JPS6039143B2 - Pitting corrosion resistant aluminum alloy - Google Patents

Pitting corrosion resistant aluminum alloy

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Publication number
JPS6039143B2
JPS6039143B2 JP10789079A JP10789079A JPS6039143B2 JP S6039143 B2 JPS6039143 B2 JP S6039143B2 JP 10789079 A JP10789079 A JP 10789079A JP 10789079 A JP10789079 A JP 10789079A JP S6039143 B2 JPS6039143 B2 JP S6039143B2
Authority
JP
Japan
Prior art keywords
alloy
corrosion
pitting corrosion
present
weight
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.)
Expired
Application number
JP10789079A
Other languages
Japanese (ja)
Other versions
JPS5633448A (en
Inventor
建 当摩
一雄 山田
庸 竹内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MA Aluminum Corp
Original Assignee
Mitsubishi Aluminum Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Aluminum Co Ltd filed Critical Mitsubishi Aluminum Co Ltd
Priority to JP10789079A priority Critical patent/JPS6039143B2/en
Publication of JPS5633448A publication Critical patent/JPS5633448A/en
Publication of JPS6039143B2 publication Critical patent/JPS6039143B2/en
Expired legal-status Critical Current

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Description

【発明の詳細な説明】 この発明は、すぐれた耐孔食性を有するアルミニウム合
金に関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aluminum alloy having excellent pitting corrosion resistance.

従来、一般に、例えばJIS5005(Mg:0.5〜
1.1%含有)や5050(Mg:1.1〜1.8%含
有、以上重量%)などの比較的Mg含有量の低いAI−
Mg合金、すなわちMg:0.5〜1.8重量%を含有
するAI−Mg合金は、比較的良好な耐食性、すぐれた
成形加工性や熔接性、そして中程度の強度を有すること
から種々の分野で広く適用されており、特に耐候性にす
ぐれていることから、建築構造物や車師などの内外装村
などに広く用いられている。
Conventionally, in general, for example, JIS5005 (Mg: 0.5~
AI- with relatively low Mg content, such as
Mg alloys, namely AI-Mg alloys containing Mg: 0.5 to 1.8% by weight, have relatively good corrosion resistance, excellent formability and weldability, and moderate strength, so they are used in various applications. It is widely applied in various fields, and because of its excellent weather resistance, it is widely used for interior and exterior construction, such as building structures and car manufacturers.

前記山一Mg合金が良好な耐食性を示すのは、その表面
にAI−Mg合金特有の強固な自然酸化皮膜が形成され
ることに起因するものである。しかしながら、この酸化
皮膜中に不可避的に不純物が含有されていたり、熱的あ
るいは機械的に傷が付与されたりすると、これらの個所
は十分な耐食性を発揮することができず、したがってこ
れらの個所は選択的に溶解され、この結果著しい局部的
腐食、すなわち孔食が発生することがいまいま起ってい
た。特にこの孔食発生の鏡向は、使用環境中にCuイオ
ンなどの重金属イオンが含有される場合に顕著に現われ
るものである。この発明は、上述のような観点から、上
記従来山一Mg合金、すなわちMg:0.5〜1.箱重
量%を含有するALMg合金のもつ良好な成形加工性、
溶接性、および機械性質などの特性を具備した状態で、
耐孔食性を著しく改善したアルミニウム合金を提供する
もので、上記従来AI−Mg合金の表面に形成される自
然酸化皮膜のもつすぐれた耐食性を、少量のZnを含有
せしめることによって低下させて、その腐食形態を全面
腐食型とするとともに、さらに、Cr,Mn,Zr,M
o,Ti、およびVなどの遷移元素の1種または2種以
上を少量含有せしめられることによって結晶粒微細化効
果を付与し、これによって腐食開始箇所所をできるだけ
増加させて、全面腐食型の腐食形態をより確実とし、苛
酷な腐食環境中でも局部的腐食および孔食を完全に抑制
するようにしたアルミニウム合金に特徴を有するもので
ある。
The reason why the Yamaichi Mg alloy exhibits good corrosion resistance is due to the formation of a strong natural oxide film unique to the AI-Mg alloy on its surface. However, if this oxide film inevitably contains impurities or is damaged thermally or mechanically, these areas will not be able to exhibit sufficient corrosion resistance. Selective dissolution, resulting in significant localized corrosion, or pitting, was now occurring. In particular, this mirror-direction of pitting corrosion appears prominently when heavy metal ions such as Cu ions are contained in the usage environment. From the above-mentioned viewpoint, the present invention is directed to the above-mentioned conventional Yamaichi Mg alloy, that is, Mg: 0.5 to 1. Good formability of ALMg alloy containing box weight %,
With properties such as weldability and mechanical properties,
The purpose is to provide an aluminum alloy with significantly improved pitting corrosion resistance.The excellent corrosion resistance of the natural oxide film formed on the surface of the conventional AI-Mg alloy is reduced by containing a small amount of Zn. In addition to making the corrosion form a general corrosion type, furthermore, Cr, Mn, Zr, M
By containing a small amount of one or more of transition elements such as O, Ti, and V, a crystal grain refining effect is imparted, thereby increasing the number of corrosion initiation points as much as possible and preventing general corrosion type corrosion. It is characterized by an aluminum alloy that has a more reliable shape and completely suppresses localized corrosion and pitting corrosion even in severe corrosive environments.

