JP2011120998A - Visible light responsive rutile type titanium dioxide photocatalyst - Google Patents
Visible light responsive rutile type titanium dioxide photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 113
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Abstract
Description
本発明は、チタンまたはチタン合金からなる基材の表面に、可視光に対する応答性のある光触媒活性を有するルチル型二酸化チタンを形成する技術に関する。より具体的には、本発明は、陽極酸化により表面に形成される光触媒活性を有するルチル型二酸化チタンに窒素と硫黄をドープせしめ、それにより可視光応答性に優れた二酸化チタン光触媒材を提供することに関する。 The present invention relates to a technique for forming rutile-type titanium dioxide having photocatalytic activity responsive to visible light on the surface of a substrate made of titanium or a titanium alloy. More specifically, the present invention provides a titanium dioxide photocatalyst material excellent in visible light response by doping nitrogen and sulfur into rutile titanium dioxide having photocatalytic activity formed on the surface by anodic oxidation. About that.
半導体的特性を有する金属酸化物、特には二酸化チタンは、紫外線領域の特定波長の光を照射することによって優れた光触媒活性を示し、その表面において気相あるいは液相（場合によっては固相）の化学物質を酸化分解する。該光触媒作用に由来する強力な酸化反応によって該二酸化チタンは、防臭、防黴、殺菌作用を発揮する。
こうした活性を有する二酸化チタンを、チタンまたはチタン合金の表面に担持せしめるための従来技術としては、蒸着法とゾルゲル法が多用されている。ゾルゲル法はディップコートやスピンコートで行う簡便な方法で、異型基材への担持が可能であるが、量産性に劣るという問題を有している。特にスピンコートでは膜の均一性が悪く平板基板にしか担持できないという短所がある。一方、蒸着法は成膜材の緻密性や均一性に優れているものの、特殊装置を用いることからコストが高く、膜厚が厚いことから剥離の可能性が高いという欠点がある。
Metal oxides, especially titanium dioxide, having semiconducting properties show excellent photocatalytic activity when irradiated with light of a specific wavelength in the ultraviolet region, and in the surface of the gas phase or liquid phase (in some cases solid phase) Oxidative decomposition of chemical substances. The titanium dioxide exhibits deodorizing, antifungal and bactericidal action by a powerful oxidation reaction derived from the photocatalytic action.
Vapor deposition and sol-gel methods are frequently used as conventional techniques for supporting titanium dioxide having such activity on the surface of titanium or a titanium alloy. The sol-gel method is a simple method performed by dip coating or spin coating, and can be supported on an irregular substrate, but has a problem that it is inferior in mass productivity. In particular, spin coating has a disadvantage in that the uniformity of the film is poor and it can only be supported on a flat substrate. On the other hand, the vapor deposition method is excellent in the denseness and uniformity of the film forming material, but has the disadvantages that the cost is high because a special apparatus is used, and the possibility of peeling is high because the film thickness is large.
こうした手法に代わるものとして、陽極酸化法により光触媒活性を有する二酸化チタン薄膜を成膜する方法が提案されている。陽極酸化法による光触媒二酸化チタン薄膜の製造の報告例では、光触媒としては、アナタース型二酸化チタンのほうが、高温型結晶として知られるルチル型二酸化チタンよりその活性が高いとして、専らアナタース型二酸化チタン膜を形成することを目的としている。 As an alternative to such a method, a method of forming a titanium dioxide thin film having photocatalytic activity by an anodic oxidation method has been proposed. In the report example of the production of photocatalytic titanium dioxide thin film by anodization method, the anatase type titanium dioxide film is exclusively used as the photocatalyst because the activity of the anatase type titanium dioxide is higher than the rutile type titanium dioxide known as a high temperature type crystal. The purpose is to form.
こうした従来技術の中で、特開2002-113369号公報〔特許文献１〕は、結晶構造がルチ
ル型の二酸化チタンを含むことを特徴とする光触媒及びその製造法を開示するが、それは酸化チタン粉末を主とする光触媒材料を成形して光触媒体を製造する技術であり、そこではルチル型二酸化チタン粉末は水素雰囲気中熱処理を行うことにより酸素欠陥を導入してアナタース型二酸化チタン粉末との混合物からなる酸化チタン粉末として得られたり、ルチル型の二酸化チタン粉末のみからなる酸化チタン粉末として得られたり、さらには膜状体に酸素欠陥導入又は原子置換を施して光触媒体を得ているといったものである。
こうした中で、本発明者等は、これまでに、意外なことに、二酸化チタン光触媒体の光触媒活性および超親水性などの性能が、二酸化チタンのルチル結晶性である薄膜においても、大変優れていることを見出している。
Among these prior arts, Japanese Patent Application Laid-Open No. 2002-113369 [Patent Document 1] discloses a photocatalyst characterized in that the crystal structure contains rutile type titanium dioxide and a method for producing the photocatalyst. Is a technology for producing a photocatalyst body by mainly forming a photocatalyst material, in which rutile type titanium dioxide powder is introduced from a mixture with anatase type titanium dioxide powder by introducing oxygen defects by heat treatment in a hydrogen atmosphere. It is obtained as a titanium oxide powder, or as a titanium oxide powder consisting only of rutile-type titanium dioxide powder, or a photocatalyst is obtained by introducing oxygen defects or substituting atoms into the film-like body. is there.
Under such circumstances, the present inventors have surprisingly been able to surprisingly achieve excellent performance such as photocatalytic activity and superhydrophilicity of the titanium dioxide photocatalyst even in a thin film of titanium dioxide having rutile crystallinity. Is found.
ところで、光触媒としての活性を利用する場合、生活空間では可視光に対する応答性があることが、より広い適用が期待できて望まれている。可視光での光触媒活性の改善には、二酸化チタンのバンドギャップの狭窄が必要である。そのための方策の一つとして、添加元素の電子軌道と二酸化チタンの価電子帯の混成により、価電子帯の上端電位を高めることが提案されており、窒素ドーピングが有効であることが報告されている（非特許文献１: Chemical Physics Letter, 123 (1986), 126、特許文献２:特開2005-240139号公報）。 By the way, when utilizing the activity as a photocatalyst, it is desired that there is responsiveness to visible light in a living space because a wider application can be expected. In order to improve the photocatalytic activity with visible light, it is necessary to narrow the band gap of titanium dioxide. As one of the measures for this, it has been proposed to increase the top potential of the valence band by hybridizing the electron orbital of the additive element and the valence band of titanium dioxide, and it has been reported that nitrogen doping is effective. (Non-Patent Document 1: Chemical Physics Letter, 123 (1986), 126, Patent Document 2: JP-A-2005-240139).
また、他方、同様の効果を期待できるとされているのが、硫黄ドーピングであるが、窒素ドーピングに比べその報告は圧倒的に少なく、効果の程も詳細には不明であったが、先
ごろ、本発明者等は、硫酸水溶液電解浴を使用した陽極酸化法により、確実に硫黄ドーピングが可能な技術の開発に成功した〔特許文献３:特願2008-327669〕。
On the other hand, it is suspected that the same effect can be expected, but sulfur doping is overwhelmingly less reported than nitrogen doping, and the effect was unknown in detail, but recently, The present inventors have succeeded in developing a technique capable of reliably performing sulfur doping by an anodic oxidation method using an aqueous sulfuric acid electrolytic bath [Patent Document 3: Japanese Patent Application No. 2008-327669].
工業的生産に適しており、且つ、簡単な手法で、均一で緻密なものとして、光触媒活性に優れた二酸化チタン薄膜を有する基材であって、さらに可視光に対する応答性に優れている二酸化チタン薄膜を有する基材を得る技術を提供することが求められている。特には、可視光領域での光触媒活性に優れた二酸化チタン薄膜を成膜する技術の開発が求められている。本発明者等は、上記のように、硫酸電解浴を使用した陽極酸化法により作製した二酸化チタンにおいて、陽極酸化膜に硫黄をドープさせることでバンドギャップの狭窄化による可視光下での活性を示す材料開発に成功している（特願2008-327669）。本発明で
はさらなるバンドギャップ狭窄を目指して、窒素と硫黄の複合添加を目指した。
Titanium dioxide that is suitable for industrial production and has a titanium dioxide thin film with excellent photocatalytic activity as a uniform and dense material by a simple method, and also has excellent response to visible light There is a need to provide a technique for obtaining a substrate having a thin film. In particular, development of a technique for forming a titanium dioxide thin film excellent in photocatalytic activity in the visible light region is required. As described above, the present inventors, in titanium dioxide produced by an anodizing method using a sulfuric acid electrolytic bath, have an activity under visible light by narrowing the band gap by doping sulfur into the anodized film. We have succeeded in developing the materials shown (Japanese Patent Application No. 2008-327669). In the present invention, with the aim of further narrowing the band gap, a combined addition of nitrogen and sulfur was aimed at.
本発明者等は、鋭意研究の結果、基板チタンあるいはチタン合金に、窒化物を形成しない程度に窒化処理を施し、それを基板にして陽極酸化を行い、陽極酸化後に熱処理を施すことにより、基板にドープした固溶窒素を酸化膜に拡散させ、二酸化チタンへの窒素と硫黄の複合添加を行うことに成功した。そして、このようにして作製した二酸化チタンは400 nm以上の長波長の光照射下で、有機物酸化分解および超親水性に優れることを見出した。またこれらの機能は紫外線照射下での機能の劣化を伴わないことも見出した。 As a result of diligent research, the inventors of the present invention performed nitriding treatment on the substrate titanium or titanium alloy to such an extent that nitrides are not formed, anodized the substrate, and heat-treated after the anodic oxidation. Nitrogen-doped solid solution nitrogen was diffused into the oxide film and succeeded in the combined addition of nitrogen and sulfur to titanium dioxide. And it discovered that the titanium dioxide produced in this way was excellent in organic substance oxidative decomposition | disassembly and super hydrophilicity under the light irradiation of 400 nm or more long wavelength. It has also been found that these functions are not accompanied by deterioration of the functions under ultraviolet irradiation.
かくして、本発明は、次なるものを提供する。
〔１〕チタンまたはチタン合金からなる基材の表面に陽極酸化を施して光触媒活性ルチル型二酸化チタン被覆材を製造する方法において、当該基材のチタンまたはチタン合金に窒化処理を施し、該窒化処理された基材を陽極酸化に付し、前記陽極酸化を施して作製した膜に、熱処理を施して、可視光領域で高い光触媒活性を示し且つ窒素と硫黄がドープされたルチル型二酸化チタン被覆材料を得ることを特徴とする可視光応答性に優れた光触媒ルチル型二酸化チタンを製造する方法。
〔２〕前記窒化処理は、窒素雰囲気下加熱による窒化あるいはプラズマ窒化であることを特徴とする上記〔１〕に記載の方法。
〔３〕前記窒化処理は、窒素含有のガスの存在下、350〜850℃の処理温度、200〜1000Pa
の範囲のガス圧の条件で、10分間〜24時間の範囲でプラズマ窒化するものであることを特徴とする上記〔１〕又は〔２〕に記載の方法。
〔４〕前記窒化処理は、窒素と水素の混合ガスの容量比N2:H2=おおよそ1.2:0.8〜N2:H2=
おおよそ1:4である窒素源のガスの存在下、650〜750℃の処理温度、450〜1000Paの範囲のガス圧の条件で、1.5〜3.5時間の範囲でプラズマ窒化するものであることを特徴とする上記〔１〕〜〔３〕のいずれか一に記載の方法。
〔５〕陽極酸化が、0.02〜1.6mol/Lの硫酸濃度の硫酸水溶液中で、100〜300Vの電位を印
加し、約10〜約60分間の範囲の間行われるものであることを特徴とする上記〔１〕〜〔４〕のいずれか一に記載の方法。
〔６〕陽極酸化が、電流約180〜220mAで、電流密度45〜55mA/cm2の条件下に行われるものであることを特徴とする上記〔１〕〜〔５〕のいずれか一に記載の方法。
〔７〕熱処理が、400〜500℃の範囲の温度で、約１〜約20時間の期間なされるものであることを特徴とする上記〔１〕〜〔６〕のいずれか一に記載の方法。
〔８〕熱処理が、430〜470℃の範囲の温度で、約４〜約６時間の期間なされるものであることを特徴とする上記〔１〕〜〔７〕のいずれか一に記載の方法。
〔９〕該ルチル型二酸化チタンが、結晶性に優れ、Ｘ線回折におけるルチル110回折線の
半価幅が0.4未満のルチル型二酸化チタンを90％以上含有する二酸化チタン皮膜であるこ
と及び該ルチル型二酸化チタンは、窒素と硫黄がドープされたものであることを特徴とする上記〔１〕〜〔８〕のいずれか一に記載の方法。
〔10〕前記陽極酸化される基板は窒素雰囲気下加熱による窒化あるいはプラズマ窒化処理されたもので、該ルチル型二酸化チタンは、窒素と硫黄がドープされたもので、二酸化チタン中に約0.5〜2.0 at%の窒素と400ppm (0.04%)〜20000ppm (2.0%)の硫黄とを含有して
いることを特徴とする上記〔１〕〜〔９〕のいずれか一に記載の方法。
〔11〕チタンまたはチタン合金からなる基材であって、窒素雰囲気下加熱による窒化あるいはプラズマ窒化処理された基材が用いられてその基材表面に形成されている二酸化チタン皮膜を有する光触媒体であって、Ｘ線回折におけるルチル110回折線の半価幅が0.4未満のルチル型二酸化チタンを90％以上含有すること及び該ルチル型二酸化チタンは、窒素と硫黄がドープされた陽極酸化薄膜であることを特徴とする二酸化チタン可視光応答性光触媒体。
〔12〕該ルチル型二酸化チタンは、可視光領域で高い光触媒活性を示すことを特徴とする上記〔11〕に記載の光触媒体。
〔13〕該ルチル型二酸化チタンは、可視光領域の約440nmの波長の光に対して約30％以上
のメチレンブルー(MB)分解率を示す高い光触媒活性を示すことを特徴とする上記〔11〕又は〔12〕に記載の光触媒体。
Thus, the present invention provides the following.
