JP3154638B2 - Anodized film and method for forming the same - Google Patents
Anodized film and method for forming the sameInfo
- Publication number
- JP3154638B2 JP3154638B2 JP07820795A JP7820795A JP3154638B2 JP 3154638 B2 JP3154638 B2 JP 3154638B2 JP 07820795 A JP07820795 A JP 07820795A JP 7820795 A JP7820795 A JP 7820795A JP 3154638 B2 JP3154638 B2 JP 3154638B2
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- JP
- Japan
- Prior art keywords
- pore radius
- oxide film
- anodic oxide
- radius distribution
- present
- 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
- Other Surface Treatments For Metallic Materials (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は陽極酸化皮膜及びそれを
形成させる方法に関し、特に２５Å〜２５０Åの間に細
孔半径分布のピークを少なくとも一つ有する陽極酸化皮
膜及びそれを形成させる方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anodized film and a method for forming the same, and more particularly to an anodized film having at least one pore radius distribution peak between 25 DEG and 250 DEG and a method for forming the same.
【０００２】[0002]
【従来の技術】アルミニウムの陽極酸化技術によって得
られた多孔質アルミナ皮膜は公知であり、電解コンデン
サの絶縁皮膜、アルミサッシや装飾品の表面処理、車体
や機体などの表面の防蝕処理、カーテンウォールの発色
等、様々な用途に利用されている。一方、陽極酸化によ
って得られる多孔質酸化皮膜の細孔半径は３００Å程度
と大きいため、ＢＥＴ表面積が小さく、触媒の担体とし
ては不十分であった。2. Description of the Related Art Porous alumina coatings obtained by anodizing aluminum are well known, such as insulating coatings for electrolytic capacitors, surface treatment of aluminum sashes and decorative articles, corrosion protection of surfaces of bodies and bodies, curtain walls. It is used for various purposes such as color development. On the other hand, since the pore radius of the porous oxide film obtained by anodic oxidation is as large as about 300 °, the BET surface area was small, and it was insufficient as a catalyst carrier.
【０００３】これに対し、近年、陽極酸化皮膜を５０℃
以上の水又は蒸気で熱水処理した場合には、細孔半径が
２０Å程度となり、その結果ＢＥＴ表面積が著しく増大
し、触媒担体表面として十分に使用することのできるこ
とが判明した（特開平２−１４４１５４及び同４０−２
００７４５号公報）。しかしながら、これらの熱水処理
によっては２０Å以上の細孔半径分布を持たせることは
できなかった（アルトピア、１０巻、９〜１２頁（１９
９３））。On the other hand, in recent years, an anodic oxide film has been
In the case of the above-mentioned hot water treatment with water or steam, the pore radius becomes about 20 °, and as a result, the BET surface area is remarkably increased, and it has been found that the BET surface area can be sufficiently used as a catalyst carrier surface (Japanese Patent Laid-Open No. Hei 2- 144154 and 40-2
0074). However, these hot water treatments could not provide a pore radius distribution of 20 ° or more (Altopia, Vol. 10, pp. 9-12 (19)
93)).
【０００４】[0004]
【発明が解決しようとする課題】上記の熱水処理は、技
術的にはアルミナ細孔の水和封孔処理であるが、本発明
者らは、１０℃以下の低温でも、時間さえかければ水和
封孔処理が可能であること、及び、処理温度が４５℃以
下である場合にはアルミナの細孔半径を広く制御するこ
とができることを見出し、本発明に到達した。The above-mentioned hydrothermal treatment is technically a hydration sealing treatment of the pores of alumina. The present inventors have found that the hydration sealing treatment can be performed, and that the pore radius of alumina can be controlled widely when the treatment temperature is 45 ° C. or lower, and arrived at the present invention.
