JPS6056096A - Anodic oxidation of titanium or titanium alloy - Google Patents
Anodic oxidation of titanium or titanium alloyInfo
- Publication number
- JPS6056096A JPS6056096A JP16565683A JP16565683A JPS6056096A JP S6056096 A JPS6056096 A JP S6056096A JP 16565683 A JP16565683 A JP 16565683A JP 16565683 A JP16565683 A JP 16565683A JP S6056096 A JPS6056096 A JP S6056096A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- soln
- prepd
- adjusting
- 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.)
- Pending
Links
Landscapes
- Electrochemical Coating By Surface Reaction (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はチタン又はチタン合金の陽極酸化方法、特に安
定なる白色酸化皮膜を形成する陽極酸化方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for anodizing titanium or a titanium alloy, and particularly to an anodizing method for forming a stable white oxide film.
。.
チタン又はチタン合金の陽極酸化皮膜は耐食性がすぐれ
、而も誘電率も高いため化学装置、航空機材料或は電解
コンデンサーへの使用が試みられている。Anodic oxide films of titanium or titanium alloys have excellent corrosion resistance and high dielectric constant, so attempts have been made to use them in chemical equipment, aircraft materials, and electrolytic capacitors.
チタンを硫酸、りん酸の水溶液にて陽極酸化する場合は
、時間の経過とともに黄金−赤紫一青紫一赤緑一紫一青
緑一淡灰一灰緑一灰色の如きA単位(約5θθ人)の干
渉色皮膜が形成されるが、μ単位(/θ〜30μ程得)
以上の安定なるTh0zルチル型皮膜を形成することは
極めて田畑である。When titanium is anodized with an aqueous solution of sulfuric acid or phosphoric acid, over time it becomes a unit of A (approximately 5θθ) such as gold-red-purple, blue-purple, red-green, purple, blue-green, pale gray, gray-green, and gray. An interference color film of
It is extremely difficult to form such a stable Th0z rutile film.
又陽極酸化皮膜を形成する方法としてエチレングリコー
ル、アルコールの如き非水電解液又は硫酸塩、硝M塩の
如き溶融塩をt屑線として使用する方法が知られている
が、前者は電導性が乏しく、又後者は高温であるため何
れも操業上に難点を有している。Also, as a method of forming an anodic oxide film, a method is known in which a non-aqueous electrolyte such as ethylene glycol or alcohol or a molten salt such as sulfate or nitrate M salt is used as a T-scrap wire, but the former has low conductivity. In addition, the latter has high temperatures, so both have operational difficulties.
本発明は斯る欠点t−解消すべく、2段階電解法を使用
する陽極酸化皮膜形成法により極めて良質な白色酸化皮
膜を形成せんとするものである。本発明者は、さきに硼
弗化アンモニウム水溶液をアルカリにて中和した溶液を
第7電解液とし、かつ酒石酸アルカリ水溶液をハロダン
イオンを含有する酸にて中和した溶液を泥a電解液とし
て使用し、第1を解工程においてチタン表面に絶縁性の
酸化皮膜を形成せしめ、次いで第1電解工程において、
上記絶縁皮膜を一旦破壊し、その上に新規に酸化皮膜を
生成せしめることにエフ厚い酸化皮膜を形成せしめるこ
とに成功した(%願昭!;A−/67弘コg号(%開昭
3g−A7.g9!r号公報)参照)。In order to eliminate such drawbacks, the present invention attempts to form an extremely high quality white oxide film by an anodic oxide film forming method using a two-step electrolytic method. The present inventor used a solution obtained by neutralizing an aqueous ammonium borofluoride solution with an alkali as the seventh electrolyte, and a solution obtained by neutralizing an aqueous alkaline tartrate solution with an acid containing halodane ions as a mud a electrolyte. Then, in the first electrolysis step, an insulating oxide film is formed on the titanium surface, and then in the first electrolysis step,
By once destroying the above insulation film and forming a new oxide film on it, we succeeded in forming a thick oxide film. -A7.g9!r publication)).
本発明者はこの様に良質な白色酸化皮膜を形成すべく種
々研究して前述の特定の電解液を使用し、而もこの電解
液全特定の溶液にてpHを調整しかつ2段階の陽極酸化
により安定な白色nO2ルチル型皮膜を形成することに
成功したが、さらに研究の結果、上記酒石酸アルカリ電
解液の代りに酢酸アルカリを電解液として使用しても同
様に良質の酸化皮膜を生成し得ることを発見したもので
ある。In order to form such a high-quality white oxide film, the present inventor conducted various studies and used the above-mentioned specific electrolyte, and adjusted the pH of the electrolyte using the specific solution and created a two-stage anode. Although we succeeded in forming a stable white nO2 rutile type film through oxidation, further research revealed that a similarly high-quality oxide film could be produced by using alkali acetate as the electrolyte instead of the alkaline tartrate electrolyte. This is what I discovered.
