JP2835724B2 - Method of controlling growth of oxide film during heat treatment of aluminum or aluminum alloy material, aluminum or aluminum alloy material whose growth of oxide film is controlled during heat treatment, and method of producing same - Google Patents
Method of controlling growth of oxide film during heat treatment of aluminum or aluminum alloy material, aluminum or aluminum alloy material whose growth of oxide film is controlled during heat treatment, and method of producing sameInfo
- Publication number
- JP2835724B2 JP2835724B2 JP63082346A JP8234688A JP2835724B2 JP 2835724 B2 JP2835724 B2 JP 2835724B2 JP 63082346 A JP63082346 A JP 63082346A JP 8234688 A JP8234688 A JP 8234688A JP 2835724 B2 JP2835724 B2 JP 2835724B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- aluminum
- alloy material
- aluminum alloy
- heat treatment
- 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 - Fee Related
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
Description
本発明は、アルミニウム又はアルミニウム合金材（以
下、単にアルミニウム合金材）の熱処理時の酸化皮膜の
成長を抑制する方法並びに熱処理時における酸化皮膜の
成長が抑制されたアルミニウム合金材及びその製造法に
関するものである。The present invention relates to a method for suppressing the growth of an oxide film during heat treatment of aluminum or an aluminum alloy material (hereinafter simply referred to as an aluminum alloy material), an aluminum alloy material in which the growth of an oxide film is suppressed during heat treatment, and a method for producing the same. It is.
アルミニウム合金材の大きな特徴の一つとして、アル
ミニウム合金材は大気中に放置されているだけで、その
表面には強固な酸化皮膜が形成されてしまうことがある
ことは周知の通りである。 そして、この表面酸化皮膜は耐食性及び絶縁性等に優
れていることから、従来においてはこの表面酸化皮膜を
積極的に利用していることが多い。 尚、この表面酸化皮膜は、アルミニウム合金材を熱処
理することによって、著しく成長させることができるも
のである。 ところが、表面酸化皮膜の存在が逆に好ましくない場
合もあり、表面には出来るだけ酸化皮膜が存在していな
い方が良い場合もある。 このような技術分野の一例として、例えばアルミニウ
ム合金材を接合する場合がある。 すなわち、例えばアルミニウム合金材よりなるチュー
ブとフィンとをろう付けによって接合する場合、これら
アルミニウム合金材の表面には酸化皮膜の形成されてい
ないことが望ましい。 この為、このような接合作業を例えば真空中で行なう
ことによって、ろう付作業時の加熱による酸化皮膜が成
長しにくくすることが行なわれている。 しかし、このような真空雰囲気下でろう付けを行なっ
ても、ろう付不良が起きることはこれまでにも指摘され
ている通りである。As one of the major features of the aluminum alloy material, it is well known that a strong oxide film may be formed on the surface of the aluminum alloy material simply by being left in the air. And since this surface oxide film is excellent in corrosion resistance, insulation properties, etc., in the past, this surface oxide film has often been actively used. The surface oxide film can be remarkably grown by heat-treating the aluminum alloy material. However, the presence of a surface oxide film may be undesirable in some cases, and in some cases, it is better that the surface has as little oxide film as possible. As an example of such a technical field, for example, there is a case where an aluminum alloy material is joined. That is, when a tube made of an aluminum alloy material and a fin are joined by brazing, for example, it is desirable that an oxide film is not formed on the surface of the aluminum alloy material. For this reason, by performing such a joining operation in, for example, a vacuum, an oxide film is hardly grown by heating during the brazing operation. However, even if brazing is performed in such a vacuum atmosphere, it has been pointed out that brazing failure occurs.