【０００５】従って、本発明の第１の目的は、２５Å〜
２５０Åの間に細孔半径分布のピークを少なくとも１つ
有する陽極酸化皮膜を提供することにある。本発明の第
２の目的は、２５Å〜２５０Åの間に細孔半径分布のピ
ークが少なくとも１つある陽極酸化皮膜を表面に有する
金属基体を提供することにある。本発明の第３の目的
は、２５Å〜２５０Åの間に細孔半径分布のピークを少
なくとも１つ有する陽極酸化皮膜を形成させる方法を提
供することにある。[0005] Therefore, a first object of the present invention is to set the angle between 25 ° and
An object of the present invention is to provide an anodized film having at least one peak of a pore radius distribution between 250 °. A second object of the present invention is to provide a metal substrate having on its surface an anodic oxide film having at least one peak of pore radius distribution between 25 ° and 250 °. A third object of the present invention is to provide a method for forming an anodic oxide film having at least one peak of pore radius distribution between 25 ° and 250 °.
【０００６】[0006]
【課題を解決するための手段】本発明の上記の諸目的は
２５Å〜２５０Åの間に細孔半径分布のピークを少なく
とも１つ有する陽極酸化皮膜及びそれを形成させる方法
によって達成された。本発明においては、陽極酸化皮膜
を形成し得る限り、対象とする金属に特に制限はない
が、一般的には、アルミニウム単体、アルミニウム層を
設けた金属、または６０重量％以上のアルミニウム含む
ジュラルミン等の合金である。The above objects of the present invention have been attained by an anodic oxide film having at least one pore radius distribution peak between 25 ° and 250 ° and a method for forming the same. In the present invention, as long as an anodic oxide film can be formed, the target metal is not particularly limited, but is generally aluminum alone, a metal provided with an aluminum layer, or duralumin containing 60% by weight or more of aluminum. Alloy.
【０００７】陽極酸化皮膜を設けた基体はいかなる形状
でも良く、用途や使用方法に応じて、板状、シート状、
リボン状、管状、ハニカム状などの形状とすることがで
きる。この場合、陽極酸化皮膜を設けた基体は、前記金
属表面を陽極酸化したままのものであってもよいが、後
述する如く、一度、陽極酸化皮膜のみを製造し、これを
例えば、プラスチックシートや紙或いは多孔質ゼオライ
ト表面に粘着したものであっても良い。[0007] The substrate provided with the anodic oxide film may be of any shape, depending on the application and method of use, a plate, a sheet, or the like.
The shape may be a ribbon shape, a tubular shape, a honeycomb shape, or the like. In this case, the substrate provided with the anodized film may be one in which the metal surface has been anodized, but as described later, only the anodized film is manufactured once, and this is, for example, a plastic sheet or It may be one adhered to paper or porous zeolite surface.
【０００８】本発明における陽極酸化は公知の方法によ
って行えば良く、処理液としては、例えばクロム酸水溶
液、シュウ酸水溶液、硫酸水溶液等を使用することがで
きる。それらの処理液のｐＨや溶液の温度、あるいは酸
の種類によって、３００Åから最大数百μｍの多孔アル
ミナ皮膜が形成される。The anodic oxidation in the present invention may be performed by a known method, and as a treatment liquid, for example, an aqueous solution of chromic acid, an aqueous solution of oxalic acid, an aqueous solution of sulfuric acid, or the like can be used. Depending on the pH of the processing solution, the temperature of the solution, or the type of acid, a porous alumina film having a thickness of 300 ° to a maximum of several hundred μm is formed.
【０００９】本発明では陽極酸化後、比抵抗が２×１０
5 Ωｃｍ以上であって脱気処理された５℃〜４５℃の水
を用い、水和封孔処理することによって、２５Å〜２５
０Åの間に細孔半径分布のピークを少なくとも１つ有す
る陽極酸化皮膜を形成させた後、３００℃〜５００℃で
焼成することによって、この細孔半径分布を有する陽極
酸化皮膜を固定する。In the present invention, the specific resistance after anodic oxidation is 2 × 10
Five 5 ° C. to 45 ° C. degassed water of Ωcm or more
And 25% to 25%
Has at least one pore radius distribution peak between 0 °
After forming an anodic oxide film,
Anode having this pore radius distribution by firing
Fix the oxide film.
