JPH06264291A - Formation of aluminum titanate film on surface of tial intermetallic compound or ti-al alloy - Google Patents
Formation of aluminum titanate film on surface of tial intermetallic compound or ti-al alloyInfo
- Publication number
- JPH06264291A JPH06264291A JP8014693A JP8014693A JPH06264291A JP H06264291 A JPH06264291 A JP H06264291A JP 8014693 A JP8014693 A JP 8014693A JP 8014693 A JP8014693 A JP 8014693A JP H06264291 A JPH06264291 A JP H06264291A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- tial intermetallic
- intermetallic compound
- aluminum titanate
- titanate 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.)
- Withdrawn
Links
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- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、ＴｉＡｌ金属間化合
物またはＴｉ−Ａｌ系合金表面にチタン酸アルミニウム
膜を溶融塩電気化学処理により形成する方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an aluminum titanate film on a surface of a TiAl intermetallic compound or a Ti-Al alloy by a molten salt electrochemical treatment.
【０００２】[0002]
【従来の技術】一般に、ＴｉＡｌ金属間化合物またはＴ
ｉ−Ａｌ系合金は、比強度（強度と密度の比）が高く、
耐熱性も優れているところから、航空機用構造材料やジ
エットエンジンのタービンブレードなどの軽量耐熱構造
材料として期待されている。Generally, TiAl intermetallic compounds or T
The i-Al alloy has a high specific strength (ratio of strength to density),
Due to its excellent heat resistance, it is expected as a lightweight heat resistant structural material for aircraft structural materials and turbine blades for jet engines.
【０００３】しかし、前記ＴｉＡｌ金属間化合物または
Ｔｉ−Ａｌ系合金は、８００℃を越える高温環境下にお
いて耐酸化性が著しく低下し、そのため、ＴｉＡｌ金属
間化合物またはＴｉ−Ａｌ系合金の表面に耐酸化性被膜
を施すことにより高温環境下における耐酸化性を改善し
ている。前記耐酸化性被膜として、近年、複合チタン酸
化物膜が注目されてきた（例えば、日本金属学会秋期大
会一般講演概要、１９９０，９，１７参照）。この複合
チタン酸化物膜は、オートクレーブ装置を用い、０．１
〜１．０ＮのＣａ（ＯＨ）2 、Ｓｒ（ＯＨ）2 およびＢ
ａ（ＯＨ）2 の内の１種または２種以上を含む水溶液
中、温度：１００〜２００℃、圧力：０．１〜２．０Ｍ
Ｐａで処理する水熱処理方法により生成されている。However, the TiAl intermetallic compound or Ti-Al alloy has a markedly reduced oxidation resistance in a high temperature environment exceeding 800 ° C. Therefore, the surface of the TiAl intermetallic compound or Ti-Al alloy is resistant to acid. The oxidation resistance under high temperature environment is improved by applying a chemical conversion coating. In recent years, a composite titanium oxide film has attracted attention as the oxidation resistant film (see, for example, General Lecture of Autumn Meeting of the Japan Institute of Metals, 1990, 9, 17). This composite titanium oxide film was used in an autoclave apparatus to
~ 1.0 N Ca (OH) 2 , Sr (OH) 2 and B
In an aqueous solution containing one or more of a (OH) 2 , temperature: 100 to 200 ° C., pressure: 0.1 to 2.0 M
It is produced by the hydrothermal treatment method of treating with Pa.
【０００４】[0004]
【発明が解決しようとする課題】かかる水熱処理により
生成される複合チタン酸化物膜はＣａＴｉＯ3 、ＢａＴ
ｉＯ3 、ＳｒＴｉＯ3 、（Ｃａ，Ｓｒ）ＴｉＯ3 、（Ｃ
ａ，Ｂａ）ＴｉＯ3 、（Ｓｒ，Ｂａ）ＴｉＯ3 、（Ｃ
ａ，Ｓｒ）ＴｉＯ3 などからなるものであるが、これら
複合チタン酸化物膜は、チタン酸アルミニウム膜よりは
熱衝撃に弱く、さらに耐熱性の点で劣ると言われてお
り、これに対してチタン酸アルミニウム膜はこれらの欠
点がなく、チタン酸アルミニウム膜をＴｉＡｌ金属間化
合物またはＴｉ−Ａｌ系合金の表面に形成することによ
り一層過酷な高温環境下における耐酸化性の向上を計る
ことができると考えられている。しかしながらチタン酸
アルミニウム膜を形成する方法としてはゾルゲル法でコ
ーティングして焼く方法などが知られているだけで、か
かるゾルゲル法でコーティングして焼く方法は高温で焼
成するために、大規模な設備を必要すること、さらにＴ
ｉＡｌ基板の酸化を防ぐのが難しいなどの問題があり、
簡単にチタン酸アルミニウム膜を形成する方法は今だ知
られていない。The composite titanium oxide film produced by such hydrothermal treatment is made of CaTiO 3 , BaT.
