JPH0570927A - Tin coated ti member having high corrosion resistance and production of it - Google Patents
Tin coated ti member having high corrosion resistance and production of itInfo
- Publication number
- JPH0570927A JPH0570927A JP23834691A JP23834691A JPH0570927A JP H0570927 A JPH0570927 A JP H0570927A JP 23834691 A JP23834691 A JP 23834691A JP 23834691 A JP23834691 A JP 23834691A JP H0570927 A JPH0570927 A JP H0570927A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- tin
- coated
- nitrogen
- high corrosion
- 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- Withdrawn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
Landscapes
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｔｉ製部材の耐食性向
上技術に関し、特にＴｉ製部材が腐食され得る塩酸、硫
酸水溶液などの非酸化性の酸および塩素ガス、ふっ素ガ
ス等のハロゲンガスに対してＴｉの腐食率の低減を図っ
た高耐食性ＴｉＮ被覆Ｔｉ製部材およびその製造法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for improving the corrosion resistance of Ti-made members, and more particularly to non-oxidizing acids such as hydrochloric acid and sulfuric acid aqueous solution which can corrode Ti-made members and halogen gas such as chlorine gas and fluorine gas. On the other hand, the present invention relates to a TiN-coated Ti member having high corrosion resistance and a method for manufacturing the same, in which the corrosion rate of Ti is reduced.
【０００２】[0002]
【従来の技術】従来よりＴｉは耐食性に優れている金属
としてよく知られており、化学プラント等の工業用の構
造材料として使用されているが、使用される環境によっ
てはその耐食性に関し、十分であるとはいえない場合が
ある。2. Description of the Related Art Conventionally, Ti is well known as a metal having excellent corrosion resistance and is used as a structural material for industrial use in chemical plants and the like. In some cases, it cannot be said.
【０００３】Ｔｉは特に硝酸等の酸化性の腐食環境およ
び海水やその他の塩化物を含有する腐食環境には優れた
耐食性を示す。Ti exhibits excellent corrosion resistance particularly in an oxidizing corrosive environment such as nitric acid and a corrosive environment containing seawater or other chlorides.
【０００４】しかし、塩酸、硫酸等の非酸化性の環境に
おいては上記に説明したほど優れた耐食性を示さない。
また、塩素ガス、ふっ素ガス等のハロゲンガス中におい
てはＴｉはそれらと激しく反応し、ハロゲン化物を作り
腐食が促進される。However, in a non-oxidizing environment such as hydrochloric acid or sulfuric acid, it does not show the excellent corrosion resistance as described above.
Further, in halogen gas such as chlorine gas and fluorine gas, Ti reacts violently with them to form a halide and promote corrosion.
【０００５】このように、Ｔｉが比較的に腐食を受け易
い環境における問題を解決するために、Ｔｉに種々の合
金元素を含有させた耐食性Ｔｉ基合金がすでに提案さ
れ、かつ一般に市販されている。As described above, in order to solve the problem in an environment where Ti is relatively susceptible to corrosion, a corrosion-resistant Ti-based alloy containing various alloying elements in Ti has already been proposed and is commercially available. ..
【０００６】[0006]
【発明が解決しようとする課題】そして、これらのＴｉ
基合金としてはＴｉ−Ｐｄ合金、Ｔｉ−Ｎｉ−Ｍｏ合金
が挙げられるが、上記環境が高温、高濃度になった場合
の耐食性能は満足できるものではない。[Problems to be Solved by the Invention] And these Ti
Examples of the base alloy include Ti-Pd alloy and Ti-Ni-Mo alloy, but the corrosion resistance performance is not satisfactory when the environment becomes high temperature and high concentration.
【０００７】本発明は前述した、特定の環境下における
Ｔｉの耐食性を改善し、耐食性を大幅に改善したＴｉ製
部材およびその製造法を提供することを目的としてい
る。It is an object of the present invention to provide a Ti member and a method for producing the same, which have improved Ti corrosion resistance under a specific environment and have significantly improved corrosion resistance.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
に、本発明者らは、鋭意研究を重ねた結果、Ｔｉと密着
性の高いセラミック皮膜を被覆形成させることがＴｉの
耐食性改善に効果的であることを知見し、本発明を完成
するに至った。In order to achieve the above object, the inventors of the present invention have conducted extensive studies, and as a result, forming a ceramic film having high adhesion with Ti is effective in improving the corrosion resistance of Ti. Therefore, the present invention has been completed.