【００１０】水和封孔処理温度が５℃以下では必要な処
理時間が長くなり過ぎ、又、４５℃を越えると水和封孔
反応が速すぎて細孔半径が略２０Åとなるので、その分
布を制御することが困難となる。また、比抵抗が２×１
０5 Ωｃｍ以上の水は、蒸留やイオン交換法によって容
易に得ることができるが、特に、製造容易性の観点から
イオン交換水を使用することが好ましい。If the hydration sealing temperature is 5 ° C. or less, the necessary
Hydraulic sealing if the processing time is too long, or if it exceeds 45 ° C
The reaction is too fast and the pore radius becomes about 20 °,
It becomes difficult to control the cloth. Moreover, the specific resistance is 2 × 1
0Five Water of Ωcm or more can be stored by distillation or ion exchange method.
It can be easily obtained, especially from the viewpoint of manufacturability.
It is preferable to use ion exchange water.
【００１１】低温で長時間水和封孔処理する程、２５Å
〜２５０Åの細孔半径分布が平坦に近くなる一方、温度
を上げる程、前記細孔半径範囲内に極大値を有する様に
なり、極大値を２０Å〜３００のÅの間に２箇所持たせ
ることも容易である。処理時間は、水和封孔処理する温
度、及び、所望する細孔半径分布によって、数分〜数時
間の範囲で適宜調整すれば良い。[0011] The longer the hydration sealing treatment at low temperature, the more
While the pore radius distribution of ~ 250 ° becomes nearly flat, as the temperature is increased, the pore radius has a maximum value within the pore radius range, and the maximum value is provided at two places between 20 ° ~ 300mm. Is also easy. The treatment time may be appropriately adjusted within a range from several minutes to several hours depending on the temperature of the hydration sealing treatment and the desired pore radius distribution.
【００１２】処理条件によって、２つのピークが２５Å
〜２５０Åの間に入るようにすることも、１つのピーク
のみが２５Å〜２５０Åの間に入るようにすることもで
きる。尚、本発明における細孔半径は、窒素脱離法又は
水銀圧入法によって測定される。また、陽極酸化皮膜を
単独に得る場合には、例えば、公知の塩酸／塩化銅溶液
法（市村ら、化学工学第５９年会、Ｊ１２３、１９９４
年）に従えば良い。Depending on the processing conditions, the two peaks are 25 °
Å250 ° or only one peak can be between 25 ° and 250 °. The pore radius in the present invention is measured by a nitrogen desorption method or a mercury intrusion method. When the anodic oxide film is obtained alone, for example, a known hydrochloric acid / copper chloride solution method (Ichimura et al., 59th Annual Meeting of Chemical Engineering, J123, 1994)
Year).
【００１３】本発明の陽極酸化皮膜は、それが有する細
孔半径分布によって、例えば、分子篩いとして機能する
分離膜として応用することができる。本発明の陽極酸化
皮膜を有する基体は、高伝熱触媒担体として、細孔中に
金属を析出させて高密度磁気膜として、細孔中に蛍光体
をドーピングさせてＥＬ素子として、或いは従来にはな
い色調を有する装飾品等として応用することができる。The anodic oxide film of the present invention can be applied, for example, as a separation membrane functioning as a molecular sieve, depending on the pore radius distribution of the anodic oxide film. The substrate having the anodic oxide film of the present invention can be used as a high heat transfer catalyst carrier, as a high-density magnetic film by depositing a metal in pores, or as an EL element by doping a phosphor in pores, or a conventional method. It can be applied as a decorative product having no color tone.
【００１４】[0014]
【発明の効果】本発明の細孔構造を有する陽極酸化皮膜
は、その細孔半径分布に従って、種々の用途に応用する
ことができる。又、本発明の陽極酸化皮膜表面を有する
基体は、複数の反応に対応する触媒担体として用いた
り、従来と異なった色調の装飾品を実現することもでき
る。また、本発明の陽極酸化皮膜の細孔半径分布制御方
法は、５℃〜４５℃のイオン交換水等で処理するという
簡単なものであるので、工業化も極めて容易である。The anodic oxide film having the pore structure of the present invention can be applied to various uses according to the pore radius distribution. Further, the substrate having the surface of the anodic oxide film of the present invention can be used as a catalyst carrier corresponding to a plurality of reactions, or a decorative article having a color tone different from the conventional one can be realized. Further, the method for controlling the pore radius distribution of the anodic oxide film of the present invention is a simple method of treating with ion-exchanged water at 5 ° C. to 45 ° C., so that industrialization is extremely easy.
