JPH02173255A - Production of titanium material having excellent corrosion resistance - Google Patents
Production of titanium material having excellent corrosion resistanceInfo
- Publication number
- JPH02173255A JPH02173255A JP32480888A JP32480888A JPH02173255A JP H02173255 A JPH02173255 A JP H02173255A JP 32480888 A JP32480888 A JP 32480888A JP 32480888 A JP32480888 A JP 32480888A JP H02173255 A JPH02173255 A JP H02173255A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- oil
- corrosion resistance
- titanium material
- excellent 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.)
- Granted
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 39
- 230000007797 corrosion Effects 0.000 title claims abstract description 36
- 238000005260 corrosion Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 6
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011247 coating layer Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 2
- 150000003608 titanium Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- -1 titanium carbides Chemical class 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010977 Ti—Pd Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は１表面に耐食性に優れた層を形成せしめたチタ
ン材の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a titanium material having a layer with excellent corrosion resistance formed on one surface.
（従来の技術）
チタンは、それ自体優れた耐食性を有しており、現在種
々の分野に使用されているが、近年益々きびしい腐食環
境下で使われるようになってきたため、より強い腐食環
境下での全面腐食や隙間腐食の問題が生じるようになっ
た。(Prior art) Titanium itself has excellent corrosion resistance and is currently used in various fields, but in recent years it has been used in increasingly severe corrosive environments. Problems with general corrosion and crevice corrosion have started to occur.
このような点を改菩するにあたり、Ｔｉ−Ｐｄのような
耐食性改良チタン合金を使用する方法もあるが、一方で
はチタンの表面処理により耐食性を高める方法も検討さ
れている。In order to improve these points, there is a method of using a titanium alloy with improved corrosion resistance such as Ti-Pd, but on the other hand, a method of increasing the corrosion resistance by surface treatment of titanium is also being considered.
（発明が解決しようとする問題点）
上記の改良チタン合金であるＴ ｉ −Ｐ ｄ合金等の
耐食性チタン合金は、高価な貴金属を添加するため価格
が非常に高くなる欠点がある。他方それにかわる上記の
表面処理方法では、例えばパラジウム、ルテニウム又は
その酸化物を表面に塗布する方法や、窒化チタン、炭窒
化チタンを表面にイオンブレーティングやガス処理によ
り付着させる方法が開発されているが、前者の方法では
、高価な金属を使用するため費用が高くなり、後者の方
法は雰囲気処理であるために煩雑な工程となることや、
熱処理温度が変態点を越えるのでチタン材料の劣化をま
ねく欠点があった。(Problems to be Solved by the Invention) Corrosion-resistant titanium alloys such as T i -P d alloys, which are the improved titanium alloys mentioned above, have the drawback of being extremely expensive due to the addition of expensive noble metals. On the other hand, alternative surface treatment methods have been developed, such as applying palladium, ruthenium or their oxides to the surface, and attaching titanium nitride or titanium carbonitride to the surface by ion blasting or gas treatment. However, the former method is expensive because it uses expensive metals, and the latter method is a complicated process because it requires atmospheric treatment.
Since the heat treatment temperature exceeds the transformation point, it has the disadvantage of causing deterioration of the titanium material.
本発明者らは前記の事情に鑑み、チタンの耐食性を向上
させる表面処理方法を種々検討した結果、従来にない全
く新しい方法としてチタン表面に油を保有させて加工を
加え、しかる後熱処理を加えることによってチタンの耐
食性を著しく向上させる方法を提案した（特願６２−２
２６８６７）。In view of the above circumstances, the present inventors investigated various surface treatment methods to improve the corrosion resistance of titanium, and as a result, they found a completely new method that had not existed before, in which the titanium surface was treated with oil and then heat treated. proposed a method to significantly improve the corrosion resistance of titanium (Patent Application No. 62-2).
26867).
ここで、加工時にチタン表面に油を保有させるのは加工
時に露出する活性なチタン表面と油を接触させ、加工時
に発生する熱で油を焼きつかせるためである。この場合
、油の種類は圧延油またはこれに類似したものであれば
何らさしつかえない。Here, the reason why the titanium surface retains oil during processing is to bring the oil into contact with the active titanium surface exposed during processing, and to cause the oil to be burned by the heat generated during processing. In this case, the type of oil may be any rolling oil or similar oil.
そしてさらに加工後熱処理を加えることによって表面に
強固に焼きついた油を分解させ、チタンと反応して生成
されるチタン炭化物及び又は窒化物（Ｔｉ、Ｎ、 Ｔｉ
Ｃ，Ｔｉ（ＣＮ）等）の耐食性に優れた表面層を形成す
るものである。Further heat treatment is applied after processing to decompose the oil that is strongly baked on the surface and react with titanium to form titanium carbides and/or nitrides (Ti, N, Ti
C, Ti (CN), etc.) to form a surface layer with excellent corrosion resistance.
本発明者らは、さらに上記の方法について詳細な研究を
つみ重ねた結果、加工を施す前に、予めチタン材を１５
０ ℃以上４００℃以下に加熱保持し、しかる後加工、
熱処理を行ううことによってチタンの６を食性が著しく
向上することを見出した。As a result of further detailed research on the above method, the inventors of the present invention have determined that titanium material is
Heating and holding at a temperature of 0°C or more and 400°C or less, then processing,
It has been found that the edibility of titanium 6 is significantly improved by heat treatment.