【０００９】すなわち本発明は、Ｔｉ製部材上に、ドラ
イプレーティングによって被覆形成したＴｉＮ皮膜を備
えるＴｉ製部材であり、該ＴｉＮ皮膜のＴｉと窒素の原
子数比Ｎ／Ｔｉが０．８以上であるＴｉＮ被覆Ｔｉ製部
材を要旨とし、また、窒素含有雰囲気中で、Ｔｉをター
ゲットとしたスパッタリングにより、あるいはガス化し
たＴｉハロゲン化物を分解してＴｉと窒素の原子数比Ｎ
／Ｔｉが０．８以上であるＴｉＮ皮膜を表面に被覆形成
する高耐食性ＴｉＮ被覆Ｔｉ製部材の製造法を要旨とし
ている。That is, the present invention is a Ti member having a TiN film formed by coating on a Ti member by dry plating, and the atomic ratio N / Ti of Ti to nitrogen in the TiN film is 0.8 or more. A TiN-coated Ti member is used as a gist, and the atomic ratio N of Ti and nitrogen is N by sputtering targeting Ti in a nitrogen-containing atmosphere or by decomposing gasified Ti halide.
The gist is a method of manufacturing a TiN-coated Ti-made member having high corrosion resistance, in which a TiN film having a Ti content of 0.8 or more is formed on the surface.
【００１０】[0010]
【作用】本発明の構成と作用を説明する。本発明では、
一般に金属よりも耐食性が優れているといわれているセ
ラミックスを選び、その中でも最も一般的で、かつＴｉ
との密着性が良いと考えられるＴｉＮを取り上げた。Ｔ
ｉＮ皮膜をＴｉ表面に被覆形成する手段は、周知のドラ
イプレーティング法、すなわちＣＶＤ，ＰＶＤ，あるい
はスパッタリングなどで行なうことが出来る。The structure and operation of the present invention will be described. In the present invention,
Ceramics, which are generally said to have better corrosion resistance than metals, are the most popular among them, and Ti
We picked up TiN, which is considered to have good adhesion with. T
Means for forming the iN coating on the Ti surface can be performed by a well-known dry plating method, that is, CVD, PVD, sputtering, or the like.
【００１１】本発明に係る高耐食性ＴｉＮ被覆Ｔｉ製部
材を得るＴｉ表面被覆として、ドライコーティングの成
膜条件を種々変更し、Ｔｉ製部材上に被覆し、成膜条件
と耐食性の相関について調べた。As the Ti surface coating for obtaining the TiN-coated Ti member with high corrosion resistance according to the present invention, the film forming conditions of the dry coating were variously changed, and the Ti member was coated, and the correlation between the film forming conditions and the corrosion resistance was investigated. ..
【００１２】その結果、特定の成膜条件では、ＴｉＮ皮
膜のＴｉと窒素の原子数比Ｎ／Ｔｉが０．８以上である
場合、他の条件で作成したＴｉＮ被覆Ｔｉ製部材より
も、耐食性が著しく向上することを見いだした。As a result, under the specific film forming conditions, when the Ti / nitrogen atomic ratio N / Ti of the TiN film is 0.8 or more, the corrosion resistance is higher than that of the TiN-coated Ti member prepared under other conditions. Has been found to significantly improve.
【００１３】これはＴｉＮ皮膜のＴｉと窒素の原子数比
Ｎ／Ｔｉが１：１の化学量論組成に近付くことで、Ｔｉ
Ｎ皮膜が化学的により安定になり、他の物質と反応しに
くくなるためである。This is because the TiN film has a Ti / nitrogen atomic ratio N / Ti approaching a stoichiometric composition of 1: 1.
