JPS6213438B2 - - Google Patents
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- Publication number
- JPS6213438B2 JPS6213438B2 JP16485082A JP16485082A JPS6213438B2 JP S6213438 B2 JPS6213438 B2 JP S6213438B2 JP 16485082 A JP16485082 A JP 16485082A JP 16485082 A JP16485082 A JP 16485082A JP S6213438 B2 JPS6213438 B2 JP S6213438B2
- Authority
- JP
- Japan
- Prior art keywords
- silicate
- aluminum
- film
- electrolysis
- molar ratio
- 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
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- Electrochemical Coating By Surface Reaction (AREA)
Description
【発明の詳細な説明】
本発明はケイ酸塩水溶液を用いたアルミニウム
またはアルミニウム合金（以下、両者を併せてア
ルミニウムと称する）の電解着色方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for electrolytically coloring aluminum or an aluminum alloy (hereinafter both are collectively referred to as aluminum) using an aqueous silicate solution.
従来、水ガラス中でアルミニウムを陽極酸化す
ると「アニオン凝集膜」が形成されるため、火花
放電も起り、多孔質皮膜は得られないと言われて
いる。同様に硫酸浴などで作られた多孔質酸化皮
膜を有するアルミニウムを水ガラス水溶液中で再
陽極酸化しても、アニオン凝集膜が形成されて、
酸化皮膜の孔中にはケイ酸は析出しない。従つて
再陽極酸化しても試料の外観変化は肉眼的には認
められない。 Conventionally, it has been said that when aluminum is anodized in water glass, an "anion agglomerated film" is formed, spark discharge also occurs, and a porous film cannot be obtained. Similarly, when aluminum with a porous oxide film made in a sulfuric acid bath or the like is re-anodized in a water glass solution, an anion aggregation film is formed.
Silicic acid does not precipitate in the pores of the oxide film. Therefore, no change in the external appearance of the sample is visible to the naked eye even after re-anodizing.
本願発明者は、ケイ酸塩の組成、水溶液濃度と
多孔質酸化皮膜を有するアルミニウムの再陽極酸
化の関係について検討を重ね、特定の条牛下では
酸化皮膜の孔中にケイ酸コロイドが析出し、皮膜
が灰色に着色されることを見出し、本発明を完成
した。 The inventor of this application has repeatedly investigated the relationship between the composition of silicate, the concentration of aqueous solution, and the re-anodization of aluminum with a porous oxide film, and found that under certain conditions, silicate colloids precipitate in the pores of the oxide film. discovered that the film was colored gray and completed the present invention.
本発明の目的は、従来得ることのできなかつた
ケイ酸塩水溶液を用いてアルミニウムを灰色系に
着色せしめる方法を提供することに在る。 An object of the present invention is to provide a method of coloring aluminum in gray using an aqueous silicate solution, which has not been previously available.
すなわち、アルミニウムまたはアルミニウム合
金上に多孔質陽極酸化皮膜を形成せしめた後、
M2O・nSiO2（Ｍ：アルカリ金属原子）で示され
るケイ酸塩のSiO2／M2Oモル比が2.0以上で濃度
が0.05ｇ／〜2.0ｇ／の水溶液中で120V以上
の電圧で再陽極酸化することを、発明の要旨とす
るものである。 That is, after forming a porous anodic oxide film on aluminum or aluminum alloy,
At a voltage of 120 V or more in an aqueous solution with a molar ratio of SiO 2 /M 2 O of M 2 O・nSiO 2 (M: alkali metal atom) of 2.0 or more and a concentration of 0.05 g/~2.0 g/ The gist of the invention is to re-anodize.
アルミニウムをケイ酸塩水溶液で電解処理する
方法としては特開昭50―78535号公報に、記載が
あるが、これはアルミニウムに化成被膜を形成せ
しめ、モル比0.5以上で10％程度の高濃度ケイ酸
塩水溶液を用い、化成被膜とケイ酸による無機質
複合被膜を形成せしめるものであり、本発明とは
異なるものである。 A method of electrolytically treating aluminum with an aqueous silicate solution is described in Japanese Patent Application Laid-Open No. 78535/1983, which forms a chemical conversion film on aluminum and contains a high concentration of silicon of about 10% at a molar ratio of 0.5 or more. This method uses an aqueous acid salt solution to form an inorganic composite film of a chemical conversion film and silicic acid, and is different from the present invention.
