JP2005177572A - Process for producing chemical conversion coating film of titanium oxide - Google Patents
Process for producing chemical conversion coating film of titanium oxide Download PDFInfo
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- JP2005177572A JP2005177572A JP2003419789A JP2003419789A JP2005177572A JP 2005177572 A JP2005177572 A JP 2005177572A JP 2003419789 A JP2003419789 A JP 2003419789A JP 2003419789 A JP2003419789 A JP 2003419789A JP 2005177572 A JP2005177572 A JP 2005177572A
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- titanium oxide
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- 239000000126 substance Substances 0.000 title claims abstract description 96
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007739 conversion coating Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 8
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract 3
- 238000007654 immersion Methods 0.000 description 15
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 2
- 229940107698 malachite green Drugs 0.000 description 2
- OWEZKDSVCUYVNT-UHFFFAOYSA-I sodium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[Na+].[Ti+4] OWEZKDSVCUYVNT-UHFFFAOYSA-I 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- LPLMZAJYUPAYQZ-UHFFFAOYSA-N diazanium;difluoride Chemical compound [NH4+].[NH4+].[F-].[F-] LPLMZAJYUPAYQZ-UHFFFAOYSA-N 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- WSLQHGMJTGELSF-UHFFFAOYSA-L dipotassium;difluoride Chemical compound [F-].[F-].[K+].[K+] WSLQHGMJTGELSF-UHFFFAOYSA-L 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
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- Catalysts (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、アルミニウム材の表面に、光触媒能を有する酸化チタン化成皮膜を、製造する方法に関するものである。 The present invention relates to a method for producing a titanium oxide chemical conversion film having photocatalytic activity on the surface of an aluminum material.
アルミニウム材の表面に形成された、光触媒能を有する酸化チタン皮膜は、公知である。しかし、そのような酸化チタン皮膜は、アルミニウム材表面に形成した多孔質の陽極酸化皮膜に、酸化チタンを固定させることにより、生成されていた（特許文献１参照）。 A titanium oxide film having photocatalytic activity formed on the surface of an aluminum material is known. However, such a titanium oxide film has been generated by fixing titanium oxide to a porous anodic oxide film formed on the surface of an aluminum material (see Patent Document 1).
一方、アルミニウム材の表面に皮膜を形成する方法として、化成処理方法は公知である（特許文献２参照）。
しかしながら、陽極酸化皮膜を利用した上記のような酸化チタン皮膜では、酸化チタンの密度に限界があるために、光触媒能に限界があった。 However, the above-described titanium oxide film using an anodic oxide film has a limit in photocatalytic ability due to a limit in the density of titanium oxide.
一方、化成処理方法により形成された化成皮膜は、一般に極めて薄いものであるため、耐久性に劣り、実用的ではないと考えられていた。 On the other hand, since the chemical conversion film formed by the chemical conversion treatment method is generally extremely thin, it has been considered to be inferior in durability and impractical.
本発明は、優れた光触媒能を発揮でき、実用的な耐久性も有している、酸化チタン化成皮膜を得ることができる、製造方法を、提供することを目的とする。 An object of this invention is to provide the manufacturing method which can exhibit the outstanding photocatalytic capability and can obtain the titanium oxide chemical conversion film which also has practical durability.
請求項１記載の発明は、アルミニウム材の表面に、光触媒能を有する酸化チタン化成皮膜を、製造する方法であって、アルミニウム材を、フッ化チタン塩と過酸化水素との混合溶液に晒して、アルミニウム材表面に化成皮膜を生成させる、化成処理工程、を有することを特徴としている。 The invention according to claim 1 is a method for producing a titanium oxide chemical conversion film having photocatalytic activity on the surface of an aluminum material, wherein the aluminum material is exposed to a mixed solution of a titanium fluoride salt and hydrogen peroxide. And a chemical conversion treatment step of generating a chemical conversion film on the surface of the aluminum material.
なお、フッ化チタン塩としては、例えば、フッ化チタンアンモニウム、フッ化チタンナトリウム塩、フッ化チタンカリウム塩などを用いることができる。 In addition, as a titanium fluoride salt, titanium fluoride ammonium, titanium fluoride sodium salt, titanium fluoride potassium salt etc. can be used, for example.