[1] In a method for producing a photocatalytically active rutile-type titanium dioxide coating material by anodizing the surface of a substrate made of titanium or a titanium alloy, the titanium or titanium alloy of the substrate is subjected to nitriding treatment, and the nitriding treatment A rutile type titanium dioxide coating material that is subjected to anodic oxidation of the base material that has been subjected to the anodic oxidation and heat-treated to exhibit high photocatalytic activity in the visible light region and is doped with nitrogen and sulfur A method for producing a photocatalytic rutile-type titanium dioxide excellent in visible light responsiveness.
[2] The method according to [1], wherein the nitriding is nitriding by heating in a nitrogen atmosphere or plasma nitriding.
[3] The nitriding treatment is performed at a treatment temperature of 350 to 850 ° C. and 200 to 1000 Pa in the presence of a nitrogen-containing gas.
The method according to [1] or [2] above, wherein plasma nitriding is performed in a range of 10 minutes to 24 hours under a gas pressure condition of
[4] The nitriding treatment is performed using a volume ratio of a mixed gas of nitrogen and hydrogen N 2 : H 2 = approximately 1.2: 0.8 to N 2 : H 2 =
It is characterized by plasma nitriding in the range of 1.5 to 3.5 hours in the presence of nitrogen source gas, which is approximately 1: 4, at a processing temperature of 650 to 750 ° C. and a gas pressure of 450 to 1000 Pa. The method according to any one of [1] to [3] above.
[5] The anodization is performed in a sulfuric acid aqueous solution having a sulfuric acid concentration of 0.02 to 1.6 mol / L by applying a potential of 100 to 300 V for a range of about 10 to about 60 minutes. The method according to any one of [1] to [4] above.
[6] The method according to any one of [1] to [5] above, wherein the anodization is performed under a current density of 45 to 55 mA / cm 2 at a current of about 180 to 220 mA. the method of.
[7] The method according to any one of [1] to [6] above, wherein the heat treatment is performed at a temperature in the range of 400 to 500 ° C. for a period of about 1 to about 20 hours. .
[8] The method according to any one of [1] to [7], wherein the heat treatment is performed at a temperature in the range of 430 to 470 ° C. for a period of about 4 to about 6 hours. .
[9] The rutile-type titanium dioxide is a titanium dioxide film containing 90% or more of rutile-type titanium dioxide having excellent crystallinity and having a half-value width of rutile 110 diffraction line in X-ray diffraction of less than 0.4, and the rutile The method according to any one of [1] to [8] above, wherein the titanium dioxide is doped with nitrogen and sulfur.
[10] The substrate to be anodized is nitrided by heating or plasma nitriding in a nitrogen atmosphere, and the rutile titanium dioxide is doped with nitrogen and sulfur, and about 0.5 to 2.0 in titanium dioxide. The method according to any one of [1] to [9] above, which contains at% nitrogen and 400 ppm (0.04%) to 20000 ppm (2.0%) sulfur.
[11] A photocatalyst having a titanium dioxide film formed on a surface of a base material made of titanium or a titanium alloy, wherein the base material is subjected to nitriding or plasma nitriding treatment by heating in a nitrogen atmosphere. 90% or more of rutile type titanium dioxide having a half-value width of rutile 110 diffraction line of less than 0.4 in X-ray diffraction, and the rutile type titanium dioxide is an anodized thin film doped with nitrogen and sulfur A titanium dioxide visible light responsive photocatalyst characterized by the above.
[12] The photocatalyst described in [11] above, wherein the rutile titanium dioxide exhibits high photocatalytic activity in the visible light region.
[13] The rutile-type titanium dioxide exhibits a high photocatalytic activity exhibiting a decomposition rate of methylene blue (MB) of about 30% or more with respect to light having a wavelength of about 440 nm in the visible light region [11] Or the photocatalyst as described in [12].
本発明では、工業的生産に適しており、且つ、簡単な手法で、均一で緻密なものとして、光触媒活性に優れた二酸化チタン薄膜を有する基材であって、さらに可視光に対する応答性に優れている二酸化チタン薄膜を有する基材が製造でき、当該二酸化チタン薄膜は、窒素と硫黄がドープされた陽極酸化薄膜であり、当該基材は、製造コストの点で有利なもので且つ膜が剥離する可能性もなくて、耐久性に優れると考えられ、光触媒として可視光応答性が優れるので、医療分野、室内の壁材などの分野、ビル外壁および屋根に使用されるチタン製建造物や資材、厨房ダクトなどの各種広範な用途に対して非常に有用である。
本発明のその他の目的、特徴、優秀性及びその有する観点は、以下の記載より当業者にとっては明白であろう。しかしながら、以下の記載及び具体的な実施例等の記載を含めた本件明細書の記載は本発明の好ましい態様を示すものであり、説明のためにのみ示されているものであることを理解されたい。本明細書に開示した本発明の意図及び範囲内で、種々の変化及び／又は改変（あるいは修飾）をなすことは、以下の記載及び本明細書のその他の部分からの知識により、当業者には容易に明らかであろう。本明細書で引用されている全ての特許文献及び参考文献は、説明の目的で引用されているもので、それらは本明細書の一部としてその内容はここに含めて解釈されるべきものである。
In the present invention, it is a base material having a titanium dioxide thin film excellent in photocatalytic activity, which is suitable for industrial production and is simple and uniform, and has excellent photocatalytic activity, and further has excellent responsiveness to visible light. The titanium dioxide thin film can be manufactured, and the titanium dioxide thin film is an anodized thin film doped with nitrogen and sulfur. The substrate is advantageous in terms of manufacturing cost and the film is peeled off. Titanium structures and materials used in fields such as the medical field, indoor wall materials, building exterior walls and roofs, because they are considered durable and have excellent visible light responsiveness as photocatalysts. It is very useful for a wide variety of applications such as kitchen ducts.
Other objects, features, excellence and aspects of the present invention will be apparent to those skilled in the art from the following description. However, it is understood that the description of the present specification, including the following description and the description of specific examples and the like, show preferred embodiments of the present invention and are presented only for explanation. I want. Various changes and / or modifications (or modifications) within the spirit and scope of the present invention disclosed herein will occur to those skilled in the art based on the following description and knowledge from other parts of the present specification. Will be readily apparent. All patent documents and references cited herein are cited for illustrative purposes and are not to be construed as a part of this specification. is there.
本発明は、陽極酸化法を用いて可視光領域において高い光触媒活性を有している二酸化チタン薄膜をチタンまたはチタン合金の基材上にコーティングする方法並びに該方法で得られた可視光領域に高い光触媒活性を持つ二酸化チタン薄膜被覆チタンまたはチタン合金の基材を提供する。
本発明は、硫黄のみならず窒素もドープされたルチル構造の二酸化チタン薄膜で被覆されたチタンまたはチタン合金基材が、可視光領域でも高い光触媒活性を持つこと、そして当該材料が、基板との密着強度が強く剥離しにくい材料作製手法として利点を有し且つ経済性に優れた陽極酸化法で得ることができるとの知見も利用している。本発明では、さらに、陽極酸化法で形成された二酸化チタン膜、所定の熱処理を施すことで、可視光応答性の光触媒活性が高いという性質をはじめとした優れた機能（例えば、超親水性と酸化分解性能の二つの機能を同時に満たしているなどを含めてよい高機能）の膜の製造が可能となるとの知見も利用している。
The present invention relates to a method for coating a titanium dioxide thin film having a high photocatalytic activity in the visible light region on the substrate of titanium or a titanium alloy by using an anodic oxidation method, and a high visible light region obtained by the method. A titanium dioxide thin film-coated titanium or titanium alloy substrate having photocatalytic activity is provided.
The present invention relates to the fact that a titanium or titanium alloy base material coated with a rutile titanium dioxide thin film doped not only with sulfur but also with nitrogen has a high photocatalytic activity even in the visible light region, and that the material is in contact with the substrate. The knowledge that it can be obtained by an anodic oxidation method which has an advantage as a method for producing a material having high adhesion strength and is difficult to peel off and is excellent in economy is also utilized. In the present invention, a titanium dioxide film formed by an anodic oxidation method, and a predetermined heat treatment are performed so that an excellent function including a property of high photocatalytic activity of visible light response (for example, super hydrophilicity and It also utilizes the knowledge that it is possible to produce a high-performance membrane that may include the simultaneous fulfillment of two functions of oxidative decomposition performance.
本発明において用いられる基材は、チタン含有金属材料からなるものが挙げられ、該基材としてはチタン（純チタンを含む）またはチタン合金からなるものが包含される。チタン合金とは、チタンを含有する合金を包含するものである。該チタン含有金属材料は、実質的に100％チタンからなる純チタンであってもよく、ここで該「実質的に」とは、本発
明の効果を損なわない程度の不純物、混合物の存在を包含する意味を有するものであってよい。純チタンとしては、例えば、JIS1種、JIS2種、JIS3種、JIS4種、ASTM G1、ASTM G2、ASTM G3、ASTM G4、AMS4902、AMS4900、AMS4901、AMS4921などが挙げられる。典型的な場合では、得られる金属材料の光触媒性能などの性能（超親水性能が含まれてよい）の観点から、成膜部分（表面並びにその近傍など）では基体に使用される合金全体におけるチタン含有量は80％以上であることが望ましい。
Examples of the substrate used in the present invention include those made of a titanium-containing metal material, and examples of the substrate include those made of titanium (including pure titanium) or a titanium alloy. Titanium alloys include alloys containing titanium. The titanium-containing metal material may be pure titanium consisting essentially of 100% titanium, where the “substantially” includes the presence of impurities and a mixture that do not impair the effects of the present invention. It may have the meaning to do. Examples of pure titanium include JIS type 1, JIS type 2, JIS type 3, JIS type 4, ASTM G1, ASTM G2, ASTM G3, ASTM G4, AMS4902, AMS4900, AMS4901, AMS4921, and the like. In a typical case, from the viewpoint of performance (such as superhydrophilic performance) such as photocatalytic performance of the obtained metal material, titanium in the entire alloy used for the substrate is used in the film formation part (surface and its vicinity). The content is desirably 80% or more.
チタンと共に合金を構成する金属は、チタンとの相溶性が良好であれば特に制限はなく、目的に応じて、様々な元素から選択されてよく、当該分野で知られたものを使用してよい。チタン合金としては、例えば、チタン基合金が挙げられ、５族元素(5A族元素)、６族元素(6A族元素)、７族元素(7A族元素)、鉄族元素、白金族元素、11族元素(1B族元素)、14族元素(4B族元素)、３族元素(3A族元素、ランタノイド、アクチノイド、ミッシュメタル
を包含する）よりなる群から選択される元素の少なくとも１種を含有するもの、チタンとの金属間化合物を形成する元素の少なくとも１種を含有するものなどが挙げられる。
The metal constituting the alloy together with titanium is not particularly limited as long as the compatibility with titanium is good, and may be selected from various elements according to the purpose, and those known in the art may be used. . Titanium alloys include, for example, titanium-based alloys, group 5 elements (group 5A elements), group 6 elements (group 6A elements), group 7 elements (group 7A elements), iron group elements, platinum group elements, 11 Contains at least one element selected from the group consisting of group elements (group 1B elements), group 14 elements (group 4B elements), group 3 elements (including group 3A elements, lanthanoids, actinoids, misch metals) And those containing at least one element forming an intermetallic compound with titanium.