さきの発明においては、第2次電解に使用する酒石酸ア
ルカリ電解液のpu調整VCはハロダン(弗素を除く)
イオンを含有する酸、例えは塩酸、次亜塩素酸、臭化水
素酸などを使用することを特徴の一つとしているが、本
発明においてもPl&に弱酸性である硼弗化アンモニウ
ム水溶液を苛性アルカリにて中和してpHを6.θ〜g
、θに調整したものを第1電解液として化成電圧90〜
/、20V程度で灰緑色までの皮膜を形成し、然る後ア
ルカリ性である酢酸アルカリを塩素イオンの如きハロゲ
ン(弗素を除く)イオンを含有する酸にて中和した第2
電解gにおいて、前記第1電解工程において生成された
灰緑色までの皮膜を一旦破壊してその絶縁性を破ジ、そ
の上に新fcに第2次電解にょシ厚い白色酸化皮膜を形
成せしめるものである。In the previous invention, the pu adjustment VC of the alkaline tartrate electrolyte used for the secondary electrolysis is halodane (excluding fluorine).
One of the characteristics of this invention is the use of acids containing ions, such as hydrochloric acid, hypochlorous acid, and hydrobromic acid, but in the present invention, a weakly acidic ammonium borofluoride aqueous solution is used as a caustic agent for Pl&. Neutralize with alkali to pH 6. θ~g
, the first electrolyte was adjusted to θ and the formation voltage was 90~
/, forming a gray-green film at about 20V, and then neutralizing the alkali acetate with an acid containing halogen (excluding fluorine) ions such as chlorine ions.
In electrolysis g, the film of gray-green color produced in the first electrolysis step is once destroyed, its insulation is destroyed, and a thick white oxide film is formed on the new fc in the second electrolysis step. It is.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
チタン又はチタン合金は當法通り例えは下記の如き予備
処理を行なう:(1)表面仕上研磨(研磨紙す6θθ使
用);(2)水洗;(3)アルコール洗浄;O4)アル
カリ脱脂(苛性ノーダ又は燐酸ソーダ/θチ水溶液、6
0〜70℃、70分) ; (5)水洗’; (61化
学研磨(硝酸/θVolチ、弗化水素酸/ OVolチ
、水g 0Vol %、20〜.30℃、20〜30秒
);(7)水洗;(8)活性化(10チHCt、 70
分);(9)水洗−以上の予備処理をしたチタン又はチ
タン合金を次のように陽極酸化する:
第1電解液:
硼弗化アンモニウム6θf/l、KOHにてpHを乙、
S〜り、Sに調整し、6θC以下で陰極にチタン又は炭
素を使用して下、記の通り電解する。Titanium or titanium alloys are subjected to the following preliminary treatments according to the standard procedure: (1) Surface polishing (using abrasive paper 6θθ); (2) Water washing; (3) Alcohol washing; O4) Alkaline degreasing (caustic nodizer) or sodium phosphate/θ-chi aqueous solution, 6
(0 to 70°C, 70 minutes); (5) Water washing'; (61 Chemical polishing (nitric acid/θVol, hydrofluoric acid/OVol, water g 0Vol%, 20 to 30°C, 20 to 30 seconds); (7) Washing with water; (8) Activation (10 HCt, 70
(9) Washing with water - The titanium or titanium alloy pretreated above is anodized as follows: First electrolyte: ammonium borofluoride 6θf/l, pH adjusted with KOH,
The temperature is adjusted to S to S, and electrolysis is carried out as described below using titanium or carbon as a cathode at 6θC or less.
/ 0.、l 、2゜ 2 左0 赤緑 36θ紫 り ざθ 青緑 39θ g ioo 入線 7//。/ 0. ,l ,2゜ 2 Left 0 Red Green 36theta purple Riza θ blue-green 39θ g ioo entry line 7//.
1 //乙
タ //7
/θ I/、2θ
第、2[解液;
酢酸カリA Of/l、 HC1VCテpHt−t 、
g 〜7、.2に砕整、緩衝液としてθ、コM/を硼
砂4tIIL11 θ、/N塩酸A tttlを添加し
、第1次電解後水洗して得たチタン又はチタン合金を第
7次電解と同様にして、下記の辿り電解する。1 //Ota //7 /θ I/, 2θ th, 2 [solution; Potassium acetate A Of/l, HC1VCtepHt-t,
g ~7,. The titanium or titanium alloy obtained by crushing 2 and adding 4tIIL11 θ, /N hydrochloric acid A tttl to borax as a buffer solution and washing with water after the first electrolysis was treated in the same manner as in the seventh electrolysis. , follow the electrolysis below.
/ ハθ 100
.2 μ 灰縁
17g
1Jt7グ 灰色
3 7.2
67/
7 7/
g 7/
97/
10 7/ 灰白色
/S l り7
25 70 白色
30 7/
l10 71
50 7/
乙θ 7/
以上のように第コ電解においてはHClにエリpl+を
調整しているが、これを酢酸の如き有機酸、硫酸の如き
ハロゲンを含有しない酸で中和すると白色皮ah得られ
ることがあるが再現性の低いことが知見された。/ Haθ 100. 2 μ Gray edge 17g 1Jt7g Gray 3 7.2 67/ 7 7/ g 7/ 97/ 10 7/ Gray white/S l 7 25 70 White 30 7/ l10 71 50 7/ Otsu θ 7/ As above In the first electrolysis, Elypl+ is adjusted to HCl, but if this is neutralized with an organic acid such as acetic acid or a halogen-free acid such as sulfuric acid, a white skin ah may be obtained, but the reproducibility is low. was discovered.