この知見に基づき、本発明は非常に簡単にかつ安価にし
て著しく耐食性の優れたチタン材の製造方法を提供する
ことを目的としている。Based on this knowledge, an object of the present invention is to provide a method for producing a titanium material that is extremely simple and inexpensive and has excellent corrosion resistance.
（問題点を解決するための手段）
すなわち本発明は、予めチタン材を１５０ °Ｃ以上４
００”Ｃ以下に加熱保持した後、該チタン材表面に油を
保有させて全加工度１０％以上の加工を加え、その後３
００℃以上の温度で熱処理することによりチタン材の表
面にチタン炭化物及び又は窒化物（ＴｉｚＮ、 ＴｉＣ
，Ｔｉ（ＣＮ）等）を含有する被覆層を形成させること
を特徴とする耐食性に優れたチタン材の製造方法に関す
る。(Means for Solving the Problems) That is, the present invention provides a method for heating titanium material in advance to 150 °C or higher.
After heating and maintaining the titanium material below 00"C, the surface of the titanium material retains oil and is processed to a total processing degree of 10% or more, and then 3
Titanium carbide and/or nitride (TizN, TiC
, Ti(CN), etc.).
ここで、チタン材（加工素材）を予め加熱するのは材料
温度を高めこれによって加工時に焼きつく油の量を増加
させるためである。その後、熱処理して多量に焼きつい
た油を分解させ材料表面にチタン炭化物及び又は窒化物
（Ｔｉ２Ｎ、 ＴｉＣ，Ｔｉ（ＣＮ）等）の表面層を形
成させ、著しく耐食性を向上せしめる。Here, the reason why the titanium material (processing material) is preheated is to raise the temperature of the material and thereby increase the amount of oil burned during processing. Thereafter, heat treatment is performed to decompose a large amount of baked-on oil and form a surface layer of titanium carbide and/or nitride (Ti2N, TiC, Ti(CN), etc.) on the surface of the material, significantly improving corrosion resistance.
ここでチタン材（加工用素材）の温度を１５０℃以上と
したのは、１５０℃より低い温度では材料温度が低く、
常温で加工した場合とほとんどかわらず、耐食性の向上
は望めないからである。また、加工用素材の温度を４０
０℃以下としたのは４００℃より高い温度では、素材表
面での酸化が著しくなり、油の焼きつきが阻害され、熱
処理後の耐食性の向上が望めないからである。さらに。Here, the temperature of the titanium material (processing material) was set at 150°C or higher because the material temperature is low at temperatures lower than 150°C.
This is because it is almost the same as when processed at room temperature, and no improvement in corrosion resistance can be expected. In addition, the temperature of the processing material was increased to 40
The reason why the temperature is set to be 0°C or lower is that at a temperature higher than 400°C, oxidation on the surface of the material becomes significant, oil seizing is inhibited, and no improvement in corrosion resistance after heat treatment can be expected. moreover.
この場合生成した酸化スケールは脆く加工時に破壊し１
表面品質を悪化させるため好ましくない。In this case, the generated oxide scale is brittle and destroyed during processing.
This is undesirable because it deteriorates the surface quality.
もちろん、酸化のおこらない真空もしくは不活性雰囲気
で加工を行った場合、４００℃より高い温度でも著しい
耐食性の向上が望めるが、雰囲気を調節する設備的な負
担が大きく、経済的に不利である。Of course, if the processing is carried out in a vacuum or inert atmosphere where oxidation does not occur, a significant improvement in corrosion resistance can be expected even at temperatures higher than 400°C, but this is economically disadvantageous due to the heavy equipment burden of adjusting the atmosphere.
以上の理由からチタン材（加工用素材）の温度を１５０
℃以上４００℃以下とした。For the above reasons, the temperature of titanium material (processing material) was set to 150.
℃ or higher and 400℃ or lower.
次に、加工時の全加工度を１０％以上としたのは、これ
より小さい加工度では活性なチタン材表面と油との反応
が不十分で熱処理後の耐食性の向上が望めないからであ
る。また、熱処理温度を３００℃以上としたのは、これ
より低い温度では、焼きついた油とチタンとの反応が不
十分で耐食性の向上が望めないからである。この熱処理
は通常真空中又は不活性ガス雰囲気中で行うが、酸化が
ある程度許容される場合には大気中でも行うことができ
る。Next, the reason why the total working degree during processing was set to 10% or more is because if the working degree is smaller than this, the reaction between the active titanium material surface and the oil will be insufficient, and no improvement in corrosion resistance after heat treatment can be expected. . Further, the reason why the heat treatment temperature is set to 300° C. or higher is that at a temperature lower than this, the reaction between the baked oil and titanium is insufficient and no improvement in corrosion resistance can be expected. This heat treatment is usually carried out in a vacuum or in an inert gas atmosphere, but if oxidation is allowed to some extent, it can also be carried out in the air.