チタン合金に配合される代表的な元素としては、５族元素では、例えば、V, Nb, Taな
ど、６族元素では、例えば、Cr, Mo, Wなど、７族元素では、例えば、Mn, Reなど、鉄族
元素では、例えば、Fe, Co, Niなど、白金族元素では、例えば、Ru, Rh, Pd, Os, Ir, Ptなど、11族元素では、例えば、Cu, Ag, Auなど、14族元素では、例えば、Si, Sn, Pbなど、３族元素では、Y, La, Ce, Nd, Sm, Tb, Er, Yb, Acなどが挙げられ、それらは単独あ
るいは複数のものをTiに対して配合されているものでよい。典型的な場合、本発明で用いる好ましいチタン合金としては、例えばMo, Nb, Ta, V, Ag, Co, Cr, Cu, Fe, Mn, Ni, Pb, Si, Wの元素の少なくとも１種を合金元素として含有するチタン合金が挙げられる。
Typical elements to be blended in the titanium alloy include, for example, V, Nb, Ta, etc. for Group 5 elements, for example, Cr, Mo, W, etc. for Group 6, for example, Mn, For iron group elements such as Re, for example, Fe, Co, Ni, etc.For platinum group elements, for example, Ru, Rh, Pd, Os, Ir, Pt, etc., for Group 11 elements, for example, Cu, Ag, Au, etc. Examples of group 14 elements include Si, Sn, and Pb. Examples of group 3 elements include Y, La, Ce, Nd, Sm, Tb, Er, Yb, and Ac. It may be blended with Ti. In a typical case, preferable titanium alloys used in the present invention include, for example, at least one element of Mo, Nb, Ta, V, Ag, Co, Cr, Cu, Fe, Mn, Ni, Pb, Si, and W. The titanium alloy contained as an alloy element is mentioned.
代表的なチタン合金としては、当該分野で知られたものを使用してよく、例えば、Ti-Nb-Sn合金、Ti-Fe-O合金、Ti-Fe-O-Si合金、Ti-Pd合金、Ti-Ni-Pd-Ru-Cr合金、Ti-Al-V合
金、Ti-Al-Sn-Zr-Mo合金、Ti-Al-Mo-V-Fe-Si-C合金、Ti-V-Cr-Sn-Al合金、Ti-Mo-Zr-Al合金、Ti-Mo-Ni合金、Ti-Ta合金、Ti-Al-Sn合金、Ti-Al-Mo-V合金、Ti-Al-Sn-Zn-Mo-Si-C-Ta合金、Ti-Al-Nb-Ta合金、Ti-Al-V-Sn合金、Ti-Al-Sn-Zr-Cr-Mo合金、Ti-V-Fe-Al合金、Ti-V-Cr-Al合金、Ti-V-Sn-Al-Nb合金、Ti-Al-Nb合金、Ti-Al-V-S合金などが挙げられる。
例えば、Ti-5Al-2.5Sn合金、Ti-6Al-4V合金、Ti-15Mo-5Zr-3Al合金等の如きチタン合金を使用することができる。
As typical titanium alloys, those known in the art may be used, for example, Ti-Nb-Sn alloy, Ti-Fe-O alloy, Ti-Fe-O-Si alloy, Ti-Pd alloy. , Ti-Ni-Pd-Ru-Cr alloy, Ti-Al-V alloy, Ti-Al-Sn-Zr-Mo alloy, Ti-Al-Mo-V-Fe-Si-C alloy, Ti-V-Cr -Sn-Al alloy, Ti-Mo-Zr-Al alloy, Ti-Mo-Ni alloy, Ti-Ta alloy, Ti-Al-Sn alloy, Ti-Al-Mo-V alloy, Ti-Al-Sn-Zn -Mo-Si-C-Ta alloy, Ti-Al-Nb-Ta alloy, Ti-Al-V-Sn alloy, Ti-Al-Sn-Zr-Cr-Mo alloy, Ti-V-Fe-Al alloy, Ti-V-Cr-Al alloy, Ti-V-Sn-Al-Nb alloy, Ti-Al-Nb alloy, Ti-Al-VS alloy and the like can be mentioned.
For example, a titanium alloy such as Ti-5Al-2.5Sn alloy, Ti-6Al-4V alloy, Ti-15Mo-5Zr-3Al alloy can be used.
本発明技術では、チタンまたはチタン合金からなる金属基材は、予め、板状や箔等あるいは目的とする使用形態に適合した所望の形状（チタン又はチタン合金メッキされたものも包含する）に加工したのち、窒化処理、その後の陽極酸化処理に付される。金属基材の形状は、特に限定されるものではなく、板状、棒状、円柱状、網状、繊維状、多孔質状（スポンジ状）、粉体や繊維を圧縮加工してなる成形体、塊状物等を用いることもできる。所望の形状に成形加工したものは、通常、表面洗浄を施された後、窒化処理に付される。該基材は、窒化処理や陽極酸化処理を行う前に、熱処理等の前処理を施してあってもよい。 In the technology of the present invention, a metal substrate made of titanium or a titanium alloy is processed into a desired shape (including those plated with titanium or a titanium alloy) in advance, such as a plate shape or foil, or an intended use form. After that, it is subjected to nitriding treatment and subsequent anodic oxidation treatment. The shape of the metal substrate is not particularly limited, and is a plate shape, rod shape, columnar shape, net shape, fiber shape, porous shape (sponge shape), a compact formed by compressing powder or fiber, or a lump shape. A thing etc. can also be used. What is molded into a desired shape is usually subjected to nitriding after surface cleaning. The substrate may be subjected to pretreatment such as heat treatment before nitriding or anodizing.
本発明技術では、チタンまたはチタン合金基材は、窒素ドープされた二酸化チタン薄膜層を基材に形成することを保障するため、窒化処理される。窒化処理は、基板チタンまたはチタン合金に、窒化物を形成しない程度に施されるのが望ましい。本発明で適用される窒化処理は、窒素雰囲気下加熱による窒化あるいはプラズマ窒化である。チタンまたはチタン合金基材は、純窒素ガス(N2)中で高温保持すれば窒化され、例えば、温度としては、800〜1000℃程度が挙げられる。当該プラズマ窒化は、金属材料の分野でプラズマ窒化プ
ロセスとして知られたプロセス並びにそのための装置を使用して行うことができる。プラズマ窒化法は、荷電された粒子・イオンと電子からなるプラズマ状態を利用しておこなう窒化法であり、イオン化されたガスの原子あるいは分子を利用する。プラズマ窒化では、窒化速度は迅速であり、雰囲気のガス組成を調整することによりターゲット材料の表面に形成される窒化層の組成のコントロールも可能であり、適切な処理を加えることで、ターゲット材料の表面に酸化皮膜をきたすことなく窒化できる。プラズマイオンは、陰極側にあるターゲット試料に対して加速されて、運動エネルギーを有する窒素イオンが試料表面に入ることとなる。該プラズマ窒化プロセスでは、通常、真空ポンプで排気した放電処理炉に窒素ガス(N2)と水素ガス(H2)との混合ガスを導入し、ガス圧を所定の圧力に設定し、処理試料を陰極として、数百ボルトの直流電圧を印加し、グロー放電を発生させることにより、窒化を行う。
In the present technique, the titanium or titanium alloy substrate is nitrided to ensure that a nitrogen-doped titanium dioxide thin film layer is formed on the substrate. The nitriding treatment is desirably performed to the extent that nitride is not formed on the substrate titanium or titanium alloy. The nitriding treatment applied in the present invention is nitriding by heating in a nitrogen atmosphere or plasma nitriding. The titanium or titanium alloy base material is nitrided if kept at a high temperature in pure nitrogen gas (N 2 ). For example, the temperature may be about 800 to 1000 ° C. The plasma nitridation can be performed using a process known as a plasma nitridation process in the field of metal materials and an apparatus therefor. The plasma nitriding method is a nitriding method that uses a plasma state composed of charged particles / ions and electrons, and uses atoms or molecules of ionized gas. In plasma nitridation, the nitriding rate is rapid, and the composition of the nitride layer formed on the surface of the target material can be controlled by adjusting the gas composition of the atmosphere. Nitridation can be performed without causing an oxide film on the surface. The plasma ions are accelerated with respect to the target sample on the cathode side, and nitrogen ions having kinetic energy enter the sample surface. In the plasma nitriding process, a mixed gas of nitrogen gas (N 2 ) and hydrogen gas (H 2 ) is usually introduced into a discharge treatment furnace evacuated by a vacuum pump, the gas pressure is set to a predetermined pressure, and a processed sample Nitriding is performed by applying a direct current voltage of several hundred volts and generating glow discharge.
本発明のプラズマ窒化における一つの具体的な態様では、処理温度としては、例えば、350〜850℃であり、好ましくは500〜800℃であり、より好ましくは600〜750℃である。プラズマ源の放電領域、加速領域、そして、窒化処理槽は、真空ポンプなどを使用して、真空に近い状態、例えば、数Pa程度の真空状態とされてから、そこに処理用ガス、すなわち、窒素源のプラズマ用原料ガスが、所要の圧力となるように導入される。上記真空状態は、上述の範囲を好適に使用できるが、これに限定されるものではない。
該窒素源のプラズマ用原料ガスとしては、窒素含有のガス、例えば、純窒素ガス、窒素と水素の混合ガス、窒素ガスとアルゴンガスとの混合ガス、窒素ガスと水素ガスとアルゴンガスとの混合ガスなどを使用できる。窒素と水素の混合ガスの容量比は、望ましい結果が得られる限り特に限定されることなく適切に選択できるが、典型的な場合、N2/H2=10/1〜1/100の範囲から適宜選択でき、例えば、N2/H2=5/1〜1/5の範囲を選ぶことができ、好
ましくはN2/H2=2/1〜1/2の範囲であり、特に好ましくはN2:H2=おおよそ1:1である。
In one specific embodiment of the plasma nitriding according to the present invention, the processing temperature is, for example, 350 to 850 ° C, preferably 500 to 800 ° C, more preferably 600 to 750 ° C. The discharge region of the plasma source, the acceleration region, and the nitriding treatment tank are brought into a state close to vacuum using a vacuum pump or the like, for example, a vacuum state of about several Pa, and then a processing gas, that is, A nitrogen source plasma source gas is introduced so as to have a required pressure. Although the above-mentioned range can use the above-mentioned range suitably, it is not limited to this.
The nitrogen source plasma source gas includes nitrogen-containing gas, for example, pure nitrogen gas, mixed gas of nitrogen and hydrogen, mixed gas of nitrogen gas and argon gas, mixed of nitrogen gas, hydrogen gas and argon gas Gas can be used. The volume ratio of the mixed gas of nitrogen and hydrogen can be appropriately selected without particular limitation as long as a desired result is obtained, but in a typical case, from the range of N 2 / H 2 = 10/1 to 1/100 For example, a range of N 2 / H 2 = 5/1 to 1/5 can be selected, preferably N 2 / H 2 = 2/1 to 1/2, and particularly preferably N 2 : H 2 = approximately 1: 1.
該プラズマ窒化プロセスのターゲット試料は、加熱されていることも可能であり、適宜、外部加熱、内部加熱のいずれも採用可能である。該窒素源のプラズマ用原料ガスの窒化処理槽内でのガス圧としては、望ましい結果が得られる限り特に限定されることなく適切に選択できるが、典型的な場合、200〜1000Paの範囲から適宜選択でき、例えば、350〜750Paの範囲を選ぶことができ、好ましくは400〜650Paの範囲であり、特に好ましくはおお
よそ500Paである。該プラズマ窒化の処理時間は、適用される処理温度、使用窒素源ガス
の種類、ガス圧などのパラメーターに応じて、所望の窒化の程度を勘案して適宜選択され、望ましい結果が得られる限り特に限定されることなく適切に選択できるが、典型的な場合、30分間〜24時間の範囲から適宜選択でき、例えば、１〜10時間の範囲を選ぶことができ、好ましくは1.5〜５時間の範囲であり、特に好ましくはおおよそ３時間である。
本プラズマ窒化プロセスは、当該分野で知られた装置あるいは当該分野で入手可能な装置、例えば、プラズマ窒化炉、イオン窒化炉などを使用して行うことができるが、所要の目的を達成することのできる装置であればこれらに限定されず使用可能である。
The target sample of the plasma nitriding process can be heated, and either external heating or internal heating can be employed as appropriate. The gas pressure in the nitriding treatment tank of the nitrogen source plasma source gas can be appropriately selected without particular limitation as long as a desired result is obtained, but in a typical case, it is appropriately selected from the range of 200 to 1000 Pa. For example, a range of 350 to 750 Pa can be selected, preferably 400 to 650 Pa, particularly preferably about 500 Pa. The plasma nitriding treatment time is appropriately selected in consideration of the desired degree of nitriding according to parameters such as the applied processing temperature, the type of nitrogen source gas used, and the gas pressure. Although it can select suitably without being limited, typically, it can select suitably from the range of 30 minutes-24 hours, for example, can select the range of 1-10 hours, Preferably it is the range of 1.5-5 hours And particularly preferably about 3 hours.
