JPH11140571A - Clad material for heat exchanger excellent in pitting corrosion resistance in strongly alkaline environment - Google Patents
Clad material for heat exchanger excellent in pitting corrosion resistance in strongly alkaline environmentInfo
- Publication number
- JPH11140571A JPH11140571A JP9305615A JP30561597A JPH11140571A JP H11140571 A JPH11140571 A JP H11140571A JP 9305615 A JP9305615 A JP 9305615A JP 30561597 A JP30561597 A JP 30561597A JP H11140571 A JPH11140571 A JP H11140571A
- Authority
- JP
- Japan
- Prior art keywords
- clad
- heat exchanger
- corrosion resistance
- alkaline environment
- pitting corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/016—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys
Landscapes
- Laminated Bodies (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、熱交換器の構造
用部材、特に熱交換器の冷媒流通経路材として用いるア
ルカリ環境下での耐孔食性に優れたクラッド材に関する
ものであり、特に自動車の熱交換器の冷媒流通経路材と
して用いる強アルカリ環境下での耐孔食性に優れたクラ
ッド材（特にブレージングシート）に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structural member of a heat exchanger, and more particularly, to a clad material having excellent pitting corrosion resistance in an alkaline environment used as a refrigerant flow path material of the heat exchanger, and particularly to an automobile. The present invention relates to a clad material (particularly a brazing sheet) having excellent pitting corrosion resistance under a strong alkaline environment used as a refrigerant flow path material for a heat exchanger.
【０００２】[0002]
【従来の技術】アルミニウムやアルミニウム合金は強固
な自然酸化皮膜で覆われているので、特に中性の環境で
は耐食性に優れていることおよび熱伝導性に優れている
ところから、自動車の熱交換器の冷媒流通経路材として
用いられている。しかし、この酸化皮膜が何らかの原因
で局部的に破れると、他の部分が強固なため、欠陥部に
腐食が集中していわゆる「孔食」が発生し、早期に貫通
孔が生じるという欠点もあった。この対策として、自動
車の熱交換器のラジエータなどでは芯材の片面に芯材よ
りも電気的に卑なＡｌ合金の犠牲陽極皮材を張り合わせ
たクラッド材が用いられていた。2. Description of the Related Art Since aluminum and aluminum alloys are covered with a strong natural oxide film, they have excellent corrosion resistance and heat conductivity especially in a neutral environment. Used as a refrigerant flow path material. However, if this oxide film is locally torn for some reason, the other parts are strong, so that corrosion concentrates on the defective part, so-called "pitting" occurs, and there is a disadvantage that a through-hole is formed early. Was. As a countermeasure, a radiator of a heat exchanger of an automobile uses a clad material in which a sacrificial anode skin material of an Al alloy, which is more base than the core material, is bonded to one surface of the core material.
【０００３】最も一般的に用いられている前記クラッド
材としては、ＪＩＳ ３００３（重量％で、Ｍｎ：１．
０〜１．５％、Ｃｕ：０．１〜０．２０％、Ｓｉ：０．
６％以下、Ｆｅ：０．７５以下％、Ｚｎ：０．１０以下
％、残部：Ａｌおよび不可避不純物からなるＡｌ−Ｍｎ
系合金）を芯材とし、この芯材の片面または両面にＪＩ
Ｓ ７０７２からなる犠牲陽極皮材を張り合わせた犠牲
陽極皮材、またはＪＩＳ ３００３の片面にＪＩＳ ７
０７２からなる犠牲陽極皮材を張り合わせ、他方の片面
にＡｌ−Ｓｉ系あるいはＡｌ−Ｓｉ−Ｚｎ系ろう材を張
り合わせたクラッド材（ブレージングシート）が知られ
ている。これらクラッド材は、皮材と芯材の電気化学的
性質の差によって皮材が主として腐食し、芯材の孔食を
抑制するものである。[0003] The most commonly used clad material is JIS 3003 (Mn: 1% by weight).
0 to 1.5%, Cu: 0.1 to 0.20%, Si: 0.
6% or less, Fe: 0.75% or less, Zn: 0.10% or less, balance: Al-Mn composed of Al and unavoidable impurities
System alloy) as a core material, and JI is applied to one or both sides of this core material.
A sacrificial anode skin made of S7072 and a JIS 7 on one side of JIS 3003
There is known a clad material (brazing sheet) in which a sacrificial anode skin material made of O.072 is bonded and an Al-Si-based or Al-Si-Zn-based brazing material is bonded to the other surface. In these clad materials, the skin material mainly corrodes due to a difference in electrochemical properties between the skin material and the core material, and suppresses pitting of the core material.
【０００４】[0004]
【発明が解決しようとする課題】しかし、近年、自動
車、特に寒冷地で使用されている自動車の熱交換器の冷
媒流通経路で孔食が発生し、冷媒流通経路から冷却水が
漏れ出る事故が多発していることが分かったのである。
本発明者らはこの原因について調査した結果、下記の事
項が判明したのである。すなわち、自動車の熱交換器に
は、従来、中性または弱アルカリ性（ｐＨ：７〜８）の
不凍液含有冷却水が使用されていたが、近年、自動車の
冷却水の不凍性を高めるためにｐＨ：９〜１１の強アル
カリ性を示す不凍液含有冷却水が使用されるようにな
り、特に寒冷地の自動車の熱交換器には前記ｐＨ：９〜
１１の強アルカリ性を示す不凍液含有冷却水が広く使用
されていることが分かったのである。However, in recent years, there has been an accident that pitting occurs in a refrigerant circulation path of a heat exchanger of an automobile, particularly an automobile used in a cold region, and that cooling water leaks from the refrigerant circulation path. It turned out that it occurred frequently.
