WO2019073746A1 - Method for manufacturing titanium or titanium alloy thin oxide film having micropores - Google Patents

Method for manufacturing titanium or titanium alloy thin oxide film having micropores Download PDF

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WO2019073746A1
WO2019073746A1 PCT/JP2018/034101 JP2018034101W WO2019073746A1 WO 2019073746 A1 WO2019073746 A1 WO 2019073746A1 JP 2018034101 W JP2018034101 W JP 2018034101W WO 2019073746 A1 WO2019073746 A1 WO 2019073746A1
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titanium
sulfuric acid
acid solution
electrolytic
titanium alloy
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PCT/JP2018/034101
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French (fr)
Japanese (ja)
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南美 吉村
永井　達夫
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栗田工業株式会社
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Priority to US16/754,751 priority Critical patent/US20200318251A1/en
Priority to CN201880059921.1A priority patent/CN111094634A/en
Publication of WO2019073746A1 publication Critical patent/WO2019073746A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

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  • the present invention relates to a method of producing an oxide thin film of titanium or titanium alloy having fine pores, and more particularly to a method of producing an oxide thin film of titanium or titanium alloy having fine pores suitable for forming fine pores of 100 nm or less.
  • Titanium or titanium alloy members are light metals with high hardness and strength, and are widely used because they have excellent properties such as high corrosion resistance and high ductility. Furthermore, by anodizing titanium and titanium alloy members to form an anodized film, not only coloring, improvement of abrasion resistance, and the function of photocatalyst are expressed, but the biocompatibility is high because medical treatment is high. Its applications such as for use are expanding.
  • anodic oxide film on titanium or titanium alloy is, for example, that electrolytic processing is performed in an electrolytic solution such as a mixed solution of sulfuric acid, phosphoric acid and hydrogen peroxide using titanium or titanium alloy as an anode.
  • an electrolytic solution such as a mixed solution of sulfuric acid, phosphoric acid and hydrogen peroxide using titanium or titanium alloy as an anode.
  • the formed hole is as large as about 1 ⁇ m.
  • the pores formed in the anodized film are large, there is a problem that the tissue is not densely embedded when bonding the titanium oxide film to a substrate such as a human tissue, which makes it difficult to fix.
  • the present invention is made in view of the above-mentioned subject, and an object of the present invention is to provide a method of manufacturing a titanium or titanium alloy oxide thin film having a hole of 100 nm or less from a titanium or titanium alloy thin film.
  • the present invention uses a titanium or titanium alloy thin film as an anode and a sulfuric acid solution in which a hydrogen fluoride compound is dissolved by 0.5 wt% or less or a hydrogen fluoride compound by 0.5 wt% or less
  • a method of producing a titanium or titanium alloy oxide thin film having fine pores which is electrolytically treated at a current density of 1 to 20 A / dm 2 in an electrolytic sulfuric acid solution having an oxidant concentration of 5 g / L or more (Invention 1).
  • holes of 100 nm or less, particularly 50 nm or less can be formed in the oxide thin film of titanium or titanium alloy by the etching effect by the electrolytic treatment using the hydrogen fluoride compound.
  • the sulfuric acid concentration of the said sulfuric acid solution or electrolytic sulfuric acid solution is 10 weight% or more (invention 2).
  • the hole of 100 nm or less can be formed in a short time in the oxide thin film of titanium or titanium alloy.
  • the said hydrogen fluoride compound is ammonium fluoride (invention 3).
  • a hole of 100 nm or less can be easily formed in the oxide thin film of titanium or titanium alloy.
  • the treatment time of the electrolytic treatment with the sulfuric acid solution or electrolytic sulfuric acid solution in which the hydrogen fluoride compound is dissolved is preferably 30 to 60 seconds (Invention 4).
  • the hole of 100 nm or less can be efficiently formed in the oxide thin film of titanium or titanium alloy.
  • the electrolytic treatment after the second stage does not dissolve the hydrogen fluoride compound
  • the hole of 100 nm or less of the oxide thin film of titanium or titanium alloy can be stabilized.
  • the titanium or titanium alloy thin film is used as an anode at a predetermined current density in a sulfuric acid solution or an electrolytic sulfuric acid solution in which a hydrogen fluoride compound is dissolved.
  • electrolytic treatment holes of 100 nm or less, particularly 50 nm or less can be formed while forming an oxide thin film of titanium or titanium alloy by the etching effect of the hydrogen fluoride compound and the oxidizing power of the electrolytic sulfuric acid solution.
  • FIG. 1 is a schematic view showing a processing apparatus to which a method of manufacturing a titanium or titanium alloy oxide thin film having micropores according to an embodiment of the present invention is applicable.
  • FIG. 1 conceptually shows a processing apparatus to which a method of manufacturing a titanium or titanium alloy oxide thin film having fine pores according to an embodiment of the present invention can be applied.
  • the cathode member 4 and the anode member 5 installed in the processing tank 2 are provided, and the cathode member 4 and the anode member 5 are respectively connected to the negative electrode and the positive electrode of the DC power supply 3.
  • the treatment bath 2 can be provided with a constant temperature heater (not shown) for keeping the solution in the treatment bath 2 at a desired temperature.
  • the anode member 5 is a member to be treated, and a member using a thin film made of titanium or a titanium alloy is used.
  • the cathode member 4 is not particularly limited as long as it is a conductive material, but a member (including a thin film) made of titanium or a titanium alloy can be used in terms of conductivity, corrosion resistance, and the like.
  • a sulfuric acid solution or an electrolytic sulfuric acid solution S in which a hydrogen fluoride compound is dissolved is used as a solution of the electrolytic treatment contained in the treatment tank 2 of the treatment apparatus 1. Since only a sulfuric acid solution has no oxidizing power, titanium or a titanium alloy only dissolves, and the pore diameter of the micropores can be 100 nm or less, but it is difficult to be 30 nm or less. In order to form finer pores, an electrolytic sulfuric acid solution having oxidizing power is used.
  • the oxidizing agent concentration in the case of this electrolytic sulfuric acid solution may be an oxidizing agent concentration that can be generated when electrolytic sulfuric acid is produced by electrolyzing sulfuric acid, but if it is less than 5 g / L, the oxidation rate becomes slow, The pore diameter of the micropores formed in the thin film made of titanium or titanium alloy used for the anode member 5 is increased.
  • the upper limit of the oxidizing agent concentration is not particularly limited, but about 10 g / L is realistic from the viewpoint of the efficiency when electrolytic sulfuric acid is produced by electrolyzing sulfuric acid.