The plasma nitridation process can be performed using an apparatus known in the art or an apparatus available in the art, for example, a plasma nitriding furnace, an ion nitriding furnace, and the like. Any device that can be used can be used without being limited thereto.
本発明では、該窒化チタン含有金属材料を電圧印加の下に陽極酸化処理することにより、基体上にルチル型二酸化チタンを含む陽極酸化膜が形成され、このルチル型二酸化チタンが可視光領域における高い光触媒活性（及び／又は超親水性）を有するといったものが得られるのである。別の態様では、当該窒化チタン含有金属材料を高電流密度条件下に陽極酸化処理することにより、基体上にルチル型二酸化チタンを含む陽極酸化膜が形成され、このルチル型二酸化チタンが可視光領域における高い光触媒活性（及び／又は超親水性）を有するものが得られる。本陽極酸化処理では、均一で緻密な処理が可能で、複雑な形状でも簡単に処理しうるし、光触媒活性を有する層の強度に優れる。 In the present invention, the titanium nitride-containing metal material is anodized under voltage application to form an anodized film containing rutile type titanium dioxide on the substrate, and this rutile type titanium dioxide is high in the visible light region. Those having photocatalytic activity (and / or super hydrophilicity) can be obtained. In another embodiment, the titanium nitride-containing metal material is anodized under a high current density condition to form an anodized film containing rutile titanium dioxide on the substrate, and the rutile titanium dioxide has a visible light region. Having a high photocatalytic activity (and / or superhydrophilicity) is obtained. In this anodizing treatment, uniform and precise treatment is possible, even complex shapes can be easily treated, and the strength of the layer having photocatalytic activity is excellent.
本発明技術では、基材の陽極酸化は、酸性溶液中で行われる。代表的な酸性溶液としては、希硫酸水溶液などの希薄鉱酸水溶液が挙げられる。希硫酸水溶液における硫酸の濃度としては、所要の結果が得られるものを選択でき、例えば、0.02〜1.6mol/L、より好ましくは1.0〜1.5mol/Lで行うのがよく、さらに好ましくは1.1〜1.3mol/L、もっと好ましくはおおよそ1.2mol/Lで行うのがよい。別の態様では、希硫酸水溶液における硫酸の濃度としては、8.8〜12.3重量%(wt%)、あるいは、8.8〜11.4重量%(wt%)、より好ましくは9.7〜11.4重量%で行うのがよく、さらに好ましくは約10.5重量%で行うのがよい。 In the technique of the present invention, the anodic oxidation of the substrate is performed in an acidic solution. Typical acidic solutions include dilute mineral acid aqueous solutions such as dilute sulfuric acid aqueous solution. As the concentration of sulfuric acid in the dilute sulfuric acid aqueous solution, one that can achieve the required result can be selected, for example, 0.02 to 1.6 mol / L, more preferably 1.0 to 1.5 mol / L, and even more preferably 1.1 to 1.5 mol / L. It should be carried out at 1.3 mol / L, more preferably at approximately 1.2 mol / L. In another embodiment, the concentration of sulfuric acid in the dilute sulfuric acid aqueous solution is 8.8 to 12.3 wt% (wt%), or 8.8 to 11.4 wt% (wt%), more preferably 9.7 to 11.4 wt%. More preferably, it is carried out at about 10.5% by weight.
陽極酸化の際の極間の電圧は、例えば、50〜500V、より好ましくは100〜500V、さらに
好ましくは150〜500Vの電位で行うのがよく、さらには、好ましくは160〜500V、もっと好ましくは210〜450Vの電位で行うのがよい。ある場合には、該陽極酸化処理は、100〜400V、より好ましくは150〜400Vの電位で行うのがよく、別の態様では、100〜350V、もっと好ましくは150〜300Vの電位で行うものであってよい。該陽極酸化処理は、200〜400V、より好ましくは200〜350Vの電位で行うことがよい場合もあり、さらには、好ましくは200〜275V、もっと好ましくは200〜250Vの電位で行うものであってよい。
本陽極酸化処理は、１分間〜50時間、好ましくは２分間〜24時間、さらに好ましくは３分間〜12時間行うものであってよく、さらには９分間〜5時間あるいは10分間〜3時間行うものであってよいし、さらには20分間〜3時間行うものであってよい。
The voltage between the electrodes at the time of anodization is, for example, 50 to 500 V, more preferably 100 to 500 V, more preferably 150 to 500 V, more preferably 160 to 500 V, more preferably It is good to carry out at the potential of 210-450V. In some cases, the anodization treatment may be performed at a potential of 100-400V, more preferably 150-400V, and in another embodiment, at a potential of 100-350V, more preferably 150-300V. It may be. In some cases, the anodizing treatment may be performed at a potential of 200 to 400 V, more preferably 200 to 350 V, and more preferably 200 to 275 V, more preferably 200 to 250 V. Good.
This anodizing treatment may be performed for 1 minute to 50 hours, preferably 2 minutes to 24 hours, more preferably 3 minutes to 12 hours, and further 9 minutes to 5 hours or 10 minutes to 3 hours. Or may be performed for 20 minutes to 3 hours.
別の態様としては、電圧を上げる代わりに電流密度を高めることができる。電流密度は電流値と試料表面積で算出される。本陽極酸化の際の電流密度としては、所要の結果が得られるものを選択でき、例えば、少なくとも25mA/cm2以上であればよいが、好適に、30mA/cm2以上としてもよいし、さらに50mA/cm2以上でも好ましい結果が得られ、70mA/cm2以上が望ましい場合もあり、100mA/cm2以上としてもよい。高い電流密度を採用できる場合に
は、化成電圧を、例えば、100〜500Vとすることができるし、さらに、120〜500Vとしてもよく、また150〜500Vの電位で行ってよいし、さらには、好ましくは180〜500V、もっと好ましくは200〜450Vの電位で行ってもよい。本態様では、該陽極酸化処理は、１分間〜100
時間、好ましくは２分間〜48時間、さらに好ましくは３分間〜12時間行うものであってよく、さらには９分間〜5時間あるいは10分間〜3時間行うものであってよいし、さらには20分間〜3時間行うものであってよい。
As another aspect, the current density can be increased instead of increasing the voltage. The current density is calculated from the current value and the sample surface area. The current density during the anodic oxidation, can select those required results, for example, it may be at least 25mA / cm 2 or more, but preferably, may be 30 mA / cm 2 or more, further Preferred results are obtained even at 50 mA / cm 2 or higher, and 70 mA / cm 2 or higher may be desirable, or may be 100 mA / cm 2 or higher. When a high current density can be adopted, the formation voltage can be set to, for example, 100 to 500 V, or 120 to 500 V, or a potential of 150 to 500 V. It may be carried out at a potential of preferably 180 to 500V, more preferably 200 to 450V. In this embodiment, the anodizing treatment is performed for 1 minute to 100.
Time, preferably 2 minutes to 48 hours, more preferably 3 minutes to 12 hours, more preferably 9 minutes to 5 hours, or 10 minutes to 3 hours, or even 20 minutes It may be performed for ~ 3 hours.
陽極酸化は、通常、室温で行われる。陽極酸化処理は、直流、交直重畳、又はパルス波を印加して行ってよい。又は、サイリスタ方式による直流電源を用いて、単相半波、三相半波、六相半波を印加して行うことも可能である。
本陽極酸化処理によれば、微細で均一な表面酸化が可能なため、複雑な形状の金属材料も、均一で、且つ、すぐれた光触媒機能や超親水性能を持つものに簡単に加工することができる。酸化電圧をコントロールすることにより、形成される陽極酸化膜の膜厚を様々に制御することもできる。また、酸化時の電流密度をコントロールすることにより、形成される陽極酸化膜の膜厚を様々に制御することもできる。本陽極酸化処理は、非常に簡便な方法であり、且つ、大面積を有する表面への成膜が容易であり、便利である。しかも、複雑な形状の基板に対しても成膜が可能であり、工業的に有用な方法である。
Anodization is usually performed at room temperature. The anodizing treatment may be performed by applying direct current, AC / DC superimposition, or a pulse wave. Alternatively, a single-phase half-wave, a three-phase half-wave, and a six-phase half-wave can be applied using a thyristor type DC power supply.
Since this anodizing treatment enables fine and uniform surface oxidation, it is possible to easily process even complex metal materials with uniform, excellent photocatalytic function and superhydrophilic performance. it can. By controlling the oxidation voltage, the thickness of the formed anodic oxide film can be variously controlled. In addition, by controlling the current density during oxidation, the thickness of the formed anodic oxide film can be controlled in various ways. This anodizing treatment is a very simple method and is easy to form a film on a surface having a large area and is convenient. Moreover, it is possible to form a film on a substrate having a complicated shape, which is an industrially useful method.
典型的な態様では、プラズマ窒化処理及びその後の陽極酸化処理は、次のようにされる。まず、所望の形状に成形され、前処理を施されたチタン含有金属材料からなる成形体（例えば、板状をなす基材）は、プラズマ窒化炉に配置され、真空ポンプで炉内の排気を行った後、窒素と水素の混合ガスの容量比N2:H2=おおよそ1.2:0.8〜N2:H2=おおよそ1:4である窒素源のガス（代表的には、窒素と水素の混合ガスの容量比N2:H2=おおよそ1:1である
窒素源のガス）を導入する。プラズマ窒化の条件を、圧力おおよそ450〜1000Paの範囲（
代表的には、圧力おおよそ500Pa）、電圧おおよそ550V、処理温度おおよそ650〜750℃（
代表的には、処理温度おおよそ700℃）として、おおよそ1.5〜3.5時間の範囲（代表的に
は、おおよそ３時間）窒化せしめる。表面をプラズマ窒化せしめたチタン含有金属試料は、次に、アノードに接続され、カソードには純チタンかステンレスあるいは白金を素材とし、板か棒あるいはメッシュの形状の金属が接続される。セル中には、適当な電解質を含有する水溶液（おおよそ0.02〜1.6mol/Lの硫酸濃度の硫酸水溶液、典型的な本態様においてはおおよそ1.2mol/L硫酸水溶液）が満たされ、前記成形体と純チタンかステンレスあるいは白金を素材とし、板か棒あるいはメッシュの形状の金属が浸漬されている。電圧計、電流計を観察して、直流電流を調整しながら、直流電力供給装置により電力を供給して、電圧約210〜500V程度（電流密度が少なくとも25mA/cm2以上の場合では電圧約120〜500V程度）で、陽極酸化処理を行う。すなわち、得られた金属材料成形体を、陽極酸化処理装置のアノードに取り付けて、1.2mol/L硫酸水溶液中で、電圧210〜500Vで陽極酸化処理（あ
るいは少なくとも25mA/cm2以上の電流密度条件下で陽極酸化処理）を行って、金属材料、特にそこに含まれるチタンを酸化し、表面にルチル型二酸化チタン膜（陽極酸化膜）を形成させるものである。本陽極酸化された基材は、通常、十分に水洗される。また、該基材は、メタノール、エタノール、アセトンなどの有機溶媒で洗浄されてもよい。
In a typical embodiment, the plasma nitridation process and the subsequent anodization process are as follows. First, a molded body (for example, a plate-like base material) made of a titanium-containing metal material that has been formed into a desired shape and pretreated is placed in a plasma nitriding furnace, and the exhaust inside the furnace is evacuated by a vacuum pump. After performing the nitrogen source gas volume ratio N 2 : H 2 = approximately 1.2: 0.8 to N 2 : H 2 = approximately 1: 4 (typically the nitrogen and hydrogen gas The volume ratio of the mixed gas N 2 : H 2 = a nitrogen source gas that is approximately 1: 1) is introduced. Plasma nitriding conditions are set to a pressure range of approximately 450 to 1000 Pa (
Typically, the pressure is approximately 500 Pa, the voltage is approximately 550 V, the processing temperature is approximately 650 to 750 ° C. (
Typically, nitriding is performed at a processing temperature of approximately 700 ° C. in a range of approximately 1.5 to 3.5 hours (typically approximately 3 hours). The titanium-containing metal sample whose surface is plasma-nitrided is then connected to the anode, and the cathode is made of pure titanium, stainless steel, or platinum, and a metal in the form of a plate, bar, or mesh is connected. The cell is filled with an aqueous solution containing an appropriate electrolyte (a sulfuric acid aqueous solution having a sulfuric acid concentration of approximately 0.02 to 1.6 mol / L, typically approximately 1.2 mol / L sulfuric acid aqueous solution in this embodiment), and Pure titanium, stainless steel, or platinum is used as a material, and a metal in the form of a plate, a bar, or a mesh is immersed therein. While observing the voltmeter and ammeter and adjusting the DC current, power is supplied by the DC power supply device, and the voltage is about 210 to 500 V (when the current density is at least 25 mA / cm 2 or more, the voltage is about 120 Anodizing is performed at about 500V). That is, the obtained metal material molded body is attached to the anode of an anodizing apparatus and anodized at a voltage of 210 to 500 V in a 1.2 mol / L sulfuric acid aqueous solution (or at least a current density condition of 25 mA / cm 2 or more). Anodization is performed below to oxidize a metal material, particularly titanium contained therein, to form a rutile titanium dioxide film (anodized film) on the surface. The anodized substrate is usually sufficiently washed with water. Further, the substrate may be washed with an organic solvent such as methanol, ethanol, or acetone.