The present inventors have investigated the cause and found the following. That is, conventionally, neutral or weakly alkaline (pH: 7 to 8) antifreeze-containing cooling water has been used for heat exchangers of automobiles. Antifreeze-containing cooling water exhibiting a strong alkalinity of pH: 9 to 11 has been used. Particularly, in a heat exchanger of an automobile in a cold region, the pH: 9 to 11 is used.
It has been found that the antifreeze-containing cooling water showing strong alkalinity of 11 is widely used.
【０００５】前記中性（ｐＨ：７）やｐＨ：８を上限と
する弱アルカリ性の不凍液含有冷却水を使用している限
り、従来の熱交換器用クラッド材でも十分に耐孔食性を
有するが、ｐＨ：９〜１１の強アルカリ環境下では皮材
の十分な犠牲陽極効果は働かず、冷媒流通経路に孔食が
多く発生し、近年の寒冷地における自動車の熱交換器の
冷媒である不凍液含有冷却水の漏れの原因になってい
た。As long as the neutral (pH: 7) or weakly alkaline antifreeze-containing cooling water having an upper limit of pH: 8 is used, a conventional heat exchanger clad material has sufficient pitting corrosion resistance. Under a strong alkaline environment of pH: 9 to 11, the sacrificial anode effect of the skin material does not work sufficiently, pitting occurs frequently in the refrigerant distribution channel, and contains antifreeze, which is a refrigerant of a heat exchanger of an automobile in a cold region in recent years. This was causing leakage of cooling water.
【０００６】[0006]
【課題を解決するための手段】そこで本発明者らは、か
かる観点から、強アルカリ環境下でも耐孔食性に優れた
熱交換器用クラッド材を得るべく研究を行った結果、
（イ）強アルカリ環境下での孔食は、腐食によって溶解
したアルミニウムイオンＡｌ3+が水酸化物となって再度
アルミニウム合金の表面に緻密な水酸化皮膜を形成する
ことにより、孔食の発生数が減少し、少ない数の孔食の
成長速度が大きくなって巨視的な孔食に成長させること
によるものであるから、耐孔食性を向上させるためには
強アルカリ環境下での腐食形態を全面腐食型として巨視
的な孔食の発生を抑制すればよい、（ロ）そのために
は、犠牲陽極皮材に形成される水酸化皮膜を粗なものと
して全面に腐食が発生するようにすればよく、水酸化皮
膜を粗なものとするためには犠牲陽極皮材に含まれるＦ
ｅ、Ｍｇ、ＺｎおよびＳｎの含有量を調整すればよく、
特に全面腐食型に大きな影響を及ぼすＦｅ含有量を多め
に含有するように調整すればよい、などの知見を得たの
である。From the above viewpoint, the present inventors have conducted research on obtaining a clad material for a heat exchanger having excellent pitting corrosion resistance even in a strongly alkaline environment.
(A) Pitting in a strong alkaline environment is caused by the formation of a dense hydroxide film on the surface of the aluminum alloy by turning the aluminum ions Al 3+ dissolved by corrosion into hydroxides. Because the number of pits decreases and the growth rate of a small number of pits grows and grows into macroscopic pits, in order to improve the pitting resistance, the corrosion form in a strong alkaline environment must be improved. It is sufficient to suppress the occurrence of macroscopic pitting corrosion as a full-corrosion type. (B) To achieve this, the corrosion is generated over the entire surface by making the hydroxide film formed on the sacrificial anode skin material rough. Often, in order to make the hydroxide film coarse, the F contained in the sacrificial anode skin material
What is necessary is just to adjust the content of e, Mg, Zn and Sn,
In particular, it has been found that it is necessary to adjust the Fe content, which has a great effect on the general corrosion type, to a large amount.
【０００７】この発明は、かかる知見に基づいて成され
たものであって、（１）重量％で、Ｍｎ：０．８〜２．
０％、Ｓｉ：０．１〜１．０％、Ｃｕ：０．１〜０．７
％、Ｚｒ：０．０５〜０．１５％を含有し、残りがＡｌ
および不可避不純物からなる組成のＡｌ合金芯材の片面
あるいは両面に、Ｆｅ：０．７５〜１．２％、Ｍｇ：
０．５〜２．５％を含有し、さらにＺｎ：１〜８％およ
びＳｎ：０．０５〜０．３５％のうちの１種または２種
を含有し、残りがＡｌおよび不可避不純物からなる組成
を有する犠牲陽極皮材をクラッドしてなる強アルカリ環
境下での耐孔食性に優れた熱交換器用クラッド材、
（２）重量％で、Ｍｎ：０．８〜２．０％、Ｓｉ：０．
１〜１．０％、Ｃｕ：０．１〜０．７％、Ｚｒ：０．０
５〜０．１５％を含有し、残りがＡｌおよび不可避不純
物からなる組成のＡｌ合金芯材の片面に、Ｆｅ：０．７
５〜１．２％、Ｍｇ：０．５〜２．５％を含有し、さら
にＺｎ：１〜８％およびＳｎ：０．０５〜０．３５％の
うちの１種または２種を含有し、残りがＡｌおよび不可
避不純物からなる組成を有する犠牲陽極皮材をクラッド
し、他方の片面にＡｌ−Ｓｉ系あるいはＡｌ−Ｓｉ−Ｚ
ｎ系ろう材をクラッドしてなる強アルカリ環境下での耐
孔食性に優れた熱交換器用クラッド材、（３）重量％
で、Ｍｎ：０．８〜２．０％、Ｓｉ：０．１〜１．０
％、Ｃｕ：０．１〜０．７％、Ｚｒ：０．０５〜０．１
５％を含有し、さらにＴｉ：０．０５〜０．２５％、Ｍ
ｇ：０．０５〜０．２０％、Ｖ：０．０５〜０．１５
％、Ｃｒ：０．０５〜０．１５％のうちの１種または２
種以上を含有し、残りがＡｌおよび不可避不純物からな
る組成のＡｌ合金芯材の片面あるいは両面に、Ｆｅ：
０．７５〜１．２％、Ｍｇ：０．５〜２．５％を含有
し、さらにＺｎ：１〜８％、Ｓｎ：０．０５〜０．３５
％のうちの１種または２種を含有し、残りがＡｌおよび
不可避不純物からなる組成を有する犠牲陽極皮材をクラ
ッドしてなる強アルカリ環境下での耐孔食性に優れた熱
交換器用クラッド材、（４）重量％で、Ｍｎ：０．８〜
２．０％、Ｓｉ：０．１〜１．０％、Ｃｕ：０．１〜
０．７％、Ｚｒ：０．０５〜０．１５％を含有し、さら
にＴｉ：０．０５〜０．２５％、Ｍｇ：０．０５〜０．
２０％、Ｖ：０．０５〜０．１５％、Ｃｒ：０．０５〜
０．１５％のうちの１種または２種以上を含有し、残り
がＡｌおよび不可避不純物からなる組成のＡｌ合金芯材
の片面に、Ｆｅ：０．７５〜１．２％、Ｍｇ：０．５〜
２．５％を含有し、さらにＺｎ：１〜８％およびＳｎ：
０．０５〜０．３５％のうちの１種または２種を含有
し、残りがＡｌおよび不可避不純物からなる組成を有す
る犠牲陽極皮材をクラッドし、他方の片面にＡｌ−Ｓｉ
系あるいはＡｌ−Ｓｉ−Ｚｎ系ろう材をクラッドしてな
る強アルカリ環境下での耐孔食性に優れた熱交換器用ク
ラッド材、に特徴を有するものである。The present invention has been made on the basis of such findings, and (1) Mn: 0.8 to 2.% by weight.