  • any salt of hydrofluoric acid and a basic substance may be used, and ammonium fluoride is preferable in terms of good handleability and versatility.
  • the concentration is 0.5% by weight or less. If the concentration of ammonium fluoride exceeds 0.5% by weight, the dissolution of titanium proceeds too much, the pores become large, and the pores become tubular.
  • the lower limit of the concentration of ammonium fluoride is less than 0.1% by weight, the dissolution of titanium does not proceed, the formation of micropores is not sufficient, and the dissolution of titanium does not proceed, so an oxide film formed Also, it is not preferable because it becomes thin and can not penetrate the titanium base material.
  • the concentration of ammonium fluoride is preferably 0.25 ⁇ 0.05% by weight in view of the formation of micropores. Even in the case of a hydrogen fluoride compound other than ammonium fluoride, its concentration may be 0.5 wt% or less.
  • the concentration of sulfuric acid in the sulfuric acid solution or electrolytic sulfuric acid solution S when the concentration of sulfuric acid is less than 5% by weight, the amount of H + (H 3 O + ) ions by electrolysis of sulfuric acid in electrolytic treatment described later is small. Dissolution rate of titanium or titanium alloy as a part) is slowed, an oxide film is formed on the surface and reaction does not proceed, but if the concentration of sulfuric acid exceeds 50% by weight, the dissolution rate of titanium becomes too fast. It is preferable to set the content to 5 to 50% by weight because dissolution proceeds preferentially and it becomes difficult to form an oxide film of titanium. In particular, the concentration of sulfuric acid is preferably 10 to 40% by weight.
  • the cathode member 4 as a processing member connected to the DC power supply 3 and the anode member 5 formed of a member using a thin film made of titanium or titanium alloy are suspended in the processing tank 2, the processing tank 2 is sulfuric acid solution or electrolytic sulfuric acid Fill with solution S.
  • the current density applied here is lower than 1 A / dm 2 , stable control becomes difficult, while when the current density is higher than 20 A / dm 2 , the current density becomes too large, and therefore, a thin film made of titanium or titanium alloy is formed. Not only does the hole diameter increase, but the hole becomes a tube. Accordingly, the current density is 1 to 20 A / dm 2 , preferably 3 to 10 A / dm 2 .
  • the temperature of the sulfuric acid solution or electrolytic sulfuric acid solution S in this electrolytic treatment is not particularly limited, but when the temperature of the sulfuric acid solution or electrolytic sulfuric acid solution S is less than 10 ° C., the effect of the oxidizing agent in the electrolytic sulfuric acid solution is sufficient While it is not exhibited and an oxide film is not sufficiently formed, if the temperature exceeds 50 ° C., the oxidation rate increases, and the formation of a passive oxide film prevents dissolution of titanium and makes it difficult to form pores, which is a substrate It is not preferable because it becomes difficult to penetrate a thin film made of titanium or titanium alloy. Therefore, the preferred temperature of the sulfuric acid solution or electrolytic sulfuric acid solution S is 10 to 50 ° C., particularly 20 to 50 ° C. In the treatment tank 2, it is preferable to maintain the temperature of the sulfuric acid solution or the electrolytic sulfuric acid solution S at a predetermined temperature by a constant temperature heater (not shown) as necessary so as to reach the above-mentioned temperature.
  • the time of the above-mentioned electrolytic treatment is not particularly limited, but if it is less than 30 seconds, the dissolution of titanium is insufficient and micropores are hardly formed.
  • the upper limit of the electrolytic treatment time is not less than 360 seconds because dissolution of titanium proceeds too much and the formed pores become large and uneven, and the treatment efficiency decreases, if too long.
  • the treatment time is preferably about 40 to 60 seconds.
  • the anodizing treatment of titanium or titanium alloy is a competitive reaction of the dissolution of Ti of formula (1) and the oxidation of Ti of formula (2), and the oxidation is performed by the action of Ti oxidation and etching of TiO 2 by hydrogen fluoride compound. It becomes possible to make fine holes while forming a film.
  • concentration of the hydrogen fluoride compound is too high or the exposure time is long, the titanium dioxide penetrates into the interior of TiO 2 and the titanium inside also dissolves. This increases the possibility of causing the formation of a tube-like weak oxide film, so the concentration of sulfuric acid and oxidizing agent, the concentration of hydrogen fluoride compound, and the electrolytic treatment conditions of this sulfuric acid solution or electrolytic sulfuric acid solution S are increased. It is desirable to give due consideration.
  • the conditions of the second stage electrolytic treatment may be basically the same as the first electrolytic treatment described above, but the treatment time is the thickness of the thin film made of titanium or titanium alloy used for the anode member 5 It may be set appropriately according to the situation.
  • the pores of 100 nm or less of the titanium or titanium alloy oxide thin film can be stabilized.
  • the manufacturing method of the oxide thin film of the titanium or titanium alloy which has a micropore of this invention was demonstrated based on said each embodiment, this invention is not limited to the said Example, and various deformation
  • the anode member 5 may be a thin film made of titanium or a titanium alloy, and the surface of the metal electrode material may be covered with a thin film made of titanium or a titanium alloy.
  • the pore diameter of the micropores formed varies depending on the concentration of the hydrogen fluoride compound, the concentration of the sulfuric acid, the concentration of the sulfuric acid, the current density, the temperature of the electrolytic sulfuric acid and the time of the electrolytic treatment, these conditions are appropriately selected according to the desired micropores. It can be adjusted.
  • Example 1 and Comparative Example 1 A test piece of pure titanium of 100 mm ⁇ 100 mm ⁇ 0.04 mm (t) was prepared, and using this test piece, the cathode member 4 and the anode member 5 were formed to constitute the processing apparatus 1 shown in FIG. Anodizing treatment was performed by setting the treatment conditions of the first stage electrolytic treatment as shown in Table 1 by this treatment apparatus 1. That is, the electrolytic treatment in the first step is an electrolytic sulfuric acid solution S in which 0.25 wt% of ammonium fluoride is dissolved in an electrolytic sulfuric acid solution having a sulfuric acid concentration of 10 wt% and an oxidant concentration of 10 g / L. The processing time was 40 seconds at 3.5 A / dm 2 . Next, the second stage electrolytic treatment was performed for 60 seconds only with the electrolytic sulfuric acid solution having the same concentration as the first stage without dissolving ammonium fluoride.