本発明者は、前記の問題点に対する研究を鋭意押し進
めていくうちに、酸化皮膜にフッ素を介在（存在）させ
ておくと、その後に熱処理といった酸化皮膜が成長させ
られるような環境下に置かれても、この酸化皮膜の成長
が大幅に抑制されることを見出し、本発明を為し遂げた
のである。 すなわち、本発明は、表面酸化皮膜にフッ素を存在さ
せておくアルミニウム合金材の熱処理時の酸化皮膜の成
長抑制方法を提供するものである。 尚、上記のアルミニウム合金材の熱処理時の酸化皮膜
の成長抑制方法において、表面酸化皮膜中に存在させら
れるフッ素の割合は0.01原子％以上であることが望まし
い。 又、上記のアルミニウム合金材の熱処理時の酸化皮膜
の成長抑制方法において、表面酸化皮膜中におけるフッ
素が酸化皮膜と複合体を構成するようにすることが望ま
しい。 又、上記の熱処理時における酸化皮膜の成長が抑制さ
れたアルミニウム合金材において、表面酸化皮膜中にお
けるフッ素が酸化皮膜と複合体を構成したものであるこ
とが望ましい。 又、本発明は、表面酸化皮膜にフッ素を存在させた熱
処理時における酸化皮膜の成長が抑制されたアルミニウ
ム合金材を提供するものである。 尚、上記の熱処理時における酸化皮膜の成長が抑制さ
れたアルミニウム合金材において、表面酸化皮膜中に存
在させられたフッ素の割合は0.01原子％以上であること
が望ましい。 又、本発明は、アルミニウム合金材をフッ素イオン含
有溶液で処理する熱処理時における酸化皮膜の成長が抑
制されたアルミニウム合金材の製造法を提供するもので
ある。 尚、上記の熱処理時における酸化皮膜の成長が抑制さ
れたアルミニウム合金材の製造法において、フッ素イオ
ン含有溶液のpHは５以下であることが望ましい。 又、上記の熱処理時における酸化皮膜の成長が抑制さ
れたアルミニウム合金材の製造法において、フッ素イオ
ン含有溶液中のフッ素の割合は100ppm以上であることが
望ましい。 尚、フッ素イオン含有溶液のpH5以下としたのは、あ
らかじめ形成されている厚い酸化皮膜を溶解除去し、フ
ッ素が取り込まれた新しくて薄い皮膜を形成する為であ
り、そして該溶液中におけるフッ素の割合が100ppm以上
のものとしたのは、酸化皮膜中におけるフッ素の存在割
合を0.01原子％以上のものとする為である。 又、フッ素イオン含有溶液による処理の具体例として
は、例えば浸漬あるいはシャワー処理等がある。 尚、本発明において、酸化皮膜にフッ素が存在させら
れていると酸化皮膜の成長が抑制されるのは、酸化皮膜
とフッ素との複合体による層が酸素に対してバリヤーと
しての機能を発揮しているからであると推察される。The inventor of the present invention has made the oxide film to intervene (exist) during the research on the above-mentioned problems, and is placed in an environment where the oxide film can be grown by heat treatment. However, they have found that the growth of this oxide film is greatly suppressed, and have accomplished the present invention. That is, the present invention provides a method for suppressing the growth of an oxide film during heat treatment of an aluminum alloy material in which fluorine is present in a surface oxide film. In the above-described method for suppressing the growth of an oxide film during heat treatment of an aluminum alloy material, the ratio of fluorine present in the surface oxide film is desirably 0.01 atomic% or more. Further, in the above-described method for suppressing the growth of an oxide film during heat treatment of an aluminum alloy material, it is preferable that fluorine in the surface oxide film forms a composite with the oxide film. Further, in the aluminum alloy material in which the growth of the oxide film during the heat treatment is suppressed, it is desirable that fluorine in the surface oxide film forms a composite with the oxide film. Another object of the present invention is to provide an aluminum alloy material in which the growth of an oxide film during a heat treatment in which fluorine is present in a surface oxide film is suppressed. In addition, in the aluminum alloy material in which the growth of the oxide film during the heat treatment is suppressed, the ratio of fluorine present in the surface oxide film is desirably 0.01 atomic% or more. Another object of the present invention is to provide a method for producing an aluminum alloy material in which the growth of an oxide film during heat treatment for treating the aluminum alloy material with a solution containing fluorine ions is suppressed. In the method for producing an aluminum alloy material in which the growth of the oxide film during the heat treatment is suppressed, the pH of the fluorine ion-containing solution is desirably 5 or less. In the method for producing an aluminum alloy material in which the growth of the oxide film during the heat treatment is suppressed, it is desirable that the proportion of fluorine in the fluorine ion-containing solution is 100 ppm or more. The reason why the pH of the fluorine ion-containing solution was set to 5 or less was to dissolve and remove the thick oxide film formed in advance, to form a new thin film in which fluorine was taken in, and to determine the fluorine in the solution. The ratio is set to 100 ppm or more in order to make the content ratio of fluorine in the oxide film 0.01 atomic% or more. Further, specific examples of the treatment with the fluorine ion-containing solution include, for example, immersion or shower treatment. In the present invention, when fluorine is present in the oxide film, the growth of the oxide film is suppressed because the layer formed of the composite of the oxide film and fluorine functions as a barrier against oxygen. It is presumed that it is.