0%, Si: 0.1 to 1.0%, Cu: 0.1 to 0.7
%, Zr: 0.05-0.15%, the balance being Al
And on one or both sides of an Al alloy core material having a composition consisting of unavoidable impurities, Fe: 0.75 to 1.2%, Mg:
0.5 to 2.5%, further contains one or two of Zn: 1 to 8% and Sn: 0.05 to 0.35%, and the remainder is composed of Al and inevitable impurities. Cladding material for heat exchanger with excellent pitting corrosion resistance under strong alkaline environment, which is clad with sacrificial anode skin material having composition,
(2) In terms of% by weight, Mn: 0.8 to 2.0%, Si: 0.
1 to 1.0%, Cu: 0.1 to 0.7%, Zr: 0.0
One side of an Al alloy core material having a composition of 5 to 0.15%, with the balance being Al and unavoidable impurities,
5 to 1.2%, Mg: 0.5 to 2.5%, and one or two of Zn: 1 to 8% and Sn: 0.05 to 0.35%. And a cladding of a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities, and Al-Si or Al-Si-Z on the other surface.
Clad material for heat exchanger with excellent pitting corrosion resistance under strong alkaline environment, clad with n-type brazing material, (3) wt%
, Mn: 0.8 to 2.0%, Si: 0.1 to 1.0
%, Cu: 0.1-0.7%, Zr: 0.05-0.1
5%, Ti: 0.05-0.25%, M
g: 0.05 to 0.20%, V: 0.05 to 0.15
%, Cr: one or more of 0.05 to 0.15%
Species or more, the balance being Al and unavoidable impurities.
0.75 to 1.2%, Mg: 0.5 to 2.5%, Zn: 1 to 8%, Sn: 0.05 to 0.35
%, Which is obtained by cladding a sacrificial anode skin material having a composition of Al and unavoidable impurities, the cladding material having excellent pitting corrosion resistance in a strong alkaline environment. , (4) wt%, Mn: 0.8 to
2.0%, Si: 0.1 to 1.0%, Cu: 0.1 to
0.7%, Zr: 0.05-0.15%, Ti: 0.05-0.25%, Mg: 0.05-0.
20%, V: 0.05-0.15%, Cr: 0.05-
0.15%, one or two or more of the alloys, and the remainder is composed of Al and an unavoidable impurity. 5-
2.5%, further Zn: 1-8% and Sn:
A sacrificial anode skin material containing one or two of 0.05 to 0.35% and having a balance of Al and inevitable impurities is clad, and the other surface is made of Al-Si.
A clad material for a heat exchanger, which is excellent in pitting corrosion resistance in a strong alkaline environment and clad with a brazing alloy or an Al-Si-Zn brazing material.
【０００８】この発明の強アルカリ環境下での耐孔食性
に優れた熱交換器用クラッド材は、特に熱交換器の冷媒
流通経路材として用いることが好ましく、特に自動車の
熱交換器の冷媒流通経路材として用いることが好まし
い。したがって、この発明は、前記（１）、（２）、
（３）または（４）記載の構成を有する熱交換器の冷媒
流通経路材に特徴を有するものである。[0008] The heat exchanger clad material of the present invention, which is excellent in pitting corrosion resistance in a strong alkaline environment, is preferably used as a refrigerant flow path material for a heat exchanger, and particularly a refrigerant flow path for a heat exchanger of an automobile. It is preferably used as a material. Therefore, the present invention provides the above (1), (2),
The present invention is characterized in that the refrigerant flow path member of the heat exchanger having the configuration described in (3) or (4) is characterized.
【０００９】さらに、この発明の前記（２）または
（４）記載の構成を有するアルカリ環境下での耐孔食性
に優れた熱交換器用クラッド材は、熱交換器用ブレージ
ングシート、特に自動車の熱交換器用ブレージングシー
トとして用いるのが好ましい。したがって、この発明
は、前記（２）または（４）記載の構成を有する熱交換
器用ブレージングシートに特徴を有するものである。Further, the clad material for a heat exchanger having excellent pitting corrosion resistance in an alkaline environment and having the constitution described in the above (2) or (4) is a brazing sheet for a heat exchanger, particularly, a heat exchange material for an automobile. It is preferably used as a dexterous brazing sheet. Therefore, the present invention is characterized by the brazing sheet for a heat exchanger having the configuration described in the above (2) or (4).