したがって、この発明のアルミニウム合金は、Mgを0
.5〜1.頚重量%含有する公知のAI−Mg合金に、
0.3〜1.の重量%のZnと、0.05〜0.乳重量
%の、Cr,Mn,Zr,Mo,Ti、およびVのうち
の1糧または2種以上を含有させた組成をもつことに特
徴を有するものである。
Therefore, the aluminum alloy of this invention contains 0 Mg.
.. 5-1. In the known AI-Mg alloy containing % neck weight,
0.3-1. % by weight of Zn and 0.05-0. It is characterized by having a composition containing one or more of Cr, Mn, Zr, Mo, Ti, and V in an amount of % by weight of milk.

この発明のアルミニウム合金において、ZnおよびCr
,Mn,Zr,Mo,Ti,Vの含有量をそれぞれ上記
のように限定したのは「Znの含有量が0.紅重量%未
満では、所望のすぐれた耐孔食性を付与することができ
ず、一方1.の重量%を越えて含有させると、不均一腐
食や孔食が発生するようになるとともに、腐食量が増大
するようになることから、その含有量を0.3〜1.の
重量%と限定した。
In the aluminum alloy of this invention, Zn and Cr
, Mn, Zr, Mo, Ti, and V are limited as described above because ``If the Zn content is less than 0.0% by weight, the desired excellent pitting corrosion resistance cannot be imparted.'' On the other hand, if the content exceeds 1% by weight, uneven corrosion and pitting corrosion will occur, and the amount of corrosion will increase, so the content should be adjusted to 0.3 to 1% by weight. % by weight.

