JPH04154991A - Formation of low-order titanium oxide film on titanium material - Google Patents
Formation of low-order titanium oxide film on titanium materialInfo
- Publication number
- JPH04154991A JPH04154991A JP27817190A JP27817190A JPH04154991A JP H04154991 A JPH04154991 A JP H04154991A JP 27817190 A JP27817190 A JP 27817190A JP 27817190 A JP27817190 A JP 27817190A JP H04154991 A JPH04154991 A JP H04154991A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- low
- order
- titanium oxide
- oxide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000010936 titanium Substances 0.000 title claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000007743 anodising Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910010420 TinO2n-1 Inorganic materials 0.000 abstract 1
- AZCUJQOIQYJWQJ-UHFFFAOYSA-N oxygen(2-) titanium(4+) trihydrate Chemical compound [O-2].[O-2].[Ti+4].O.O.O AZCUJQOIQYJWQJ-UHFFFAOYSA-N 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- -1 titanium hydride Chemical compound 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、装飾品や建材又は還元剤その他電子部品など
に使用されるチタン材への低次酸化チタンの形成方法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for forming lower titanium oxide on a titanium material used for ornaments, building materials, reducing agents, and other electronic parts.
（従来の技術）
以前に、この種チタン材への低次酸化チタン皮膜の形成
方法として、特開平２−９３０９７号公報を提案した。(Prior Art) Previously, JP-A-2-93097 was proposed as a method for forming a low-order titanium oxide film on this type of titanium material.
この公報の記載内容は、チタン及びチタン合金から成る
チタン材を陽極酸化処理した後に、アンモニアや一酸化
炭素又は−酸化窒素などの還元雰囲気中において、少な
くとも６００℃以上の温度で加熱することにより、黒色
系の低次酸化チタン皮膜を形成するようにしたものであ
る。The contents of this publication state that after a titanium material made of titanium and a titanium alloy is anodized, it is heated at a temperature of at least 600°C in a reducing atmosphere of ammonia, carbon monoxide, or -nitrogen oxide. It forms a blackish low-order titanium oxide film.
（発明が解決しようとする課題）
所で、以上のような低次酸化チタン皮膜の形成方法では
、チタン材を陽極酸化処理した後に、該チタン材を低次
酸化チタンに還元させるために、アンモニアや一酸化炭
素又は−酸化窒素などのガスを使用することから、工場
内に有害ガスや刺激臭などが発生し、これら有害ガスな
どを排出するために換気装置などの設備が別途必要とな
り、設備コストが高くなる問題があった。(Problems to be Solved by the Invention) However, in the method for forming a low-order titanium oxide film as described above, after the titanium material is anodized, ammonia is added to reduce the titanium material to low-order titanium oxide. Because gases such as carbon monoxide and nitrogen oxide are used, harmful gases and irritating odors are generated within the factory, and separate equipment such as ventilation equipment is required to exhaust these harmful gases. There was a problem of high costs.
本発明は以上のような問題に鑑みてなしなもので、その
目的は、有害成分を使用することなく、ン皮膜を得るこ
とができるチタン材への低次酸化チタン皮膜の形成方法
を提供することにある。The present invention was made in view of the above-mentioned problems, and its purpose is to provide a method for forming a low-order titanium oxide film on a titanium material, which can obtain a low-order titanium oxide film without using harmful components. There is a particular thing.
（課題を解決するための手段）
上記目的を達成するために、本発明にかかる低吹酸化チ
タン皮膜の形成方法は、チタン材を陽極酸化処理した後
に、１０−’ｔｏｒｒ以下の減圧下で、３００℃以上に
加熱することを特徴とするものである。(Means for Solving the Problems) In order to achieve the above object, the method for forming a low blown titanium oxide film according to the present invention includes: after anodic oxidation treatment of a titanium material, under reduced pressure of 10-'torr or less; It is characterized by heating to 300°C or higher.