【００１０】次に、この発明のアルカリ環境下での耐孔
食性に優れた熱交換器用クラッド材の成分組成を上述の
ごとく限定した理由を述べる。 （Ａ）犠牲陽極皮材 Ｍｇ：犠牲陽極皮材のＭｇは、Ｆｅとの化合物が高密度
微細に析出して局部的な歪みにより腐食速度の差を生じ
させ、その結果としてアルカリ環境中で形成される皮膜
を粗にし、犠牲陽極皮材の耐孔食性を向上させる作用あ
るが、その含有量が０．５％未満では所望の効果が得ら
れず、一方、２．５％を越えるとＦｅとの化合物が粗大
に析出して所望の効果が得られない。したがって、犠牲
陽極皮材中のＭｇの含有量は０．５〜２．５％に定め
た。Ｍｇの含有量の一層好ましい範囲は１．０〜１．５
％である。Next, the reason why the component composition of the clad material for a heat exchanger having excellent pitting resistance under an alkaline environment of the present invention is limited as described above will be described. (A) Sacrificial anode skin material Mg: Mg in the sacrificial anode skin material is formed in an alkaline environment as a result of a compound with Fe being deposited at a high density and fine density to cause a difference in corrosion rate due to local distortion. Has the effect of roughening the film to be formed and improving the pitting corrosion resistance of the sacrificial anode skin material. However, if the content is less than 0.5%, the desired effect cannot be obtained. Compound precipitates coarsely and the desired effect cannot be obtained. Therefore, the content of Mg in the sacrificial anode skin material is set to 0.5 to 2.5%. A more preferred range of the Mg content is 1.0 to 1.5.
%.
【００１１】Ｆｅ：Ｆｅは、Ｍｇの析出場所を確保し、
Ｍｇとの化合物が高密度微細に析出して局部的な歪みに
より腐食速度の差を生じさせ、その結果としてアルカリ
環境中で形成される皮膜を一層粗にし、アルカリ環境中
での犠牲陽極皮材の耐孔食性を向上させる作用あるが、
その含有量が０．７５％未満では所望の効果が得られ
ず、一方、１．２％を越えて含有すると粗大なＭｇとの
化合物が形成されてアルカリ環境中での犠牲陽極効果が
低下するので好ましくない。したがって、Ｆｅ：０．７
５〜１．２％に定めた。Ｆｅの含有量の一層好ましい範
囲は０．８〜１．０％である。Fe: Fe secures a place where Mg is deposited,
The compound with Mg precipitates finely and densely, causing a difference in corrosion rate due to local strain, and as a result, the film formed in an alkaline environment is further roughened, and a sacrificial anode skin material in an alkaline environment Has the effect of improving the pitting corrosion resistance of
If the content is less than 0.75%, the desired effect cannot be obtained. On the other hand, if the content exceeds 1.2%, a coarse compound with Mg is formed and the sacrificial anode effect in an alkaline environment is reduced. It is not preferable. Therefore, Fe: 0.7
It was set to 5 to 1.2%. A more preferable range of the Fe content is 0.8 to 1.0%.
【００１２】Ｚｎ：Ｚｎには、Ｍｇ添加による作用を一
層効果的なものにする作用があるが、その含有量が１％
未満では所望の効果が得られず、一方、８％を越えて含
有すると自己耐食性が増大し過ぎて好ましくない。した
がって、Ｚｎの含有量は１〜８％に定めた。Ｚｎの含有
量の一層好ましい範囲は３〜５％である。Zn: Zn has an effect of making the effect of Mg addition more effective, but its content is 1%.
If it is less than 10%, the desired effect cannot be obtained. On the other hand, if it exceeds 8%, the self-corrosion resistance is undesirably increased. Therefore, the content of Zn is set to 1 to 8%. A more preferable range of the Zn content is 3 to 5%.
【００１３】Ｓｎ：Ｓｎには、Ｍｇ添加による作用を一
層効果的なものにする作用があるが、その含有量が０．
０５％未満では所望の効果が得られず、一方、０．３５
％を越えて含有すると自己耐食性が増大し過ぎて好まし
くない。したがって、Ｓｎの含有量は１〜８％に定め
た。Ｓｎの含有量の一層好ましい範囲は０．１〜０．２
％である。Sn: Sn has the effect of making the effect of the addition of Mg more effective, but its content is 0.1%.
If it is less than 05%, the desired effect cannot be obtained.
%, The self-corrosion resistance is undesirably increased. Therefore, the content of Sn is set to 1 to 8%. A more preferred range of the Sn content is 0.1 to 0.2.
%.
【００１４】（Ｂ）芯材 Ｍｎ：この発明の熱交換器用クラッド材の芯材に含まれ
るＭｎは、芯材素地中にＡｌ−Ｍｎとして分散し、耐食
性を低下させることなく強度を向上させる作用がある
が、その含有量が０．８％未満では所望の効果が得られ
ず、一方、２．０％を越えて含有すると加工性が低下す
るので好ましくない。したがって、Ｍｎ：０．８〜２．
０％に定めた。Ｍｎの含有量の一層好ましい範囲は１．
０〜１．５％であ(B) Core material Mn: Mn contained in the core material of the clad material for a heat exchanger of the present invention is dispersed as Al-Mn in the core material base, and serves to improve the strength without lowering the corrosion resistance. However, if the content is less than 0.8%, the desired effect cannot be obtained. On the other hand, if the content exceeds 2.0%, the workability is undesirably reduced. Therefore, Mn: 0.8-2.
It was set to 0%. A more preferable range of the Mn content is as follows.
