JPH0319316B2 - - Google Patents
Info
- Publication number
- JPH0319316B2 JPH0319316B2 JP24559588A JP24559588A JPH0319316B2 JP H0319316 B2 JPH0319316 B2 JP H0319316B2 JP 24559588 A JP24559588 A JP 24559588A JP 24559588 A JP24559588 A JP 24559588A JP H0319316 B2 JPH0319316 B2 JP H0319316B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- sample
- film
- black
- minutes
- 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
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010407 anodic oxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 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 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000694 effects Effects 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
- 238000001556 precipitation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、主として装飾品や建材などに使用す
るチタン及びチタン合金の黒色皮膜形成法に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming a black film on titanium and titanium alloys used mainly for decorative items, building materials, and the like.
（従来の技術）
従来、この種チタン及びチタン合金（以下チタ
ンと略称する）の表面に黒色皮膜を形成する方法
として、例えば特開昭63−4076号公報に記載され
たものが知られており、この公報記載のものは、
チタンを前処理した後に、フツ酸水溶液中に浸漬
して、黒色皮膜を形成するようにしたものであ
る。(Prior Art) Conventionally, as a method of forming a black film on the surface of this type of titanium and titanium alloy (hereinafter abbreviated as titanium), the method described in, for example, JP-A-63-4076 has been known. , what is described in this publication is
After pre-treating titanium, it is immersed in an aqueous hydrofluoric acid solution to form a black film.
（発明が解決しようとする課題）
ところで、以上のような黒色皮膜形成法では、
フツ酸を使用するために、作業上非常に危険であ
り、しかも得られる黒色皮膜は、0.1μm以下の薄
膜であつて、非常に弱く、建材などに使用するこ
とは困難であつた。(Problem to be solved by the invention) By the way, in the above black film forming method,
Since hydrofluoric acid is used, it is very dangerous to work with, and the black film obtained is a thin film of 0.1 μm or less and is extremely weak, making it difficult to use it as a building material.
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、表面に、外観良好で耐侯性に優
れた厚い黒色皮膜を得ることができるチタン及び
チタン合金の黒色皮膜形成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 black film on titanium and titanium alloys, which can form a thick black film on the surface with good appearance and excellent weather resistance. It's about doing.
（課題を解決するための手段）
上記目的を達成するために、本発明では、チタ
ン及びチタン合金の表面に陽極酸化処理を施した
後に、還元雰囲気中において、少なくもと600℃
以上の温度で加熱処理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, in the present invention, after anodizing the surface of titanium and titanium alloy, the surface of titanium and titanium alloy is heated to at least 600°C in a reducing atmosphere.
It is characterized by heat treatment at a temperature above.
また、前記還元雰囲気としては、アンモニア、
一酸化炭素、一酸化窒素などのガス雰囲気が使用
される。 Further, as the reducing atmosphere, ammonia,
Gaseous atmospheres such as carbon monoxide, nitric oxide, etc. are used.
（作用及び効果）
以上のように、チタン及びチタン合金の表面に
陽極酸化処理を施した後に、還元雰囲気中におい
て、少なくもと600℃以上の温度で加熱処理する
ことにより、前記陽極酸化皮膜が還元されて、表
面に黒色の低次酸化チタンが生成され、この生成
された低次酸化チタンが外観良好で耐降性に優れ
た黒色皮膜となり、また、厚膜陽極酸化処理手段
を採用して、チタン及びチタン合金の表面に厚い
酸化皮膜を形成することにより、該酸化皮膜がベ
ースとなつて、厚い黒色皮膜を得ることができる
のである。(Functions and Effects) As described above, after anodizing the surface of titanium and titanium alloy, the anodic oxide film is heated in a reducing atmosphere at a temperature of at least 600°C. It is reduced to produce black low-order titanium oxide on the surface, and this low-order titanium oxide produced becomes a black film with good appearance and excellent precipitation resistance. By forming a thick oxide film on the surface of titanium and titanium alloys, a thick black film can be obtained using the oxide film as a base.
更に詳述すると、チタン及びチタン合金を陽極
酸化処理した場合、その表面に、灰色系の二酸化
チタン（TiO2）が生成されるのであるが、以上
の処理を施すことにより、前記二酸化チタンが還
元されて、一般式TinO2n−1（但しｎ＝１〜10）
で示される低次酸化チタンのうち、黒色の一酸化
チタン（TiO）や五酸化三チタン（TiO3O5）に
変化されるのであり、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、チタン及びチタ
ン合金の表面に表出され、外観良好で耐候性に優
れたものとなるのである。 To explain in more detail, when titanium and titanium alloys are anodized, grayish titanium dioxide (TiO 2 ) is produced on the surface, but by performing the above treatment, the titanium dioxide is reduced. , the general formula TinO 2 n- 1 (however, n = 1 to 10)
Among the lower titanium oxides shown in As a result, it is exposed on the surface of titanium and titanium alloys, giving them a good appearance and excellent weather resistance.