  • the electrolytic treatment in the first step is an electrolytic sulfuric acid solution S in which 0.25 wt%
  • the test piece of pure titanium of the anode member 5 after this treatment is observed at 100,000 times magnification with a field emission scanning electron microscope (FE-SEM), the test piece of pure titanium of the anode member 5 is obtained. It was confirmed that a titanium oxide film having pores of about 20 nm was formed.
  • the electrolytic sulfuric acid solution having the same concentration only at the same concentration as the first stage without dissolving ammonium fluoride was used at a temperature of 30 ° C. and a current density of 3.5 A / dm 2 for a treatment time of 40 seconds ( In Comparative Example 1), an oxide film of titanium was formed but fine pores were not formed.
  • Example 2 a test piece of pure titanium was treated in the same manner except that the electrolytic treatment conditions of the first stage were set as shown in Table 1.
  • Table 1 also shows the processing conditions of Example 1 and Comparative Example 1.
  • the surface of the test piece of pure titanium of the anode member 5 after these treatments is observed by a field emission scanning electron microscope (FE-SEM) at a magnification of 100,000 to obtain a test piece of pure titanium of the anode member 5
  • FE-SEM field emission scanning electron microscope
  • Example 2 in which the temperature of the electrolytic sulfuric acid solution S in the first stage electrolytic treatment is 10 ° C., a titanium oxide thin film having micropores of about 15 nm is formed. did it. Further, in Example 3 in which the processing time was as long as 300 seconds, it was possible to manufacture a titanium oxide thin film in which fine pores of about 40 nm were formed. Furthermore, in Example 4 in which the electrolytic treatment in the first stage was performed only with sulfuric acid in which ammonium fluoride was dissolved, a titanium oxide thin film having a relatively large pore size could be produced. From these examples, it is understood that the pore diameter of the micropores formed in the titanium oxide thin film can be adjusted by adjusting the conditions of the electrolytic treatment.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A processing device 1 has a processing tank 2 and a negative electrode member 4 and a positive electrode member 5 placed inside this processing tank 2. This negative electrode member 4 and positive electrode member 5 are connected to the negative terminal and positive terminal of a direct current power supply 3, respectively. In this processing device 1, the positive electrode member 5 is a member to be processed, and a member using a thin film formed from titanium or titanium alloy is used therefor. A sulfuric acid solution or an electrolytic sulfuric acid solution S with an oxidizing agent concentration of at least 5g/L wherein a hydrofluoric compound is dissolved at 0.5% by weight or less is accommodated in the processing tank 2 and electrolysis processing is performed at a current density of 1 – 20 A/dm2. This processing device is applicable to a method for manufacturing a thin oxide film of titanium or a titanium alloy that has 100 nm or less holes from a thin titanium or titanium alloy film.

Description

微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法Method of manufacturing oxide film of titanium or titanium alloy having fine pores
　本発明は、微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法に関し、特に１００ｎｍ以下の微細孔を形成するのに好適な、微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法に関する。 The present invention relates to a method of producing an oxide thin film of titanium or titanium alloy having fine pores, and more particularly to a method of producing an oxide thin film of titanium or titanium alloy having fine pores suitable for forming fine pores of 100 nm or less.
　チタン又はチタン合金部材は、高い硬度と強度とを備えた軽い金属であり、かつ耐食性が高く、延性に富むという優れた特性を有することから広く利用されている。さらに、チタン及びチタン合金部材に陽極酸化処理を施して陽極酸化皮膜を形成することによって、着色、耐摩耗性の向上、光触媒の機能が発現されるだけでなく、生態適合性が高いことから医療用などその用途が拡大されている。 Titanium or titanium alloy members are light metals with high hardness and strength, and are widely used because they have excellent properties such as high corrosion resistance and high ductility. Furthermore, by anodizing titanium and titanium alloy members to form an anodized film, not only coloring, improvement of abrasion resistance, and the function of photocatalyst are expressed, but the biocompatibility is high because medical treatment is high. Its applications such as for use are expanding.
　このチタン又はチタン合金への陽極酸化皮膜の形成方法は、例えばチタン又はチタン合金を陽極として、硫酸、リン酸、過酸化水素の混合液などの電解液中で電解処理を行うことが知られている（例えば特許文献１、特許文献２など）。これらの文献によると、１００Ｖ以上の高い電圧をかけて火花放電処理することにより、微細孔を形成することで光触媒の機能を付与し、有機化合物や細菌などの有害物質を除去することができるようになる。 It is known that the method of forming an anodic oxide film on titanium or titanium alloy is, for example, that electrolytic processing is performed in an electrolytic solution such as a mixed solution of sulfuric acid, phosphoric acid and hydrogen peroxide using titanium or titanium alloy as an anode. (E.g., Patent Document 1, Patent Document 2, etc.). According to these documents, by performing spark discharge treatment by applying a high voltage of 100 V or more, the function of the photocatalyst can be imparted by forming micropores, and harmful substances such as organic compounds and bacteria can be removed. become.
特公平６－４１６４０号公報Japanese Examined Patent Publication No. 6-41640 特公平８－９８４号公報Japanese Examined Patent Publication 8-984
　しかしながら、高電圧をかける火花放電処理によりチタン又はチタン合金の陽極酸化皮膜に孔を形成した場合には、形成される孔が約１μｍと大きい。このように陽極酸化皮膜に形成される孔が大きいと、チタン酸化皮膜と人体組織などの基体との結合の際に組織が密に埋まらず、固定するのが困難となる、という問題点がある。また、１μｍより小さい微細孔の孔を開けることができる技術もあるが、孔がチューブ状となっているため貫通した際に皮膜が離れてしまい、膜としての形状を維持できない、という問題点がある。 However, when a hole is formed in the anodized film of titanium or a titanium alloy by spark discharge treatment applying a high voltage, the formed hole is as large as about 1 μm. As described above, when the pores formed in the anodized film are large, there is a problem that the tissue is not densely embedded when bonding the titanium oxide film to a substrate such as a human tissue, which makes it difficult to fix. . In addition, there is also a technology that can make fine holes smaller than 1 μm, but because the holes are tube-shaped, the film separates when it is penetrated and the shape of the film can not be maintained. is there.
　本発明は、上記課題に鑑みてなされたものであり、チタン又はチタン合金薄膜から１００ｎｍ以下の孔を有するチタン又はチタン合金の酸化薄膜を製造する方法を提供することを目的とする。 The present invention is made in view of the above-mentioned subject, and an object of the present invention is to provide a method of manufacturing a titanium or titanium alloy oxide thin film having a hole of 100 nm or less from a titanium or titanium alloy thin film.