0-1.5%
【００１５】Ｓｉ：芯材に含まれるＳｉは、Ｍｎおよび
Ｓｉは共存させることによりＡｌ−Ｍｎ−Ｓｉ化合物を
なって素地中に分散し、あるいはマトリックスに固溶し
て強度を向上させる作用を有するが、Ｓｉ：０．１％未
満では所望の効果が得られず、一方、Ｓｉ：１．０％を
越えるて含有させると、融点が低下し、さらにろう付性
が低下するので好ましくない。従ってＳｉ：０．１〜
１．０％に定めた。Ｓｉの含有量の一層好ましい範囲は
０．１５〜０．５％である。Si: Si contained in the core material has an action of dispersing Al-Mn-Si compound in a matrix by coexisting Mn and Si, or dissolving in a matrix to improve strength. However, if the content of Si is less than 0.1%, the desired effect cannot be obtained. On the other hand, if the content of Si exceeds 1.0%, the melting point is reduced and the brazing property is further reduced, which is not preferable. Therefore, Si: 0.1 ~
It was set to 1.0%. A more preferable range of the content of Si is 0.15 to 0.5%.
【００１６】Ｃｕ：芯材に含まれるＣｕは、マトリック
スに固溶して強度を向上させ、また芯材の電気化学的性
質を貴にし、皮材（及びろう材）との電位差を大きくす
る作用を有するが、Ｃｕ：０．１％未満では所望の効果
が得られず、一方、Ｃｕ：０．７％を越えるて含有させ
ると、融点が低下し、さらにろう付時に溶融し、さらに
粒界腐食が起こりやすく。耐食性が低下するので好まし
くない。従ってＣｕ：０．１〜０．７％に定めた。Ｃｕ
の含有量の一層好ましい範囲は０．３〜０．５％であ
る。Cu: Cu contained in the core material acts as a solid solution in the matrix to improve the strength, to make the electrochemical properties of the core material noble, and to increase the potential difference between the skin material (and the brazing material). However, if Cu is less than 0.1%, the desired effect cannot be obtained. On the other hand, if Cu is contained in excess of 0.7%, the melting point is lowered, and further, it is melted at the time of brazing, and the grain boundaries are further reduced. Corrosion easily occurs. It is not preferable because the corrosion resistance is reduced. Therefore, Cu was set to 0.1 to 0.7%. Cu
Is more preferably in the range of 0.3 to 0.5%.
【００１７】Ｚｒ：芯材に含まれるＺｒは、ろう付け後
に微細な金属間化合物として素地中に分散し、強度を向
上させる作用を有するが、Ｚｒ：０．０５％未満では所
望の効果が得られず、一方、Ｚｒ：０．１５％を越える
て含有させると、加工性が低下するので好ましくない。
従ってＺｒ：０．０５〜０．１５％に定めた。Ｚｒの含
有量一層好ましい範囲は０．１〜０．１２％である。Zr: Zr contained in the core material is dispersed as a fine intermetallic compound in the base material after brazing and has an effect of improving the strength, but if Zr: less than 0.05%, the desired effect is obtained. On the other hand, if Zr is contained in excess of 0.15%, workability is undesirably reduced.
Therefore, Zr was set to 0.05 to 0.15%. A more preferable range of the Zr content is 0.1 to 0.12%.
【００１８】Ｔｉ，Ｍｇ，Ｖ，Ｃｒ：芯材に含まれるこ
れら成分は、ろう付け後に微細な金属間化合物として素
地中に分散し、強度を向上させる作用を有するので必要
に応じて添加するが、Ｔｉ：０．０５％未満、Ｍｇ：
０．０５％未満、Ｖ：０．０５％未満、Ｃｒ：０．０５
％未満では所望の効果が得られず、一方、Ｔｉ：０．２
５％を越え、Ｍｇ：０．２０％を越え、Ｖ：０．１５％
を越え、Ｃｒ：０．１５％を越えるて含有させると、Ｍ
ｇの場合はろう付け性を低下させ、その他の成分は加工
性が低下するので好ましくない。従ってＴｉ：０．０５
〜０．２５％、Ｍｇ：０．０５〜０．２０％、Ｖ：０．
０５〜０．１５％、Ｃｒ：０．０５〜０．１５％に定め
た。Ｔｉ，Ｍｇ，Ｖ，Ｃｒの内でもＶを含むことが最も
好ましい。Ti, Mg, V, Cr: These components contained in the core material are dispersed as fine intermetallic compounds in the base material after brazing and have an effect of improving the strength. , Ti: less than 0.05%, Mg:
Less than 0.05%, V: less than 0.05%, Cr: 0.05
%, The desired effect cannot be obtained, while Ti: 0.2
Exceeds 5%, Mg: Exceeds 0.20%, V: 0.15%
If the content of Cr exceeds 0.15%, M
In the case of g, the brazing property is lowered, and the other components are not preferable because the processability is lowered. Therefore, Ti: 0.05
0.25%, Mg: 0.05-0.20%, V: 0.
05 to 0.15%, Cr: 0.05 to 0.15%. Most preferably, V is included among Ti, Mg, V, and Cr.
【００１９】（Ｃ）ろう材 この発明の熱交換器用ブレージングシートで使用するろ
う材は通常のＡｌ−Ｓｉ系Ａｌ合金ろう材であればよ
く、特に限定されるものではないが、ろう材中に含まれ
るＳｉはろう材の融点を下げると共に流動性を付与する
成分であり、その含有量が５％未満では所望の効果が得
られず、一方、１５％を越えて含有するとかえって流動
性が低下するので好ましくない。したがって、ろう材中
のＳｉの含有量を５〜１５％に定めた。ろう材中のＳｉ
の含有量の一層好ましい範囲は７〜１１％である。ま
た、この発明の熱交換器用ブレージングシートで使用す
るＡｌ−Ｓｉ系Ａｌ合金ろう材には、Ｚｎ：１．０〜
５．０％を含有してもよい。(C) Brazing material The brazing material used in the brazing sheet for a heat exchanger of the present invention may be any ordinary Al-Si-based Al alloy brazing material, and is not particularly limited. The contained Si is a component that lowers the melting point of the brazing filler metal and imparts fluidity. If the content is less than 5%, the desired effect cannot be obtained. On the other hand, if the content exceeds 15%, the fluidity decreases. Is not preferred. Therefore, the content of Si in the brazing material is set to 5 to 15%. Si in brazing material
Is more preferably in the range of 7 to 11%. The Al-Si-based Al alloy brazing material used in the heat exchanger brazing sheet of the present invention includes Zn: 1.0 to 1.0.