請求項２記載の発明は、請求項１記載の発明において、生成した化成皮膜を熱処理する、熱処理工程、を更に有するものである。 The invention according to claim 2 further includes a heat treatment step of heat-treating the produced chemical conversion film in the invention according to claim 1.
請求項３記載の発明は、請求項２記載の発明において、熱処理後の化成皮膜を、アルミン酸ナトリウムと、水酸化ナトリウムと、しゅう酸ナトリウムとの混合溶液に晒して、厚膜化する、増膜処理工程、を更に有するものである。 According to a third aspect of the invention, in the invention of the second aspect, the chemical conversion film after the heat treatment is exposed to a mixed solution of sodium aluminate, sodium hydroxide and sodium oxalate to increase the film thickness. A film processing step.
請求項４記載の発明は、請求項１記載の発明において、化成処理工程では、アルミニウム材を上記混合溶液に浸漬させるものである。 According to a fourth aspect of the invention, in the first aspect of the invention, in the chemical conversion treatment step, the aluminum material is immersed in the mixed solution.
請求項５記載の発明は、請求項３記載の発明において、増膜処理工程では、化成皮膜を上記混合溶液に浸漬させるものである。 The invention according to claim 5 is the invention according to claim 3, wherein the chemical conversion film is immersed in the mixed solution in the film increasing treatment step.
請求項６記載の発明は、請求項４記載の発明において、化成処理工程において、フッ化チタン塩の濃度が０．００１〜４．０モル／リットルであり、過酸化水素の濃度が０．０１〜１．０モル／リットルであり、上記混合溶液の温度が２０〜１００℃であるものである。 The invention according to claim 6 is the invention according to claim 4, wherein in the chemical conversion treatment step, the concentration of the titanium fluoride salt is 0.001 to 4.0 mol / liter, and the concentration of hydrogen peroxide is 0.01 It is -1.0 mol / liter, and the temperature of the said mixed solution is 20-100 degreeC.
請求項７記載の発明は、請求項５記載の発明において、増膜処理工程において、アルミン酸ナトリウムの濃度が０．００１〜０．４モル／リットルであり、水酸化ナトリウムの濃度が０．００１〜０．０４モル／リットルであり、しゅう酸ナトリウムの濃度が０．００１〜０．５モル／リットルであり、上記混合溶液の温度が２０〜１００℃であるものである。 The invention according to claim 7 is the invention according to claim 5, wherein, in the film increasing treatment step, the concentration of sodium aluminate is 0.001 to 0.4 mol / liter, and the concentration of sodium hydroxide is 0.001. The concentration of sodium oxalate is 0.001 to 0.5 mol / liter, and the temperature of the mixed solution is 20 to 100 ° C.
請求項８記載の発明は、請求項２記載の発明において、熱処理工程において、熱処理温度が１００〜４００℃であるものである。 The invention according to claim 8 is the invention according to claim 2, wherein the heat treatment temperature is 100 to 400 ° C. in the heat treatment step.
請求項１記載の発明によれば、化成処理工程により、光触媒能を発揮でき且つ実用に耐え得る膜厚を有する、酸化チタン化成皮膜を生成できる。 According to invention of Claim 1, the chemical conversion treatment process can produce | generate the titanium oxide chemical conversion film which can exhibit photocatalytic ability and has a film thickness which can be practically used.
請求項２記載の発明によれば、熱処理工程により、無定形酸化チタンからなる酸化チタン化成皮膜を、光触媒能を有するアナターゼ型の酸化チタンを含む酸化チタン化成皮膜とすることができる。従って、化成処理工程で得られた酸化チタン化成皮膜の光触媒能を向上できる。 According to invention of Claim 2, the titanium oxide chemical conversion film which consists of amorphous titanium oxide can be made into the titanium oxide chemical conversion film containing the anatase type titanium oxide which has a photocatalytic capability by a heat treatment process. Therefore, the photocatalytic ability of the titanium oxide chemical conversion film obtained in the chemical conversion treatment step can be improved.