iO 3 , SrTiO 3 , (Ca, Sr) TiO 3 , (C
a, Ba) TiO 3 , (Sr, Ba) TiO 3 , (C
a, Sr) TiO 3 and the like, these composite titanium oxide films are said to be weaker to thermal shock and inferior in heat resistance than aluminum titanate films. The aluminum titanate film does not have these drawbacks, and by forming the aluminum titanate film on the surface of the TiAl intermetallic compound or the Ti-Al alloy, it is possible to improve the oxidation resistance in a more severe high temperature environment. It is believed that. However, as a method of forming an aluminum titanate film, only a method of coating and baking with a sol-gel method is known, and such a method of coating and baking with a sol-gel method involves baking a large-scale facility because it is baked at a high temperature. What you need, more T
There is a problem that it is difficult to prevent the oxidation of the iAl substrate,
A method for easily forming an aluminum titanate film is not yet known.
【０００５】[0005]
【課題を解決する手段】そこで、本発明者らは、適切な
処理を行ってＴｉＡｌ金属間化合物またはＴｉ−Ａｌ系
合金の表面にチタン酸アルミニウム膜を形成する方法を
開発すべく研究を行った結果、アルカリ金属およびアル
カリ土類金属水酸化物の内の１種または２種にアルカリ
金属硝酸塩を加えてなる混合溶融塩中にＴｉＡｌ金属間
化合物またはＴｉ−Ａｌ系合金が陽極となるように浸漬
して通電し、前記混合溶融塩中でＴｉＡｌ金属間化合物
またはＴｉ−Ａｌ系合金表面に放電を発生させると、Ｔ
ｉＡｌ金属間化合物またはＴｉ−Ａｌ系合金表面に比較
的短時間で数μｍ〜数十μｍの密着性の良いチタン酸ア
ルミニウム膜を形成することができることを知見し、こ
の発明に至ったのである。Therefore, the inventors of the present invention conducted research to develop a method for forming an aluminum titanate film on the surface of a TiAl intermetallic compound or a Ti--Al alloy by performing an appropriate treatment. As a result, a TiAl intermetallic compound or a Ti-Al alloy is immersed in a mixed molten salt obtained by adding an alkali metal nitrate to one or two of alkali metal and alkaline earth metal hydroxides so as to serve as an anode. Then, electricity is applied to generate a discharge on the surface of the TiAl intermetallic compound or the Ti—Al based alloy in the mixed molten salt.
The inventors have found that it is possible to form an aluminum titanate film having a good adhesion of several μm to several tens of μm on the surface of an iAl intermetallic compound or a Ti—Al-based alloy in a relatively short time, and arrived at the present invention.
【０００６】この発明は、かかる知見に基づいてなされ
たものであって、アルカリ金属またはアルカリ土類金属
の水酸化物の内の１種または２種以上に、アルカリ金属
の硝酸塩の内の１種または２種以上を加えてなる混合溶
融塩中に、ＴｉＡｌ金属間化合物またはＴｉ−Ａｌ系合
金が陽極となるように浸漬して通電し、ＴｉＡｌ金属間
化合物またはＴｉ−Ａｌ系合金表面で放電を発生させ
る、ＴｉＡｌ金属間化合物またはＴｉ−Ａｌ系合金表面
にチタン酸アルミニウム膜を形成する方法に特徴を有す
るものである。The present invention has been made on the basis of such findings, and is one kind or two or more kinds of alkali metal or alkaline earth metal hydroxides and one kind of alkali metal nitrates. Alternatively, a TiAl intermetallic compound or a Ti-Al alloy is immersed in a mixed molten salt containing two or more kinds of materials so as to serve as an anode, and an electric current is applied, and discharge is performed on the surface of the TiAl intermetallic compound or the Ti-Al alloy. It is characterized by a method of forming an aluminum titanate film on the surface of a TiAl intermetallic compound or a Ti-Al alloy.
【０００７】この発明で用いる混合溶融塩は、溶融状態
にあればいかなる温度に保持されていてもよいが、混合
溶融塩が高温であると、浸漬したＴｉＡｌ金属間化合物
またはＴｉ−Ａｌ系合金は溶解し、ＴｉＡｌ金属間化合
物またはＴｉ−Ａｌ系合金が薄板の場合、短時間で消滅
してしまうので、可能な限り低温の混合溶融塩を用いる
ことが好ましく、３００℃以下の温度の混合溶融塩を用
いることが好ましい。The mixed molten salt used in the present invention may be kept at any temperature as long as it is in a molten state. However, when the mixed molten salt is at a high temperature, the immersed TiAl intermetallic compound or Ti-Al alloy is When the TiAl intermetallic compound or the Ti-Al-based alloy is melted and disappears in a short time, it is preferable to use the mixed molten salt at a temperature as low as possible, and the mixed molten salt at a temperature of 300 ° C or lower. Is preferably used.