It may contain 5.0%.
【００２０】[0020]
【実施例】表１〜表２に示す成分組成のＡｌ合金を溶解
し、鋳造してインゴットを製造し、このインゴットを通
常の条件で均質化処理後、熱間圧延を行い、厚さ：３０
ｍｍの熱延板とし、犠牲陽極皮材Ａ〜Ｕを作製した。EXAMPLE An Al alloy having the composition shown in Tables 1 and 2 was melted and cast to produce an ingot. The ingot was homogenized under ordinary conditions and then hot-rolled to a thickness of 30.
mm, and sacrificial anode skin materials A to U were prepared.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 ※印は、本発明外の合金であることを示す。 ＊印は、本発明から外れた成分組成であることを示す。[Table 2] * Indicates that the alloy is outside the present invention. An asterisk indicates that the component composition deviates from the present invention.
【００２３】次に、表３〜表４に示す成分組成のＡｌ合
金を溶解し、鋳造してインゴットを製造し、このインゴ
ットを通常の条件で均質化処理後、熱間圧延を行い、厚
さ：１５０ｍｍの熱延板とし、芯材ａ〜ｒを作製した。Next, an Al alloy having a component composition shown in Tables 3 and 4 is melted and cast to produce an ingot. The ingot is homogenized under ordinary conditions, and then hot-rolled to obtain a thickness. : Hot rolled sheets of 150 mm were prepared, and core materials a to r were produced.
【００２４】[0024]
【表３】 [Table 3]
【００２５】[0025]
【表４】 [Table 4]
【００２６】さらに、表５に示す成分組成のＡｌ合金を
溶解し、鋳造してインゴットを製造し、このインゴット
を通常の条件で均質化処理後、熱間圧延を行い、厚さ：
２０ｍｍの熱延板とし、ろう材ア〜オを作製した。Further, an Al alloy having a component composition shown in Table 5 was melted and cast to produce an ingot. The ingot was homogenized under ordinary conditions, and then hot-rolled to obtain a thickness:
A 20 mm hot-rolled plate was used to prepare brazing filler metals A to O.
【００２７】[0027]
【表５】 [Table 5]
【００２８】表１〜表２に示す成分組成の犠牲陽極皮材
Ａ〜Ｖ、表３〜表４に示す成分組成の芯材ａ〜ｒ、およ
び表５に示す成分組成のろう材イ〜オを表６〜表８に示
す組み合わせで重ね合わせ、熱間圧延によりクラッド
し、続いて適宜中間焼鈍を行いながら冷間圧延を行卯こ
とにより、板厚：０．３ｍｍ、皮材およびろう材のクラ
ッド率：１０％、調質Ｈ１４の本発明熱交換器用クラッ
ド材（以下、本発明クラッド材という）１〜２２、比較
熱交換器用クラッド材（以下、比較クラッド材という）
１〜７およびＦｅ含有量の少ない犠牲陽極皮材Ｕを被覆
した従来熱交換器用クラッド材（以下、従来クラッド材
という）を作製した。Sacrificial anode skin materials A to V having the component compositions shown in Tables 1 and 2, core materials a to r having the component compositions shown in Tables 3 and 4, and brazing materials A to O having the component compositions shown in Table 5 Are overlapped in the combinations shown in Tables 6 to 8, clad by hot rolling, and then cold rolled while appropriately performing intermediate annealing to obtain a sheet thickness: 0.3 mm, Cladding rate: 10%, temper H14 clad material for heat exchanger of the present invention (hereinafter referred to as clad material of the present invention) 1-22, clad material for comparative heat exchanger (hereinafter referred to as comparative clad material)
A clad material for a conventional heat exchanger coated with a sacrificial anode skin material U having 1 to 7 and a small Fe content (hereinafter, referred to as a conventional clad material) was produced.
【００２９】これら本発明クラッド材１〜２２、比較ク
ラッド材１〜７および従来クラッド材を用い、犠牲陽極
皮材を内面にしたクラッド管を作製し、このクラッド管
を窒素雰囲気中（片面にろう材が被覆されているクラッ
ド管の場合は１０-3ｔｏｒｒの真空中）、６００℃に３
分間保持後、冷却速度：１００℃／ｍｉｎで室温まで冷
却の条件でろう付け相当熱処理を行った。次に、これら
クラッド管内に、ＮａＯＨでｐＨ：１０の強アルカリに
調整したＣｕ2+１０ｐｐｍ添加水道水を、自動車用熱交
換器の冷却水を想定して８０℃に８時間保持した後、室
温で１６時間保持の温度サイクルを加えながら１０００
時間流し続け、１０００時間経過後の最大孔食深さを測
定し、その結果を表６〜表８に示し、強アルカリ環境下
での耐孔食性を評価した。Using these clad materials 1 to 22 of the present invention, comparative clad materials 1 to 7 and the conventional clad material, a clad tube having a sacrificial anode skin material on the inner surface is produced, and the clad tube is placed in a nitrogen atmosphere (waxed on one side). In the case of a clad tube coated with a material, a vacuum of 10 -3 torr)
After holding for one minute, a heat treatment equivalent to brazing was performed under the condition of cooling to room temperature at a cooling rate of 100 ° C./min. Next, 10 ppm of Cu 2+ added tap water adjusted to a strong alkali having a pH of 10 with NaOH was held in these clad tubes at 80 ° C. for 8 hours assuming cooling water for an automobile heat exchanger, and then room temperature was maintained. 1000 while applying a temperature cycle of 16 hours
The flow was continued for a period of time, and the maximum pit depth after 1000 hours was measured. The results are shown in Tables 6 to 8, and the pitting resistance under a strong alkaline environment was evaluated.