【００１５】[0015]
【実施例】以下、本発明を実施例によって更に詳述する
が、本発明はこれによって限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００１６】実施例１〜３と比較例１．ＪＩＳ−Ａ１０
５０規格の、厚さ０．３ｍｍのアルミニウムを２０重量
％水酸化ナトリウム水溶液中で３分間洗浄した後、３０
重量％の硝酸水溶液中で１分間中和処理する前処理を行
った。次いで２０℃、４重量％のシュウ酸水溶液中に
て、電流密度を５０Ａ／ｍ2とし、１６時間掛けて陽極
酸化処理をした。Examples 1 to 3 and Comparative Example 1 JIS-A10
After washing aluminum having a thickness of 0.3 mm of 50 standard in a 20% by weight aqueous sodium hydroxide solution for 3 minutes,
A pretreatment of neutralizing for 1 minute in a weight% aqueous nitric acid solution was performed. Next, in a 4% by weight oxalic acid aqueous solution at 20 ° C., the current density was set to 50 A / m 2, and anodizing treatment was performed for 16 hours.
【００１７】次いで陽極酸化されたアルミニウム表面
を、比抵抗が約１０6 Ωｃｍであって脱気処理された４
０℃のイオン交換水を用いて、それぞれを０時間（陽極
酸化のみ、比較例１）、１時間（実施例１）、 １．５
時間（実施例２）及び ２時間（実施例３）水和封孔処
理した後、４５０℃で３時間空気焼成して、多孔質陽極
酸化皮膜を形成した。得られた陽極酸化皮膜の細孔半径
分布を、窒素脱離法によって測定した結果は図１に示し
た通りである。Next, the anodized aluminum surface
Has a specific resistance of about 106 Ωcm and degassed 4
Using ion-exchanged water at 0 ° C. for 0 hour (anode
Oxidation only, Comparative Example 1), 1 hour (Example 1), 1.5
Time (Example 2) and 2 hours (Example 3) hydration sealing
After baking for 3 hours at 450 ° C, the porous anode
An oxide film was formed. Pore radius of the obtained anodic oxide film
Fig. 1 shows the distribution measured by the nitrogen desorption method.
As expected.
【００１８】比較例２．水和封孔処理を、５０℃で１５
分間行った他は実施例１と全く同様にしたところ、陽極
酸化皮膜の細孔半径は２０Åであり、水和封孔反応が極
めて速いため、２０Åの細孔半径しか形成されないこと
が確認された。得られた陽極酸化皮膜の細孔半径分布
は、図２に示した通りである。Comparative Example 2 Hydration sealing treatment is performed at 50 ° C for 15 minutes.
The same procedure as in Example 1 was carried out except for one minute, and it was confirmed that the pore radius of the anodic oxide film was 20 ° and the hydration sealing reaction was extremely fast, so that only a pore radius of 20 ° was formed. . The pore radius distribution of the obtained anodic oxide film is as shown in FIG.
【００１９】比較例３．水和封孔処理を、４℃で３時間
行った他は実施例１と全く同様にしたところ、陽極酸化
皮膜の細孔半径は２８０Åであり、水和封孔処理の進行
が極めて遅く、実用的でないことが確認された。得られ
た陽極酸化皮膜の細孔半径分布は図３に示した通りであ
る。Comparative Example 3 Except that the hydration sealing treatment was performed at 4 ° C. for 3 hours, the hydration sealing treatment was performed in exactly the same manner as in Example 1. The pore radius of the anodic oxide film was 280 °, and the progress of the hydration sealing treatment was extremely slow. It was confirmed that it was not a target. The pore radius distribution of the obtained anodic oxide film is as shown in FIG.