【０００８】この発明の方法で生成されるチタン酸アル
ミニウム膜は、従来の水熱処理方法のように水溶液中に
含まれるイオンが作用して形成されるものではなく、Ｔ
ｉＡｌ金属間化合物またはＴｉ−Ａｌ系合金自身が放電
により酸化し、チタン酸アルミニウム膜が形成されるも
のと考えられる。このようにして得られたＴｉＡｌ金属
間化合物またはＴｉ−Ａｌ系合金表面のチタン酸アルミ
ニウム膜は、高融点で低熱膨張係数を有する。The aluminum titanate film produced by the method of the present invention is not formed by the action of ions contained in the aqueous solution as in the conventional hydrothermal treatment method, but T
It is considered that the iAl intermetallic compound or the Ti—Al-based alloy itself is oxidized by discharge to form an aluminum titanate film. The TiAl intermetallic compound or the aluminum titanate film on the surface of the Ti-Al alloy thus obtained has a high melting point and a low thermal expansion coefficient.
【０００９】[0009]
【実施例】縦：１０ｍｍ、横：１０ｍｍ、厚さ：１ｍｍ
の寸法を有し、Ｔｉ−３７重量％Ａｌの成分組成を有す
るＴｉＡｌ金属間化合物板を用意し、この板をエメリー
研磨紙にて＃１０００の表面仕上げした。[Example] Length: 10 mm, width: 10 mm, thickness: 1 mm
And a TiAl intermetallic compound plate having a composition of Ti-37 wt% Al was prepared, and the plate was surface-finished with emery polishing paper to # 1000.
【００１０】アルカリ土類金属水酸化物としてＣａ（Ｏ
Ｈ）2 、Ｓｒ（ＯＨ）2 、Ｂａ（ＯＨ）2 を、アルカリ
金属水酸化物としてＮａＯＨ、ＫＯＨ、ＬｉＯＨを、さ
らにアルカリ金属硝酸塩としてＫＮＯ3 、ＬｉＮＯ3 、
ＮａＮＯ3 をそれぞれ用意し、これら塩類を表１〜表３
に示される割合となるように白金るつぼに充填し、加熱
して表１〜表３に示される温度の混合溶融塩を作製し、
この混合溶融塩中に前記ＴｉＡｌ金属間化合物板を陽極
とし、前記白金るつぼを陰極となるようにして浸漬し、
表１〜表３に示される定電流密度の電流を１時間流しな
がら、本発明法１〜７および比較法１〜３を実施した。As an alkaline earth metal hydroxide, Ca (O
H) 2 , Sr (OH) 2 , Ba (OH) 2 , NaOH, KOH, LiOH as alkali metal hydroxides, and KNO 3 , LiNO 3 as alkali metal nitrates,
NaNO 3 is prepared respectively, and these salts are shown in Tables 1 to 3
The platinum crucible was filled so as to have the ratio shown in, and heated to prepare a mixed molten salt having a temperature shown in Tables 1 to 3,
The TiAl intermetallic compound plate was used as an anode in this mixed molten salt, and the platinum crucible was immersed as a cathode,
The methods 1 to 7 of the present invention and the comparative methods 1 to 3 were carried out while applying a current having a constant current density shown in Tables 1 to 3 for 1 hour.
【００１１】前記本発明法１〜７および比較法１〜３に
よりＴｉＡｌ金属間化合物板表面に形成された膜をＸ線
回折分析したところ、この膜はいずれもＡｌ2 ＴｉＯ5
単一相であり、ＴｉＯ2 、Ａｌ2 Ｏ3 などの酸化物は同
定されなかった。またＳＥＭ観察により、この膜は基板
との密着性が良いことが分かった。The films formed on the surface of the TiAl intermetallic compound plate by the methods 1 to 7 of the present invention and the comparative methods 1 to 3 were subjected to X-ray diffraction analysis. All the films were Al 2 TiO 5
It was a single phase, and oxides such as TiO 2 and Al 2 O 3 were not identified. Further, by SEM observation, it was found that this film had good adhesion to the substrate.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【表２】 [Table 2]
【００１４】[0014]
【表３】 [Table 3]
【００１５】表１〜表３に示される結果から、本発明法
１〜７と比較法１〜３を対比すると、放電を発生させる
本発明法１〜７によりＴｉＡｌ金属間化合物表面に形成
された膜は、Ａｌ2 ＴｉＯ5 単一相膜であるに対し、放
電が生じない比較法１および３では基板が溶解してＡｌ
2 ＴｉＯ5 単一相膜が形成されず、さらに混合溶融塩の
温度が高すぎる比較法２でも基板が溶解してＡｌ2 Ｔｉ
Ｏ5 単一相膜が得られないことが分かる。From the results shown in Tables 1 to 3, when the methods 1 to 7 of the present invention and the comparative methods 1 to 3 are compared, it was formed on the surface of the TiAl intermetallic compound by the methods 1 to 7 of the present invention which generate a discharge. The film is an Al 2 TiO 5 single-phase film, but in Comparative methods 1 and 3 in which no discharge occurs, the substrate melts and Al
2 TiO 5 single phase film is not formed, the dissolved substrate even comparison method 2 further temperature of the mixed molten salt is excessively high Al 2 Ti
It can be seen that an O 5 single phase film cannot be obtained.