本発明を説明すると、常法により脱脂洗浄され
たアルミニウムに硫酸法等で多孔質型陽極酸化皮
膜を形成せしめた後、ケイ酸塩水溶液中で再陽極
酸化を行なう。本発明に用いるケイ酸塩はモル比
が２以上、すなわちM2O・nSiO2（Ｍ：アルカリ
金属原子）で示したとき、SiO2／M2Oモル比ｎ
が2.0以上であることが必要である。ｎ＝0.5のオ
ルト・ケイ酸塩、ｎ＝１のメタ・ケイ酸塩はその
水溶液が高アルカリ性であるので、１次皮膜を溶
解してしまうことがあり、またPH緩衝能力が弱い
ので、アニオン凝集を起し易く不適当である。本
発明に使用されるケイ酸塩を例示すると、ナトリ
ウム塩ではNa2O・2SiO2，Na2O・3SiO2，
Na2O・4SiO2等があり、カリウム塩リチウム塩も
同様に用いられる。カリウム塩としてはK2O・
2SiO2，K2O・3SiO2，K2O・4SiO2；リチウム塩
ではLi2O・2SiO2，Li2O・3SiO2，Li2O・4SiO2等
が挙げられる。 To explain the present invention, a porous anodic oxide film is formed on aluminum that has been degreased and cleaned by a conventional method using a sulfuric acid method or the like, and then re-anodized in an aqueous silicate solution. The silicate used in the present invention has a molar ratio of 2 or more, that is, when expressed as M 2 O・nSiO 2 (M: alkali metal atom), the SiO 2 /M 2 O molar ratio n
must be 2.0 or higher. The aqueous solution of ortho-silicate with n=0.5 and meta-silicate with n=1 is highly alkaline, so it may dissolve the primary film, and the pH buffering ability is weak, so anion It is unsuitable because it tends to cause agglomeration. Examples of silicates used in the present invention include sodium salts such as Na 2 O・2SiO 2 , Na 2 O・3SiO 2 ,
There are Na 2 O, 4SiO 2, etc., and potassium salts and lithium salts are also used. As a potassium salt, K 2 O・
2SiO 2 , K 2 O.3SiO 2 , K 2 O.4SiO 2 ; Lithium salts include Li 2 O.2SiO 2 , Li 2 O.3SiO 2 , Li 2 O.4SiO 2 and the like.
次にケイ酸塩水溶液の濃度としては0.05ｇ／
〜2.0ｇ／の範囲が好ましく、0.05ｇ／以下
では着色不充分のため不適当であり、2.0ｇ／
以上では酸化皮膜の孔中へのケイ酸コロイドの析
出が不充分で同様に不充分な着色しか得られな
い。これは酸化皮膜の表面にケイ酸アニオンが吸
着して孔を塞ぐために、孔中へのケイ酸コロイド
の析出を妨害しているものと思われる。 Next, the concentration of the silicate aqueous solution is 0.05g/
The range of ~2.0g/ is preferable, and below 0.05g/ is inappropriate due to insufficient coloring, and 2.0g/
In the above case, precipitation of the silicic acid colloid into the pores of the oxide film is insufficient, and similarly, insufficient coloration is obtained. This is thought to be because silicate anions are adsorbed onto the surface of the oxide film and close the pores, thereby hindering the precipitation of silicate colloid into the pores.