This is because the N film is chemically more stable and less likely to react with other substances.
【００１４】[0014]
【実施例】本発明に係る高耐食性ＴｉＮ被覆Ｔｉ製部材
の実施例を説明するが本発明はこれにより限定されるも
のではない。EXAMPLES Examples of the high corrosion resistance TiN-coated Ti member according to the present invention will be described, but the present invention is not limited thereto.
【００１５】常法により製造したＴｉ製部材に対し、反
応性スパッタリングにより、表１に示す成膜条件で、同
表に併せて示す種々のＴｉと窒素の原子数比Ｎ／Ｔｉを
持つＴｉＮ皮膜をＴｉ製部材上に形成した。A TiN film having various atomic ratios of Ti and nitrogen N / Ti shown in Table 1 under the film forming conditions shown in Table 1 by reactive sputtering of a Ti member manufactured by a conventional method. Was formed on a Ti member.
【００１６】[0016]
【表１】 [Table 1]
【００１７】上記表１に示すＴｉＮ被覆を施したＴｉ製
部材を、沸騰５％塩酸水溶液および沸騰５％硫酸水溶液
を用いて耐食性試験を行った。その結果を表２に示す。
なお、表２における耐食性評価は、沸騰５％塩酸水溶液
および沸騰５％硫酸水溶液中での分極曲線測定から腐食
速度を算出することで行なった。The TiN-coated members shown in Table 1 above were subjected to a corrosion resistance test using a boiling 5% hydrochloric acid aqueous solution and a boiling 5% sulfuric acid aqueous solution. The results are shown in Table 2.
The corrosion resistance evaluation in Table 2 was performed by calculating the corrosion rate from polarization curve measurements in a boiling 5% hydrochloric acid aqueous solution and a boiling 5% sulfuric acid aqueous solution.
【００１８】[0018]
【表２】 [Table 2]
【００１９】表１、表２より明らかなように、Ｔｉ部材
上にＴｉＮを被覆することでＴｉ部材の腐食速度を沸騰
５％塩酸水溶液中で約１／１０００に、沸騰５％硫酸水
溶液中で約１／１８００に低下できることがわかる。As is clear from Tables 1 and 2, the Ti member is coated with TiN to reduce the corrosion rate of the Ti member to about 1/1000 in a boiling 5% hydrochloric acid aqueous solution and in a boiling 5% sulfuric acid aqueous solution. It can be seen that it can be reduced to about 1/1800.
【００２０】また、Ｔｉと窒素の原子数比Ｎ／Ｔｉが増
加するほど腐食速度が低下し、さらに原子数比が０．８
以上になった場合、沸騰５％塩酸水溶液中および沸騰５
％硫酸水溶液中での腐食速度はいずれの場合も０．０３
０ｍｍ／年＝３０μｍ／年程度であり、被覆ＴｉＮが薄
膜であることを考慮してもこの値はＴｉＮ被覆Ｔｉ製部
材を実際に構造用部材として使用できる値である。Further, as the atomic ratio N / Ti of Ti and nitrogen increases, the corrosion rate decreases, and the atomic ratio 0.8
In case of above, boiling in 5% hydrochloric acid aqueous solution and boiling 5
% Corrosion in 0.0% sulfuric acid aqueous solution is 0.03 in any case
The value is 0 mm / year = about 30 μm / year, and this value is a value at which the TiN-coated Ti member can be actually used as a structural member even considering that the coated TiN is a thin film.
【００２１】試料番号 4〜 8のＴｉと窒素の原子数比が
０．８以下のものについては、腐食速度はおよそ０．１
０ｍｍ／年＝１００μｍ／年であり、被覆ＴｉＮが薄膜
であるため、試料番号 4〜 8の前記成膜条件で作成した
ＴｉＮ被覆Ｔｉ製部材を構造用部材として使用するには
無理がある。For sample Nos. 4 to 8 in which the atomic ratio of Ti to nitrogen is 0.8 or less, the corrosion rate is about 0.1.
Since 0 mm / year = 100 μm / year, and the coated TiN is a thin film, it is unreasonable to use the TiN-coated Ti members prepared under the film forming conditions of sample numbers 4 to 8 as structural members.