また、本発明技術では、該陽極酸化後に行われる熱処理は、酸化性雰囲気中300〜1000
℃、より好ましくは300〜1000℃、さらにより好ましくは400〜600℃の温度範囲で行うこ
とが望ましい。該温度域における保持時間は30分間〜20時間程度であるが、好ましい保持時間は1〜10時間程度であって、より好ましくは、熱処理が400℃程度で行われる場合、30分間〜10時間程度であり、熱処理が450℃程度で行われる場合、30分間〜5時間程度であり、典型的には約3時間程度である。酸化性雰囲気は、特に限定されないが、典型的には酸
素が存在する雰囲気であり、通常は大気雰囲気が挙げられる。本熱処理で、金属材料基体の表面に形成された陽極酸化膜を固定化し、強度、密着性を向上させ、且つ、光触媒特性や超親水性の特性を向上させることができる。本発明によると、基材の種類や形状、陽極酸化条件および熱処理条件を適宜変更することによって、種々の特徴を有する光触媒材料を製造することが可能である。
In the technique of the present invention, the heat treatment performed after the anodic oxidation is performed in an oxidizing atmosphere at 300 to 1000.
It is desirable to carry out in a temperature range of ° C, more preferably 300 to 1000 ° C, and still more preferably 400 to 600 ° C. The holding time in the temperature range is about 30 minutes to 20 hours, but the preferable holding time is about 1 to 10 hours, more preferably about 30 minutes to 10 hours when the heat treatment is performed at about 400 ° C. When the heat treatment is performed at about 450 ° C., it is about 30 minutes to 5 hours, and typically about 3 hours. The oxidizing atmosphere is not particularly limited, but is typically an atmosphere in which oxygen is present, and usually includes an air atmosphere. With this heat treatment, the anodic oxide film formed on the surface of the metal material substrate can be fixed, strength and adhesion can be improved, and photocatalytic properties and superhydrophilic properties can be improved. According to the present invention, it is possible to produce photocatalytic materials having various characteristics by appropriately changing the type and shape of the substrate, the anodizing conditions, and the heat treatment conditions.
本発明方法の代表的な態様では、上記したようなチタンまたはチタン合金からなる基材は、まず、プラズマ窒化装置にて、窒素ガスと水素ガスとの混合ガスを原料ガスとして使用し、容量比N2:H2=おおよそ1.2:0.8〜N2:H2=おおよそ1:4の雰囲気（例えば、H2:N2=おおよそ1:1の雰囲気）、ガス圧力450〜550Pa、例えば、約500Paのプラズマ窒化の条件にて、650〜750℃で1.5〜3.5時間処理して、例えば、約700℃で約2.0時間あるいは約3.0時間処
理し、チタンまたはチタン合金基板をプラズマ窒化する。次に、プラズマ窒化せしめられた基材は、約0.1〜約1.6mol/Lまでの濃度の硫酸水溶液中で、その表面に約150〜約300Vまでの電圧を約20分間〜約1時間の間印加して陽極酸化を施し、次に得られた該基材上成膜
に約400〜約500℃までの温度で、約1〜約20時間の間熱処理を施して、結晶性に優れたル
チル型二酸化チタンを製造する方法が提供される。
In a typical embodiment of the method of the present invention, a substrate made of titanium or a titanium alloy as described above is first used in a plasma nitriding apparatus using a mixed gas of nitrogen gas and hydrogen gas as a raw material gas, N 2: H 2 = approximate 1.2: 0.8~N 2: H 2 = approximately 1: 4 atmosphere (e.g., H 2: N 2 = approximately 1: 1 atmosphere), the gas pressure 450～550Pa, for example, about 500Pa The plasma nitriding is performed at 650 to 750 ° C. for 1.5 to 3.5 hours, for example, at about 700 ° C. for about 2.0 hours or about 3.0 hours to plasma nitride the titanium or titanium alloy substrate. Next, the plasma nitrided substrate is subjected to a voltage of about 150 to about 300 V on its surface in an aqueous sulfuric acid solution having a concentration of about 0.1 to about 1.6 mol / L for about 20 minutes to about 1 hour. Applying anodization, and then subjecting the resulting film on the substrate to a heat treatment at a temperature of about 400 to about 500 ° C. for about 1 to about 20 hours to produce rutile having excellent crystallinity A method of producing a type titanium dioxide is provided.
また、本発明の別の代表的な態様では、上記チタンまたはチタン合金からなる基材は、プラズマ窒化装置にて、窒素ガスと水素ガスとの混合ガスを原料ガスとして使用し、例えば、H2:N2=おおよそ1:1の雰囲気、ガス圧力、例えば、約500Paのプラズマ窒化の条件にて、例えば、約700℃で約2.0時間あるいは約3.0時間処理し、プラズマ窒化されたチタンま
たはチタン合金基板を製造し、次に、該プラズマ窒化された基板を、例えば、約1.0〜約1.3mol/Lまでの濃度の硫酸水溶液中で、その表面に約200〜約220Vまでの高電圧（例えば、電流約180〜220mA、電流密度45〜55mA/cm2）を印加して、約20〜約60分間の間陽極酸化を施し、次に得られた該基材上の成膜に約430〜約470℃の温度で、約2〜約６時間の間熱処
理を施して、結晶性に優れたルチル型二酸化チタンを製造する方法が提供される。
In another exemplary embodiment of the present invention, the base material made of titanium or a titanium alloy uses a mixed gas of nitrogen gas and hydrogen gas as a source gas in a plasma nitriding apparatus, for example, H 2 : N 2 = titanium or titanium alloy that has been plasma-nitrided at about 700 ° C. for about 2.0 hours or about 3.0 hours, for example, under conditions of plasma nitridation of about 500 Pa under an atmosphere and gas pressure of about 1: 1 The substrate is then fabricated, and the plasma nitrided substrate is then applied to its surface at a high voltage (e.g., about 200 to about 220 V) in a sulfuric acid solution having a concentration of about 1.0 to about 1.3 mol / L. A current density of about 180-220 mA, a current density of 45-55 mA / cm 2 ), and anodizing for about 20 to about 60 minutes, and then forming a film on the substrate of about 430-about Heat treatment at 470 ° C for about 2 to about 6 hours to produce rutile titanium dioxide with excellent crystallinity A method of building is provided.
本発明の典型的な態様の一つでは、チタンまたはチタン合金からなる基材の表面に、プラズマ窒化を施し、例えば、プラズマ窒化装置にて、窒素ガスと水素ガスとの混合ガスを原料ガスとして使用し、H2:N2=おおよそ1:1の雰囲気、ガス圧力約500Paのプラズマ窒化の条件にて、約700℃で約2.0時間あるいは約3.0時間処理し、プラズマ窒化されたチタンま
たはチタン合金基板を製造し、次に、該プラズマ窒化された基板を、例えば、約1.2mol/Lの濃度の硫酸水溶液中で、その表面に約210Vの高電圧（例えば、電流約200mA、電流密度
約50mA/cm2）を印加して、約30分間陽極酸化を施し、次に得られた該基材上の成膜に約450℃の温度で、約５時間熱処理を施して、結晶性に優れたルチル型二酸化チタンを製造す
る方法が提供される。
In one of the typical embodiments of the present invention, plasma nitriding is performed on the surface of a substrate made of titanium or a titanium alloy, and a mixed gas of nitrogen gas and hydrogen gas is used as a source gas in a plasma nitriding apparatus, for example. use, H 2: N 2 = approximately 1: 1 atmosphere, under conditions of plasma nitriding gas pressure of about 500 Pa, and at about 700 ° C. to about 2.0 hours or about 3.0 hours, plasma nitrided titanium or titanium alloy A substrate is manufactured, and then the plasma-nitrided substrate is subjected to a high voltage of about 210 V (for example, a current of about 200 mA, a current density of about 50 mA, for example) in a sulfuric acid aqueous solution having a concentration of about 1.2 mol / L. / cm 2 ), and anodized for about 30 minutes, and then the film formed on the substrate was heat-treated at a temperature of about 450 ° C. for about 5 hours to obtain excellent crystallinity. A method for producing rutile titanium dioxide is provided.
本発明は、本明細書で開示の方法で得られ且つ基体上にルチル型二酸化チタン被膜を有し、さらに、特定の優れた光触媒活性、例えば、可視光領域での応答性に優れている光触媒活性を有する材料を提供する。ある場合には、当該材料は、超親水性を有する点でも優れていることが認められよう。当該材料は、図１〜６に示されたデータをその材料の特性値として有するルチル型二酸化チタン被膜をもつ基材である。当該材料の特性値としては、可視光に対する応答性で評価される光触媒能試験で得られる可視光で誘導されるMB分解率が挙げられる。また、当該材料の特性値としては、超親水性性能試験で得られる接触角などであってもよい。
本発明で得られる上記基材の上に形成される結晶性に優れた二酸化チタン薄膜が、ルチル型二酸化チタンであることは、図３より明らかである。本発明で得られる上記結晶性に優れたルチル型二酸化チタンは、薄膜Ｘ線回折におけるルチル110回折線の半価幅が0.4未満のルチル型二酸化チタンを少なくとも85％以上、好ましくは少なくとも90％以上、更に好ましくは少なくとも95％以上、より好ましくは少なくとも96％以上、もっと好ましくは少なくとも97％以上含有するものである。典型的な場合、本発明で得られる当該基体上の上記ルチル型二酸化チタンとは、薄膜Ｘ線回折におけるルチル110回折線の半価幅が0.4未満のルチル型二酸化チタンを98％以上含有する二酸化チタン皮膜である。一つの代表例では、本発明で得られる当該基体上の上記ルチル型二酸化チタンとは、薄膜Ｘ線回折におけるルチル110回折線の半価幅が0.4未満のルチル型二酸化チタンを99％以上含有する二酸化チタン薄膜である。
The present invention is a photocatalyst obtained by the method disclosed herein and having a rutile-type titanium dioxide coating on a substrate, and further excellent in specific photocatalytic activity, for example, responsiveness in the visible light region. An active material is provided. In some cases, it will be appreciated that the material is also superior in that it is superhydrophilic. The material is a base material having a rutile type titanium dioxide film having the data shown in FIGS. 1 to 6 as characteristic values of the material. Examples of the characteristic value of the material include MB decomposition rate induced by visible light obtained by a photocatalytic ability test evaluated by responsiveness to visible light. Further, the characteristic value of the material may be a contact angle obtained by a superhydrophilic performance test.
It is clear from FIG. 3 that the titanium dioxide thin film excellent in crystallinity formed on the base material obtained in the present invention is rutile type titanium dioxide. The rutile titanium dioxide having excellent crystallinity obtained in the present invention is at least 85% or more, preferably at least 90% or more rutile titanium dioxide having a half-value width of rutile 110 diffraction line in thin film X-ray diffraction of less than 0.4. More preferably, it contains at least 95% or more, more preferably at least 96% or more, more preferably at least 97% or more. In a typical case, the rutile type titanium dioxide on the substrate obtained in the present invention refers to a dioxide containing 98% or more of rutile type titanium dioxide having a half width of rutile 110 diffraction line of less than 0.4 in thin film X-ray diffraction. It is a titanium film. In one representative example, the rutile-type titanium dioxide on the substrate obtained in the present invention contains 99% or more of rutile-type titanium dioxide in which the half-value width of the rutile 110 diffraction line in thin film X-ray diffraction is less than 0.4. It is a titanium dioxide thin film.