また、Cr,Mn.Zr,Mo,Ti,Vなどの遷移元
素の含有量が0.05重量%未満では、結晶粒微細化作
用が十分でないので、全面腐食型の腐食形態を強化して
不均一腐食や孔食の発生を防止する効果がほとんど現わ
れず、一方0.3重量%を越えて含有させると鋳造時に
巨大晶出物が形成されやすく、不均一腐食や孔食が発生
するのでZn添加による耐孔食性改善の効果が失われる
とともに、腐食豊か著しく増大するようになることに加
えて、材料の加工性や機械的性質等にも悪影響を生ずる
こととなるので、その含有量を0.05〜0.3重量%
とした。このCr,Mn,Zr,Mo,Ti,Vの遷移
元素の各々が、耐孔食性の改善に均等な効果を発揮する
ことは言うまでもないことである。なお、Mgの含有量
を0.5〜1.紅重量%に限定したのは、公知のように
、Mgの含有量が0.2重量%未満では必要な機械的強
度を得ることができないとともに、耐食性向上の効果が
期待できず、一方2.1重量%を越えて含有させると、
熱間加工性が悪くなるとともに耐食性も再び低下するこ
とから、その含有量を0.5〜1.8重量%と限定した
ものである。一般に、アルミニウム合金は、Znを添加
することによって電気化学的に卑になる。
In addition, Cr, Mn. If the content of transition elements such as Zr, Mo, Ti, and V is less than 0.05% by weight, the crystal grain refining effect is not sufficient, so overall corrosion type is strengthened to prevent uneven corrosion and pitting corrosion. There is almost no effect in preventing the occurrence of Zn, and on the other hand, if it is added in excess of 0.3% by weight, giant crystallized substances are likely to be formed during casting, causing uneven corrosion and pitting corrosion, so the pitting corrosion resistance is improved by adding Zn. In addition to losing its effectiveness and significantly increasing corrosion resistance, it also has an adverse effect on the workability and mechanical properties of the material, so the content should be reduced to 0.05 to 0.3. weight%
And so. It goes without saying that each of the transition elements Cr, Mn, Zr, Mo, Ti, and V exerts an equal effect on improving pitting corrosion resistance. In addition, the content of Mg is 0.5 to 1. The reason for limiting the Mg content to 0.2% by weight is that, as is known, if the content of Mg is less than 0.2% by weight, the necessary mechanical strength cannot be obtained and the effect of improving corrosion resistance cannot be expected. If it is contained in excess of 1% by weight,
Since hot workability deteriorates and corrosion resistance also decreases again, its content is limited to 0.5 to 1.8% by weight. Generally, aluminum alloys become electrochemically less noble by adding Zn.

このような特性は徴量の遷移元素の添加の影響をほとん
ど受けないので、徴量のZnおよび遷移元素を含有する
本発明合金は、電気化学的により貴なアルミニウム合金
の芯材に、皮材としてクラツドすることによって耐孔食
性にすぐれた複合材料を構成し得るという利点もある。
従来も、JIS7072合金を皮村としてクラツドした
複合材がこの種の目的のために広く使用されていたが、
この皮村は耐孔食性が必ずしも十分でなく、孔食が容易
に芯村まで到達し、芯村オと皮材の境界面が優先的に腐
食されて皮材のはがれが生じたりするなど、防食上種々
の問題があった。これに対して、本発明合金を皮材とし
てクラッドした複合材は、皮材のすぐれた耐孔食性に加
えて、犠牲陽極効果を併せもつことになり、孔食が極め
て発生しにくく、万一発生しても、皮村が芯村オをよく
防食し、芯材が侵食を受けることを防止してくれるとい
う効果を有するものである。このような効果の期待でき
る芯材としては、本発明合金よりも電気化学的に貴な材
料、すなわち、純アルミニウム、AI−Cu系〜AI−
Mn系、N−Sj系、AI−Mg系、AI−Mg−Si
系の各合金などが該当する。ついで、この発明のアルミ
ニウム合金を実施例により、従来公知のAI−Mg合金
と、これに微量のZnを含有させた材料、および公知の
複合材料と比較しながら説明する。
Since such properties are hardly affected by the addition of characteristic transition elements, the alloy of the present invention containing characteristic amounts of Zn and transition elements has a core material of an electrochemically more noble aluminum alloy and a skin material. There is also the advantage that by cladding as a composite material, a composite material with excellent pitting corrosion resistance can be constructed.
Conventionally, composite materials made of JIS 7072 alloy as a skin layer have been widely used for this type of purpose.
This skin material does not necessarily have sufficient pitting corrosion resistance, and pitting corrosion easily reaches the core material, and the interface between the core material and the skin material is preferentially corroded, causing peeling of the skin material. There were various problems in terms of corrosion protection. In contrast, a composite material clad with the alloy of the present invention as a skin material has a sacrificial anode effect in addition to the excellent pitting corrosion resistance of the skin material, making it extremely difficult for pitting corrosion to occur. Even if corrosion occurs, the skin has the effect of effectively preventing corrosion of the core material and preventing the core material from being eroded. Core materials that can be expected to have such effects include materials that are electrochemically more noble than the alloy of the present invention, such as pure aluminum, AI-Cu series ~ AI-
Mn series, N-Sj series, AI-Mg series, AI-Mg-Si
This applies to each type of alloy. Next, the aluminum alloy of the present invention will be explained using Examples while comparing it with a conventionally known AI-Mg alloy, a material containing this alloy with a trace amount of Zn, and a known composite material.