再陽極酸化電解に際しては、均一に多孔質皮膜
にケイ酸コロイドを析出した着色材を得るために
は、定電圧電解よりも、低電流密度による定電流
電解の方が好ましい。また、再陽極酸化電解の印
加電圧は120V以上が必要である。印加電圧が
120Vより低いと、多孔質皮膜のバリヤー層が再
形成されるだけであつて、ケイ酸コロイドの析出
は120V以上の電圧で行なわれる。すなわち120V
以上の場合には、バリヤー層上での水のアノード
分解反応が起り、この際発生した水素イオンによ
り、ケイ酸アニオンが中和されて、ケイ酸コロイ
ドとして孔中に析出する。 In re-anodizing electrolysis, constant current electrolysis using a low current density is preferable to constant voltage electrolysis in order to obtain a coloring material in which silicic acid colloid is uniformly deposited on a porous film. In addition, the applied voltage for re-anodizing electrolysis needs to be 120V or more. The applied voltage
Below 120V, the barrier layer of the porous coating is only reformed, and the silicic acid colloid deposition takes place at voltages above 120V. i.e. 120V
In the above case, an anodic decomposition reaction of water occurs on the barrier layer, and the hydrogen ions generated at this time neutralize silicate anions and precipitate in the pores as silicate colloid.
以下、本発明を実施例により具体的に説明す
る。 Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例
純度99.5のアルミニウム（JIS Ｈ 4000の1050
材）で縦100mm、横100mm、厚さ1.2mmの試片を作
成し、15％硫酸水溶液中で温度20℃で直流電圧
17Vで定電圧電解し、15μｍの多孔質酸化皮膜を
化成せしめた。Example Aluminum with purity 99.5 (JIS H 4000 1050
A specimen with a length of 100 mm, a width of 100 mm and a thickness of 1.2 mm was prepared from the material), and a DC voltage was applied at a temperature of 20°C in a 15% sulfuric acid aqueous solution.
A porous oxide film of 15 μm was formed by constant voltage electrolysis at 17 V.
試片を充分に洗浄した後、モル比2.0，3.0およ
び4.0のケイ酸ナトリウム水溶液；モル比3.0のケ
イ酸カリウム水溶液およびモル比3.0のケイ酸リ
チウム水溶液で、対極にステンレス板を使用し浴
温20℃で再陽極酸化電解を行なつた。なお、ケイ
酸塩水溶液の濃度は、何れの場合も、0.5ｇ／
とした。 After thoroughly washing the specimen, a stainless steel plate was used as a counter electrode and the bath temperature was heated with sodium silicate aqueous solutions with a molar ratio of 2.0, 3.0, and 4.0; potassium silicate aqueous solution with a molar ratio of 3.0; and lithium silicate aqueous solution with a molar ratio of 3.0. Re-anodization electrolysis was performed at 20°C. In addition, the concentration of the silicate aqueous solution is 0.5 g/
And so.
再陽極酸化電解は、直流電流密度0.05A／ｄm2
の定電流電解で行なつた。電圧は電解時間と共に
上昇して行つたが、最大電圧を150Vまたは、
200Vとした。最大電圧の状況下で電解を継続す
ると電流は減少して行く。このような状況下で再
陽極酸化電解を各試片について、５分間実施し
た。 Re-anodizing electrolysis uses a DC current density of 0.05A/dm 2
This was done using constant current electrolysis. The voltage increased with the electrolysis time, but the maximum voltage was 150V or
It was set to 200V. If electrolysis continues under conditions of maximum voltage, the current will decrease. Under these conditions, re-anodizing electrolysis was carried out for 5 minutes on each specimen.
電解浴の種類が異なつても、最大電圧150Vの
ときは同様に試片は灰白色に着色され、最大電圧
200Vのときには各試片は灰黒色に着色された。 Even if the type of electrolytic bath is different, when the maximum voltage is 150V, the specimen will be colored grayish white, and the maximum voltage will be 150V.
At 200V, each specimen was colored gray-black.
試片が灰色に着色するのは多孔質皮膜の孔中に
析出したケイ酸コロイドが、光を散乱させるから
である。なお、試片断面についてＸ線マイクロア
ナライザー分析を行なつたところ、ケイ酸ナトリ
ウムの場合と同じく、ケイ酸カリウム、ケイ酸リ
チウムの場合も、それぞれ多量のケイ素の存在が
確認され、カチオンの異なることによる影響は認
められなかつた。 The specimen is colored gray because the silicic acid colloid deposited in the pores of the porous film scatters light. In addition, when X-ray microanalyzer analysis was performed on the cross section of the specimen, the presence of large amounts of silicon was confirmed in the case of potassium silicate and lithium silicate, as well as in the case of sodium silicate, indicating that the cations were different. No influence was observed.