【実施例１】 JIS A1050材を圧延して1mm厚の板材を得、これを室温
下において１％フッ酸水溶液（pH2.1）中に約１〜60秒
間、例えば約10秒間浸漬し、この浸漬処理後水洗及び乾
燥処理を行なう。Example 1 A JIS A1050 material was rolled to obtain a 1 mm thick plate material, which was immersed in a 1% hydrofluoric acid aqueous solution (pH 2.1) at room temperature for about 1 to 60 seconds, for example, about 10 seconds. After the immersion treatment, washing and drying are performed.
【実施例２】 実施例１において、JIS A1050材の代りにJIS A3003材
を用いて同様に行なう。[Example 2] In the same manner as in Example 1, JIS A3003 material is used instead of JIS A1050 material.
【実施例３】 実施例１において、JIS A1050材の代りにJIS A4004材
を用いて同様に行なう。[Example 3] In the same manner as in Example 1, JIS A4004 material is used instead of JIS A1050 material.
【実施例４】 実施例１において、１％フッ酸水溶液の代わりに0.05
％フッ酸水溶液（pH3.4）を用いて同様に行なう。Example 4 In Example 1, 0.05% aqueous solution of hydrofluoric acid was used instead of 1% hydrofluoric acid.
% Hydrofluoric acid aqueous solution (pH 3.4).
【比較例１】 実施例１において、フッ酸水溶液中への浸漬処理を省
略した他は同様に行なう。Comparative Example 1 The procedure of Example 1 was repeated except that the immersion treatment in the hydrofluoric acid aqueous solution was omitted.
【比較例２】 実施例３において、フッ酸水溶液中への浸漬処理を省
略した他は同様に行なう。Comparative Example 2 The same operation as in Example 3 was performed except that the immersion treatment in the hydrofluoric acid aqueous solution was omitted.
【比較例３】 実施例１において、常温下でのフッ酸水溶液への浸漬
処理の代りに、90℃でpH1のリン酸−クロム酸混合水溶
液への浸漬処理を行ない、その他は同様に行う。Comparative Example 3 In Example 1, instead of immersion in a hydrofluoric acid aqueous solution at room temperature, immersion in a phosphoric acid-chromic acid mixed aqueous solution at pH 1 at 90 ° C. was performed, and the other steps were performed in the same manner.
【比較例４】 実施例１において、フッ酸水溶液の代わりにKAlF4−K
3AlF6フラックスの５％水溶液を用いて同様に行う。Comparative Example 4 In Example 1, KAlF 4 -K was used instead of the hydrofluoric acid aqueous solution.
The same procedure is performed using a 5% aqueous solution of 3 AlF 6 flux.
上記各例で得たアルミニウム合金材を大気中にて550
℃に加熱処理し、この加熱処理前後での表面酸化皮膜の
厚みを測定したので、その結果を表に示す。 これによれば、アルミニウム合金材表面の酸化皮膜中
にフッ素が存在させられた場合にあっては、その後に高
温加熱処理が行なわれても酸化皮膜の成長が大幅に抑制
されていることを理解できる。 これに対して、酸化皮膜中にフッ素が存在させられて
いない場合には、その後に高温加熱処理が行なわれる
と、酸化皮膜の成長が著しいことを理解できる。 従って、例えばアルミニウム合金材よりなるフィンと
チューブとをろう付けによって接合し、熱交換器を組み
立てる場合に本発明を応用した場合にあっては、そのろ
う付作業時にアルミニウム合金材の表面に酸化皮膜が大
幅に成長することがないので、フィンとチューブとの接
合強度が高く優れた熱交換器を提供できたのである。The aluminum alloy material obtained in each of the above examples was
C. and the thickness of the surface oxide film before and after the heat treatment was measured. The results are shown in the table. According to this, it is understood that when fluorine is present in the oxide film on the surface of the aluminum alloy material, the growth of the oxide film is greatly suppressed even if high-temperature heat treatment is performed thereafter. it can. On the other hand, when fluorine is not present in the oxide film, it can be understood that the growth of the oxide film is remarkable when a high-temperature heat treatment is performed thereafter. Therefore, for example, when the present invention is applied to a case where a fin and a tube made of an aluminum alloy material are joined by brazing and a heat exchanger is assembled, an oxide film is formed on the surface of the aluminum alloy material during the brazing operation. Therefore, the heat exchanger can be provided with a high joining strength between the fin and the tube because the heat exchanger does not grow significantly.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C21D 1/70 C22F 1/04 B23K 35/363──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) C21D 1/70 C22F 1/04 B23K 35/363
Claims (7)
って表面酸化皮膜にフッ素を存在させておくことを特徴
とするアルミニウム又はアルミニウム合金材の熱処理時
の酸化皮膜の成長抑制方法。1. A method for suppressing the growth of an oxide film during heat treatment of an aluminum or aluminum alloy material, wherein fluorine is present in a surface oxide film by treating with a fluorine ion-containing solution.