請求項３記載の発明によれば、増膜処理工程により、酸化チタン化成皮膜を厚膜化して耐久性を向上させることができる。従って、光触媒能を発揮でき、しかも、優れた耐久性を有している、酸化チタン化成皮膜、を得ることができる。 According to the invention described in claim 3, it is possible to increase the durability by increasing the thickness of the titanium oxide chemical conversion film by the film increasing treatment step. Therefore, it is possible to obtain a titanium oxide chemical conversion film that can exhibit photocatalytic activity and has excellent durability.
請求項４記載の発明によれば、簡単な操作で化成処理工程を実施できる。 According to invention of Claim 4, a chemical conversion treatment process can be implemented by simple operation.
請求項５記載の発明によれば、簡単な操作で増膜処理工程を実施できる。 According to the fifth aspect of the present invention, the film-increasing treatment step can be performed with a simple operation.
請求項６記載の発明によれば、酸化チタン化成皮膜を確実に生成させることができる。 According to invention of Claim 6, a titanium oxide chemical conversion film can be produced | generated reliably.
請求項７記載の発明によれば、酸化チタン化成皮膜を確実に厚膜化することができる。 According to the invention of claim 7, the titanium oxide chemical conversion film can be reliably thickened.
請求項８記載の発明によれば、無定形酸化チタンの一部又は全部をアナターゼ型に変えて光触媒能を持たせることができる。例えば、熱処理温度が２００℃の場合は、一部がアナターゼ型となるが、４００℃の場合は、全部がアナターゼ型となる。 According to the eighth aspect of the present invention, a part or all of amorphous titanium oxide can be changed to anatase type to have photocatalytic activity. For example, when the heat treatment temperature is 200 ° C., a part is anatase type, but when it is 400 ° C., the whole is anatase type.
本発明の製造方法は、次の（１）、（２）の工程を順次実施して行うものであるが、好ましくは、（３）の工程、更には（４）の工程を、続けて順次実施して行う。 The production method of the present invention is carried out by sequentially performing the following steps (1) and (2). Preferably, the step (3) and further the step (4) are successively carried out successively. Perform it.
（１）前処理工程
アルミニウム材を、市販のノニオン系界面活性剤の浴に浸漬させることにより、脱脂処理した。なお、浴温度は５０℃、浸漬時間は５分間とした。また、アルミニウム材としては、純アルミニウム材（純度９９．９９９％）又は６０００系アルミニウム材を用いた。アルミニウム材の形状は、５０ｍｍ×３０ｍｍ×０．４ｍｍの板状とした。
(1) Pretreatment process The aluminum material was degreased by immersing it in a commercially available nonionic surfactant bath. The bath temperature was 50 ° C. and the immersion time was 5 minutes. As the aluminum material, a pure aluminum material (purity 99.999%) or a 6000 series aluminum material was used. The shape of the aluminum material was a plate shape of 50 mm × 30 mm × 0.4 mm.
（２）化成処理工程
脱脂処理後のアルミニウム材を、フッ化チタンアンモニウムと過酸化水素との混合溶液の浴に浸漬させた。これにより、化成皮膜を生成させた。なお、フッ化チタンアンモニウムの濃度は０．００１〜４．０モル／リットル、過酸化水素の濃度は０．０１〜１．０モル／リットル、浴温度は２０〜１００℃、浸漬時間は１０〜１２０分間とした。なお、フッ化チタンアンモニウムに代えて、他の他のフッ化チタン塩、例えば、フッ化チタンナトリウム塩又はフッ化チタンカリウム塩を用いてもよい。
(2) Chemical conversion treatment process The aluminum material after the degreasing treatment was immersed in a bath of a mixed solution of ammonium titanium fluoride and hydrogen peroxide. Thereby, the chemical conversion film was produced | generated. The concentration of ammonium ammonium fluoride is 0.001 to 4.0 mol / liter, the concentration of hydrogen peroxide is 0.01 to 1.0 mol / liter, the bath temperature is 20 to 100 ° C., and the immersion time is 10 to 10 ° C. 120 minutes. Instead of titanium ammonium fluoride, other titanium fluoride salts such as sodium fluoride titanium salt or potassium potassium fluoride fluoride may be used.