通常の熔解鋳造法により第1表に示される最終成分組成
をもった本発明合金1〜i5および比較合金1〜4をそ
れぞれ製造した。
Alloys 1 to i5 of the present invention and comparative alloys 1 to 4 having the final component compositions shown in Table 1 were manufactured by a conventional melt casting method.

比較合金1はJIS5005合金に準じた成分組成をも
ったものであり「 この比較合金1にZnを0.5重量
%含有させたものが比較合金2であり、この比較合金2
にCrをそれぞれ0.050.10,0.20,0.3
5重量%含有させたものが、本発明合金1〜3と比較合
金3である。また、比較合金2にそれぞれ0.15重量
%のMn,Zr,Mo,Ti,Vをを含有させたものが
本発明合金4〜8である。比較合金4はJIS505川
合金に準じた成分組成をもつたものであり、これにZn
を0.3重量%とMnを0.2重量%含有させたものが
本発明合金9である。さらに、比較合金2にそれぞれC
r,Mn,Zr,Mo,およびVのうちの2種以上を含
有させたものが本発明合金10〜15である。また、第
1表には、複合材の芯材および比較材として、純アルミ
ニウム、JIS3003に準ずるAI−Mn合金および
JIS7072に準ずるAI−Zn合金およびJIS7
072に準ずるN−Zn合金を通常の溶解鋳造法によっ
て製造したものの最終成分組成をも示した。このように
漆製した本発明合金1〜15と比較合金1〜4に対して
、均質化処理を施した後、袷間圧延によって1肋の板厚
を有する板材とした。
Comparative Alloy 1 has a composition similar to JIS5005 alloy, and "Comparative Alloy 2 contains 0.5% by weight of Zn in Comparative Alloy 1.
and 0.050.10, 0.20, 0.3 of Cr, respectively.
Invention alloys 1 to 3 and comparative alloy 3 contain 5% by weight. Alloys 4 to 8 of the present invention are Comparative Alloy 2 containing 0.15% by weight of Mn, Zr, Mo, Ti, and V, respectively. Comparative alloy 4 has a composition similar to JIS505 river alloy, and has Zn.
Alloy 9 of the present invention contains 0.3% by weight of Mn and 0.2% by weight of Mn. Furthermore, C
Alloys 10 to 15 of the present invention contain two or more of r, Mn, Zr, Mo, and V. Table 1 also lists pure aluminum, an AI-Mn alloy according to JIS 3003, an AI-Zn alloy according to JIS 7072, and a JIS 7
The final component composition of an N-Zn alloy similar to No. 072 manufactured by a normal melting and casting method is also shown. The lacquer-made alloys of the present invention 1 to 15 and comparative alloys 1 to 4 were subjected to homogenization treatment, and then rolled into plates having a thickness of one rib.

