WO2019073746A1 - Procédé de fabrication d'un film d'oxyde mince de titane ou d'alliage de titane ayant des micropores - Google Patents

Procédé de fabrication d'un film d'oxyde mince de titane ou d'alliage de titane ayant des micropores Download PDF

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Publication number
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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Prior art keywords
titanium
sulfuric acid
acid solution
electrolytic
titanium alloy
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PCT/JP2018/034101
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English (en)
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/zh
Publication of WO2019073746A1 publication Critical patent/WO2019073746A1/fr

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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

Definitions

  • 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 & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un dispositif de traitement 1 qui comprend un réservoir de traitement 2 et un élément d'électrode négative 4 et un élément d'électrode positive 5 placé à l'intérieur de ce réservoir de traitement 2. Cet élément d'électrode négative 4 et cet élément d'électrode positive 5 sont respectivement raccordés à la borne négative et à la borne positive d'une alimentation en courant continu 3. Dans ce dispositif de traitement 1, l'élément d'électrode positive 5 est un élément à traiter, et un élément utilisant un film mince formé de titane ou d'alliage de titane est utilisé pour celui-ci. Une solution d'acide sulfurique ou une solution d'acide sulfurique électrolytique S ayant une concentration d'agent oxydant d'au moins 5 g/l dans laquelle un composé fluorhydrique est dissous à 0,5 % en poids ou moins est reçue dans le réservoir de traitement 2 et un traitement d'électrolyse est effectué à une densité de courant de 1 à 20 A/dm2. Ce dispositif de traitement est applicable à un procédé de fabrication d'un film d'oxyde mince de titane ou d'un alliage de titane qui a des trous de 100 nm ou moins à partir d'un film mince titane ou d'alliage de titane.
PCT/JP2018/034101 2017-10-12 2018-09-14 Procédé de fabrication d'un film d'oxyde mince de titane ou d'alliage de titane ayant des micropores WO2019073746A1 (fr)

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US16/754,751 US20200318251A1 (en) 2017-10-12 2018-09-14 Method for manufacturing titanium or titanium alloy thin oxide film having micro-holes
CN201880059921.1A CN111094634A (zh) 2017-10-12 2018-09-14 有微孔的钛或钛合金的氧化薄膜的制造方法

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JP2017-198830 2017-10-12
JP2017198830A JP6512257B1 (ja) 2017-10-12 2017-10-12 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

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Cited By (2)

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CN111437006A (zh) * 2020-04-27 2020-07-24 首都医科大学宣武医院 取栓支架及其制备方法、取栓装置
CN114618505A (zh) * 2020-12-10 2022-06-14 中国科学院大连化学物理研究所 一种负载型氧化物薄膜及其制备方法、应用

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
JP6706012B1 (ja) * 2019-03-05 2020-06-03 栗田工業株式会社 微細孔を封孔したチタン又はチタン合金の酸化薄膜の製造方法
WO2020209104A1 (fr) 2019-04-08 2020-10-15 Ricoh Company, Ltd. Module d'extension, système de module, et système informatique

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JPH11315398A (ja) * 1998-02-20 1999-11-16 Daiwa House Ind Co Ltd 光触媒用チタン陽極酸化皮膜の生成方法
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JP2009197284A (ja) * 2008-02-22 2009-09-03 Daiso Co Ltd 電極及びその製造方法
JP2011202206A (ja) * 2010-03-24 2011-10-13 Daiso Co Ltd 不溶性電極及びその製造方法

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JPH11315398A (ja) * 1998-02-20 1999-11-16 Daiwa House Ind Co Ltd 光触媒用チタン陽極酸化皮膜の生成方法
JP2009507752A (ja) * 2005-09-09 2009-02-26 ユニバーシティ・オブ・ネバダ・リノ 酸素空孔を有するナノチューブ状チタニア基材の製造及び水の光電気分解におけるそれらの使用
JP2009197284A (ja) * 2008-02-22 2009-09-03 Daiso Co Ltd 電極及びその製造方法
JP2011202206A (ja) * 2010-03-24 2011-10-13 Daiso Co Ltd 不溶性電極及びその製造方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111437006A (zh) * 2020-04-27 2020-07-24 首都医科大学宣武医院 取栓支架及其制备方法、取栓装置
CN111437006B (zh) * 2020-04-27 2022-04-19 首都医科大学宣武医院 取栓支架及其制备方法、取栓装置
CN114618505A (zh) * 2020-12-10 2022-06-14 中国科学院大连化学物理研究所 一种负载型氧化物薄膜及其制备方法、应用

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JP6512257B1 (ja) 2019-05-15
JP2019073746A (ja) 2019-05-16
CN111094634A (zh) 2020-05-01
US20200318251A1 (en) 2020-10-08

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