（３）熱処理工程
生成した化成皮膜を熱処理した。なお、熱処理温度は１００〜４００℃とした。
(3) Heat treatment process The produced chemical conversion film was heat-treated. The heat treatment temperature was 100 to 400 ° C.
（４）増膜処理工程
熱処理後の化成皮膜を、アルミン酸ナトリウムと、水酸化ナトリウムと、しゅう酸ナトリウムとの混合溶液の浴に浸漬させた。これにより、化成皮膜を厚膜化した。なお、アルミン酸ナトリウムの濃度は０．００１〜０．４モル／リットル、水酸化ナトリウムの濃度は０．００１〜０．０４モル／リットル、しゅう酸ナトリウムの濃度は０．００１〜０．５モル／リットル、浴温度は２０〜１００℃とした。
(4) Thickening treatment process The chemical conversion film after heat treatment was immersed in a bath of a mixed solution of sodium aluminate, sodium hydroxide, and sodium oxalate. Thereby, the chemical conversion film was thickened. The concentration of sodium aluminate is 0.001 to 0.4 mol / liter, the concentration of sodium hydroxide is 0.001 to 0.04 mol / liter, and the concentration of sodium oxalate is 0.001 to 0.5 mol. / L, and the bath temperature was 20 to 100 ° C.
なお、上記工程（２）及び（４）では、アルミニウム材を浴中に浸漬させているが、その代わりに、アルミニウム材に浴中の溶液をスプレーしてもよい。 In the above steps (2) and (4), the aluminum material is immersed in the bath, but instead, the solution in the bath may be sprayed onto the aluminum material.
（実施例）
前処理した純アルミニウム材を、化成処理した。具体的には、フッ化チタンアンモニウムの濃度を０．０４モル／リットル、過酸化水素の濃度を０．３０モル／リットル、浴温度を８０℃、浸漬時間を６０分間とした。これにより、黄色で膜厚１０μｍの化成皮膜が得られた。
(Example)
The pretreated pure aluminum material was subjected to chemical conversion treatment. Specifically, the titanium fluoride ammonium concentration was 0.04 mol / liter, the hydrogen peroxide concentration was 0.30 mol / liter, the bath temperature was 80 ° C., and the immersion time was 60 minutes. As a result, a yellow chemical conversion film having a thickness of 10 μm was obtained.
次に、得られた化成皮膜を、熱処理した。具体的には、２００℃で１５分間熱処理した。これにより、上記化成皮膜の黄色が少し脱色された。膜厚には変化がなかった。 Next, the obtained chemical conversion film was heat-treated. Specifically, heat treatment was performed at 200 ° C. for 15 minutes. Thereby, the yellow color of the chemical conversion film was slightly decolorized. There was no change in film thickness.
そして、熱処理後の化成皮膜を、増膜処理した。具体的には、アルミン酸ナトリウムの濃度を０．０８モル／リットル、水酸化ナトリウムの濃度を０．０１モル／リットル、しゅう酸ナトリウムの濃度を０．０２モル／リットル、浴温度を７０℃、浸漬時間を１２０分間とした。これにより、上記化成皮膜は、略白色となり、膜厚２４μｍとなった。 Then, the chemical conversion film after the heat treatment was subjected to a film increase treatment. Specifically, the concentration of sodium aluminate is 0.08 mol / liter, the concentration of sodium hydroxide is 0.01 mol / liter, the concentration of sodium oxalate is 0.02 mol / liter, the bath temperature is 70 ° C., The immersion time was 120 minutes. Thereby, the said chemical conversion film became substantially white and became a film thickness of 24 micrometers.
（作用）
上記製造方法においては、次のような反応が生じていると考えられる。
上記工程（２）においては、アルミニウム材の表面から水素が発生しながら、該表面に黄色化成皮膜が生成する。この黄色化成皮膜を、Ｘ線回折装置（理学電気株式会社製、型番ＲＩＮＴ２０００）を用いてＸ線回折したところ、図１に示すように、Ａｌのピークしか確認できなかった。従って、この黄色化成皮膜は、ペルオキソチタンフッ化物を含む無定形酸化チタンであると考えられる。
(Function)
In the above production method, it is considered that the following reaction occurs.