【００３０】[0030]
【表６】 [Table 6]
【００３１】[0031]
【表７】 [Table 7]
【００３２】[0032]
【表８】 [Table 8]
【００３３】[0033]
【発明の効果】表１〜表８に示される結果から、Ｆｅ：
０．７５〜１．２％、Ｍｇ：０．５〜２．５％を含有
し、さらにＺｎ：１〜８％、Ｓｎ：０．０５〜０．３５
％のうちの１種または２種を含有する犠牲陽極皮材を張
り合わせた本発明クラッド材１〜２２は、Ｆｅ：０．５
％含有の犠牲陽極皮材を張り合わせた従来クラッド材に
比べて、強アルカリ環境下での最大孔食深さが小さいと
ころから、強アルカリ環境下での耐孔食性に優れている
ことが分かる。しかし、この発明の範囲から外れて含有
する比較クラッド材１〜７は、耐孔食性にやや劣ること
が分かる。上述のように、この発明の熱交換器用クラッ
ド材は、強アルカリ環境下での耐孔食性に優れていると
ころから、寒冷地で使用する自動車の熱交換器の冷媒流
通経路材として用いることができ、自動車の熱交換器の
寿命の向上に大いに貢献し得るものである。From the results shown in Tables 1 to 8, it can be seen that Fe:
0.75 to 1.2%, Mg: 0.5 to 2.5%, Zn: 1 to 8%, Sn: 0.05 to 0.35
% Of the clad materials of the present invention bonded with a sacrificial anode skin material containing one or two of Fe.
% Pitting depth under a strong alkaline environment is smaller than that of a conventional clad material laminated with a sacrificial anode skin material containing 0.1% by weight. However, it can be seen that the comparative clad materials 1 to 7 contained out of the scope of the present invention are slightly inferior in pitting corrosion resistance. As described above, the heat exchanger clad material of the present invention is excellent in pitting corrosion resistance under a strong alkaline environment, and therefore can be used as a refrigerant flow path material of a heat exchanger of an automobile used in a cold region. It can greatly contribute to the improvement of the life of the heat exchanger of the automobile.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２３Ｆ 13/00 Ｃ２３Ｆ 13/00 Ｐ Ｆ２８Ｆ 19/06 Ｆ２８Ｆ 19/06 Ｂ 21/08 21/08 Ｄ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C23F 13/00 C23F 13/00 PF28F 19/06 F28F 19/06 B 21/08 21/08 D
Claims (6)
のＡｌ合金芯材の片面あるいは両面に、重量％で、 Ｆｅ：０．７５〜１．２％、 Ｍｇ：０．５〜２．５％、 を含有し、さらに、 Ｚｎ：１〜８％、 Ｓｎ：０．０５〜０．３５％、 のうちの１種または２種を含有し、残りがＡｌおよび不
可避不純物からなる組成を有する犠牲陽極皮材をクラッ
ドしてなることを特徴とする強アルカリ環境下での耐孔
食性に優れた熱交換器用クラッド材。1. Mn: 0.8 to 2.0%, Si: 0.1 to 1.0%, Cu: 0.1 to 0.7%, Zr: 0.05 to 0. On the one or both sides of an Al alloy core material having a composition consisting of Al and inevitable impurities on the one or both sides, Fe: 0.75 to 1.2%, Mg: 0.5 to 2. And further contains one or two of Zn: 1 to 8%, Sn: 0.05 to 0.35%, and the remainder has a composition of Al and unavoidable impurities. A clad material for heat exchangers that is excellent in pitting corrosion resistance in a strong alkaline environment, characterized by being clad with a sacrificial anode skin material.
のＡｌ合金芯材の片面に、重量％で、 Ｆｅ：０．７５〜１．２％、 Ｍｇ：０．５〜２．５％、 を含有し、さらに、 Ｚｎ：１〜８％、 Ｓｎ：０．０５〜０．３５％、 のうちの１種または２種を含有し、残りがＡｌおよび不
可避不純物からなる組成を有する犠牲陽極皮材をクラッ
ドし、他方の片面にＡｌ−Ｓｉ系あるいはＡｌ−Ｓｉ−
Ｚｎ系ろう材をクラッドしてなることを特徴とする強ア
ルカリ環境下での耐孔食性に優れた熱交換器用クラッド
材。2. In% by weight, Mn: 0.8-2.0%, Si: 0.1-1.0%, Cu: 0.1-0.7%, Zr: 0.05-0. On the one side of an Al alloy core material having a composition of 15%, and the balance consisting of Al and inevitable impurities, Fe: 0.75 to 1.2%, Mg: 0.5 to 2.5% Further, a sacrificial anode containing one or two of Zn: 1 to 8%, Sn: 0.05 to 0.35%, and the balance consisting of Al and unavoidable impurities. A cladding material is clad, and the other side is made of Al-Si or Al-Si-
A clad material for a heat exchanger having excellent pitting corrosion resistance in a strong alkaline environment, characterized by being clad with a Zn-based brazing material.