さらに、本発明で基材上に形成せしめられたルチル型二酸化チタン物質は、優れた可視光応答性を有しており、有用である。該ルチル型二酸化チタン被膜物質は、二酸化チタン中に硫黄と共に窒素がドープされたものであることが見出されている。これまで二酸化チタン形成物に窒素と共に硫黄が添加されたもの、そして、実際に、本発明で得られる製品のように優れた可視光応答性を達成したものは、得られたとの報告はなく、従来のものは、本発明のもののように二酸化チタン中に窒素と共に硫黄がドープされたものとは考え難い。本発明で基材上に形成せしめられたルチル型二酸化チタン被膜物質の幾つかの例の分析から、膜厚は約7μmで、二酸化チタン中の硫黄濃度は、1441ppm(0.144%)までは確実に
ドープされていることが見出されている。こうしたことから、二酸化チタン中の硫黄濃度の上限としては20000ppm (2.0%)程度であり、一方、硫黄濃度の下限としては250ppm (0.025%)以下であり、例えば、200ppm (0.02%)程度であると考えられる。一つの典型的な態様では、本発明で基材上に形成せしめられたルチル型二酸化チタン被膜物質は、硫黄がドープされたもので、二酸化チタン中に400ppm (0.04%)〜10000ppm (1.0%)の硫黄を含有して
いるもので、ある場合には、二酸化チタン中に600ppm (0.06%)〜4000ppm (0.4%)の硫黄を含有しているもので、好ましくは、二酸化チタン中に800ppm (0.08%)〜2000ppm (0.2%)の硫黄を含有しているものである。
Furthermore, the rutile-type titanium dioxide material formed on the substrate in the present invention has an excellent visible light response and is useful. The rutile titanium dioxide coating material has been found to be titanium dioxide doped with nitrogen along with sulfur. There has been no report that a titanium dioxide formed product has been added with sulfur together with nitrogen, and actually has achieved excellent visible light response like the product obtained in the present invention. The conventional one is unlikely to be doped with sulfur together with nitrogen in titanium dioxide as in the present invention. From the analysis of some examples of rutile titanium dioxide coating material formed on a substrate according to the present invention, the film thickness is about 7 μm and the sulfur concentration in titanium dioxide is sure to be up to 1441 ppm (0.144%). It has been found to be doped. Therefore, the upper limit of the sulfur concentration in titanium dioxide is about 20000 ppm (2.0%), while the lower limit of the sulfur concentration is 250 ppm (0.025%) or less, for example, about 200 ppm (0.02%). it is conceivable that. In one exemplary embodiment, the rutile-type titanium dioxide coating material formed on a substrate in the present invention is doped with sulfur and is 400 ppm (0.04%) to 10000 ppm (1.0%) in titanium dioxide. In some cases, the titanium dioxide contains 600 ppm (0.06%) to 4000 ppm (0.4%) sulfur, preferably 800 ppm (0.08%) in the titanium dioxide. %) To 2000 ppm (0.2%) of sulfur.
該二酸化チタン中の窒素濃度は、1.2 at%、1.3 at%から、1.35 at%とか1.6 at%などの
値が得られ、そうした値までは確実にドープされていることが見出されている。こうしたことから、二酸化チタン中の窒素濃度の上限としては2.0 at%程度まで、例えば、約1.7 at%までであり、一方、窒素濃度の下限としては0.5 at%以上、例えば、約1.0 at%以上が好適であるというものであり、例えば、約1.3〜1.65 at%で、より好適な結果がえられるも
のと考えられる。一つの典型的な態様では、本発明で基材上に形成せしめられたルチル型二酸化チタン被膜物質は、窒素と硫黄がドープされたもので、二酸化チタン中に、約0.5
〜2.0 at%の窒素と400ppm (0.04%)〜10000ppm (1.0%)の硫黄を含有しているもので、ある場合には、二酸化チタン中に約1.0〜1.7 at%の窒素と600ppm (0.06%)〜5000ppm (0.5%)の硫黄を含有しているもので、好ましくは、二酸化チタン中に約1.3〜1.65 at%の窒素と800ppm (0.08%)〜2000ppm (0.2%)の硫黄を含有しているものである。
It has been found that the nitrogen concentration in the titanium dioxide ranges from 1.2 at% and 1.3 at% to values such as 1.35 at% and 1.6 at%, and that value is surely doped. Therefore, the upper limit of the nitrogen concentration in titanium dioxide is about 2.0 at%, for example, up to about 1.7 at%, while the lower limit of the nitrogen concentration is 0.5 at% or more, for example, about 1.0 at% or more. For example, it is considered that a more preferable result can be obtained at about 1.3 to 1.65 at%. In one exemplary embodiment, the rutile titanium dioxide coating material formed on a substrate in the present invention is doped with nitrogen and sulfur and is about 0.5% in titanium dioxide.
Contains ~ 2.0 at% nitrogen and 400 ppm (0.04%) to 10000 ppm (1.0%) sulfur, in some cases about 1.0-1.7 at% nitrogen and 600 ppm (0.06%) in titanium dioxide ) To 5000 ppm (0.5%) sulfur, preferably about 1.3 to 1.65 at% nitrogen and 800 ppm (0.08%) to 2000 ppm (0.2%) sulfur in titanium dioxide. It is what.
本発明の方法で得られた光触媒活性を有しかつ優れた超親水性を有するルチル型二酸化チタン薄膜を有する材料は、脱臭、防黴、防汚性、殺菌作用等を示し、防黴、防汚などの効果を有する建築材、空調機器、浄水設備等に用いられる各種部材として有効に活用することができる。
本発明の金属材料の使用方法としては、金属タイルや、内装材としてそのまま使用するほか、本発明の構造を有する金属材料の薄板を作製し、既存の建築材料であるセラミックス、モルタル、硝子、鉄板、アルミ板等に接合して、複合材料として使用することもできる。このように、既存材料の上に接合して用いる方法によれば、光触媒活性を有する金属材料の使用量の低減が可能となり、優れた防臭、殺菌機能等の光触媒活性を有する種々の複合材料を安価に提供できる。
本発明の方法で得られた光触媒活性を有しかつ優れた超親水性を有するルチル型二酸化チタン薄膜を有する材料は、水浄化に使用できる。、当該ルチル型二酸化チタン薄膜によりクリーンな光エネルギーを利用して、水中の希薄な有機物の除去をするといった浄化法を可能とする。
The material having a rutile type titanium dioxide thin film having photocatalytic activity and excellent super hydrophilicity obtained by the method of the present invention exhibits deodorization, antifouling, antifouling properties, bactericidal action, etc. It can be effectively used as various members used in building materials having effects such as dirt, air conditioning equipment, water purification facilities, and the like.
The metal material of the present invention can be used as it is as a metal tile or as an interior material, as well as by producing a thin sheet of metal material having the structure of the present invention, ceramics, mortar, glass, iron plate, which are existing building materials It can also be used as a composite material by bonding to an aluminum plate or the like. As described above, according to the method of joining on the existing material, it is possible to reduce the amount of the metal material having photocatalytic activity, and various composite materials having photocatalytic activity such as excellent deodorization and sterilizing functions can be obtained. Can be provided at low cost.
The material having a rutile-type titanium dioxide thin film having photocatalytic activity and excellent superhydrophilicity obtained by the method of the present invention can be used for water purification. The rutile-type titanium dioxide thin film makes it possible to use a purification method that uses clean light energy to remove dilute organic substances in water.
本発明の方法で得られたルチル型二酸化チタン薄膜を有する材料は、工場プラント用建築資材を含めた各種建築材料やその他の機器、医療用材料などを含めた材料、例えば、建築物の内，外装材、調理用器具、食器類、衛生機器、空調機器、その他下水管等の土木用材料、道路の遮音壁、冷蔵庫などの食品保管庫用材料などに使用できる。本発明で得られる材料の有する光触媒作用を利用し、自浄、空気清浄化、殺菌作用をもった資材が提供で
きる。本発明の方法で得られたルチル型二酸化チタンに太陽光や照明器具などからの紫外線や可視光を含めた光を照射すると、光エネルギーが化学エネルギーに変換されて、有機物などを分解する光触媒作用を発揮し、オフィス、住宅室内で発生する代表的アレルゲンであるホルムアルデヒドの分解除去の他にも、抗菌、消臭及び防汚効果が得られる。本発明の技術で作製された二酸化チタン（薄膜又は薄膜材料）は400 nm以上の長波長の光照射下で、有機物酸化分解および超親水性に優れる。また、これらの機能は紫外線照射下での機能に関してその機能劣化を伴わないことも大きな特徴である。
The material having a rutile-type titanium dioxide thin film obtained by the method of the present invention includes various building materials including building materials for factory plants and other equipment, materials including medical materials, for example, It can be used for exterior materials, cooking utensils, tableware, sanitary equipment, air conditioning equipment, other civil engineering materials such as sewage pipes, sound insulation walls for roads, food storage materials such as refrigerators, etc. By utilizing the photocatalytic action of the material obtained in the present invention, a material having self-cleaning, air cleaning, and sterilizing action can be provided. Photocatalytic action of decomposing organic matter by converting light energy into chemical energy when rutile titanium dioxide obtained by the method of the present invention is irradiated with light including ultraviolet light and visible light from sunlight and lighting equipment. In addition to the decomposition and removal of formaldehyde, which is a typical allergen generated in offices and residential rooms, antibacterial, deodorizing and antifouling effects can be obtained. Titanium dioxide (thin film or thin film material) produced by the technique of the present invention is excellent in organic oxidative decomposition and super hydrophilicity under irradiation with light having a long wavelength of 400 nm or longer. Another major feature of these functions is that they do not deteriorate with respect to the functions under ultraviolet irradiation.
可視光活性光触媒の多くは、窒素ドープ型であり、幾つか市販もされている。しかし、その形態は粉末を出発原料とするために、基板への固定化に問題があると共に、触媒としての活用後の回収の点で煩雑あるいは困難であるという実用上の問題がある。また繰り返し使用に伴い、基板との密着性が低下し剥離するという欠点もある。発明者らはチタン上に熱力学的に安定な二酸化チタンを陽極酸化法で創製し、酸化分解性能に優れる電気化学条件を模索してきた。その結果、従来は性能に劣ると言われていたルチル構造の二酸化チタンにおいて、光触媒及び超親水性の両者において、優れた酸化分解性能を発揮するものが得られることを見出している。これは、化成電圧や電流密度制御による結晶性の向上、酸化膜の溶出に伴う多孔質化による表面積の増加、そして電解浴からの硫黄ドープによることを学術的に解明した。こうしたことを基礎に、本発明では、さらなる機能改善を目指し、バンド構造改質をすべく、基板そのものに窒素ドーピングを施し、そのドーピングした窒素の拡散により酸化膜の電子構造の改質を目指したものである。その際には、上述の硫黄によるバンド構造改質も同時に行わせることができており、硫黄ドープ材を超える優れた性能を引き出したものである。 Many of visible light active photocatalysts are nitrogen dope types, and some are also marketed. However, since the form uses powder as a starting material, there is a problem in immobilization on a substrate, and there is a practical problem that it is complicated or difficult in terms of recovery after use as a catalyst. In addition, with repeated use, there is also a drawback that the adhesion with the substrate is lowered and peeling occurs. The inventors have created titanium dioxide that is thermodynamically stable on titanium by an anodic oxidation method, and have been searching for electrochemical conditions excellent in oxidative decomposition performance. As a result, it has been found that titanium dioxide having a rutile structure, which has been conventionally inferior in performance, can exhibit excellent oxidative degradation performance in both photocatalyst and superhydrophilic property. It has been clarified scientifically that this is due to the improvement of crystallinity by controlling the formation voltage and current density, the increase of the surface area due to the porosity due to the elution of the oxide film, and the sulfur doping from the electrolytic bath. Based on these facts, the present invention aims to further improve the function, and in order to modify the band structure, the substrate itself is doped with nitrogen, and the electronic structure of the oxide film is modified by diffusion of the doped nitrogen. Is. In that case, the band structure modification by the above-mentioned sulfur can be performed simultaneously, and the outstanding performance exceeding a sulfur dope material is drawn.