（実施例）
以下本発明にかかるチタン及びチタン合金の黒
色皮膜形成法を、具体例を挙げて説明する。(Example) The method for forming a black film on titanium and titanium alloy according to the present invention will be described below by giving specific examples.
具体例 １
先ず、30グラム・／リツトルの硫酸と、20グラ
ム／リツトルの燐酸と、10グラム／リツトルの過
酸化水素水とから成る電解浴を調製し、また、試
料として純純チタンを使用して、この試料を前記
電解浴中において、電圧300V、直流で30分間陽
極酸化処理した。Specific example 1 First, an electrolytic bath consisting of 30 g/liter of sulfuric acid, 20 g/liter of phosphoric acid, and 10 g/liter of hydrogen peroxide was prepared, and pure titanium was used as a sample. Then, this sample was anodized in the electrolytic bath at a voltage of 300 V and direct current for 30 minutes.
この結果、試料の表面に、灰色系で膜厚7.2μm
の酸化皮膜が得られた。 As a result, a gray film with a thickness of 7.2 μm was formed on the surface of the sample.
An oxide film was obtained.
次に、前記試料を、電気炉において、アンモニ
アガスを10ml／minの速度で流しながら、700℃
で、０〜120分間にわたつて経時的に加熱処理し
た。 Next, the sample was heated to 700°C in an electric furnace while flowing ammonia gas at a rate of 10ml/min.
Heat treatment was carried out over time for 0 to 120 minutes.
この結果、加熱時間が約60分を経過した後、前
記試料の表面が黒色に着色された。 As a result, the surface of the sample was colored black after about 60 minutes of heating time.
具体例 ２
前記具体例１で陽極酸化処理した試料を使用し
て、該試料を、電気炉中において、アンモニアガ
スを10ml／minの速度で流しながら、800℃で、
０〜120分間にわたつて経時的に加熱処理した。Specific Example 2 Using the sample anodized in Specific Example 1 above, the sample was heated at 800°C in an electric furnace while flowing ammonia gas at a rate of 10 ml/min.
Heat treatment was performed over time for 0 to 120 minutes.
この結果、加熱時間が約30分を経過した後、前
記試料の表面が黒色に着色された。 As a result, the surface of the sample was colored black after about 30 minutes of heating time.
以上の各具体例１，２で得られた皮膜は、Ｘ線
回折した所、その何れもが、一酸化チタンと五酸
化三チタンを成分とする黒色皮膜であつた。 X-ray diffraction analysis of the films obtained in each of the above specific examples 1 and 2 revealed that both were black films containing titanium monoxide and trititanium pentoxide as components.
また、第１図は、縦軸に反射率（％）を、横軸
に波長（nm）をとつた反射率曲線を示しており、
同図中、具体例１で得られた皮膜は点線グラフ
で、又具体例２で得られた皮膜は実線グラフで表
示している。 In addition, Figure 1 shows a reflectance curve with reflectance (%) on the vertical axis and wavelength (nm) on the horizontal axis.
In the figure, the film obtained in Example 1 is represented by a dotted line graph, and the film obtained in Example 2 is represented by a solid line graph.
以上の第１図から明らかなごとく、前記各具体
例で得られた各皮膜は、その何れもが、波長によ
る反射率の変化が殆ど起こらず、このことから前
記各皮膜は黒色皮膜であることが理解される。 As is clear from Fig. 1 above, the reflectance of each of the films obtained in each of the above-mentioned specific examples shows almost no change depending on the wavelength, and from this fact, each of the films obtained above is a black film. is understood.
第２図は、縦軸にＬ値（Ｌ，ａ，ｂ系表色法に
おける明度）を、横軸に時間（分）をとつた黒色
皮膜の生成過程を示しており、同図中、具体例１
で得られた皮膜は点線グラフで、又具体例２で得
られた皮膜は実線グラフで表示している。 Figure 2 shows the formation process of a black film, with the vertical axis representing the L value (lightness in the L, a, b color system) and the horizontal axis representing time (minutes). Example 1
The film obtained in Example 2 is shown in a dotted line graph, and the film obtained in Example 2 is shown in a solid line graph.
以上の第２図から明らかなごとく、前記各具体
例で形成された陽極酸化皮膜をもつ各試料を、前
述した特定の条件下で加熱処理することにより、
特に加熱時間が30分〜60分を越えた領域で、前記
各試料の陽極酸化皮膜つまり二酸化チタンが、一
酸化チタンや五酸化三チタンに変化されて、黒色
皮膜になることが理解できるのである。 As is clear from FIG. 2 above, by heat-treating each sample with the anodic oxide film formed in each of the specific examples above under the specific conditions mentioned above,
It can be seen that especially in the region where the heating time exceeds 30 to 60 minutes, the anodic oxide film of each sample, that is, titanium dioxide, is converted to titanium monoxide and trititanium pentoxide, resulting in a black film. .