び不可避不純物からなる組成のＡｌ合金芯材の片面ある
いは両面に、重量％で、 Ｆｅ：０．７５〜１．２％、 Ｍｇ：０．５〜２．５％、 を含有し、さらに、 Ｚｎ：１〜８％、 Ｓｎ：０．０５〜０．３５％、 のうちの１種または２種を含有し、残りがＡｌおよび不
可避不純物からなる組成を有する犠牲陽極皮材をクラッ
ドしてなることを特徴とする強アルカリ環境下での耐孔
食性に優れた熱交換器用クラッド材。3. Mn: 0.8 to 2.0%, Si: 0.1 to 1.0%, Cu: 0.1 to 0.7%, Zr: 0.05 to 0. 15%, and Ti: 0.05 to 0.25%, Mg: 0.05 to 0.20%, V: 0.05 to 0.15%, Cr: 0.05 to 0.1%. Fe: 0.75 to 1.2% by weight% on one or both sides of an Al alloy core material having a composition comprising Al and unavoidable impurities. , Mg: 0.5 to 2.5%, and Zn: 1 to 8%, Sn: 0.05 to 0.35%, and one or two of the following: A heat exchanger excellent in pitting corrosion resistance in a strong alkaline environment, characterized by being clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. Cladding material.
び不可避不純物からなる組成のＡｌ合金芯材の片面に、
重量％で、 Ｆｅ：０．７５〜１．２％、 Ｍｇ：０．５〜２．５％、 を含有し、さらに、 Ｚｎ：１〜８％、 Ｓｎ：０．０５〜０．３５％、 のうちの１種または２種を含有し、残りがＡｌおよび不
可避不純物からなる組成を有する犠牲陽極皮材をクラッ
ドし、他方の片面にＡｌ−Ｓｉ系あるいはＡｌ−Ｓｉ−
Ｚｎ系ろう材をクラッドしてなることを特徴とする強ア
ルカリ環境下での耐孔食性に優れた熱交換器用クラッド
材。4. Mn: 0.8 to 2.0%, Si: 0.1 to 1.0%, Cu: 0.1 to 0.7%, Zr: 0.05 to 0. 15%, and Ti: 0.05 to 0.25%, Mg: 0.05 to 0.20%, V: 0.05 to 0.15%, Cr: 0.05 to 0.1%. 15%, on one surface of an Al alloy core material having a composition comprising at least one of
% By weight, Fe: 0.75 to 1.2%, Mg: 0.5 to 2.5%, Zn: 1 to 8%, Sn: 0.05 to 0.35%, One or two of the above, and the rest is clad with a sacrificial anode skin material having a composition of Al and inevitable impurities, and the other surface is made of an Al-Si or Al-Si-
A clad material for a heat exchanger having excellent pitting corrosion resistance in a strong alkaline environment, characterized by being clad with a Zn-based brazing material.
熱交換器の冷媒流通経路材であることを特徴とする請求
項１、２、３または４記載の強アルカリ環境下での耐孔
食性に優れた熱交換器用クラッド材。5. The pitting corrosion resistance in a strong alkaline environment according to claim 1, wherein the heat exchanger clad material is a refrigerant flow path material for a heat exchanger of an automobile. Excellent heat exchanger clad material.
て用いる強アルカリ環境下での耐孔食性に優れた熱交換
器用ブレージングシートであることを特徴とする請求項
２または４記載の熱交換器用クラッド材。6. A heat exchange brazing sheet according to claim 2, which is a brazing sheet for a heat exchanger having excellent pitting corrosion resistance under a strong alkaline environment and used as a refrigerant flow path material for a heat exchanger of an automobile. Dexterous clad material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30561597A JP4058650B2 (en) | 1997-11-07 | 1997-11-07 | Clad material for heat exchangers with excellent pitting corrosion resistance in a strong alkaline environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30561597A JP4058650B2 (en) | 1997-11-07 | 1997-11-07 | Clad material for heat exchangers with excellent pitting corrosion resistance in a strong alkaline environment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11140571A true JPH11140571A (en) | 1999-05-25 |
| JP4058650B2 JP4058650B2 (en) | 2008-03-12 |
Family
ID=17947278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30561597A Expired - Fee Related JP4058650B2 (en) | 1997-11-07 | 1997-11-07 | Clad material for heat exchangers with excellent pitting corrosion resistance in a strong alkaline environment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4058650B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297673A (en) * | 2006-04-28 | 2007-11-15 | Furukawa Sky Kk | High corrosion resistant aluminum alloy composite material for heat exchanger, and aluminum alloy heat exchanger |
| JP2010202919A (en) * | 2009-03-02 | 2010-09-16 | Kobe Steel Ltd | Aluminum alloy cladding material |
| US20120279694A1 (en) * | 2009-09-21 | 2012-11-08 | Denso Corporation | High-corrosion-resistant aluminum alloy brazing sheet, method of manufacturing such sheet, and corrosive-resistant heat exchanger using such sheet |
| JP2013040360A (en) * | 2011-08-12 | 2013-02-28 | Mitsubishi Alum Co Ltd | Aluminum alloy pipe member for heat exchanger |
-
1997
- 1997-11-07 JP JP30561597A patent/JP4058650B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297673A (en) * | 2006-04-28 | 2007-11-15 | Furukawa Sky Kk | High corrosion resistant aluminum alloy composite material for heat exchanger, and aluminum alloy heat exchanger |
| JP2010202919A (en) * | 2009-03-02 | 2010-09-16 | Kobe Steel Ltd | Aluminum alloy cladding material |
| US20120279694A1 (en) * | 2009-09-21 | 2012-11-08 | Denso Corporation | High-corrosion-resistant aluminum alloy brazing sheet, method of manufacturing such sheet, and corrosive-resistant heat exchanger using such sheet |
| US9095934B2 (en) * | 2009-09-21 | 2015-08-04 | Denso Corp. | High-corrosion-resistant aluminum alloy brazing sheet, method of manufacturing such sheet, and corrosive-resistant heat exchanger using such sheet |
| JP2013040360A (en) * | 2011-08-12 | 2013-02-28 | Mitsubishi Alum Co Ltd | Aluminum alloy pipe member for heat exchanger |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4058650B2 (en) | 2008-03-12 |
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