従来技術としては、蒸着法とゾルゲル法が多用されている。しかし、ゾルゲル法はデイップコートやスピンコートで行う簡便な方法で、異型基材への担持が可能ではあるが、量産性に劣るという問題がある。特に、スピンコートでは膜の均一性が悪く平板基板にしか担持できないという決定的な短所がある。一方、蒸着法は成膜材の緻密性や均一性に優れているものの、特殊装置を用いることから、コストが高くなり、膜厚が厚いことから剥離の可能性が高いという重大な欠点がある。
陽極酸化法は、従来、着色技術として広く実用されてきたが、光触媒としての報告はほとんどない。そのなかで注目すべきものとしては、特開2005-240139号公報があり、陽極
酸化の際に高電圧を印加して成膜している技術が示されているが、比較すると、本発明よりも印加電圧は低いものである。当該報告ではMB分解性能が、もっとも優れた陽極酸化膜で、6時間の紫外線照射で分解率が15%程度であることが開示されるが、本発明の未熱処理材の65.3%を大きく下回るものでしかない。また高温でのガス窒化処理を行っているが、
本発明では熱処理を施すと、MB分解率は97.5%まで増加し、明らかに、上記特許文献に開
示のものよりも優れる。
一方、陽極酸化法で成膜した二酸化チタンの超親水性については、それを開示する学術文献および特許文献はまったく報告されていない。
As the prior art, a vapor deposition method and a sol-gel method are frequently used. However, the sol-gel method is a simple method performed by dip coating or spin coating, and can be supported on an irregular substrate, but has a problem that it is inferior in mass productivity. In particular, spin coating has a decisive disadvantage that film uniformity is poor and can be supported only on a flat substrate. On the other hand, although the vapor deposition method is excellent in the denseness and uniformity of the film forming material, the use of a special apparatus has a serious disadvantage that the cost is high and the possibility of peeling is high due to the thick film thickness. .
Anodization has been widely used as a coloring technique in the past, but there are few reports as a photocatalyst. Among them, there is JP-A-2005-240139 as a notable one, which shows a technique for forming a film by applying a high voltage at the time of anodization. The applied voltage is low. The report discloses that the MB decomposition performance is the most excellent anodic oxide film, and the decomposition rate is about 15% after 6 hours of UV irradiation, but it is much lower than 65.3% of the unheat treated material of the present invention. Only it is. In addition, gas nitriding treatment is performed at high temperature.
In the present invention, when heat treatment is performed, the MB decomposition rate increases to 97.5%, which is clearly superior to that disclosed in the above-mentioned patent document.
On the other hand, regarding the superhydrophilicity of titanium dioxide formed by an anodic oxidation method, no academic literature and patent literature are disclosed.
殆どの報告は超親水性と酸化分解性能の二つの機能のうち片方のみを扱っているが、本発明では、紫外光だけでなく可視光照射下でも超親水性と同時に酸化分解性能に優れた二酸化チタンをつくり、セルフクリーニング機能として活用することを目指している。本発明者は課題解決の具体的な方法として、二酸化チタンの結晶性向上、表面積増加、バンド構造改質を考えて研究を進めている。問題解決の方策として採用した、硫黄と窒素の複合添加を陽極酸化法で行うという発想はこれまでにない。また上述の二つの機能を紫外光だけでなく可視光領域でも得ようとする点にも特徴があり、屋外太陽光を利用した建造物の外壁清浄化などに活用できると考える。
本発明で得られる二酸化チタン薄膜を有する製品は、可視光応答性が優れるので、医療分野、室内の壁材などの分野、ビル外壁および屋根に使用されるチタン製建造物、厨房ダ
クトなどに非常に有用である。
Most reports deal with only one of the two functions of superhydrophilicity and oxidative degradation performance. In the present invention, not only ultraviolet light but also visible light irradiation, super hydrophilicity and oxidative degradation performance are excellent. The aim is to make titanium dioxide and use it as a self-cleaning function. The present inventor has been conducting research in consideration of improvement in crystallinity of titanium dioxide, increase in surface area, and modification of band structure as a specific method for solving the problem. There has never been an idea of adopting the combined addition of sulfur and nitrogen by the anodic oxidation method, which was adopted as a solution to the problem. In addition, there is a feature in that the above-mentioned two functions are obtained not only in the ultraviolet light but also in the visible light region, and it can be used for cleaning the outer wall of a building using outdoor sunlight.
Since the product having a titanium dioxide thin film obtained by the present invention has excellent visible light responsiveness, it is very useful in the medical field, the field of indoor wall materials, titanium buildings used for building outer walls and roofs, kitchen ducts, etc. Useful for.
本発明で得られる二酸化チタン薄膜を有するチタン又はチタン合金材においては、当該二酸化チタンのルチル構造の結晶性が向上せしめられている。当該ルチル型二酸化チタン薄膜形成材は、紫外光ばかりでなく可視光を含めた光照射により酸素空孔が形成され易くなっており、酸素空孔への水酸基の吸着が促進されて超親水性が改善されたものとなっている。本発明では、ルチル型二酸化チタン薄膜により、大変優れた可視光領域での応答性を有する光触媒活性および超親水性などの性能が得られるので、超親水性と酸化分解性能の二つの機能を同時に満たす膜の製造が可能となる。
以下に実施例を掲げ、本発明を具体的に説明するが、この実施例は単に本発明の説明のため、その具体的な態様の参考のために提供されているものである。これらの例示は本発明の特定の具体的な態様を説明するためのものであるが、本願で開示する発明の範囲を限定したり、あるいは制限することを表すものではない。本発明では、本明細書の思想に基づく様々な実施形態が可能であることは理解されるべきである。
全ての実施例は、他に詳細に記載するもの以外は、標準的な技術を用いて実施したもの、又は実施することのできるものであり、これは当業者にとり周知で慣用的なものである。
In the titanium or titanium alloy material having the titanium dioxide thin film obtained in the present invention, the crystallinity of the rutile structure of the titanium dioxide is improved. In the rutile type titanium dioxide thin film forming material, oxygen vacancies are easily formed by light irradiation including not only ultraviolet light but also visible light, and the adsorption of hydroxyl groups to the oxygen vacancies is promoted, resulting in super hydrophilicity. It has been improved. In the present invention, the rutile-type titanium dioxide thin film can provide performance such as photocatalytic activity and superhydrophilicity having excellent responsiveness in the visible light region, so that the two functions of superhydrophilicity and oxidative degradation performance can be achieved simultaneously. It is possible to produce a film that fills.
The present invention will be described in detail with reference to the following examples, which are provided merely for the purpose of illustrating the present invention and for reference to specific embodiments thereof. These exemplifications are for explaining specific specific embodiments of the present invention, but are not intended to limit or limit the scope of the invention disclosed in the present application. In the present invention, it should be understood that various embodiments based on the idea of the present specification are possible.
All examples were performed or can be performed using standard techniques, except as otherwise described in detail, and are well known and routine to those skilled in the art. .
〔二酸化チタン膜の形成〕
Ti圧延板(JIS1種Ti; 20mm×10mm×1mm)の表面を化学研磨仕上げし、次に窒化処理を施
した。窒化処理は、プラズマ窒化を施した。プラズマ窒化では、日本電子工業社製JIN-1Sを使用し、次なる条件を使用した： 電圧550V; 圧力500Pa; 処理温度700℃; 処理時間３
時間。原料ガスは窒素ガスと水素ガスとの混合ガス、該混合ガスにアルゴンガスを添加したものなどを使用した。
表面をプラズマ窒化したTi板を陽極試料とし、0.02〜1.2mol/L硫酸水溶液のいずれかの濃度の硫酸水溶液中に浸漬した。電流を200mA（電流密度50mA/cm2）として、化成電圧を210V（最終電位）として、30分間の陽極酸化処理を施した。陽極酸化処理は室温で行った
。陽極酸化後はメタノールにて洗浄後乾燥させたものを未熱処理材サンプルとする。陽極酸化後の基材を450℃において、５時間の大気酸化を施したものを熱処理材サンプルとす
る。
[Formation of titanium dioxide film]
The surface of a Ti rolled plate (JIS type 1 Ti; 20 mm × 10 mm × 1 mm) was chemically polished and then subjected to nitriding treatment. As the nitriding treatment, plasma nitriding was performed. In plasma nitriding, JIN-1S manufactured by JEOL Ltd. was used and the following conditions were used: Voltage 550V; Pressure 500Pa; Processing temperature 700 ° C; Processing time 3
time. As the source gas, a mixed gas of nitrogen gas and hydrogen gas, or a mixture of the mixed gas with argon gas was used.
A Ti plate whose surface was plasma-nitrided was used as an anode sample and immersed in a sulfuric acid aqueous solution having a concentration of 0.02 to 1.2 mol / L sulfuric acid aqueous solution. Anodization was performed for 30 minutes at a current of 200 mA (current density of 50 mA / cm 2 ) and a formation voltage of 210 V (final potential). The anodizing treatment was performed at room temperature. After anodic oxidation, a sample that has been washed with methanol and dried is used as an unheated material sample. A heat-treated material sample is obtained by subjecting the anodized substrate to atmospheric oxidation at 450 ° C. for 5 hours.
〔光触媒能試験〕
作製した二酸化チタン膜被覆サンプルを、0.1mmol/L(3.19ppm)メチレンブルー(MB)水溶液(2mL)を満たしたポリメチルメタクリレート(PMMA)製セルに浸漬し、所定の時間、光照
射した。被検サンプルは、本MB分解試験の前に前処理を行って触媒表面への吸着に配慮した。前処理は、6.38 ppmのMB水溶液(2mL)に12時間以上浸漬することにより行った。
光源は、朝日分光製Xeランプ(MAX-302)を使用し、ミラーモジュール、JIS規格のバンドパスフィルター(５種)を組合せて、365、400、440、500、そして530nmの光(バンド幅約10nm)を３時間照射した。光強度は、0.3mW/cm2を用いた。色素増感作用による分解、直接光分解を排除するようにして測定を行った。一定時間照射後に石英セルからMB水溶液を採取し、分光光度計(日本分光V-550)にて664nmのMB吸光度変化から、MB分解率を算出した。
[Photocatalytic test]
The prepared titanium dioxide film-coated sample was immersed in a polymethyl methacrylate (PMMA) cell filled with 0.1 mmol / L (3.19 ppm) methylene blue (MB) aqueous solution (2 mL) and irradiated with light for a predetermined time. The sample to be tested was pretreated before the MB decomposition test in consideration of adsorption on the catalyst surface. The pretreatment was performed by immersing in a 6.38 ppm MB aqueous solution (2 mL) for 12 hours or more.
The light source uses an Xe lamp (MAX-302) manufactured by Asahi Spectroscope, and combines 365, 400, 440, 500, and 530 nm light (bandwidth approx. 10 nm) for 3 hours. The light intensity was 0.3 mW / cm 2 . The measurement was carried out so as to exclude degradation due to dye sensitization and direct photolysis. An MB aqueous solution was collected from the quartz cell after irradiation for a certain period of time, and the MB decomposition rate was calculated from the change in MB absorbance at 664 nm with a spectrophotometer (JASCO V-550).
〔超親水性性能試験〕
サンプルに365nmの紫外線を0.2 mW/cm2の強度で、所定の時間（0.5、１、1.5、２、2.5、３時間）照射した。一定時間照射後に1.0mLの蒸留水を滴下し、θ/2法にて接触角を測
定した。
[Superhydrophilic performance test]
The sample was irradiated with ultraviolet rays of 365 nm at an intensity of 0.2 mW / cm 2 for a predetermined time (0.5, 1, 1.5, 2 , 2.5, 3 hours). After irradiation for a certain time, 1.0 mL of distilled water was added dropwise, and the contact angle was measured by the θ / 2 method.
得られた結果を、図１に示す。
図１中、blankは陽極酸化処理したのみの試料であり、TiN anは窒化基板(TiN)上に陽極酸化処理した試料を熱処理（アニール処理）した試料で、TiN asは窒化基板(TiN)上に陽
極酸化処理した試料で熱処理を施していない試料、そして、Ti anはチタン基板(Ti)上に
陽極酸化処理した試料をアニール処理して得られた試料である。
この結果から、プラズマ窒化処理されたチタン基板を陽極酸化法で成膜し、熱処理して得られたルチル型二酸化チタン薄膜形成体(TiN an)では、陽極酸化した試料でアニールしてない試料(TiN as)やプラズマ窒化処理されていないチタン基板を陽極酸化法で成膜した試料をアニール化した薄膜形成体(Ti an)よりも、可視光領域(通常、360〜400nmよりも長波長側)にてMB分解率が高い（高い光触媒活性を示す）ことがわかる。窒素がドープされ
ていることで、可視光領域での高い光触媒活性となっていることが示されている。また熱処理を施すことで、光触媒活性は向上することがわかる。
また、電解浴の硫酸濃度0.02〜1.2mol/Lにて陽極酸化して得られた試料のＸ線回折プロファイルを、図３に示す。本図３より、電解浴の硫酸濃度を0.02mol/Lから1.2mol/Lに増
加せしめるにつれて、アナタースからルチルに変化していることから、ルチル型二酸化チタンが得られていることが明らかである。
The obtained results are shown in FIG.