　上記目的を達成するために本発明は、チタン又はチタン合金製薄膜を陽極として、フッ化水素化合物を０．５重量％以下溶解した硫酸溶液又はフッ化水素化合物を０．５重量％以下溶解した酸化剤濃度５ｇ／Ｌ以上の電解硫酸液中で１～２０Ａ／ｄｍ２の電流密度で電解処理する、微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法を提供する（発明１）。 In order to achieve the above object, the present invention uses a titanium or titanium alloy thin film as an anode and a sulfuric acid solution in which a hydrogen fluoride compound is dissolved by 0.5 wt% or less or a hydrogen fluoride compound by 0.5 wt% or less Provided is a method of producing a titanium or titanium alloy oxide thin film having fine pores, which is electrolytically treated at a current density of 1 to 20 A / dm 2 in an electrolytic sulfuric acid solution having an oxidant concentration of 5 g / L or more (Invention 1).
　かかる発明（発明１）によれば、フッ化水素化合物を用いた電解処理によるエッチング効果により、チタン又はチタン合金の酸化薄膜に１００ｎｍ以下、特に５０ｎｍ以下の孔を形成することができる。 According to this invention (Invention 1), holes of 100 nm or less, particularly 50 nm or less can be formed in the oxide thin film of titanium or titanium alloy by the etching effect by the electrolytic treatment using the hydrogen fluoride compound.
　上記発明（発明１）においては、前記硫酸溶液又は電解硫酸液の硫酸濃度が１０重量％以上であることが好ましい（発明２）。 In the said invention (invention 1), it is preferable that the sulfuric acid concentration of the said sulfuric acid solution or electrolytic sulfuric acid solution is 10 weight% or more (invention 2).
　かかる発明（発明２）によれば、チタン又はチタン合金の酸化薄膜に１００ｎｍ以下の孔を短時間で形成することができる。 According to this invention (invention 2), the hole of 100 nm or less can be formed in a short time in the oxide thin film of titanium or titanium alloy.
　上記発明（発明１，２）においては、前記フッ化水素化合物が、フッ化アンモニウムであることが好ましい（発明３）。 In the said invention (invention 1 and 2), it is preferable that the said hydrogen fluoride compound is ammonium fluoride (invention 3).
　かかる発明（発明３）によれば、チタン又はチタン合金の酸化薄膜に１００ｎｍ以下の孔を容易に形成することができる。 According to this invention (invention 3), a hole of 100 nm or less can be easily formed in the oxide thin film of titanium or titanium alloy.
　上記発明（発明１～３）においては、前記フッ化水素化合物を溶解した硫酸溶液又は電解硫酸液による電解処理の処理時間が３０～６０秒であることが好ましい（発明４）。 In the above inventions (Inventions 1 to 3), the treatment time of the electrolytic treatment with the sulfuric acid solution or electrolytic sulfuric acid solution in which the hydrogen fluoride compound is dissolved is preferably 30 to 60 seconds (Invention 4).
　かかる発明（発明４）によれば、チタン又はチタン合金の酸化薄膜に効率良く１００ｎｍ以下の孔を形成することができる。 According to this invention (invention 4), the hole of 100 nm or less can be efficiently formed in the oxide thin film of titanium or titanium alloy.
　上記発明（発明１～４）においては、前記フッ化水素化合物を溶解した硫酸溶液又は電解硫酸液による電解処理の後、フッ化水素化合物を溶解しない電解硫酸液中で電解処理することが好ましい（発明５）。 In the above inventions (Inventions 1 to 4), after electrolytic treatment with the sulfuric acid solution or electrolytic sulfuric acid solution in which the hydrogen fluoride compound is dissolved, it is preferable to carry out electrolytic treatment in an electrolytic sulfuric acid solution in which the hydrogen fluoride compound is not dissolved ( Invention 5).
　かかる発明（発明５）によれば、１段目の電解処理をフッ化水素化合物を溶解した硫酸溶液又は電解硫酸液で行った後、２段目の電解処理をフッ化水素化合物を溶解しない電解硫酸液中で行うことにより、チタン又はチタン合金の酸化薄膜の１００ｎｍ以下の孔を安定化することができる。 According to this invention (Invention 5), after performing the electrolytic treatment of the first stage with the sulfuric acid solution or electrolytic sulfuric acid solution in which the hydrogen fluoride compound is dissolved, the electrolytic treatment after the second stage does not dissolve the hydrogen fluoride compound By carrying out in a sulfuric acid solution, the hole of 100 nm or less of the oxide thin film of titanium or titanium alloy can be stabilized.
　本発明の微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法によれば、チタン又はチタン合金製薄膜を陽極としてフッ化水素化合物を溶解した硫酸溶液又は電解硫酸液中で所定の電流密度で電解処理することで、フッ化水素化合物のエッチング効果と電解硫酸液の酸化力とにより、チタン又はチタン合金の酸化薄膜を形成しつつ１００ｎｍ以下、特に５０ｎｍ以下の孔を形成することができる。 According to the method of producing a titanium or titanium alloy thin film having fine pores of the present invention, the titanium or titanium alloy thin film is used as an anode at a predetermined current density in a sulfuric acid solution or an electrolytic sulfuric acid solution in which a hydrogen fluoride compound is dissolved. By electrolytic treatment, holes of 100 nm or less, particularly 50 nm or less can be formed while forming an oxide thin film of titanium or titanium alloy by the etching effect of the hydrogen fluoride compound and the oxidizing power of the electrolytic sulfuric acid solution.
本発明の一実施形態による微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法を適用可能な処理装置を示す概略図である。FIG. 1 is a schematic view showing a processing apparatus to which a method of manufacturing a titanium or titanium alloy oxide thin film having micropores according to an embodiment of the present invention is applicable.
