comparative Example 4, intergranular corrosion did not occur because the amount of Mn was large, but the corrosion depth was deep.
In Comparative Example 5, since the amount of Mg was large, the corrosion depth was shallow, but intergranular corrosion occurred.
In Comparative Example 6, the intergranular corrosion did not occur because the amount of Mn was large, but the corrosion depth was deep.
In Comparative Example 7, since the amount of Mg was large and Cu and Mn were also contained, the corrosion depth was deep and intergranular corrosion also occurred.
In Comparative Example 8, since the amount of Mg was large and Cu was contained, the corrosion depth was deep and intergranular corrosion also occurred.
In Comparative Example 9, since the amount of Mg was large and Mn was contained, the corrosion depth was deep and intergranular corrosion also occurred.
(Invention Examples 22-33 and Comparative Examples 10-15)
表１に示す組成のアルミニウム合金材およびアルミニウム合金複合材の各構成を通常の半連続鋳造により合金のスラブを鋳造した。さらに６００℃、３ｈの均質化処理を施し、熱間圧延で３．５ｍｍまで、冷間圧延で１ｍｍまで圧延し、アルミニウム合金材およびアルミニウム合金複合材を作製した。次いで、６０５℃、３ｍｉｎのろう付加熱相当熱処理を行った後、１００℃／ｍｉｎの速度で室温まで冷却し、導電率を測定した。さらに、表４に示す熱処理を行ない、導電率を測定した。 Alloy slabs were cast by ordinary semi-continuous casting of each of the aluminum alloy materials and aluminum alloy composite materials having the compositions shown in Table 1. Furthermore, the homogenization process of 600 degreeC and 3 h was performed, and it rolled to 3.5 mm by hot rolling and 1 mm by cold rolling, and produced the aluminum alloy material and the aluminum alloy composite material. Next, after performing heat treatment corresponding to brazing addition heat at 605 ° C. for 3 minutes, it was cooled to room temperature at a rate of 100 ° C./min, and the conductivity was measured. Furthermore, the heat treatment shown in Table 4 was performed, and the conductivity was measured.
評価は、３電極式の導電率計による導電率の測定、ＣＡＳＳ ５００ｈによる腐食深さ、１ｍＡ／ｃｍ２、６ｈの定電流電解試験による断面観察から粒界腐食発生の有無を判断した。結果を表３に示す。判定方法として、ＣＡＳＳによる耐食性では、腐食深さが０．２ｍｍ以下を◎、０．２ｍｍを越え０．７ｍｍ以下を○、０．７ｍｍを越えた場合を×とした。粒界腐食感受性では、粒界腐食が発生しなかった場合を○、発生した場合を×とした。 In the evaluation, the presence or absence of occurrence of intergranular corrosion was determined from the measurement of conductivity using a three-electrode type conductivity meter, the corrosion depth by CASS 500h, and the cross-sectional observation by a constant current electrolysis test of 1 mA / cm 2 , 6h. The results are shown in Table 3. As a judgment method, in the corrosion resistance by CASS, the case where the corrosion depth is 0.2 mm or less is ◎, the case where it exceeds 0.2 mm and 0.7 mm or less is ○, and the case where it exceeds 0.7 mm is ×. In the case of intergranular corrosion susceptibility, the case where no intergranular corrosion occurred was marked with ◯, and the case where it occurred was marked with x.
表５から明らかなように、本発明例２２〜３３は、本発明の範囲を満たすため、腐食深さが浅く、粒界腐食感受性がなかった。
比較例１０では、本発明の式（１）のＸが１より小さいために、導電率の変化が小さく、腐食深さは浅いが、粒界腐食が発生した。
比較例１１では、本発明の式（１）のＸが２より大きいために、導電率の変化が大きく、粒界腐食が発生しないが、腐食深さが深い。
比較例１２では、本発明の式（１）のＸが１より小さいために、導電率の変化が小さく、腐食深さは浅いが、粒界腐食が発生した。
比較例１３では、本発明の式（１）のＸが２より大きいために、導電率の変化が大きく、粒界腐食が発生しないが、腐食深さが深い。
比較例１４では、本発明の式（１）のＸが１より小さいために、導電率の変化が小さく、腐食深さは浅いが、粒界腐食が発生した。
比較例１５では、本発明の式（１）のＸが２より大きいために、導電率の変化が大きく、粒界腐食が発生しないが、腐食深さが深い。
As is apparent from Table 5, Examples 22 to 33 of the present invention satisfy the scope of the present invention, so that the corrosion depth is shallow and there is no intergranular corrosion sensitivity.
In Comparative Example 10, since X in the formula (1) of the present invention was smaller than 1, the change in conductivity was small, and the corrosion depth was shallow, but intergranular corrosion occurred.
In Comparative Example 11, since X in the formula (1) of the present invention is larger than 2, the change in conductivity is large and no intergranular corrosion occurs, but the corrosion depth is deep.
In Comparative Example 12, since the X in the formula (1) of the present invention is smaller than 1, the change in conductivity is small and the corrosion depth is shallow, but intergranular corrosion occurs.
In Comparative Example 13, since X in the formula (1) of the present invention is larger than 2, the change in conductivity is large and no intergranular corrosion occurs, but the corrosion depth is deep.
In Comparative Example 14, since X in the formula (1) of the present invention was smaller than 1, the change in conductivity was small, and the corrosion depth was shallow, but intergranular corrosion occurred.
In Comparative Example 15, since the X in the formula (1) of the present invention is larger than 2, the change in conductivity is large, and no intergranular corrosion occurs, but the corrosion depth is deep.