（作用・効果）
チタン材を陽極酸化処理することにより、灰色系の二酸
化チタンが（ＴｉＯ２）が形成され、この二酸化チタン
を１０ ”−３ｔｏｒｒ以下の減圧下で、３００℃以上
に加熱することにより、前記二酸化チタンが還元されて
、一般式Ｔ１ｎ０２ｎ−１（但しｎ＝１〜１０）で示さ
れる低次酸化チタンの内、黒色系のンが黒色皮膜となっ
て前記チタン材の表面に表出され、外観良好で耐候性に
優れた装飾品や建材となる。また、前記低次酸化チタン
は、酸素吸着機能に優れているため、還元剤としても使
用可能である。尚、前記陽極酸化処理を施したチタン材
を還元するに際して、１０−３ｔｏｒｒ以上の圧力条件
とする場合、また、３００°Ｃ以下の加熱条件とする場
合には、何れも陽極酸化処理で形成された前記二酸化チ
タンの還元作用が行われ難く、即ち、前記−酸化チタン
や五酸化二チタンの形成が充分に行われず、初期の目的
が達成できないために、前述した条件下で行うものであ
る。(Function/Effect) By anodizing titanium material, grayish titanium dioxide (TiO2) is formed, and by heating this titanium dioxide to 300°C or higher under reduced pressure of 10''-3 torr or less. , the titanium dioxide is reduced, and among the lower titanium oxides represented by the general formula T1n02n-1 (where n = 1 to 10), blackish ions become a black film and are exposed on the surface of the titanium material. This makes it a decorative item or building material with good appearance and excellent weather resistance.In addition, the lower titanium oxide has an excellent oxygen adsorption function, so it can also be used as a reducing agent. When reducing the titanium material that has been subjected to anodic oxidation treatment, if the pressure condition is 10-3 torr or more, or if the heating condition is 300°C or less, the reduction of the titanium dioxide formed by anodizing treatment is required. The process is carried out under the above-mentioned conditions because the initial objective cannot be achieved because the formation of titanium oxide and dititanium pentoxide is difficult to achieve.
（実施例）
以下本発明にかかるチタン材への低次酸化チタン皮膜の
形成方法を、具体例を挙げて説明する。(Example) The method of forming a low-order titanium oxide film on a titanium material according to the present invention will be described below by giving a specific example.
具体例１
先ず、３０ ｇ／ｊの硫酸と、２０ ｇ／ｌのリン酸及
びＬｏｇ／ｊの過酸化水素水とから成る電解浴を調製し
た。また、試料として純チタン板を使用し、この試料を
前記電解洛中において、電圧５０，１００．１５０．２
００Ｖで、それぞれ１０分間陽極酸化した。そして、前
記各試料の表面に、電圧５０Ｖの場合は１５０ｎｍ、電
圧１００Ｖの場合は３７０ ｎｍ、電圧１５０Ｖの場合
は１．Ｉ μｍ、電圧２００Ｖの場合は５．３μｍの
灰色皮膜をそれぞれ形成した。Specific Example 1 First, an electrolytic bath consisting of 30 g/j sulfuric acid, 20 g/l phosphoric acid, and Log/j hydrogen peroxide solution was prepared. In addition, a pure titanium plate was used as a sample, and this sample was subjected to the electrolysis at a voltage of 50,100.150.2.
00V for 10 minutes each. Then, the surface of each sample was coated with a thickness of 150 nm when the voltage was 50V, 370 nm when the voltage was 100V, and 1.5 nm when the voltage was 150V. In the case of I μm and voltage of 200 V, a gray film of 5.3 μm was formed.
次に、前記各試料を密封容器中にそれぞれ封入して、１
０−’ｔｏｒｒに減圧し、これら各容器の全体を４５０
℃に加熱した電気炉中に装填して、１２０分間放置した
。この結果、次表で示すような皮膜の色調変化が得られ
た。Next, each sample was sealed in a sealed container, and 1
Reduce the pressure to 0-'torr and reduce the entire volume of each container to 450
It was loaded into an electric furnace heated to 0.degree. C. and left for 120 minutes. As a result, changes in the color tone of the film as shown in the following table were obtained.
具体例２
前述した具体例１と同一条件で陽極酸化処理された各試
料を使用した。また、前記各試料の還元作用を促進させ
ることを目的として、該各試料と共に水素化チタンをそ
れぞれ密封容器中に封入して、１０−’ｔｏｒｒに減圧
し、これら各容器の全体を３５０°Ｃに加熱した電気炉
中に装填して、 １０分間放置した。この結果、次表で
示すような皮膜の色調変化が得られた。Specific Example 2 Each sample was anodized under the same conditions as in Specific Example 1 described above. In addition, in order to promote the reduction action of each sample, titanium hydride was sealed together with each sample in a sealed container, the pressure was reduced to 10-'torr, and the entire container was heated to 350°C. It was loaded into an electric furnace heated to 100 mL and left for 10 minutes. As a result, changes in the color tone of the film as shown in the following table were obtained.