　図１は本発明の一実施形態による微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法を適用可能な処理装置を概念的に示しており、図１において処理装置１は、処理槽２とこの処理槽２内に設置された陰極部材４及び陽極部材５とを有し、これら陰極部材４及び陽極部材５はそれぞれ直流電源３のマイナス極及びプラス極に接続している。なお、処理槽２には該処理槽２内の溶液を所望の温度に保つための恒温ヒータ（図示せず）を設けることができる。このような処理装置１において、陽極部材５は被処理部材となるものであり、チタン又はチタン合金製の薄膜を用いた部材を用いる。また、陰極部材４としては、通電性の材料であれば特に制限はないが、導電性、耐食性などの点でチタン又はチタン合金製の部材（薄膜を含む）を用いることができる。 FIG. 1 conceptually shows a processing apparatus to which a method of manufacturing a titanium or titanium alloy oxide thin film having fine pores according to an embodiment of the present invention can be applied. In FIG. The cathode member 4 and the anode member 5 installed in the processing tank 2 are provided, and the cathode member 4 and the anode member 5 are respectively connected to the negative electrode and the positive electrode of the DC power supply 3. The treatment bath 2 can be provided with a constant temperature heater (not shown) for keeping the solution in the treatment bath 2 at a desired temperature. In such a processing apparatus 1, the anode member 5 is a member to be treated, and a member using a thin film made of titanium or a titanium alloy is used. The cathode member 4 is not particularly limited as long as it is a conductive material, but a member (including a thin film) made of titanium or a titanium alloy can be used in terms of conductivity, corrosion resistance, and the like.
　１段目の電解処理では、このような処理装置１の処理槽２に収容する電解処理の溶液として、フッ化水素化合物を溶解した硫酸溶液又は電解硫酸液Ｓを用いる。硫酸溶液のみでは酸化力がないためチタン又はチタン合金が溶解するのみで、その微細孔の孔径は１００ｎｍ以下とすることはできるが、３０ｎｍ以下とするのは困難である。より微細孔を形成するためには、酸化力を有する電解硫酸液を使用する。この電解硫酸液の場合における酸化剤濃度は、硫酸を電解して電解硫酸液を作製する際に生成可能な酸化剤濃度であればよいが、５ｇ／Ｌ未満では酸化速度が遅くなってしまい、陽極部材５に用いたチタン又はチタン合金製の薄膜に形成される微細孔の孔径が大きくなってしまう。なお、酸化剤濃度の上限については特に制限はないが、硫酸を電解して電解硫酸液を作製する際の効率の点から１０ｇ／Ｌ程度が現実的である。 In the first-stage electrolytic treatment, a sulfuric acid solution or an electrolytic sulfuric acid solution S in which a hydrogen fluoride compound is dissolved is used as a solution of the electrolytic treatment contained in the treatment tank 2 of the treatment apparatus 1. Since only a sulfuric acid solution has no oxidizing power, titanium or a titanium alloy only dissolves, and the pore diameter of the micropores can be 100 nm or less, but it is difficult to be 30 nm or less. In order to form finer pores, an electrolytic sulfuric acid solution having oxidizing power is used. The oxidizing agent concentration in the case of this electrolytic sulfuric acid solution may be an oxidizing agent concentration that can be generated when electrolytic sulfuric acid is produced by electrolyzing sulfuric acid, but if it is less than 5 g / L, the oxidation rate becomes slow, The pore diameter of the micropores formed in the thin film made of titanium or titanium alloy used for the anode member 5 is increased. The upper limit of the oxidizing agent concentration is not particularly limited, but about 10 g / L is realistic from the viewpoint of the efficiency when electrolytic sulfuric acid is produced by electrolyzing sulfuric acid.
　前記フッ化水素化合物としては、フッ酸と塩基性物質との塩であれば良く、フッ化アンモニウムが取扱い性が良好で汎用的である点で好ましい。例えば、フッ化水素化合物がフッ化アンモニウムの場合、その濃度は０．５重量％以下である。フッ化アンモニウムの濃度が０．５重量％を超えると、チタンの溶解が進み過ぎて孔が大きくなり、孔がチューブ状となったりする。また、フッ化アンモニウムの濃度の下限については０．１重量％未満では、チタンの溶解が進まず、微細孔の形成が十分でなく、また、チタンの溶解が進まないことから形成される酸化皮膜も薄くなり、チタン基材を貫通できないため好ましくない。特に微細孔の形成の点でフッ化アンモニウムの濃度を０．２５±０．０５重量％とすることが好ましい。なお、フッ化アンモニウム以外のフッ化水素化合物の場合であってもその濃度は０．５重量％以下とすればよい。 As the hydrogen fluoride compound, any salt of hydrofluoric acid and a basic substance may be used, and ammonium fluoride is preferable in terms of good handleability and versatility. For example, when the hydrogen fluoride compound is ammonium fluoride, the concentration is 0.5% by weight or less. If the concentration of ammonium fluoride exceeds 0.5% by weight, the dissolution of titanium proceeds too much, the pores become large, and the pores become tubular. In addition, if the lower limit of the concentration of ammonium fluoride is less than 0.1% by weight, the dissolution of titanium does not proceed, the formation of micropores is not sufficient, and the dissolution of titanium does not proceed, so an oxide film formed Also, it is not preferable because it becomes thin and can not penetrate the titanium base material. In particular, the concentration of ammonium fluoride is preferably 0.25 ± 0.05% by weight in view of the formation of micropores. Even in the case of a hydrogen fluoride compound other than ammonium fluoride, its concentration may be 0.5 wt% or less.
　さらに硫酸溶液又は電解硫酸液Ｓにおける硫酸濃度については、硫酸濃度が５重量％未満では、後述する電解処理における硫酸の電解によるＨ＋（Ｈ３Ｏ＋）イオンが少ないため陽極部材５（被処理部材）としてのチタン又はチタン合金の溶解速度が遅くなり、表面に酸化皮膜が形成されてしまい反応が進まなくなる一方、硫酸濃度が５０重量％を超えるとチタンの溶解速度が速くなり過ぎ、チタンの溶解が優先的に進んでしまい、チタンの酸化皮膜が形成されにくくなるため５～５０重量％とすることが好ましい。特に硫酸濃度を１０～４０重量％とすることが好ましい。 Furthermore, as for the concentration of sulfuric acid in the sulfuric acid solution or electrolytic sulfuric acid solution S, when the concentration of sulfuric acid is less than 5% by weight, the amount of H + (H 3 O + ) ions by electrolysis of sulfuric acid in electrolytic treatment described later is small. Dissolution rate of titanium or titanium alloy as a part) is slowed, an oxide film is formed on the surface and reaction does not proceed, but if the concentration of sulfuric acid exceeds 50% by weight, the dissolution rate of titanium becomes too fast. It is preferable to set the content to 5 to 50% by weight because dissolution proceeds preferentially and it becomes difficult to form an oxide film of titanium. In particular, the concentration of sulfuric acid is preferably 10 to 40% by weight.