【００２２】[0022]
【発明の効果】本発明は以上説明したように構成されて
いるから、非酸化性の環境における耐食性が優れたＴｉ
製部材を提供することが可能となり、さらにハロゲンガ
ス中での耐食性の向上、粒界腐食の防止をも期待するこ
とが出来て、産業上極めて有用である。Since the present invention is constructed as described above, Ti having excellent corrosion resistance in a non-oxidizing environment is used.
It becomes possible to provide a manufactured member, and further, it can be expected to improve corrosion resistance in a halogen gas and prevent intergranular corrosion, which is extremely useful in industry.
Claims (4)
によって被覆形成したＴｉＮ皮膜を備えるＴｉ製部材で
あり、該ＴｉＮ皮膜のＴｉと窒素の原子数比Ｎ／Ｔｉが
０．８以上であることを特徴とする高耐食性ＴｉＮ被覆
Ｔｉ製部材。1. A Ti member having a TiN film formed by dry plating on a Ti member, wherein the TiN film has an atomic ratio N / Ti of Ti to nitrogen of 0.8 or more. Characteristically high corrosion resistance TiN coated Ti member.
としたスパッタリングによりＴｉと窒素の原子数比Ｎ／
Ｔｉが０．８以上であるＴｉＮ皮膜を表面に被覆形成す
ることを特徴とする高耐食性ＴｉＮ被覆Ｔｉ製部材の製
造法。2. The atomic ratio N / N of Ti and nitrogen by sputtering targeting Ti in a nitrogen-containing atmosphere.
A method for producing a TiN-coated Ti member having high corrosion resistance, characterized by forming a TiN film having a Ti content of 0.8 or more on the surface.
ロゲン化物を分解してＴｉと窒素の原子数比Ｎ／Ｔｉが
０．８以上であるＴｉＮ皮膜を表面に被覆形成すること
を特徴とする高耐食性ＴｉＮ被覆Ｔｉ製部材の製造法。3. A TiN film having a Ti / nitrogen atomic ratio N / Ti of 0.8 or more is formed on the surface by decomposing gasified Ti halide in a nitrogen-containing atmosphere. A method of manufacturing a Ti-coated TiN member having high corrosion resistance.
ある請求項２又は３記載の高耐食性ＴｉＮ被覆Ｔｉ製部
材の製造法4. The method for producing a TiN-coated Ti member with high corrosion resistance according to claim 2 or 3, wherein the nitrogen-containing atmosphere is an ammonia decomposition gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23834691A JPH0570927A (en) | 1991-09-18 | 1991-09-18 | Tin coated ti member having high corrosion resistance and production of it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23834691A JPH0570927A (en) | 1991-09-18 | 1991-09-18 | Tin coated ti member having high corrosion resistance and production of it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0570927A true JPH0570927A (en) | 1993-03-23 |
Family
ID=17028837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23834691A Withdrawn JPH0570927A (en) | 1991-09-18 | 1991-09-18 | Tin coated ti member having high corrosion resistance and production of it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0570927A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6555455B1 (en) | 1998-09-03 | 2003-04-29 | Micron Technology, Inc. | Methods of passivating an oxide surface subjected to a conductive material anneal |
-
1991
- 1991-09-18 JP JP23834691A patent/JPH0570927A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6555455B1 (en) | 1998-09-03 | 2003-04-29 | Micron Technology, Inc. | Methods of passivating an oxide surface subjected to a conductive material anneal |
| US6559053B1 (en) * | 1998-09-03 | 2003-05-06 | Micron Technology, Inc. | Method of passivating an oxide surface subjected to a conductive material anneal |
| US6774022B2 (en) | 1998-09-03 | 2004-08-10 | Micron Technology, Inc. | Method of passivating an oxide surface subjected to a conductive material anneal |
| US6930029B2 (en) | 1998-09-03 | 2005-08-16 | Micron Technology, Inc. | Method of passivating an oxide surface subjected to a conductive material anneal |
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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: 19981203 |