In FIG. 1, blank is an anodized sample, TiN. an is a sample obtained by heat-treating (annealing) an anodized sample on a nitride substrate (TiN). as is an anodized sample on a nitride substrate (TiN), a sample not subjected to heat treatment, and Ti an is a sample obtained by annealing a sample anodized on a titanium substrate (Ti).
From this result, a ruthenium-type titanium dioxide thin film formed body (TiN) obtained by depositing a plasma-nitrided titanium substrate by anodization and heat treatment an), an anodized sample that has not been annealed (TiN as) and a thin film forming body (Ti It can be seen that the MB decomposition rate is higher (shows high photocatalytic activity) in the visible light region (usually longer than 360 to 400 nm) than an). It is shown that the high photocatalytic activity in the visible light region is obtained by doping nitrogen. Moreover, it turns out that photocatalytic activity improves by performing heat processing.
In addition, FIG. 3 shows an X-ray diffraction profile of a sample obtained by anodizing at a sulfuric acid concentration of 0.02 to 1.2 mol / L in the electrolytic bath. From FIG. 3, it is clear that rutile type titanium dioxide is obtained from the change from anatase to rutile as the sulfuric acid concentration in the electrolytic bath is increased from 0.02 mol / L to 1.2 mol / L. .
プラズマ窒化の条件として、(1)H2:N2=1:1の雰囲気、(2)H2:N2=4:1の雰囲気、(3)H2:Ar：N2=50:49:1の雰囲気のいずれかにて、700℃で２時間処理して、チタン基板を窒化した
。本窒化チタン基板を使用して、1.2mol/L硫酸水溶液電解浴中で上記と同様な条件で陽極酸化した後大気中で上記と同様な条件でもって450℃で４時間焼成した。この試料の表面
の拡散反射スペクトルを図２に示す。このスペクトルから窒化基板を用いて作製した陽極酸化膜の方が窒化を施していない基板を用いて作製した陽極酸化膜よりも、可視光側での吸収が大きいことがわかる。
The plasma nitriding conditions are as follows: (1) H 2 : N 2 = 1: 1 atmosphere, (2) H 2 : N 2 = 4: 1 atmosphere, (3) H 2 : Ar: N 2 = 50: 49 The titanium substrate was nitrided by treatment at 700 ° C. for 2 hours in any of the 1: 1 atmospheres. Using this titanium nitride substrate, it was anodized in a 1.2 mol / L sulfuric acid aqueous solution electrolytic bath under the same conditions as described above, and then calcined in air at 450 ° C. for 4 hours under the same conditions as described above. The diffuse reflection spectrum of the surface of this sample is shown in FIG. From this spectrum, it can be seen that the anodic oxide film produced using the nitride substrate has higher absorption on the visible light side than the anodic oxide film produced using the non-nitrided substrate.
超親水性性能試験の結果を図４〜６に示す。図４は、H2:N2=1:1の雰囲気下で窒化した
チタン基板を用いて作製した陽極酸化膜で、未熱処理材サンプルと熱処理材サンプルを示す。1.2mol/Lの硫酸濃度の硫酸水溶液浴での陽極酸化膜サンプルでは、熱処理前でも、接触角は低い値を示しており、紫外線未照射でも超親水性に優れていることがわかる。また熱処理を施すことで、超親水性が顕著に改善せしめられることがわかる。図５は、H2:N2=4:1の雰囲気下で窒化したチタン基板を用いて作製した陽極酸化膜で、熱処理材サンプル
を示す。
接触角は、H2:N2=1:1の雰囲気下で窒化したチタン基板を用いて作製した陽極酸化膜の接
触角よりも高いことがわかる。図６は、Ar:H2:N2=49:50:1の雰囲気下で窒化したチタン基板を用いて作製した陽極酸化膜で、熱処理材サンプルを示す。1.2mol/Lの硫酸濃度の硫酸水溶液浴での陽極酸化膜サンプルでは、紫外線未照射でも接触角は低い値を示しており、超親水性に優れていることがわかる。
The results of the superhydrophilic performance test are shown in FIGS. FIG. 4 shows an unheated material sample and a heat treated material sample, which are anodized films prepared using a titanium substrate nitrided in an atmosphere of H 2 : N 2 = 1: 1. The anodized film sample in the sulfuric acid aqueous solution bath with a sulfuric acid concentration of 1.2 mol / L shows a low contact angle even before the heat treatment, and it can be seen that it is excellent in super hydrophilicity even without being irradiated with ultraviolet rays. Moreover, it turns out that superhydrophilicity is remarkably improved by heat-processing. FIG. 5 shows a heat treatment material sample of an anodic oxide film manufactured using a titanium substrate nitrided in an atmosphere of H 2 : N 2 = 4: 1.
It can be seen that the contact angle is higher than the contact angle of an anodized film manufactured using a titanium substrate nitrided in an atmosphere of H 2 : N 2 = 1: 1. FIG. 6 shows a heat treatment material sample of an anodic oxide film manufactured using a titanium substrate nitrided in an atmosphere of Ar: H 2 : N 2 = 49: 50: 1. An anodized film sample in a sulfuric acid aqueous solution bath having a sulfuric acid concentration of 1.2 mol / L shows a low contact angle even when not irradiated with ultraviolet rays, indicating that it is excellent in super hydrophilicity.
H2:N2=1:1の雰囲気のプラズマ窒化の条件にて、700℃で２時間処理して、チタン基板を窒化し、得られた窒化チタン基板を使用して、1.2mol/L硫酸水溶液電解浴中で上記と同様な条件で陽極酸化した後大気中で上記と同様な条件にて450℃で４時間焼成した。この試
料につき、Ｘ線光電子分光法(XPS: X-ray Photoelectron Spectroscopy)を用いた表面解
析を行ったところ、窒素濃度については、可視光活性の高い方では1.35 at%、1.6 at%で
、活性の低い方では1.3 at%、1.2 at%という値であった。可視光による光触媒活性の高い試料の方が、窒素濃度は高い傾向が認められた。これらの試料の硫黄についての分析結果は、可視光活性の高い二酸化チタン層では、約0.13 at%で、可視光活性の低い二酸化チタン層では、約0.45 at%であると予想されるものであった。この硫黄量は、基板がチタンでも窒化チタンでも、大差ないと予想されるものである。
以上より、硫黄単独ドープより、窒素と硫黄の複合ドープの方が、可視光応答性はより良好となっている。つまり、硫黄に加えて、窒素が上記の値程度、二酸化チタンに添加されることで、可視光活性が改善されると考えられる。
A titanium substrate is nitrided by treatment at 700 ° C. for 2 hours under the conditions of plasma nitriding in an atmosphere of H 2 : N 2 = 1: 1, and 1.2 mol / L sulfuric acid is used using the obtained titanium nitride substrate. After anodizing in an aqueous electrolytic bath under the same conditions as described above, firing was performed in air at 450 ° C. for 4 hours under the same conditions as described above. When this sample was subjected to surface analysis using X-ray photoelectron spectroscopy (XPS), the nitrogen concentration was 1.35 at% and 1.6 at% for the higher visible light activity. The lower value was 1.3 at% and 1.2 at%. The nitrogen concentration tended to be higher in the sample with higher photocatalytic activity by visible light. The analytical results for sulfur in these samples are expected to be about 0.13 at% for the titanium dioxide layer with high visible light activity and about 0.45 at% for the titanium dioxide layer with low visible light activity. It was. This amount of sulfur is expected to be the same regardless of whether the substrate is titanium or titanium nitride.
From the above, the visible light responsiveness is better in the combined dope of nitrogen and sulfur than in the sulfur single dope. That is, it is thought that visible light activity is improved by adding nitrogen to titanium dioxide to the above value in addition to sulfur.
本発明で得られるルチル型二酸化チタン薄膜形成材料は、可視光領域の光に対しても応答して優れた光触媒活性を示し、さらに、紫外光での光触媒活性や超親水性という特性と併せて優れた光触媒作用を有する材料として有用で、さらに、その製造手法からみて、耐久性や製造コストの面でも有利なものであると期待される。したがって、可視光が普通に存在する、通常の生活空間における光触媒活性保有材料として、有用性が高く、脱臭、防黴、防汚性、殺菌作用等を示し、防黴、防汚などの効果を有する建築材（工場プラント資材を含めた各種建築材料）やその他の機器、空調機器、浄水設備、医療分野、衛生分野等に用いられる各種部材、医療用材料などを含めた材料、建築物の内，外装材、調理用器具、食器類、衛生機器、空調機器、土木用材料、道路の遮音壁、冷蔵庫などの食品保管庫用材料など、各種様々な適用・用途に使用されて、有用性を発揮できる。
本発明は、前述の説明及び実施例に特に記載した以外も、実行できることは明らかである。上述の教示に鑑みて、本発明の多くの改変及び変形が可能であり、従ってそれらも本件添付の請求の範囲の範囲内のものである。
The rutile-type titanium dioxide thin film-forming material obtained in the present invention exhibits excellent photocatalytic activity in response to light in the visible light region, and in addition to the characteristics of photocatalytic activity and superhydrophilicity in ultraviolet light. It is useful as a material having an excellent photocatalytic action, and is also expected to be advantageous in terms of durability and production cost in view of its production method. Therefore, it is highly useful as a photocatalytic activity possessing material in normal living space where visible light is normally present, exhibiting deodorization, anti-fouling, anti-fouling, bactericidal action, etc. Building materials (various building materials including factory plant materials), other equipment, air conditioning equipment, water purification equipment, various parts used in the medical field, sanitary field, materials including medical materials, and buildings , Used for various applications and applications such as exterior materials, cooking utensils, tableware, sanitary equipment, air conditioning equipment, civil engineering materials, road sound insulation walls, refrigerators and other food storage materials it can.
It will be apparent that the invention may be practiced otherwise than as particularly described in the foregoing description and examples. Many modifications and variations of the present invention are possible in light of the above teachings, and thus are within the scope of the claims appended hereto.
Claims (13)
のガス圧の条件で、10分間〜24時間の範囲でプラズマ窒化するものであることを特徴とする請求項１又は２に記載の方法。 The nitriding treatment is characterized in that plasma nitriding is performed in a range of 10 minutes to 24 hours under conditions of a treatment temperature of 350 to 850 ° C. and a gas pressure of 200 to 1000 Pa in the presence of a nitrogen-containing gas. The method according to claim 1 or 2.
そ1:4である窒素源のガスの存在下、650〜750℃の処理温度、450〜1000Paの範囲のガス圧の条件で、1.5〜3.5時間の範囲でプラズマ窒化するものであることを特徴とする請求項１〜３のいずれか一に記載の方法。 The nitriding treatment is performed at 650-750 ° C. in the presence of a nitrogen source gas in which the volume ratio of the mixed gas of nitrogen and hydrogen is N 2 : H 2 = approximately 1.2: 0.8 to N 2 : H 2 = approximately 1: 4. The method according to any one of claims 1 to 3, wherein the plasma nitridation is performed in a range of 1.5 to 3.5 hours at a treatment temperature and a gas pressure in a range of 450 to 1000 Pa.
約10〜約60分間の範囲の間行われるものであることを特徴とする請求項１〜４のいずれか一に記載の方法。 Anodization is performed by applying a potential of 100 to 300 V in a sulfuric acid aqueous solution having a sulfuric acid concentration of 0.02 to 1.6 mol / L.
5. The method of any one of claims 1-4, wherein the method is performed for a period of about 10 to about 60 minutes.
が0.4未満のルチル型二酸化チタンを90％以上含有する二酸化チタン皮膜であること及び
該ルチル型二酸化チタンは、窒素と硫黄がドープされたものであることを特徴とする請求項１〜８のいずれか一に記載の方法。 The rutile type titanium dioxide is a titanium dioxide film containing 90% or more of rutile type titanium dioxide having excellent crystallinity and having a half-value width of rutile 110 diffraction line in X-ray diffraction of less than 0.4, and the rutile type titanium dioxide. The method according to claim 1, wherein nitrogen and sulfur are doped.
とを特徴とする請求項１〜９のいずれか一に記載の方法。 The substrate to be anodized is nitrided or heated by plasma nitriding under a nitrogen atmosphere, and the rutile titanium dioxide is doped with nitrogen and sulfur, and has a titanium dioxide content of about 0.5 to 2.0 at%. 10. The process according to any one of claims 1 to 9, characterized in that it contains nitrogen and 400 ppm (0.04%) to 20000 ppm (2.0%) sulfur.
レンブルー分解率を示す高い光触媒活性を示すことを特徴とする請求項１１又は１２に記載の光触媒体。
The photocatalyst according to claim 11 or 12, wherein the rutile-type titanium dioxide exhibits a high photocatalytic activity exhibiting a methylene blue decomposition rate of about 30% or more with respect to light having a wavelength of about 440 nm in a visible light region. .
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