　次に上述したような処理装置１を用いた微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法について説明する。まず、処理槽２に直流電源３に接続した被処理部材としての陰極部材４及びチタン又はチタン合金製の薄膜を用いた部材からなる陽極部材５を吊設したら処理槽２を硫酸溶液又は電解硫酸液Ｓで満たす。 Next, a method of manufacturing a titanium or titanium alloy oxide thin film having fine pores using the above-described processing apparatus 1 will be described. First, when the cathode member 4 as a processing member connected to the DC power supply 3 and the anode member 5 formed of a member using a thin film made of titanium or titanium alloy are suspended in the processing tank 2, the processing tank 2 is sulfuric acid solution or electrolytic sulfuric acid Fill with solution S.
　そして、直流電源３から電流を印加する。これにより、陽極部材５のチタン又はチタン合金製の薄膜が酸化皮膜となる一方、フッ化水素化合物のエッチング効果により微細孔が形成される。ここで印加する電流密度は１Ａ／ｄｍ２よりも低いと安定した制御が困難となる一方、２０Ａ／ｄｍ２よりも高いと電流密度が大きくなりすぎるため、チタン又はチタン合金製の薄膜に形成される孔径が大きくなってしまうばかりか、孔がチューブとなったりする。したがって、電流密度は１～２０Ａ／ｄｍ２、好ましくは３～１０Ａ／ｄｍ２である。 Then, a current is applied from the DC power supply 3. Thereby, while the thin film made of titanium or titanium alloy of the anode member 5 becomes an oxide film, micropores are formed by the etching effect of the hydrogen fluoride compound. When the current density applied here is lower than 1 A / dm 2 , stable control becomes difficult, while when the current density is higher than 20 A / dm 2 , the current density becomes too large, and therefore, a thin film made of titanium or titanium alloy is formed. Not only does the hole diameter increase, but the hole becomes a tube. Accordingly, the current density is 1 to 20 A / dm 2 , preferably 3 to 10 A / dm 2 .
　この電解処理における硫酸溶液又は電解硫酸液Ｓの温度については、特に制限はないが、硫酸溶液又は電解硫酸液Ｓの温度が１０℃未満であると電解硫酸液中の酸化剤の効果が十分に発揮されず、十分に酸化皮膜が形成されない一方、５０℃を超えると酸化速度が上がってしまい、不動態である酸化皮膜の形成によりチタンの溶解が進まなくなり孔を形成しにくくなり、基材であるチタン又はチタン合金製の薄膜を貫通することが困難となるため好ましくない。したがって、好ましい硫酸溶液又は電解硫酸液Ｓの温度は１０～５０℃、特に２０～５０℃とする。処理槽２では硫酸溶液又は電解硫酸液Ｓの温度が上述した温度となるように必要に応じて恒温ヒータ（図示せず）により所定の温度に保持することが好ましい。 The temperature of the sulfuric acid solution or electrolytic sulfuric acid solution S in this electrolytic treatment is not particularly limited, but when the temperature of the sulfuric acid solution or electrolytic sulfuric acid solution S is less than 10 ° C., the effect of the oxidizing agent in the electrolytic sulfuric acid solution is sufficient While it is not exhibited and an oxide film is not sufficiently formed, if the temperature exceeds 50 ° C., the oxidation rate increases, and the formation of a passive oxide film prevents dissolution of titanium and makes it difficult to form pores, which is a substrate It is not preferable because it becomes difficult to penetrate a thin film made of titanium or titanium alloy. Therefore, the preferred temperature of the sulfuric acid solution or electrolytic sulfuric acid solution S is 10 to 50 ° C., particularly 20 to 50 ° C. In the treatment tank 2, it is preferable to maintain the temperature of the sulfuric acid solution or the electrolytic sulfuric acid solution S at a predetermined temperature by a constant temperature heater (not shown) as necessary so as to reach the above-mentioned temperature.
　上述したような電解処理の時間は特に制限はないが３０秒未満では、チタンの溶解が不十分で微細孔が形成されにくい。なお、電解処理時間の上限については、あまり長すぎるとチタンの溶解が進み、形成される孔が大きく、不均一となってしまうばかりか、処理効率が低下するため、３６０秒未満とするのが好ましい、特に処理時間は４０～６０秒程度とすることが好ましい。 The time of the above-mentioned electrolytic treatment is not particularly limited, but if it is less than 30 seconds, the dissolution of titanium is insufficient and micropores are hardly formed. The upper limit of the electrolytic treatment time is not less than 360 seconds because dissolution of titanium proceeds too much and the formed pores become large and uneven, and the treatment efficiency decreases, if too long. The treatment time is preferably about 40 to 60 seconds.
　上述した電解処理により以下のようにして微細孔が形成された微細孔を有するチタン又はチタン合金の酸化薄膜となる。すなわち、硫酸溶液又は電解硫酸液Ｓ中の硫酸とフッ化水素化合物による電解処理により、陽極ではＴｉ３＋が溶出し、微細孔を形成する。
　　Ｔｉ＋３Ｈ＋→Ｔｉ３＋＋３／２Ｈ２　　…（１）
　電解硫酸液Ｓ中に電解硫酸が含まれる場合には以下の反応も進みＴｉＯ２を形成する。
　　Ｔｉ＋２Ｈ２Ｏ→ＴｉＯ２＋４Ｈ＋＋４ｅ－　　…（２） It becomes an oxide thin film of titanium or a titanium alloy having fine pores in which fine pores are formed as follows by the above-mentioned electrolytic treatment. That is, by the electrolytic treatment with the sulfuric acid solution or the sulfuric acid and the hydrogen fluoride compound in the electrolytic sulfuric acid solution S, Ti 3+ is eluted at the anode to form fine pores.
Ti + 3H + → Ti 3+ + 3 / 2H 2 (1)
When electrolytic sulfuric acid is contained in the electrolytic sulfuric acid solution S, the following reaction also proceeds to form TiO 2 .