【００１６】[0016]
【発明の効果】この発明によると、ＴｉＡｌ金属間化合
物またはＴｉ−Ａｌ系合金表面にチタン酸アルミニウム
膜を電気化学処理により簡単に形成することができ、Ｔ
ｉＡｌ金属間化合物またはＴｉ−Ａｌ系合金の高温環境
下において耐酸化性を著しく改善し、ＴｉＡｌ金属間化
合物またはＴｉ−Ａｌ系合金の応用分野を広げるために
顕著な効果を奏するものである。According to the present invention, the aluminum titanate film can be easily formed on the surface of the TiAl intermetallic compound or the Ti--Al alloy by the electrochemical treatment.
The iAl intermetallic compound or the Ti—Al-based alloy is remarkably improved in oxidation resistance in a high temperature environment, and exerts a remarkable effect for expanding the application field of the TiAl intermetallic compound or the Ti—Al-based alloy.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 八島 正知 神奈川県横浜市緑区藤が丘２−41−21− 508 (72)発明者 漆原 亘 神奈川県大和市下鶴間1549 コーポタクミ 303 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masatomo Yashima 2-41-21-508 Fujigaoka, Midori-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Wataru Urushihara 1549 Shimotsuruma, Yamato-shi, Kanagawa Prefecture Kopotakumi 303
Claims (1)
水酸化物の内の１種または２種にアルカリ金属硝酸塩を
加えてなる混合溶融塩にＴｉＡｌ金属間化合物またはＴ
ｉ−Ａｌ系合金を浸漬し、ＴｉＡｌ金属間化合物または
Ｔｉ−Ａｌ系合金が陽極となるように接続して通電し、
ＴｉＡｌ金属間化合物またはＴｉ−Ａｌ系合金表面に放
電を発生させることを特徴とするＴｉＡｌ金属間化合物
またはＴｉ−Ａｌ系合金表面にチタン酸アルミニウム膜
を形成する方法。1. A mixed molten salt obtained by adding an alkali metal nitrate to one or two kinds of hydroxides of an alkali metal and an alkaline earth metal, and a TiAl intermetallic compound or T.
Immerse the i-Al-based alloy, connect so that the TiAl intermetallic compound or Ti-Al-based alloy serves as the anode, and apply current,
A method of forming an aluminum titanate film on a surface of a TiAl intermetallic compound or a Ti-Al alloy, characterized in that a discharge is generated on the surface of the TiAl intermetallic compound or a Ti-Al alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8014693A JPH06264291A (en) | 1993-03-15 | 1993-03-15 | Formation of aluminum titanate film on surface of tial intermetallic compound or ti-al alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8014693A JPH06264291A (en) | 1993-03-15 | 1993-03-15 | Formation of aluminum titanate film on surface of tial intermetallic compound or ti-al alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06264291A true JPH06264291A (en) | 1994-09-20 |
Family
ID=13710144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8014693A Withdrawn JPH06264291A (en) | 1993-03-15 | 1993-03-15 | Formation of aluminum titanate film on surface of tial intermetallic compound or ti-al alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06264291A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009249664A (en) * | 2008-04-03 | 2009-10-29 | Kobe Steel Ltd | Hard film, method for forming the same, and member coated with hard film |
| WO2016086914A3 (en) * | 2014-12-04 | 2016-09-29 | Meotec GmbH & Co. KG | Component of a turbo device, internal combustion engine comprising a turbo device, and method for manufacturing a component of a turbo device |
-
1993
- 1993-03-15 JP JP8014693A patent/JPH06264291A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009249664A (en) * | 2008-04-03 | 2009-10-29 | Kobe Steel Ltd | Hard film, method for forming the same, and member coated with hard film |
| WO2016086914A3 (en) * | 2014-12-04 | 2016-09-29 | Meotec GmbH & Co. KG | Component of a turbo device, internal combustion engine comprising a turbo device, and method for manufacturing a component of a turbo device |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20000530 |