JPH05320872A - Metallic article with corrosion resistant coating film and its production - Google Patents
Metallic article with corrosion resistant coating film and its productionInfo
- Publication number
- JPH05320872A JPH05320872A JP15007292A JP15007292A JPH05320872A JP H05320872 A JPH05320872 A JP H05320872A JP 15007292 A JP15007292 A JP 15007292A JP 15007292 A JP15007292 A JP 15007292A JP H05320872 A JPH05320872 A JP H05320872A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- coating layer
- corrosion resistant
- crn
- metal article
- 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
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、被膜付き金属物品に関
し、特に耐食性に優れた被膜付き金属物品及びその製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated metal article, and more particularly to a coated metal article having excellent corrosion resistance and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より耐食性の高い金属物品を得る方
法として、イオンプレーティング法により金属物品の表
面にＣｒＮの被膜層を形成することが行われている。こ
のイオンプレーティング法は低温で処理することができ
るので、上記金属物品を熱で変質させることなく、平滑
で寸法変形のない被膜を形成でき、有用な方法である。2. Description of the Related Art Conventionally, as a method for obtaining a metal article having high corrosion resistance, a CrN coating layer is formed on the surface of the metal article by an ion plating method. Since this ion plating method can be processed at a low temperature, it is a useful method because it can form a smooth coating film without dimensional deformation without degrading the metal article by heat.
【０００３】しかし、上記ＣｒＮの被膜層を形成した金
属物品では、酸性溶液に長時間接触させた場合に腐食が
進行してしまう。これは、従来の被膜形成方法によって
得られるＣｒＮの被膜層は結晶子径が微細であるために
結晶界面の総面積が広く、またこの結晶界面は侵食が進
み易いためであると考える。このため、酸性溶液に長時
間接触させるような過酷な条件下で使用する物品におい
ては、より耐食性に優れたものの開発が待たれていた。However, in a metal article having a CrN coating layer formed thereon, corrosion progresses when it is brought into contact with an acidic solution for a long time. This is considered to be because the CrN coating layer obtained by the conventional coating formation method has a fine crystallite diameter and thus has a large total area of the crystal interface, and the crystal interface is apt to be eroded. Therefore, for articles used under severe conditions such as being in contact with an acidic solution for a long time, the development of a more excellent corrosion resistance has been awaited.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明の目的
は、上記従来のＣｒＮの被膜層を形成した金属物品と比
較して、より耐食性に優れた耐食性被膜付き金属物品及
びその製造方法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a metal article with a corrosion resistant coating which is more excellent in corrosion resistance as compared with the conventional metal article having a CrN coating layer formed thereon and a method for producing the same. To do.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
の本発明の耐食性被膜付き金属物品は、金属物品の表面
にＣｒＮの被膜層を有し、該ＣｒＮの被膜層の結晶子径
が１００Å以上である点に特徴がある。また、その製造
方法には金属物品の表面にイオンプレーティング法によ
りＣｒＮ被膜を形成した後、該金属物品を５００〜１５
００℃で加熱する点に特徴がある。MEANS FOR SOLVING THE PROBLEMS A metal article with a corrosion resistant coating of the present invention for achieving the above object has a CrN coating layer on the surface of the metal article, and the crystal layer diameter of the CrN coating layer is 100Å. It is characterized by the above points. In addition, the manufacturing method is such that after a CrN coating is formed on the surface of a metal article by an ion plating method, the metal article is coated with 500 to 15
It is characterized by heating at 00 ° C.
【０００６】[0006]
【作用】本発明の耐食性被膜付き金属物品は、金属物品
表面のＣｒＮ被膜層の結晶子径が従来のＣｒＮ被膜層よ
り大きく１００Å以上であり、侵食の原因となる結晶界
面の総面積が狭い。又、加熱によってピンホール、ディ
スロケーション等の結晶格子欠陥が極めて少ない。さら
に、酸化性雰囲気下で加熱処理した場合には、ＣｒＮ被
膜層の表面及び内部空隙の壁面に不動態である酸化クロ
ムが存在する。In the metal article with a corrosion resistant coating of the present invention, the crystallite diameter of the CrN coating layer on the surface of the metal article is larger than that of the conventional CrN coating layer and is 100 Å or more, and the total area of the crystal interface that causes erosion is narrow. In addition, crystal lattice defects such as pinholes and dislocations due to heating are extremely small. Furthermore, when heat-treated in an oxidizing atmosphere, passive chromium oxide exists on the surface of the CrN coating layer and the wall surface of the internal voids.
