JPH0577759B2 - - Google Patents
Info
- Publication number
- JPH0577759B2 JPH0577759B2 JP27817190A JP27817190A JPH0577759B2 JP H0577759 B2 JPH0577759 B2 JP H0577759B2 JP 27817190 A JP27817190 A JP 27817190A JP 27817190 A JP27817190 A JP 27817190A JP H0577759 B2 JPH0577759 B2 JP H0577759B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- sample
- order
- low
- titanium oxide
- 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.)
- Expired - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007743 anodising Methods 0.000 claims description 3
- 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 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- 239000004566 building material Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Description
（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。
（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。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一酸化窒素など
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。
（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一酸化窒素などのガ
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つた。
本発明は以上のような問題に鑑みてなしたもの
で、その目的は、有害成分を使用することなく、
無公害でかつ設備コストの低減化を行うことがで
きながら、干渉膜程度の薄膜からミクロンオーダ
ーと厚い低次酸化チタ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。
（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
次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、10-3torr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。
（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）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TaoO2o-1（但しｎ＝１〜10）で
示される低次酸化チタンの内、黒色系の一酸化チ
タン（TiO）や五酸化三チタン（Ti3O5）へと変
化し、これら一酸化チタンや五酸化三チタンが黒
色皮膜となつ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、前記陽極酸化処理して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℃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
ンや還元作用が行われ難く、即ち、前記一酸化チ
タンや五酸化三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。
（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。
具体例 １
先ず、30ｇ／の硫酸と、20ｇ／のリン酸及
び10ｇ／と過酸化水素水とから成る電解浴を調
整した。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浴中において、電圧50、100、
150、200V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370nｍ、電圧150Vの
場合は1.1μｍ、電圧200Vの場合は5.3μｍの灰色皮
膜をそれぞれ形成した。
次に、前記各試料を密封容器中にそれぞれ封入
して、10-5torr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充填して、120分間放
置した。この結果、次表で示すような比較の色調
変化が得られた。
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、10-3torrに減圧し、これら各容器の全体を
350℃に加熱した電気炉中に充填して、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。
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、
10-4torrに減圧し、これら各容器の全体を500℃
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線による回析試験を行つた所、
何れもが一酸化チタンと五酸化三チタンから成る
黒色皮膜であつた。
次に示す表は、Ｌ、ａ、ｂ系表色法における明
度に示している。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（灰色）の明度を示してい
る。
(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. (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. The contents of this publication state that after a titanium material made of titanium and titanium alloy is anodized, it is heated at a temperature of at least 600°C in a reducing atmosphere such as ammonia, carbon monoxide, or nitrogen monoxide. It forms a blackish low-order titanium oxide film. (Problems to be Solved by the Invention) In the method for forming a low-order titanium oxide film as described above, after the titanium material is anodized, in order to reduce the titanium material to low-order titanium oxide,
Because gases such as ammonia, carbon monoxide, or nitrogen monoxide 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 equipment costs. The present invention was made in view of the above-mentioned problems, and its purpose is to
Provides a method for forming a low-order titanium oxide film on titanium materials that is non-polluting and can reduce equipment costs while producing a low-order titanium oxide film as thin as an interference film to as thick as a micrometer. It's about doing. (Means for Solving the Problems) In order to achieve the above object, the method for forming a low-order titanium oxide film according to the present invention includes: after anodic oxidation treatment of a titanium material, under a reduced pressure of 10 -3 torr or less,
It is characterized by heating to 300°C or higher. (Function/Effect) Gray titanium dioxide (TiO 2 ) is formed by anodizing titanium material, 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 to form black titanium monoxide (TiO) and trititanium pentoxide (of lower titanium oxides represented by the general formula Ta o O 2o-1 (where n = 1 to 10) Ti 3 O 5 ), and these titanium monoxide and trititanium pentoxide become a black film and are exposed on the surface of the titanium material,
It can be used as a decorative item or building material with a good appearance and excellent weather resistance.
Further, since the low-order titanium oxide has an excellent oxygen adsorption function, it can also be used as a reducing agent.