本発明は、車載用エアコンのコンデンサ、エバポレータ、オイルクーラー、ラジエータなどのアルミニウム製熱交換器の耐食性を向上させ、産業上顕著な効果を奏するものである。 INDUSTRIAL APPLICABILITY The present invention improves the corrosion resistance of aluminum heat exchangers such as condensers, evaporators, oil coolers, and radiators of in-vehicle air conditioners, and has a remarkable industrial effect.
Claims (4)
１ ＜ Ｘ ＜ ２ ・・・（１）
ただし、Ｘ＝（ｔ１／３０００＋ｔ２／１５００＋ｔ３／８００＋ｔ４／４２０＋ｔ５／２３０＋ｔ６／１３０＋ｔ７／７２＋ｔ８／４２＋ｔ９／２５＋ｔ１０／１５）×Ｓｉ含有量
ｔ１：加熱処理中に温度が２０５℃以上、２１５℃未満であった時間（ｍｉｎ）
ｔ２：加熱処理中に温度が２１５℃以上、２２５℃未満であった時間（ｍｉｎ）
ｔ３：加熱処理中に温度が２２５℃以上、２３５℃未満であった時間（ｍｉｎ）
ｔ４：加熱処理中に温度が２３５℃以上、２４５℃未満であった時間（ｍｉｎ）
ｔ５：加熱処理中に温度が２４５℃以上、２５５℃未満であった時間（ｍｉｎ）
ｔ６：加熱処理中に温度が２５５℃以上、２６５℃未満であった時間（ｍｉｎ）
ｔ７：加熱処理中に温度が２６５℃以上、２７５℃未満であった時間（ｍｉｎ）
ｔ８：加熱処理中に温度が２７５℃以上、２８５℃未満であった時間（ｍｉｎ）
ｔ９：加熱処理中に温度が２８５℃以上、２９５℃以下であった時間（ｍｉｎ）
ｔ１０：加熱処理中に温度が２９５℃以上、３０５℃以下であった時間（ｍｉｎ） 4. The method of manufacturing an aluminum heat exchanger according to claim 1, wherein after brazing and heating, cooling to room temperature, heat treatment is performed at a temperature of 205 to 305 ° C., and the heat treatment conditions and the amount of Si The method for producing an aluminum heat exchanger excellent in corrosion resistance, characterized in that the relationship with inequality satisfies the inequality of (1).
1 <X <2 (1)
However, X = (t 1/3000 + t 2/1500 + t 3/800 + t 4/420 + t 5/230 + t 6/130 + t 7/72 + t 8/42 + t 9/25 + t 10/15) × Si content
t 1 : Time during which the temperature was 205 ° C. or higher and lower than 215 ° C. during the heat treatment (min)
t 2 : Time (min) during which the temperature was 215 ° C. or higher and lower than 225 ° C. during the heat treatment
t 3 : Time during which the temperature was 225 ° C. or higher and lower than 235 ° C. during the heat treatment (min)
t 4 : Time during which the temperature was 235 ° C. or higher and lower than 245 ° C. during the heat treatment (min)
t 5 : Time during which the temperature was 245 ° C. or higher and lower than 255 ° C. during the heat treatment (min)
t 6 : Time during which the temperature was not lower than 255 ° C. and lower than 265 ° C. during the heat treatment (min)
t 7 : Time during which the temperature was 265 ° C. or higher and lower than 275 ° C. during the heat treatment (min)
t 8 : Time during which the temperature was 275 ° C. or higher and lower than 285 ° C. during the heat treatment (min)
t 9 : Time during which the temperature was 285 ° C. or higher and 295 ° C. or lower during the heat treatment (min)
t 10 : Time during which the temperature was 295 ° C. or higher and 305 ° C. or lower during the heat treatment (min)
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| JP2010245751A JP2012097320A (en) | 2010-11-02 | 2010-11-02 | Heat exchanger made from aluminum and manufacturing method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014157116A1 (en) * | 2013-03-29 | 2014-10-02 | 株式会社神戸製鋼所 | Brazed structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05263202A (en) * | 1992-03-16 | 1993-10-12 | Furukawa Alum Co Ltd | Production of heat exchanger made of aluminum alloy |
| JPH08243734A (en) * | 1995-03-13 | 1996-09-24 | Mitsubishi Alum Co Ltd | Production of aluminum base product |
| JP2008284558A (en) * | 2007-05-15 | 2008-11-27 | Furukawa Sky Kk | Aluminum brazing structure for heat exchanger, clad material used therefor, and method for producing aluminum brazing structure for heat exchanger |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05263202A (en) * | 1992-03-16 | 1993-10-12 | Furukawa Alum Co Ltd | Production of heat exchanger made of aluminum alloy |
| JPH08243734A (en) * | 1995-03-13 | 1996-09-24 | Mitsubishi Alum Co Ltd | Production of aluminum base product |
| JP2008284558A (en) * | 2007-05-15 | 2008-11-27 | Furukawa Sky Kk | Aluminum brazing structure for heat exchanger, clad material used therefor, and method for producing aluminum brazing structure for heat exchanger |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014157116A1 (en) * | 2013-03-29 | 2014-10-02 | 株式会社神戸製鋼所 | Brazed structure |
| CN105074026A (en) * | 2013-03-29 | 2015-11-18 | 株式会社神户制钢所 | Brazed structure |
| US10369665B2 (en) | 2013-03-29 | 2019-08-06 | Kobe Steel, Ltd. | Brazed structure |
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