Ti + 2H 2 O → TiO 2 + 4H + + 4e - ... (2)
　チタンまたはチタン合金の陽極酸化処理は式（１）のＴｉの溶解と式（２）のＴｉの酸化との競争反応であり、Ｔｉ酸化速度とフッ化水素化合物によるＴｉＯ２のエッチング作用により、酸化皮膜を形成しつつ微細な孔を開けることが可能となる。そして、このフッ化水素化合物の濃度が高すぎる場合や曝されている時間が長いとＴｉＯ２の内部に浸透し、内側のチタンも溶解してしまう。これによりチューブ状の弱い酸化皮膜が形成される原因となる可能性が高くなることから、この硫酸溶液又は電解硫酸液Ｓの硫酸濃度及び酸化剤濃度とフッ化水素化合物濃度と電解処理条件については十分に配慮するのが望ましい。 The anodizing treatment of titanium or titanium alloy is a competitive reaction of the dissolution of Ti of formula (1) and the oxidation of Ti of formula (2), and the oxidation is performed by the action of Ti oxidation and etching of TiO 2 by hydrogen fluoride compound. It becomes possible to make fine holes while forming a film. When the concentration of the hydrogen fluoride compound is too high or the exposure time is long, the titanium dioxide penetrates into the interior of TiO 2 and the titanium inside also dissolves. This increases the possibility of causing the formation of a tube-like weak oxide film, so the concentration of sulfuric acid and oxidizing agent, the concentration of hydrogen fluoride compound, and the electrolytic treatment conditions of this sulfuric acid solution or electrolytic sulfuric acid solution S are increased. It is desirable to give due consideration.
　さらに、本実施形態においては、上述した硫酸溶液又は電解硫酸液Ｓとフッ化水素化合物との電解処理（１段目の電解処理）の後、フッ化水素化合物を用いない電解硫酸液Ｓのみによる電解処理（２段目の電解処理）を行うことが好ましい。 Furthermore, in the present embodiment, after the electrolytic treatment (first electrolytic treatment) of the above-described sulfuric acid solution or electrolytic sulfuric acid solution S and the hydrogen fluoride compound, only the electrolytic sulfuric acid solution S not using the hydrogen fluoride compound is used. It is preferable to carry out electrolytic treatment (second electrolytic treatment).
　この２段目の電解処理の条件は、基本的に前述した１段目の電解処理と同じでよいが、処理時間については、陽極部材５に用いたチタン又はチタン合金製の薄膜の厚さに応じて適宜設定すればよい。このような２段目の電解処理をフッ化水素化合物を溶解しない電解硫酸液中で行うことにより、チタン又はチタン合金の酸化薄膜の１００ｎｍ以下の孔を安定化することができる。 The conditions of the second stage electrolytic treatment may be basically the same as the first electrolytic treatment described above, but the treatment time is the thickness of the thin film made of titanium or titanium alloy used for the anode member 5 It may be set appropriately according to the situation. By carrying out such second electrolytic treatment in an electrolytic sulfuric acid solution in which the hydrogen fluoride compound is not dissolved, the pores of 100 nm or less of the titanium or titanium alloy oxide thin film can be stabilized.
　以上、本発明の微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法について、前記各実施形態に基づいて説明してきたが、本発明は前記実施例に限定されず種々の変形実施が可能である。例えば、陽極部材５はチタン又はチタン合金製の薄膜を用いていればよく、金属製の電極材の表面をチタン又はチタン合金製の薄膜で覆う形状としてもよい。また、フッ化水素化合物の濃度、硫酸濃度、電流密度、電解硫酸の温度及び電解処理の時間により形成される微細孔の孔径が異なるので、所望とする微細孔に応じて、これらの条件を適宜調整することができる。 As mentioned above, although the manufacturing method of the oxide thin film of the titanium or titanium alloy which has a micropore of this invention was demonstrated based on said each embodiment, this invention is not limited to the said Example, and various deformation | transformation implementation is possible. is there. For example, the anode member 5 may be a thin film made of titanium or a titanium alloy, and the surface of the metal electrode material may be covered with a thin film made of titanium or a titanium alloy. In addition, since the pore diameter of the micropores formed varies depending on the concentration of the hydrogen fluoride compound, the concentration of the sulfuric acid, the concentration of the sulfuric acid, the current density, the temperature of the electrolytic sulfuric acid and the time of the electrolytic treatment, these conditions are appropriately selected according to the desired micropores. It can be adjusted.
　以下に実施例及び比較例を示し、本発明をより具体的に説明する。ただし、本発明はこれらの記載により何ら限定されるものではない。 The present invention will be described more specifically by showing Examples and Comparative Examples below. However, the present invention is not limited at all by these descriptions.
［実施例１及び比較例１］
　１００ｍｍ×１００ｍｍ×０．０４ｍｍ（ｔ）の純チタンの試験片を用意し、この試験片を用いて陰極部材４及び陽極部材５を形成し、図１に示す処理装置１を構成した。この処理装置１により１段目の電解処理の処理条件を表１に示すよう設定して陽極酸化処理を行った。すなわち、１段目の電解処理は、硫酸濃度１０重量％、酸化剤濃度１０ｇ／Ｌの電解硫酸液にフッ化アンモニウムを０．２５重量％溶解した電解硫酸液Ｓで、温度３０℃、電流密度３．５Ａ／ｄｍ２にて処理時間４０秒で行った。次に２段目の電解処理を、フッ化アンモニウムを溶解することなく１段目と同濃度の電解硫酸液のみで６０秒行った。 Example 1 and Comparative Example 1
A test piece of pure titanium of 100 mm × 100 mm × 0.04 mm (t) was prepared, and using this test piece, the cathode member 4 and the anode member 5 were formed to constitute the processing apparatus 1 shown in FIG. Anodizing treatment was performed by setting the treatment conditions of the first stage electrolytic treatment as shown in Table 1 by this treatment apparatus 1. That is, the electrolytic treatment in the first step is an electrolytic sulfuric acid solution S in which 0.25 wt% of ammonium fluoride is dissolved in an electrolytic sulfuric acid solution having a sulfuric acid concentration of 10 wt% and an oxidant concentration of 10 g / L. The processing time was 40 seconds at 3.5 A / dm 2 . Next, the second stage electrolytic treatment was performed for 60 seconds only with the electrolytic sulfuric acid solution having the same concentration as the first stage without dissolving ammonium fluoride.
　この処理後の陽極部材５の純チタンの試験片の表面を電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ）で１００，０００倍に拡大して観測したところ、陽極部材５の純チタンの試験片には、約２０ｎｍの孔が形成されたチタン酸化皮膜が形成されていることが確認できた。なお、比較のためにフッ化アンモニウムを溶解することなく１段目と同濃度の電解硫酸液のみで、温度３０℃、電流密度３．５Ａ／ｄｍ２にて処理時間４０秒で行ったもの（比較例１）では、チタンの酸化皮膜は形成されたが微細孔は形成されなかった。 When the surface of the test piece of pure titanium of the anode member 5 after this treatment is observed at 100,000 times magnification with a field emission scanning electron microscope (FE-SEM), the test piece of pure titanium of the anode member 5 is obtained. It was confirmed that a titanium oxide film having pores of about 20 nm was formed. In addition, for comparison, the electrolytic sulfuric acid solution having the same concentration only at the same concentration as the first stage without dissolving ammonium fluoride was used at a temperature of 30 ° C. and a current density of 3.5 A / dm 2 for a treatment time of 40 seconds ( In Comparative Example 1), an oxide film of titanium was formed but fine pores were not formed.