比較例
実施例に使用したものと同一の陽極酸化皮膜を
有する試片を使用して、モル比2.0のケイ酸ナト
リウム水溶液の濃度が0.03ｇ／および3.0ｇ／
のものを電解浴として再陽極酸化電解を行なつ
た。何れの場合も、通常の硫酸陽極酸化皮膜の銀
白色と変らず、再陽極酸化電解しないものと同じ
で、着色は生じなかつた。Comparative Example Using a sample having the same anodic oxide film as that used in the example, the concentration of sodium silicate aqueous solution with a molar ratio of 2.0 was 0.03 g/ and 3.0 g/
Re-anodizing electrolysis was carried out using this as an electrolytic bath. In either case, the silvery white color was the same as that of a normal sulfuric acid anodized film, and no coloring occurred, which was the same as that without re-anodizing.
また、実施例と同一の試片を用い、モル比1.0
のケイ酸ナトリウムを使用して実施例の条件下で
再陽極酸化電解を行なつたところ、当初15μｍの
厚さの皮膜が12μｍとなり、３μｍの皮膜厚さの
減少が生じた。また、モル比0.5のケイ酸ナトリ
ウムを用いた場合には、3.5μｍの皮膜厚さの減
少が生じた。 In addition, using the same specimen as in the example, the molar ratio was 1.0.
When re-anodizing electrolysis was carried out under the conditions of the example using sodium silicate, the film thickness was reduced from 15 μm to 12 μm, resulting in a decrease in film thickness of 3 μm. Further, when sodium silicate with a molar ratio of 0.5 was used, a decrease in film thickness of 3.5 μm occurred.
Claims (1)
孔質型陽極酸化皮膜を形成せしめた後、M2O・
nSiO2（Ｍ：アルカリ金属原子）で示されるケイ
酸塩のSiO2／M2Oモル比が2.0以上で濃度が0.05
ｇ／〜2.0ｇ／の水溶液中で120V以上の電圧
で再陽極酸化することを特徴とするアルミニウム
の着色方法。1 After forming a porous anodic oxide film on aluminum or aluminum alloy, M 2 O・
The SiO 2 /M 2 O molar ratio of the silicate represented by nSiO 2 (M: alkali metal atom) is 2.0 or more and the concentration is 0.05.
A method for coloring aluminum, characterized by re-anodizing at a voltage of 120 V or more in an aqueous solution of g/~2.0 g/.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16485082A JPS5956594A (en) | 1982-09-24 | 1982-09-24 | Method for coloring aluminum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16485082A JPS5956594A (en) | 1982-09-24 | 1982-09-24 | Method for coloring aluminum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5956594A JPS5956594A (en) | 1984-04-02 |
| JPS6213438B2 true JPS6213438B2 (en) | 1987-03-26 |
Family
ID=15801101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16485082A Granted JPS5956594A (en) | 1982-09-24 | 1982-09-24 | Method for coloring aluminum |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5956594A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS633351U (en) * | 1986-06-20 | 1988-01-11 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325698C (en) * | 2003-10-21 | 2007-07-11 | 东莞理工学院 | Preparation method of ordered porous anodic alumina template |
| CN100460092C (en) * | 2004-04-28 | 2009-02-11 | 东莞理工学院 | A method for improving the quality of nanoparticle materials |
| JP5144206B2 (en) * | 2007-10-19 | 2013-02-13 | 三菱アルミニウム株式会社 | Method for producing surface-treated aluminum material |
-
1982
- 1982-09-24 JP JP16485082A patent/JPS5956594A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS633351U (en) * | 1986-06-20 | 1988-01-11 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5956594A (en) | 1984-04-02 |
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