具体例 ３
30グラム／リツトルのリン酸と、150グラム／
リツトルの硫酸とから成る電解浴を調製し、この
電解浴中において、純チタンから成る試料を、電
圧200V、直流で25分間陽極酸化処理した結果、
前記試料の表面に、膜厚5.2μmの酸化皮膜を得
た。Example 3: 30 grams/liter of phosphoric acid and 150 grams/liter
An electrolytic bath consisting of a little sulfuric acid was prepared, and a sample made of pure titanium was anodized in this electrolytic bath with a voltage of 200 V and DC for 25 minutes.
An oxide film with a thickness of 5.2 μm was obtained on the surface of the sample.
次に、前記試料を、電気炉中において、一酸化
窒素ガスを、15ml／minの速度で流しながら、
700℃で、60分間にわたつて加熱処理した。 Next, the sample was placed in an electric furnace while flowing nitrogen monoxide gas at a rate of 15 ml/min.
Heat treatment was performed at 700°C for 60 minutes.
この結果、前記試料の表面が、黒色に着色され
た。 As a result, the surface of the sample was colored black.
具体例 ４
50グラム／リツトルの水酸化ナトリウムで電解
浴を調製し、この電解浴中において、純チタンか
ら成る試料を、電圧210V、直流で30分間陽極酸
化処理した結果、前記試料の表面に、膜厚4.5μm
の酸化皮膜を得た。Specific Example 4 An electrolytic bath was prepared with 50 g/liter of sodium hydroxide, and in this electrolytic bath, a sample made of pure titanium was anodized at a voltage of 210 V and direct current for 30 minutes. As a result, on the surface of the sample, Film thickness 4.5μm
An oxide film was obtained.
次に、前記試料を、電気炉中において、一酸化
炭素ガスを８ml／minの速度で流しながら、800
℃で、30分間にわたつて加熱処理した。 Next, the sample was placed in an electric furnace at a rate of 800 ml/min while flowing carbon monoxide gas at a rate of 8 ml/min.
Heat treatment was carried out at ℃ for 30 minutes.
この結果、前記試料の表面が、黒色に着色され
た。 As a result, the surface of the sample was colored black.
第１図は本発明で得られる黒色皮膜の反射率曲
線を示す図面、第２図は同黒色皮膜の経時的な生
成過程を示す図面である。
FIG. 1 is a diagram showing the reflectance curve of the black film obtained by the present invention, and FIG. 2 is a diagram showing the generation process of the black film over time.
Claims (1)
理を施した後に、還元雰囲気中において、少なく
とも600℃以上の温度で加熱処理することを特徴
とするチタン及びチタン合金の黒色皮膜形成法。 ２ 還元雰囲気が、アンモニア、一酸化炭素、一
酸化窒素などのガス雰囲気であることを特徴とす
る請求項１記載のチタン及びチタン合金の黒色皮
膜形成法。[Claims] 1. A black coating of titanium and titanium alloys, which is characterized by subjecting the surface of titanium and titanium alloys to anodizing treatment and then heat-treating them at a temperature of at least 600°C in a reducing atmosphere. Formation method. 2. The method for forming a black film on titanium and titanium alloys according to claim 1, wherein the reducing atmosphere is a gas atmosphere such as ammonia, carbon monoxide, or nitrogen monoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24559588A JPH0293097A (en) | 1988-09-29 | 1988-09-29 | Formation of black film made of titanium and titanium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24559588A JPH0293097A (en) | 1988-09-29 | 1988-09-29 | Formation of black film made of titanium and titanium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0293097A JPH0293097A (en) | 1990-04-03 |
| JPH0319316B2 true JPH0319316B2 (en) | 1991-03-14 |
Family
ID=17136067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24559588A Granted JPH0293097A (en) | 1988-09-29 | 1988-09-29 | Formation of black film made of titanium and titanium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0293097A (en) |
Families Citing this family (6)
| 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 |
| JP4883603B2 (en) * | 2005-09-08 | 2012-02-22 | 学校法人近畿大学 | Manufacturing method of bone substitute material |
| CN105177672B (en) * | 2015-09-15 | 2017-10-03 | 哈尔滨工业大学 | A kind of preparation method of titanium alloy surface high solar absorptivity high emissivity black matt film layer |
| CN106637349A (en) * | 2016-11-08 | 2017-05-10 | 北京星航机电装备有限公司 | Treatment method before coating of titanium alloy surface coating |
| KR102291510B1 (en) | 2016-12-28 | 2021-08-19 | 닛폰세이테츠 가부시키가이샤 | Titanium Material, Separator, Cell, and Polymer Fuel Cell |
| CN112779582B (en) * | 2020-12-24 | 2021-11-02 | 上海交通大学 | A kind of method of repairing aluminum-based material micro-arc oxidation damaged film |
-
1988
- 1988-09-29 JP JP24559588A patent/JPH0293097A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0293097A (en) | 1990-04-03 |
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