In the step (2), a yellow chemical conversion film is formed on the surface of the aluminum material while hydrogen is generated. When this yellow chemical conversion film was X-ray diffracted using an X-ray diffractometer (manufactured by Rigaku Corporation, model number RINT2000), as shown in FIG. 1, only the peak of Al was confirmed. Therefore, this yellow chemical conversion film is considered to be amorphous titanium oxide containing peroxotitanium fluoride.
上記工程（３）においては、例えば４００℃で加熱処理すると、上記工程（２）で得られた黄色化成皮膜は白色の酸化チタン化成皮膜となった。この酸化チタン化成皮膜を、上記Ｘ線回折装置を用いてＸ線回折したところ、図２に示すように、酸化チタンはアナターゼ型であった。 In the said process (3), when heat-processing at 400 degreeC, for example, the yellow chemical conversion film obtained by the said process (2) became a white titanium oxide chemical conversion film. When this titanium oxide chemical conversion film was X-ray diffracted using the above X-ray diffractometer, the titanium oxide was anatase type as shown in FIG.
しかしながら、酸化チタン化成皮膜の表面には、クラックが発生した。図３は上記工程（３）後の酸化チタン化成皮膜の表面をレーザー電子顕微鏡（キーエンス株式会社製）にて観察した写真である。図４は上記工程（３）前の同様の写真である。図３と図４とを見比べると、上記工程（３）により、クラックが発生していることがわかる。 However, cracks occurred on the surface of the titanium oxide chemical conversion film. FIG. 3 is a photograph of the surface of the titanium oxide chemical conversion film after the step (3) observed with a laser electron microscope (manufactured by Keyence Corporation). FIG. 4 is a similar photograph before the step (3). Comparing FIG. 3 with FIG. 4, it can be seen that cracks are generated by the step (3).
上記工程（４）においては、水酸化アルミニウムが生成して、酸化チタン化成皮膜が厚くなった。図５は工程（３）後の酸化チタン化成皮膜の質量分析結果を示し、図６は工程（４）後の酸化チタン化成皮膜の質量分析結果を示す。なお、質量分析は、表１に示す測定条件の下、二次イオン質量分析装置（ＣＡＭＥＣＡ製、型番ＩＭＳ−６Ｆ）を用いて行った。図５に比して図６にはアルミニウムのピークがあり、水酸化アルミニウムが生成していることがわかる。この水酸化アルミニウムは、ギブサイトが主成分であることがわかった。上記工程（４）で用いるしゅう酸ナトリウムがギブサイトの結晶化をより向上させていると考えられる。水酸化アルミニウムの生成により、１０μｍ程度であった酸化チタン化成皮膜が２０μｍを越える膜厚を有するまでに厚膜化され、酸化チタンの密着性及び耐食性が向上した。 In the said process (4), aluminum hydroxide produced | generated and the titanium oxide chemical conversion film became thick. FIG. 5 shows a mass analysis result of the titanium oxide chemical conversion film after the step (3), and FIG. 6 shows a mass analysis result of the titanium oxide chemical conversion film after the step (4). In addition, mass spectrometry was performed using the secondary ion mass spectrometer (made by CAMECA, model number IMS-6F) under the measurement conditions shown in Table 1. Compared to FIG. 5, there is an aluminum peak in FIG. 6, indicating that aluminum hydroxide is generated. This aluminum hydroxide was found to be mainly composed of gibbsite. It is considered that the sodium oxalate used in the step (4) further improves the crystallization of gibbsite. By the formation of aluminum hydroxide, the titanium oxide chemical conversion film, which was about 10 μm, was thickened to have a film thickness exceeding 20 μm, and the adhesion and corrosion resistance of titanium oxide were improved.