具体例３
前述した具体例１と同一条件で陽極酸化処理した各試料
を使用した。また、前記各試料の還元作用を促進させる
ことを目的として、該各試料と共にチタン粉末をそれぞ
れ密封容器中に封入して、１０−’ｔ、ｏｒｒに減圧し
、これら各容器の全体を５００勢℃に加熱した電気炉中
に装填して、１２０分間放置した。この結果、次表で示
すような皮膜の色調変化が得られた。また、前記具体例
１〜３で得られた皮膜について、Ｘ線による回折試験を
行った所、何れもが一酸化チタンと五酸化二チタンから
成る黒色皮膜であった。Specific Example 3 Each sample was anodized under the same conditions as in Specific Example 1 described above. In addition, for the purpose of promoting the reduction action of each sample, titanium powder was sealed together with each sample in a sealed container, the pressure was reduced to 10-'t, orr, and the entire container was heated to 500 ml. It was loaded into an electric furnace heated to 0.degree. C. and left for 120 minutes. As a result, changes in the color tone of the film as shown in the following table were obtained. Further, when the films obtained in Specific Examples 1 to 3 were subjected to an X-ray diffraction test, they were all black films composed of titanium monoxide and dititanium pentoxide.
次に示す表は、Ｌ、ａ、ｂ系表色法における明度を示し
ている。尚、同表においては、本発明の比較例として、
以上の各具体例で示したような還元処理を施すことなく
、具体例１と同一条件で陽極酸化処理した各試料く灰色
）の明度を示している。The table shown below shows the brightness in the L, a, b color system. In addition, in the same table, as a comparative example of the present invention,
The lightness of each sample (gray) that was anodized under the same conditions as in Example 1 without being subjected to the reduction treatment shown in each example above is shown.
表〈皮膜の色調変化）
以上の表から明らかなように、具体例１〜３のものは、
その何れもが比較例に較べてＬ値が低下しており、この
ことから陽極酸化処理された皮膜が、前述した還元処理
によって黒色に変化していることが理解される。尚、前
記表中、具体例３の５０Ｖ、１’ＯＯＶ、１５０Ｖにつ
いては、Ｌ値及びａ、ｂ値についての試験を行っていな
い。Table (Change in color tone of film) As is clear from the table above, in Examples 1 to 3,
In all of them, the L value was lower than that of the comparative example, and from this it can be understood that the anodized film was turned black by the reduction treatment described above. In addition, in the above table, for 50V, 1'OOV, and 150V of Specific Example 3, tests regarding L value and a, b value were not conducted.
出願人 日本アルミニクム工業株式会社同 東海電子
株式会社Applicant: Nippon Aluminum Industries Co., Ltd. Tokai Electronics Co., Ltd.
Claims (1)
ｔｏｒｒ以下の減圧下で、３００℃以上に加熱すること
を特徴とするチタン材への低次酸化チタン皮膜の形成方
法。(1) After anodizing the titanium material, 10^-^3
A method for forming a low-order titanium oxide film on a titanium material, the method comprising heating to 300° C. or higher under reduced pressure of torr or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27817190A JPH04154991A (en) | 1990-10-16 | 1990-10-16 | Formation of low-order titanium oxide film on titanium material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27817190A JPH04154991A (en) | 1990-10-16 | 1990-10-16 | Formation of low-order titanium oxide film on titanium material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04154991A true JPH04154991A (en) | 1992-05-27 |
| JPH0577759B2 JPH0577759B2 (en) | 1993-10-27 |
Family
ID=17593582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27817190A Granted JPH04154991A (en) | 1990-10-16 | 1990-10-16 | Formation of low-order titanium oxide film on titanium material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04154991A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252687A (en) * | 1994-03-16 | 1995-10-03 | Miki Netsuren Kk | Method for adhering titanium and titanium alloy |
| WO2002049965A1 (en) * | 2000-12-19 | 2002-06-27 | Toho Titanium Co., Ltd. | Method of forming titanium oxide film and titanium electrolytic capacitor |
| WO2007029602A1 (en) * | 2005-09-08 | 2007-03-15 | Kinki University | Bone substitute material, medical material containing the bone substitute material, and process for producing the bone substitute material |
| JP2017222892A (en) * | 2016-06-13 | 2017-12-21 | 新日鐵住金株式会社 | Titanium material and manufacturing method of titanium material |
| JP2018104806A (en) * | 2016-12-28 | 2018-07-05 | 新日鐵住金株式会社 | Titanium material, separator, cell and solid polymer fuel battery |
| JP2018104807A (en) * | 2016-12-28 | 2018-07-05 | 新日鐵住金株式会社 | Titanium material, separator, cell and solid polymer fuel battery |