なお、チタン材は純チタン及びチタン合金を包含するも
のである。Note that the titanium material includes pure titanium and titanium alloy.
（実施例） 次に、本発明を具体的な実施例に基づいて説明する。(Example) Next, the present invention will be explained based on specific examples.
酸洗により表面の汚れ等を除去した板、ＦＥ ２ ＋ｍ
＋の純チタン（Ｇｒａｄｅ ２ ）板を供試材とし、５
０′Ｃ〜５５０℃までの温度に加熱保持した各供試材を
圧延油を用いて全加工度４０％の圧延を行った。その後
真空中で６５０℃Ｘ３ｈｒの熱処理を行い耐食性を調査
した。その結果を比較例とともに第１表に示す。Board with surface dirt removed by pickling, FE 2 +m
A + pure titanium (Grade 2) plate was used as the test material, and 5
Each sample material heated and maintained at a temperature of 0'C to 550C was rolled using rolling oil to a total working degree of 40%. Thereafter, heat treatment was performed at 650° C. for 3 hours in a vacuum to investigate corrosion resistance. The results are shown in Table 1 along with comparative examples.
第１表において耐食性の評価は、全面腐食試駆及びすき
ま腐食試験により行った。全面腐食の耐食性は５％ＨＣ
Ｉの沸とう水溶液に供試材を浸漬させ、５時間後、２０
時間後に試験片に重量減のあったものは全面腐食が起っ
たと判断した。すきま腐食の耐食性は、１０％Ｎ ａ
Ｃｌの沸とう水溶液にすきま腐食試験片（チタン表面に
すきまを作ったもの）を浸漬させ、１０日後に取り出し
てすきま腐食発生の有無を調べ、すきま腐食発生印を計
算した。In Table 1, the corrosion resistance was evaluated by a full surface corrosion test and a crevice corrosion test. General corrosion resistance is 5% HC.
The test material was immersed in a boiling aqueous solution of I, and after 5 hours, 20
If there was a weight loss in the test piece after a period of time, it was judged that corrosion had occurred on the entire surface. The crevice corrosion resistance is 10% Na
A crevice corrosion test piece (with a gap made on the titanium surface) was immersed in a boiling aqueous solution of Cl, and after 10 days it was taken out and examined for the occurrence of crevice corrosion, and the crevice corrosion occurrence mark was calculated.
本発明に係る方法で処理したものは、全面腐ｒ（試験に
おいて２０時間後も全く腐食をおこさす完全甜食となっ
ている。さらに、すきま腐食においても１０日後も全く
すきま腐食が発生しない供試材がほとんど（発生してい
るものでも低レベルである）であり、本発明方法により
製造した材料がいかに耐食性に優れているかが理解でき
る。Items treated with the method of the present invention exhibited complete corrosion (in the test, no corrosion occurred even after 20 hours).Furthermore, in the test, no crevice corrosion occurred even after 10 days. This shows that the corrosion resistance of the material produced by the method of the present invention is very high (even if it occurs, it is at a low level).
（発明の効果）
本発明の方法によれば、チタン材の表面にチタンの炭化
物及び又は窒化物（Ｔｉ２Ｎ、 ＴｉＣ，Ｔｉ（Ｃへ）
）を含有する層が緻密に形成されるため耐食性に著しく
優れたチタン材を提供することができる。(Effects of the Invention) According to the method of the present invention, titanium carbide and/or nitride (Ti2N, TiC, Ti (to C)) is formed on the surface of the titanium material.
) is formed densely, making it possible to provide a titanium material with extremely excellent corrosion resistance.
Claims (1)
た後、該チタン材表面に油を保有させて全加工度１０％
以上の加工を加え、その後３００℃以上の温度で熱処理
することによりチタン材表面にチタン炭化物及び又は窒
化物 （Ｔｉ＿２Ｎ、ＴｉＣ、Ｔｉ（ＣＮ）等）を含有する被
覆層を形成させることを特徴とする耐食性に優れたチタ
ン材の製造方法。[Claims] After the titanium material is heated and maintained at a temperature of 150°C or higher and 400°C or lower, the surface of the titanium material is coated with oil to achieve a total working rate of 10%.
A coating layer containing titanium carbide and/or nitride (Ti_2N, TiC, Ti(CN), etc.) is formed on the surface of the titanium material by applying the above processing and then heat-treating at a temperature of 300°C or higher. A method for manufacturing titanium material with excellent corrosion resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32480888A JP2632569B2 (en) | 1988-12-24 | 1988-12-24 | Method for producing titanium material with excellent corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32480888A JP2632569B2 (en) | 1988-12-24 | 1988-12-24 | Method for producing titanium material with excellent corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02173255A true JPH02173255A (en) | 1990-07-04 |
| JP2632569B2 JP2632569B2 (en) | 1997-07-23 |
Family
ID=18169908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32480888A Expired - Fee Related JP2632569B2 (en) | 1988-12-24 | 1988-12-24 | Method for producing titanium material with excellent corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2632569B2 (en) |
-
1988
- 1988-12-24 JP JP32480888A patent/JP2632569B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2632569B2 (en) | 1997-07-23 |
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