こうして得られた酸化チタン化成皮膜の光触媒能を、分光光度計（島津製作所製、型番ＵＶ−２００Ｓ）を用いて吸光光度分析法により評価した。具体的には、マラカイトグリーンの分解速度測定により簡易的に評価した。測定条件は、マラカイトグリーンの初期濃度を２．５０ｐｐｍ一定とし、これに、酸化チタン皮膜を暗所にて６０分間浸漬させ、その後、表２に示す条件下で紫外光を照射し、波長６１８ｎｍにおける吸光度を分光光度計により１０分間隔で測定し、合計６０分間の測定を行った。 The photocatalytic ability of the titanium oxide chemical conversion film thus obtained was evaluated by spectrophotometry using a spectrophotometer (manufactured by Shimadzu Corporation, model number UV-200S). Specifically, it was simply evaluated by measuring the decomposition rate of malachite green. The measurement conditions were such that the initial concentration of malachite green was constant at 2.50 ppm, and the titanium oxide film was immersed in the dark for 60 minutes, and then irradiated with ultraviolet light under the conditions shown in Table 2, at a wavelength of 618 nm. Absorbance was measured with a spectrophotometer at 10-minute intervals, and measurements were made for a total of 60 minutes.
図７は、上記工程（２）後、上記工程（３）後、及び上記工程（４）後の、化成皮膜の吸光度を示す。なお、図において、上記工程（２）後は「化成処理後」と表示し、上記工程（３）後は「１００℃、２００℃、３００℃、４００℃」と熱処理の温度で表示し、上記工程（４）後は「増膜処理後」と表示している。 FIG. 7 shows the absorbance of the chemical conversion film after the step (2), after the step (3), and after the step (4). In the figure, after the step (2), “after chemical conversion treatment” is displayed, and after the step (3), “100 ° C., 200 ° C., 300 ° C., 400 ° C.” is displayed at the heat treatment temperature, After the step (4), “After film thickening” is displayed.
上記工程（２）で得られた酸化チタン化成皮膜は、図７からわかるように、良好な光触媒能を示しており、しかも、上記実施例で述べたように、１０μｍ程度の膜厚を有している。従って、上記工程（２）で得られた酸化チタン化成皮膜は、光触媒能を発揮する化成皮膜として実用に供することができるものである。 As can be seen from FIG. 7, the titanium oxide chemical conversion film obtained in the step (2) has a good photocatalytic activity, and has a thickness of about 10 μm as described in the above examples. ing. Therefore, the titanium oxide chemical conversion film obtained in the above step (2) can be practically used as a chemical conversion film exhibiting photocatalytic activity.
更に、上記工程（２）で得られた黄色の酸化チタン化成皮膜は、上記工程（３）における熱処理温度が３００℃及び４００℃の場合には白い皮膜となり、１００℃及び２００℃の場合には黄色が少し脱色された皮膜となった。Ｘ線回折の結果、前者の皮膜は、全てがアナターゼ型の酸化チタンであったが、後者の皮膜は、アナターゼ型酸化チタンと黄色の化合物であるペルオキソチタンフッ化物との混合物であった。図７からわかるように、２００℃の場合が最も高い光触媒能を示した。これは、ペルオキソチタンフッ化物が、酸化チタンの結合剤として機能するだけではなく、青色の光を吸収して可視光でも光触媒能を発現するからである、と考えられる。従って、上記工程（３）後の酸化チタン化成皮膜は、優れた光触媒能を発揮する化成皮膜として実用に供することができるものである。 Furthermore, the yellow titanium oxide conversion coating obtained in the step (2) becomes a white coating when the heat treatment temperature in the step (3) is 300 ° C and 400 ° C, and in the case of 100 ° C and 200 ° C. The film was slightly decolorized yellow. As a result of X-ray diffraction, the former film was all anatase-type titanium oxide, but the latter film was a mixture of anatase-type titanium oxide and peroxotitanium fluoride which is a yellow compound. As can be seen from FIG. 7, the highest photocatalytic activity was exhibited at 200 ° C. This is thought to be because peroxotitanium fluoride not only functions as a binder for titanium oxide but also absorbs blue light and develops photocatalytic activity even with visible light. Therefore, the titanium oxide chemical conversion film after the above step (3) can be put to practical use as a chemical conversion film exhibiting excellent photocatalytic ability.