このようにして得られた酸化皮膜は/S−2θμの厚み
であり、これは常法に従い封孔処理(沸騰水、5分)さ
れる。The oxide film thus obtained has a thickness of /S-2θμ, and is sealed in accordance with a conventional method (boiling water, 5 minutes).
上記実施例により生成した酸化皮膜に関し下記の如き隙
間腐食試Mを実施した処、厚さコθμ程度の上記皮膜に
は下表に示すように隙間腐食現象が全く認められなかっ
た。When the following crevice corrosion test M was performed on the oxide film produced in the above example, no crevice corrosion phenomenon was observed in the film having a thickness of about θμ as shown in the table below.
なお、本例における隙間腐食試験結果は、中心に3日g
の穴をあけた試験片(,2×りθX、!−0簡)を、同
様中心に3簡ダの穴をあけ九チタン製押え金(コメ30
×30鎮)と、両者のIi!’lに結晶bczを分散せ
しめたステロール−アクリル系元横剤全介在せしめて重
ね合せ、両者の穴にチタン製がルトナットを挿入して締
め付けた供試材を洲騰乙チNaCA水溶液中に浸漬し、
一定時間後重ね合せ面4f:開き、隙間腐食の発生の有
無を肉眼及び700倍顕微鏡にて判定したものである。Note that the crevice corrosion test results in this example are centered on the 3-day g
A test piece with 3 holes drilled in it (, 2
×30 Chin) and both Ii! The sterol-acrylic base agent containing the crystal Bcz dispersed in the sterol-acrylic material was superimposed, and a titanium lut nut was inserted into the hole of both and the sample material was tightened and immersed in an aqueous solution of NaCA. death,
After a certain period of time, the overlapping surface 4f: opened, and the presence or absence of crevice corrosion was determined with the naked eye and with a 700x microscope.
Claims (1)
ンモニウム水溶液をアルカリにてpH乙、0〜g、0に
調製した溶液を第1’11.屏液とし、かつ酢酸アルカ
リ水溶液をハロゲンイオンを含む酸にてpHA、θ〜g
、θに調製した溶液を第コ電解液として使用してコ段階
電解にて陽極酸化することを特徴とするチタン又はチタ
ン合金、の陽極酸化方法。When anodizing titanium or titanium alloy, an aqueous ammonium borofluoride solution prepared with an alkali to have a pH of 0 to 0 is prepared in the 1'11. Use the aqueous alkaline acetate solution as a filtrate and add it to pHA, θ~g, with an acid containing halogen ions.
A method for anodizing titanium or a titanium alloy, characterized by carrying out anodization by co-step electrolysis using a solution prepared at , θ as a co-electrolyte.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16565683A JPS6056096A (en) | 1983-09-08 | 1983-09-08 | Anodic oxidation of titanium or titanium alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16565683A JPS6056096A (en) | 1983-09-08 | 1983-09-08 | Anodic oxidation of titanium or titanium alloy |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6056096A true JPS6056096A (en) | 1985-04-01 |
Family
ID=15816500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16565683A Pending JPS6056096A (en) | 1983-09-08 | 1983-09-08 | Anodic oxidation of titanium or titanium alloy |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6056096A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2369809A (en) * | 2000-12-11 | 2002-06-12 | Francis Wright | Aircraft landing system utlising electromagnetic field |
WO2005090236A1 (en) * | 2004-03-19 | 2005-09-29 | Nippon Oil Corporation | Nanotube-shaped titania and method for producing same |
CN114411221A (en) * | 2021-12-21 | 2022-04-29 | 西安泰金工业电化学技术有限公司 | Surface treatment method for improving corrosion resistance of titanium side plate of cathode roller |
-
1983
- 1983-09-08 JP JP16565683A patent/JPS6056096A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2369809A (en) * | 2000-12-11 | 2002-06-12 | Francis Wright | Aircraft landing system utlising electromagnetic field |
WO2005090236A1 (en) * | 2004-03-19 | 2005-09-29 | Nippon Oil Corporation | Nanotube-shaped titania and method for producing same |
JP2005263580A (en) * | 2004-03-19 | 2005-09-29 | Nippon Oil Corp | Titania having shape of nanotube and its producing method |
US7687431B2 (en) | 2004-03-19 | 2010-03-30 | Nippon Oil Corporation | Nanotube-shaped titania and process for producing the same |
JP4585212B2 (en) * | 2004-03-19 | 2010-11-24 | Jx日鉱日石エネルギー株式会社 | Titania having a nanotube shape and method for producing the same |
CN114411221A (en) * | 2021-12-21 | 2022-04-29 | 西安泰金工业电化学技术有限公司 | Surface treatment method for improving corrosion resistance of titanium side plate of cathode roller |
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