【００２０】これらの結果から、本発明の陽極酸化皮膜
は２５Å〜２５０Åの間に細孔半径分布のピークを少な
くとも１つ有すること、及び、水和封孔処理の適当な温
度が５℃〜４５℃の範囲であることが実証された。尚、
これらのデータは陽極酸化後のＳＥＭ写真による観察デ
ータとも一致した。From these results, it is found that the anodic oxide film of the present invention has at least one peak of the pore radius distribution between 25 ° and 250 °, and that the appropriate temperature for the hydration sealing treatment is 5 ° C. to 45 ° C. It has been demonstrated to be in the range of ° C. still,
These data were consistent with the observation data by SEM photograph after anodization.
【図１】４０℃で水和封孔処理を行った場合の細孔半径
分布曲線FIG. 1 shows a pore radius distribution curve when hydration sealing treatment is performed at 40 ° C.
【図２】５０℃で水和封孔処理を行った場合の細孔半径
分布曲線FIG. 2 is a pore radius distribution curve when hydration sealing treatment is performed at 50 ° C.
【図３】４℃で水和封孔処理を行った場合の細孔半径分
布曲線FIG. 3 is a pore radius distribution curve when hydration sealing treatment is performed at 4 ° C.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 11/00 - 11/24 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) C25D 11/00-11/24
Claims (4)
ピークを少なくとも一つ有することを特徴とする陽極酸
化皮膜。1. An anodized film having at least one peak of pore radius distribution between 25 ° and 250 °.
ピークを２つ有する請求項１に記載された陽極酸化皮
膜。2. The anodic oxide film according to claim 1, which has two peaks of pore radius distribution between 20 ° and 300 °.
極酸化皮膜を表面に有する金属基体。3. A metal substrate having an anodized film according to claim 1 on a surface thereof.
×１０5 Ωｃｍ以上であって脱気処理された５℃〜４５
℃の水を用い、数分〜数時間水和封孔処理した後、３０
０℃〜５００℃で焼成することを特徴とする、２５Å〜
２５０Åの間に細孔半径分布のピークを少なくとも一つ
有する陽極酸化皮膜を形成させる方法。4. An anodized metal surface having a specific resistance of 2
× 10Five 5 ° C to 45 Ωcm or more and degassed
After hydration sealing treatment for several minutes to several hours using water at
Characterized by firing at 0 ° C. to 500 ° C., 25 ° to
At least one peak of pore radius distribution between 250 °
A method of forming an anodic oxide film having the same.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07820795A JP3154638B2 (en) | 1995-03-08 | 1995-03-08 | Anodized film and method for forming the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07820795A JP3154638B2 (en) | 1995-03-08 | 1995-03-08 | Anodized film and method for forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08246190A JPH08246190A (en) | 1996-09-24 |
| JP3154638B2 true JP3154638B2 (en) | 2001-04-09 |
Family
ID=13655597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07820795A Expired - Fee Related JP3154638B2 (en) | 1995-03-08 | 1995-03-08 | Anodized film and method for forming the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3154638B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7824535B2 (en) | 2006-02-23 | 2010-11-02 | Fujifilm Corporation | Microstructure and method of manufacturing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4536866B2 (en) | 1999-04-27 | 2010-09-01 | キヤノン株式会社 | Nanostructure and manufacturing method thereof |
| JP2008127673A (en) * | 2006-11-24 | 2008-06-05 | Fujifilm Corp | Method of manufacturing fine structure and fine structure |
| JP6491813B2 (en) * | 2013-10-30 | 2019-03-27 | 株式会社日立ハイテクノロジーズ | Manufacturing method of vacuum processing apparatus |
| WO2021049038A1 (en) * | 2019-09-13 | 2021-03-18 | 日立化成株式会社 | Treatment member, treatment method, and treatment device |
-
1995
- 1995-03-08 JP JP07820795A patent/JP3154638B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7824535B2 (en) | 2006-02-23 | 2010-11-02 | Fujifilm Corporation | Microstructure and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08246190A (en) | 1996-09-24 |
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