また皮材の厚さが全板厚の10%を占める本発明複合材
1〜3および比較複合材を前記の板厚1帆を有する板材
と上記の各材質の芯材とを熱間圧延によってクラッドし
、ついで冷間圧延によって板厚1凧とすることによって
製造した。第1表 なお、本発明複合材1は純アルミニウムを芯材とし、皮
材として本発明合金2を10%の厚さでクラッドしたも
の、本発明複合材2はAI−Mn合金(第1表参照)を
芯村とし、皮材として本発明合金2を10%の厚さでク
ラツドしたもの、本発明複合材3はAI−Mg合金すな
わち比較合金4を芯村とし、皮材として本発明合金2を
10%の厚さでクラッドしたものであり、比較複合材は
山一Mn合金を芯材とし、皮材としてAI−Zn合金(
第1表参照)を10%の厚さでクラッドしたものである
Composite materials 1 to 3 of the present invention and comparative composite materials in which the thickness of the skin material accounts for 10% of the total board thickness were prepared by hot rolling the above-mentioned board material having a board thickness of 1 sail and the core material of each of the above-mentioned materials. It was manufactured by cladding and then cold rolling to a plate thickness of 1 kite. Table 1 Note that the composite material 1 of the present invention has pure aluminum as the core material and the alloy 2 of the present invention as the skin material is clad with a thickness of 10%, and the composite material 2 of the present invention is an AI-Mn alloy (see Table 1). Composite material 3 of the present invention is made by using the AI-Mg alloy, that is, comparative alloy 4, as the core material and cladding the present invention alloy 2 with a thickness of 10% as the skin material. 2 is clad with a thickness of 10%, and the comparative composite material is made of Yamaichi Mn alloy as the core material and AI-Zn alloy (as the skin material).
(see Table 1) is clad with a thickness of 10%.

ついで、これらの板材および複合材より試験片を切り出
し、浸贋腐食試験に供した。浸漬腐食試験は、1岬pm
という多量のCuイオンを添加した4000の水道水と
、同じく1のpmのCuイオンを添加した40ooの3
%食塩水に、それぞれ1ケ月浸債の条件にて行ない、試
験後、腐食生成物を除去して腐食減量、孔食数および最
大孔食深さを測定した。この結果を第1表に示した。第
2表に示されるように、本発明合金1〜15および本発
明合金を皮材としてクラツドした本発明複合材1〜3は
、前記の食塩水試験や、孔食性の特に顕著な水道水試験
に対してすぐれた結果を得ることができ、苛酷な腐食条
件下でも顕しくすぐれた耐孔食性を有することが明らか
である。第2表なお、第2表における※印は、局部腐食
深さが10〃肌以下の全面腐食形態を示すものである。
Then, test pieces were cut out from these plate materials and composite materials and subjected to a corrosion test. Immersion corrosion test is 1 Cape pm
4000 tap water with a large amount of Cu ions added, and 40oo 3 with 1 pm of Cu ions added.
% saline solution for one month, and after the test, corrosion products were removed and the corrosion loss, number of pitting corrosion, and maximum pitting depth were measured. The results are shown in Table 1. As shown in Table 2, alloys 1 to 15 of the present invention and composite materials 1 to 3 of the present invention clad with the alloy of the present invention as a skin material were tested in the above-mentioned saline water test and in the tap water test where pitting corrosion was particularly noticeable. It is clear that the material has excellent pitting corrosion resistance even under severe corrosive conditions. Table 2 Note that the mark * in Table 2 indicates a form of general corrosion where the local corrosion depth is 10 skin or less.

つぎに、万一、複合材皮材に孔食が発生した場合の、芯
材に対する防食効果を検討した。孔食が発生すると食孔
内は溶出した金属の塩が濃縮されるので、このような環
境中での異種材料*間の接触腐食挙動は、各材料の脱気
AIC13水溶液中における自然電極電位と食塩水中で
の孔食発生電位をそれぞれ比較することによって推定す
ることができるから、本発明合金1〜15および比較合
金4、さらに上記の比較材について上記各電位を測定し
た結果を第3表に示す。
Next, we investigated the anticorrosion effect on the core material in the event that pitting corrosion occurs in the composite skin material. When pitting corrosion occurs, the eluted metal salts are concentrated in the pit, so the contact corrosion behavior between different materials* in such an environment is based on the natural electrode potential of each material in a degassed AIC13 aqueous solution. Since it can be estimated by comparing the pitting corrosion occurrence potential in saline water, Table 3 shows the results of measuring the potentials of the present invention alloys 1 to 15 and comparative alloy 4, as well as the above comparative materials. show.