［実施例２～４及び比較例２、３］
　実施例１において、１段目の電解処理条件を表１に示すよう設定した以外は同様にして純チタンの試験片を処理した。なお、表１には実施例１及び比較例１の処理条件も記載した。これらの処理後の陽極部材５の純チタンの試験片の表面を電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ）で１００，０００倍に拡大して観測し、陽極部材５の純チタンの試験片に形成されたチタン酸化皮膜の微細孔の孔径を計測した結果を実施例１及び比較例１の結果とともに表２に示す。 [Examples 2 to 4 and Comparative Examples 2 and 3]
In Example 1, a test piece of pure titanium was treated in the same manner except that the electrolytic treatment conditions of the first stage were set as shown in Table 1. Table 1 also shows the processing conditions of Example 1 and Comparative Example 1. The surface of the test piece of pure titanium of the anode member 5 after these treatments is observed by a field emission scanning electron microscope (FE-SEM) at a magnification of 100,000 to obtain a test piece of pure titanium of the anode member 5 The results of measurement of the pore diameter of the micropores of the formed titanium oxide film are shown in Table 2 together with the results of Example 1 and Comparative Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び表２から明らかなように１段目の電解処理における電解硫酸液Ｓの温度が１０℃である実施例２では、約１５ｎｍの微細孔が形成された酸化チタン薄膜を製造することができた。また、処理時間が３００秒と長い実施例３では、約４０ｎｍの微細孔が形成された酸化チタン薄膜を製造することができた。さらに、１段目の電解処理をフッ化アンモニウムを溶解した硫酸のみで行った実施例４では、比較的孔の大きな酸化チタン薄膜を製造することができた。これらの実施例により、電解処理の条件を調整することにより、酸化チタン薄膜に形成される微細孔の孔径を調整することができることがわかる。 As is apparent from Tables 1 and 2, in Example 2 in which the temperature of the electrolytic sulfuric acid solution S in the first stage electrolytic treatment is 10 ° C., a titanium oxide thin film having micropores of about 15 nm is formed. did it. Further, in Example 3 in which the processing time was as long as 300 seconds, it was possible to manufacture a titanium oxide thin film in which fine pores of about 40 nm were formed. Furthermore, in Example 4 in which the electrolytic treatment in the first stage was performed only with sulfuric acid in which ammonium fluoride was dissolved, a titanium oxide thin film having a relatively large pore size could be produced. From these examples, it is understood that the pore diameter of the micropores formed in the titanium oxide thin film can be adjusted by adjusting the conditions of the electrolytic treatment.
　これに対し、フッ化アンモニウムを０．７重量％溶解した電解硫酸液で処理した比較例２及び電流密度が２８Ａ／ｄｍ２と高い比較例３では、エッチング効果が大きすぎて微細孔がチューブ状となってしまい、得られる薄膜の機械的強度が低かった。 On the other hand, in Comparative Example 2 treated with an electrolytic sulfuric acid solution in which 0.7% by weight of ammonium fluoride is dissolved and Comparative Example 3 in which the current density is 28 A / dm 2 , the etching effect is too large and the micropores are tube-shaped The mechanical strength of the resulting thin film was low.
１　処理装置
２　処理槽
３　直流電源
４　陰極部材
５　陽極部材
Ｓ　硫酸溶液，電解硫酸液 DESCRIPTION OF SYMBOLS 1 treatment apparatus 2 treatment tank 3 DC power supply 4 cathode member 5 anode member S sulfuric acid solution, electrolytic sulfuric acid solution

Claims (5)

  1. 　チタン又はチタン合金製薄膜を陽極として、フッ化水素化合物を０．５重量％以下溶解した硫酸溶液又はフッ化水素化合物を０．５重量％以下溶解した酸化剤濃度５ｇ／Ｌ以上の電解硫酸液中で１～２０Ａ／ｄｍ２の電流密度で電解処理する、微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法。 A sulfuric acid solution in which 0.5 wt% or less of a hydrogen fluoride compound is dissolved or an electrolytic sulfuric acid solution having an oxidant concentration of 5 g / L or more in which 0.5 wt% or less of a hydrogen fluoride compound is dissolved A method of producing a titanium or titanium alloy oxide thin film having fine pores, which is electrolytically treated at a current density of 1 to 20 A / dm 2 in the above.
  2. 　前記硫酸溶液又は電解硫酸液の硫酸濃度が１０重量％以上である、請求項１に記載の微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法。 The method for producing an oxide thin film of titanium or titanium alloy having fine pores according to claim 1, wherein the sulfuric acid concentration of the sulfuric acid solution or the electrolytic sulfuric acid solution is 10% by weight or more.
  3. 　前記フッ化水素化合物が、フッ化アンモニウムである、請求項１又は２に記載の微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法。 The method for producing an oxide thin film of titanium or titanium alloy having fine pores according to claim 1 or 2, wherein the hydrogen fluoride compound is ammonium fluoride.
  4. 　前記フッ化水素化合物を溶解した硫酸溶液又は電解硫酸液による電解処理の処理時間が３０～６０秒である、請求項１～３のいずれか一項に記載の微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法。 The titanium or titanium alloy with fine pores according to any one of claims 1 to 3, wherein the treatment time of the electrolytic treatment with the sulfuric acid solution or electrolytic sulfuric acid solution in which the hydrogen fluoride compound is dissolved is 30 to 60 seconds. Method of manufacturing oxide thin film.
  5. 　前記フッ化水素化合物を溶解した硫酸溶液又は電解硫酸液による電解処理の後、フッ化水素化合物を溶解しない電解硫酸液中で電解処理する、請求項１～４のいずれか一項に記載の微細孔を有するチタン又はチタン合金の酸化薄膜の製造方法。 The fine structure according to any one of claims 1 to 4, wherein the electrolytic treatment is carried out in an electrolytic sulfuric acid solution in which the hydrogen fluoride compound is not dissolved after the electrolytic treatment with the sulfuric acid solution or electrolytic sulfuric acid solution in which the hydrogen fluoride compound is dissolved. A method of producing an oxide thin film of titanium or titanium alloy having a hole.
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