なお、上記工程（４）後の皮膜では、上記工程（３）後の皮膜よりも、光触媒能が低かった。これは、生成した水酸化アルミニウムにより、酸化チタンの比表面積が低下したためと考えられる。しかしながら、上記工程（４）後の酸化チタン化成皮膜は、２０μｍを越える膜厚を有しているので、光触媒能を発揮する化成皮膜として優れた耐久性を発揮できる。 The film after the step (4) had lower photocatalytic ability than the film after the step (3). This is presumably because the specific surface area of titanium oxide was reduced by the produced aluminum hydroxide. However, since the titanium oxide chemical conversion film after the step (4) has a film thickness exceeding 20 μm, it can exhibit excellent durability as a chemical conversion film exhibiting photocatalytic activity.
（検討）
本発明の製造方法においては、次のような検討を行った。
なお、皮膜の膜厚の測定は、次のように行った。即ち、渦電流式膜厚計（株式会社サンコウ電子研究所製、型番ＥＤＹ−１０００）を用い、対象皮膜の膜厚を５点にて測定し、その近似値３点の平均値を求め、それを対象皮膜の膜厚とした。
(Consideration)
In the production method of the present invention, the following examination was performed.
In addition, the film thickness of the film was measured as follows. That is, using an eddy current film thickness meter (manufactured by Sanko Electronic Laboratory Co., Ltd., model number EDY-1000), the film thickness of the target film was measured at 5 points, and an average value of 3 approximate values was obtained. Was the film thickness of the target film.
（ｉ）上記工程（２）における、浸漬時間と得られる化成皮膜の膜厚との関係
上記工程（２）において、浴温度を８０℃とし、種々の浸漬時間における膜厚を測定した。なお、フッ化チタンアンモニウムの濃度は０．０４モル／リットル、過酸化水素の濃度は０．３０モル／リットルとした。図８はその結果を示す。図８からわかるように、浸漬時間が長くなると膜厚は増大しており、両者の間には相関関係が認められた。しかし、浸漬時間が６０分を越えると、膜厚の増大は認められなかった。その時の膜厚は約１２μｍであった。
(I) Relationship between immersion time and film thickness of chemical conversion film obtained in the above step (2) In the above step (2), the bath temperature was set to 80 ° C., and the film thickness at various immersion times was measured. The concentration of ammonium fluoride titanium was 0.04 mol / liter, and the concentration of hydrogen peroxide was 0.30 mol / liter. FIG. 8 shows the result. As can be seen from FIG. 8, the film thickness increased as the immersion time increased, and a correlation was observed between the two. However, when the immersion time exceeded 60 minutes, no increase in film thickness was observed. The film thickness at that time was about 12 μm.
図９は浴温度を２５℃とした場合を示している。この場合でも、浸漬時間と膜厚との間には相関関係が認められたが、浸漬時間が約２０時間を越えると、膜厚の増大は認められなくなり、その時の膜厚は約１４μｍであった。 FIG. 9 shows a case where the bath temperature is 25 ° C. Even in this case, a correlation was observed between the immersion time and the film thickness, but when the immersion time exceeded about 20 hours, the increase in film thickness was not recognized, and the film thickness at that time was about 14 μm. It was.
以上から、上記工程（２）の処理においては、浸漬時間が長いほど厚い膜厚が得られるが、それには限界があり、得られる最大膜厚は約１２〜１４μｍである。 From the above, in the treatment of the above step (2), the longer the immersion time, the thicker the film thickness is obtained, but there is a limit to this, and the maximum film thickness obtained is about 12-14 μm.