第3表 第3表に示されるように、本発明合金は JIS7072合金に比べて含有Zn量が少ないにもか
かわらず、電気化学的に同等あるいはそれ以上に卑であ
り、十分な犠牲陽極効果が期待できることが明らかであ
る。
Table 3 As shown in Table 3, although the present alloy contains less Zn than the JIS 7072 alloy, it is electrochemically equivalent or even more base, and has sufficient sacrificial anode effect. It is clear that there is hope.

したがって、本発明合金単独では強度不足のために使用
できない例えば各種水タンクや配管などの分野にも、高
強度合金を芯材とし、本発明アルミニウム合金を皮材と
したクラツド材として何ら問題なく使用することができ
るので、その使用範囲が著しく広がることになるのであ
る。上述のように、この発明のアルミニウム合金は、従
釆のMg含有量の比較的低いAI−Mg合金と同等の良
好な成形加工性、溶接性、および機械的性質などを具備
した上で、さらにすぐれた耐孔食性を有するとともに、
複合材の皮村として使用した場合に、芯村に対する十分
な犠性陽極効果を有するなど、工業上有用な効果をもた
らすものである。
Therefore, in fields such as various water tanks and piping where the alloy of the present invention alone cannot be used due to insufficient strength, it can be used without any problems as a cladding material with the high-strength alloy as the core material and the aluminum alloy of the present invention as the skin material. As a result, the range of its use will be significantly expanded. As mentioned above, the aluminum alloy of the present invention has good formability, weldability, mechanical properties, etc. equivalent to the conventional AI-Mg alloy with a relatively low Mg content, and also has In addition to having excellent pitting corrosion resistance,
When used as a skin of a composite material, it brings about industrially useful effects such as having a sufficient sacrificial anode effect on the core.

Claims (1)

【特許請求の範囲】 1 Mg:0.5〜1.8%、 Zn:0.3〜1%、 を含有し、さらに、 Cr,Mn,Zr,Mo,Ti、およびVのうちの1種
または2種以上:0.05〜0.3%、を含有し、残り
がAlと不可避不純物からなる組成(以上重量%)を有
することを特徴とする耐孔食性アルミニウム合金。
[Claims] 1 Contains Mg: 0.5 to 1.8%, Zn: 0.3 to 1%, and further contains one of Cr, Mn, Zr, Mo, Ti, and V. or two or more types: 0.05 to 0.3%, and the remainder is Al and unavoidable impurities (weight %).
JP10789079A 1979-08-24 1979-08-24 Pitting corrosion resistant aluminum alloy Expired JPS6039143B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10789079A JPS6039143B2 (en) 1979-08-24 1979-08-24 Pitting corrosion resistant aluminum alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10789079A JPS6039143B2 (en) 1979-08-24 1979-08-24 Pitting corrosion resistant aluminum alloy

Publications (2)

Publication Number Publication Date
JPS5633448A JPS5633448A (en) 1981-04-03
JPS6039143B2 true JPS6039143B2 (en) 1985-09-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP10789079A Expired JPS6039143B2 (en) 1979-08-24 1979-08-24 Pitting corrosion resistant aluminum alloy

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JP (1) JPS6039143B2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6123740A (en) * 1984-07-11 1986-02-01 Kobe Steel Ltd Aluminum alloy for spinning forming
JPS62110620A (en) * 1985-11-08 1987-05-21 Nippon Gakki Seizo Kk Substrate for magnetic recording medium
JPH02258944A (en) * 1989-03-30 1990-10-19 Sky Alum Co Ltd Aluminum alloy rolled sheet having excellent pitting corrosion resistance
CN100465316C (en) * 2005-03-07 2009-03-04 东北轻合金有限责任公司 Aluminium alloy having medium mechanical strength and corrosion-proof properties and its prodn. method

Also Published As

Publication number Publication date
JPS5633448A (en) 1981-04-03

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