| JP2019071196A (en) * | 2017-10-06 | 2019-05-09 | トヨタ自動車株式会社 | Manufacturing method of separator for fuel cell |
| JP2022051582A (en) * | 2018-03-12 | 2022-03-31 | 三菱マテリアル株式会社 | Titanium base material, method for manufacturing the same, electrode for water electrolysis and water electrolysis apparatus |
-
1990
- 1990-10-16 JP JP27817190A patent/JPH04154991A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252687A (en) * | 1994-03-16 | 1995-10-03 | Miki Netsuren Kk | Method for adhering titanium and titanium alloy |
| WO2002049965A1 (en) * | 2000-12-19 | 2002-06-27 | Toho Titanium Co., Ltd. | Method of forming titanium oxide film and titanium electrolytic capacitor |
| WO2007029602A1 (en) * | 2005-09-08 | 2007-03-15 | Kinki University | Bone substitute material, medical material containing the bone substitute material, and process for producing the bone substitute material |
| JP2017222892A (en) * | 2016-06-13 | 2017-12-21 | 新日鐵住金株式会社 | Titanium material and manufacturing method of titanium material |
| JP2018104806A (en) * | 2016-12-28 | 2018-07-05 | 新日鐵住金株式会社 | Titanium material, separator, cell and solid polymer fuel battery |
| JP2018104807A (en) * | 2016-12-28 | 2018-07-05 | 新日鐵住金株式会社 | Titanium material, separator, cell and solid polymer fuel battery |
| JP2019071196A (en) * | 2017-10-06 | 2019-05-09 | トヨタ自動車株式会社 | Manufacturing method of separator for fuel cell |
| JP2022051582A (en) * | 2018-03-12 | 2022-03-31 | 三菱マテリアル株式会社 | Titanium base material, method for manufacturing the same, electrode for water electrolysis and water electrolysis apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0577759B2 (en) | 1993-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI356857B (en) | Metal oxide film, laminate, metallic member and me | |
| JPH04154991A (en) | Formation of low-order titanium oxide film on titanium material | |
| DE502004002325D1 (en) | METHOD FOR PRODUCING METAL POWDERS OR METAL HYDRIDE POWDERS OF THE ELEMENTS TI, ZR, HF, V, NB, TA AND CR | |
| US3672972A (en) | Method for forming anodic oxide coatings having improved adhesive properties | |
| Stoychev et al. | Preparation of Al2O3 thin films on stainless steel by electrochemical deposition | |
| JPH0293097A (en) | Formation of black film made of titanium and titanium alloy | |
| KR900003417A (en) | Anodized tube inside and manufacturing method thereof | |
| US3956082A (en) | Anodizing bath for composite metal material composed of aluminum or aluminum alloy and different metal having a lower ionization tendency | |
| KR101840567B1 (en) | Preparing method of colored coating layer for aluminum oxide with excellent corrosion resistance for military Using Plasma Electrolytic Oxidation | |
| KR101449187B1 (en) | Method for reducing graphene using light | |
| Allen et al. | Titanium and alloy surfaces for adhesive bonding | |
| EP0381512A3 (en) | Bilayer oxide film and process for producing same | |
| JPH03236497A (en) | Formation of black-based film of titanium and titanium alloy | |
| JPH0261052A (en) | Corrosion resistant mg-based member and production thereof | |
| JPH0762595A (en) | Laminated film of aluminum oxide formed by anodization of aluminum and its production | |
| JPH06210170A (en) | Production of titanium oxide plate for photocatalyst | |
| JP2008069414A (en) | Magnesium alloy member | |
| JPS6349220A (en) | Gas separating membrane | |
| JPS63111198A (en) | Anodic-oxidation of titanium and titanium alloy | |
| JPH02294467A (en) | Method for coloring surface of metallic material and product obtained by it | |
| Frank et al. | Films formed on stainless steel single-crystal surfaces in aqueous solutions: studies of the (100) plane by LEED, auger spectroscopy, and electrochemistry | |
| JPH03130397A (en) | Surface coloring method and surface coloring-treated article formed by using this method | |
| JPH06330349A (en) | Colored ti plated material | |
| JP2007051360A (en) | Aluminum foil having excellent corrosion resistance, and method for producing the same | |
| JPS63237816A (en) | Manufacture of colored titanium material |