又はアルミニウム合金材の熱処理時の酸化皮膜の成長抑
制方法において、表面酸化皮膜に存在させられるフッ素
の割合が0.01原子％以上であるもの。2. The method for suppressing the growth of an oxide film during heat treatment of an aluminum or aluminum alloy material according to claim 1, wherein the proportion of fluorine present in the surface oxide film is 0.01 atomic% or more.
って表面酸化皮膜にフッ素を存在させたことを特徴とす
る熱処理時における酸化皮膜の成長が抑制されたアルミ
ニウム又はアルミニウム合金材。3. An aluminum or aluminum alloy material in which the growth of an oxide film during heat treatment is suppressed, wherein fluorine is present in a surface oxide film by treating with a fluorine ion-containing solution.
ける酸化皮膜の成長が抑制されたアルミニウム又はアル
ミニウム合金材において、表面酸化皮膜に存在させられ
たフッ素の割合が0.01原子％以上であるもの。4. The aluminum or aluminum alloy material according to claim 3, wherein the growth of the oxide film during the heat treatment is suppressed, wherein the proportion of fluorine present in the surface oxide film is 0.01 atomic% or more. thing.
ッ素イオン含有溶液で処理することを特徴とする熱処理
時における酸化皮膜の成長が抑制されたアルミニウム又
はアルミニウム合金材の製造法。5. A method for producing an aluminum or aluminum alloy material in which growth of an oxide film during heat treatment is suppressed, wherein the aluminum or aluminum alloy material is treated with a solution containing fluorine ions.
ける酸化皮膜の成長が抑制されたアルミニウム又はアル
ミニウム合金材の製造法において、フッ素イオン含有溶
液のpHが５以下であるもの。6. The method for producing an aluminum or aluminum alloy material according to claim 5, wherein the growth of the oxide film during the heat treatment is suppressed, wherein the pH of the fluorine ion-containing solution is 5 or less.
処理時における酸化皮膜の成長が抑制されたアルミニウ
ム又はアルミニウム合金材の製造法において、フッ素イ
オン含有溶液中のフッ素の割合が100ppm以上であるも
の。7. The method for producing an aluminum or aluminum alloy material in which the growth of an oxide film is suppressed during the heat treatment according to claim 5 or 6, wherein the proportion of fluorine in the fluorine ion-containing solution is 100 ppm. That's all.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63082346A JP2835724B2 (en) | 1988-04-05 | 1988-04-05 | Method of controlling growth of oxide film during heat treatment of aluminum or aluminum alloy material, aluminum or aluminum alloy material whose growth of oxide film is controlled during heat treatment, and method of producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63082346A JP2835724B2 (en) | 1988-04-05 | 1988-04-05 | Method of controlling growth of oxide film during heat treatment of aluminum or aluminum alloy material, aluminum or aluminum alloy material whose growth of oxide film is controlled during heat treatment, and method of producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01255652A JPH01255652A (en) | 1989-10-12 |
| JP2835724B2 true JP2835724B2 (en) | 1998-12-14 |
Family
ID=13772007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63082346A Expired - Fee Related JP2835724B2 (en) | 1988-04-05 | 1988-04-05 | Method of controlling growth of oxide film during heat treatment of aluminum or aluminum alloy material, aluminum or aluminum alloy material whose growth of oxide film is controlled during heat treatment, and method of producing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2835724B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2873718B1 (en) * | 2004-07-28 | 2007-02-02 | Pechiney Rhenalu Sa | PROCESS FOR FORMING A CONVERSION LAYER ON AN ALUMINUM ALLOY PRODUCT FOR BREATHING |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51115214A (en) * | 1975-02-27 | 1976-10-09 | Mitsubishi Keikinzoku Kogyo Kk | Method for preventing the coloring of aluminum alloys on their heat tr eatment |
-
1988
- 1988-04-05 JP JP63082346A patent/JP2835724B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01255652A (en) | 1989-10-12 |
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