（ii）上記工程（２）における、浴温度と得られる化成皮膜の膜厚との関係
上記工程（２）において、浸漬時間を６０分とし、種々の浴温度における膜厚を測定した。なお、フッ化チタンアンモニウムの濃度は０．０４モル／リットル、過酸化水素の濃度は０．３０モル／リットルとした。図１０はその結果を示す。図１０からわかるように、高温（６０〜１００℃）では、低温（２５〜６０℃）の場合に比して、皮膜の生成速度が上昇した。しかし、低温の場合には、緻密で均一な皮膜が生成したのに対し、高温の場合には、粗で不均一な皮膜が生成した。
(Ii) Relationship between bath temperature and film thickness of resulting chemical film in step (2) In the above step (2), the immersion time was 60 minutes, and the film thicknesses at various bath temperatures were measured. The concentration of ammonium fluoride titanium was 0.04 mol / liter, and the concentration of hydrogen peroxide was 0.30 mol / liter. FIG. 10 shows the result. As can be seen from FIG. 10, at a high temperature (60-100 ° C.), the film formation rate increased as compared to a low temperature (25-60 ° C.). However, when the temperature was low, a dense and uniform film was formed, whereas when the temperature was high, a rough and non-uniform film was formed.
（iii）上記工程（２）における、浴濃度と得られる化成皮膜の膜厚との関係
上記工程（２）において、浴温度を８０℃とし、浸漬時間を６０分とし、フッ化チタンアンモニウムの種々の濃度における膜厚を測定した。なお、過酸化水素の濃度は０．３０モル／リットルとした。図１１はその結果を示す。図１１からわかるように、フッ化チタンアンモニウムの濃度が０．１モル／リットルまでは、濃度が増すに従って膜厚も増大しているが、それを越えると、濃度が増しても膜厚は殆ど増大せず、その時の膜厚は約１５μｍであった。
(Iii) Relationship between bath concentration and film thickness of chemical conversion film obtained in step (2) In the step (2), the bath temperature is set to 80 ° C., the immersion time is set to 60 minutes. The film thickness at the concentration of was measured. The concentration of hydrogen peroxide was 0.30 mol / liter. FIG. 11 shows the result. As can be seen from FIG. 11, the film thickness increases as the concentration of titanium ammonium fluoride reaches 0.1 mol / liter. However, when the concentration increases, the film thickness increases almost even when the concentration increases. The film thickness did not increase and the film thickness at that time was about 15 μm.
本発明は、優れた光触媒能と実用的な耐久性を有する新規な酸化チタン化成皮膜を得ることができる方法であるので、産業上の利用価値が大なるものである。 Since the present invention is a method capable of obtaining a novel titanium oxide chemical conversion film having excellent photocatalytic ability and practical durability, the industrial utility value is great.
Claims (8)
アルミニウム材を、フッ化チタン塩と過酸化水素との混合溶液に晒して、アルミニウム材表面に化成皮膜を生成させる、化成処理工程、を有することを特徴とする酸化チタン化成皮膜の製造方法。 A method for producing a titanium oxide conversion film having photocatalytic activity on the surface of an aluminum material,
A method for producing a titanium oxide chemical conversion film, comprising: subjecting an aluminum material to a mixed solution of a titanium fluoride salt and hydrogen peroxide to form a chemical conversion film on the surface of the aluminum material.
The manufacturing method of the titanium oxide chemical conversion film of Claim 2 whose heat processing temperature is 100-400 degreeC in a heat processing process.
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| JP2007216197A (en) * | 2006-02-20 | 2007-08-30 | Univ Kinki | Photocatalytic film, photocatalytic material and methods for manufacturing them |
| US9741467B2 (en) | 2014-08-05 | 2017-08-22 | General Cable Technologies Corporation | Fluoro copolymer coatings for overhead conductors |
| US10957467B2 (en) | 2014-01-08 | 2021-03-23 | General Cable Technologies Corporation | Coated overhead conductor |
| US11319455B2 (en) | 2015-11-13 | 2022-05-03 | General Cable Technologies Corporation | Cables coated with fluorocopolymer coatings |
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| JP2007216197A (en) * | 2006-02-20 | 2007-08-30 | Univ Kinki | Photocatalytic film, photocatalytic material and methods for manufacturing them |
| US10957467B2 (en) | 2014-01-08 | 2021-03-23 | General Cable Technologies Corporation | Coated overhead conductor |
| US9741467B2 (en) | 2014-08-05 | 2017-08-22 | General Cable Technologies Corporation | Fluoro copolymer coatings for overhead conductors |
| US11319455B2 (en) | 2015-11-13 | 2022-05-03 | General Cable Technologies Corporation | Cables coated with fluorocopolymer coatings |
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