In addition, when reducing the titanium material subjected to the anodic oxidation treatment, if the pressure condition is 10 -3 torr or more, or if the heating condition is 300°C or less,
In either case, the reduction action of the titanium dioxide formed by anodizing treatment is difficult to be performed, that is, the formation of the titanium monoxide and trititanium pentoxide is not sufficiently performed,
This is done under the conditions mentioned above because the initial objective could not be achieved. (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. Specific Example 1 First, an electrolytic bath was prepared containing 30 g of sulfuric acid, 20 g of phosphoric acid, and 10 g of hydrogen peroxide. In addition, a pure titanium plate was used as a sample,
This sample was placed in the electrolytic bath at voltages of 50, 100,
Anodic oxidation was performed at 150 and 200 V for 10 minutes each. Then, on the surface of each sample, if the voltage is 50V,
A gray film of 150 nm, 370 nm at a voltage of 100 V, 1.1 μm at a voltage of 150 V, and 5.3 μm at a voltage of 200 V was formed. Next, each sample was sealed in a sealed container, the pressure was reduced to 10 -5 torr, and the entire container was sealed.
It was filled into an electric furnace heated to 450°C and left for 120 minutes. As a result, comparative color changes as shown in the following table were obtained. 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 -3 torr, and the entire container was sealed.
It was filled into an electric furnace heated to 350°C and left for 10 minutes. As a result, changes in the color tone of the film as shown in the following table were obtained. 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,
Reduce the pressure to 10 -4 torr and heat each container to 500°C.
The sample was loaded into an electric furnace heated to 100 mL and left for 120 minutes. As a result, changes in the color tone of the film as shown in the following table were obtained. Furthermore, when an X-ray diffraction test was conducted on the films obtained in Specific Examples 1 to 3,
All were black films consisting of titanium monoxide and trititanium pentoxide. The table 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 brightness of each sample (gray) that was anodized under the same conditions as Example 1 without being subjected to the reduction treatment shown in each example above. It shows.
【表】【table】
【表】
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つ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、100V、150Vについては、Ｌ値呼びａ、ｂ
値について試験を行つていない。[Table] As is clear from the above table, the L value of each of Specific Examples 1 to 3 is lower than that of the comparative example, and this indicates that the anodized film is It is understood that the color changed to black due to the reduction treatment. In addition, in the above table, specific example 3
For 50V, 100V, 150V, L value nominal a, b
Values have not been tested.
Claims (1)
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 titanium material, 10 -3 torr
A method for forming a low-order titanium oxide film on a titanium material, which comprises heating to 300°C or higher under the following reduced pressure.
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 JPH04154991A (en) | 1992-05-27 |
| JPH0577759B2 true 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) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252687A (en) * | 1994-03-16 | 1995-10-03 | Miki Netsuren Kk | Adhesion treatment method for titanium and titanium alloys |
| TW533440B (en) * | 2000-12-19 | 2003-05-21 | Toho Titanium Co Ltd | Method for forming titanium oxide film and titanium electrolytic capacitor |
| JP4883603B2 (en) * | 2005-09-08 | 2012-02-22 | 学校法人近畿大学 | Manufacturing method of bone substitute material |
| JP6786893B2 (en) * | 2016-06-13 | 2020-11-18 | 日本製鉄株式会社 | Titanium material and manufacturing method of titanium material |
| JP6805822B2 (en) * | 2016-12-28 | 2020-12-23 | 日本製鉄株式会社 | Titanium material, separator, cell, and polymer electrolyte fuel cell |
| JP6805823B2 (en) * | 2016-12-28 | 2020-12-23 | 日本製鉄株式会社 | Titanium material, separator, cell, and polymer electrolyte fuel cell |
| JP6878239B2 (en) * | 2017-10-06 | 2021-05-26 | トヨタ自動車株式会社 | Manufacturing method of separator for fuel cell |
| WO2019176956A1 (en) * | 2018-03-12 | 2019-09-19 | 三菱マテリアル株式会社 | Titanium base material, method for producing titanium base material, electrode for water electrolysis, and water electrolysis device |
| JP7421101B2 (en) * | 2020-06-12 | 2024-01-24 | 日本製鉄株式会社 | Titanium materials, fuel cell separators, fuel cells, and fuel cell stacks |
-
1990
- 1990-10-16 JP JP27817190A patent/JPH04154991A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04154991A (en) | 1992-05-27 |
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