【０００７】ＣｒＮの被膜層を形成した金属物品を加熱
すると耐食性が向上する理由は、加熱によってＣｒＮの
結晶が成長し、腐食の原因となる被膜層中のピンホール
や結晶粒界などの欠陥部分が減少するためであるか、あ
るいは、これら欠陥部分に酸化クロムの不動態膜が生成
され、それ以降の酸化が進行しなくなるからであると考
えられる。The reason why the corrosion resistance is improved when the metal article having the CrN coating layer formed thereon is heated is that defects such as pinholes and crystal grain boundaries in the coating layer cause corrosion due to the growth of CrN crystals. It is thought that this is because the passivation film of chromium oxide is formed in these defective portions and the subsequent oxidation does not proceed.
【０００８】本発明に使用される金属物品の材料は、純
金属あるいは合金材料であり、特に鉄鋼材料において効
果がある。用いる鉄鋼材料としては、例えばＳ１５Ｃな
どの肌焼鋼、Ｓ４５Ｃなどの構造用鋼、ＳＵＰ１０など
のばね鋼、ＳＵＪ２などの軸受鋼、ＳＡＣＭ１などの窒
化鋼、ＳＫＤ６などの熱間加工用工具鋼、ＳＫＤ１１な
どの冷間加工用工具鋼、ＳＫＨ５１などの高速度鋼、Ｓ
ＵＳ３１０Ｓなどの耐熱鋼、ＳＵＳ４１０などの耐食耐
酸鋼などが挙げられる。The material of the metal article used in the present invention is a pure metal or an alloy material, and is particularly effective for steel materials. Examples of the steel material used include case-hardening steel such as S15C, structural steel such as S45C, spring steel such as SUP10, bearing steel such as SUJ2, nitrided steel such as SACM1 and tool steel for hot working such as SKD6 and SKD11. Tool steel for cold working such as, high speed steel such as SKH51, S
Examples include heat resistant steel such as US310S and corrosion resistant acid resistant steel such as SUS410.
【０００９】本発明によるＣｒＮ被膜層の厚みは２〜５
μｍが好ましく、通常３μｍ程度形成すれば十分であ
る。The thickness of the CrN coating layer according to the present invention is 2-5.
μm is preferable, and it is usually sufficient to form about 3 μm.
【００１０】本発明のＣｒＮの被膜層の形成には、ＰＶ
Ｄの一種である公知のイオンプレーティング法が用いら
れる。このイオンプレーティング法は一般に、金属を蒸
発させ、この蒸発した金属をイオン化し、さらにイオン
化した金属分子を反応性ガス雰囲気下で電界により加速
して、物品の表面に付着固定させるものである。For forming the CrN coating layer of the present invention, PV is used.
A known ion plating method, which is a type of D, is used. This ion plating method generally involves evaporating a metal, ionizing the evaporated metal, and further accelerating the ionized metal molecule by an electric field in a reactive gas atmosphere to adhere and fix the metal molecule to the surface of the article.
【００１１】金属を蒸発させるには、市販のイオンプレ
ーティング装置に備わった抵抗加熱や電子銃加熱などの
いずれを用いても良い。また、蒸発した金属のイオン化
は、公知のアーク放電、グロー放電、高周波放電、イオ
ン化電極を用いる方法、ホロカソード法のいずれでも良
い。これらの中で、アーク放電型のイオンプレーティン
グ法は金属の蒸発とイオン化とを同時に行う方式のもの
であり、他の方法に比べて金属のイオン化効率が高く、
本発明の方法で特に推奨される。To vaporize the metal, either resistance heating or electron gun heating provided in a commercially available ion plating apparatus may be used. The vaporized metal may be ionized by any of known arc discharge, glow discharge, high frequency discharge, a method using an ionization electrode, and a hollow cathode method. Among them, the arc discharge type ion plating method is a method of simultaneously vaporizing and ionizing a metal, and has a higher metal ionization efficiency than other methods,
Particularly recommended in the method of the invention.
【００１２】アーク放電型イオンプレーティング方式に
て被膜を形成する場合、イオン化した金属を加速する電
界は電圧値で５０Ｖから７００Ｖが好ましく、さらに好
ましくは１００Ｖから５００Ｖである。また、被膜の形
成に先立って物品の加熱を行う際に、イオン照射による
加熱をする場合はＣｒイオンにて行い、イオン化したＣ
ｒを加速する電界は電圧値として５００Ｖから２０００
Ｖが好ましく、さらに好ましくは８００Ｖから１５００
Ｖである。Ｃｒイオンによる加熱を行う場合には、Ｃｒ
の蒸発、イオン化を真空下で行えば良い。When the coating is formed by the arc discharge type ion plating method, the electric field for accelerating the ionized metal has a voltage value of preferably 50 V to 700 V, and more preferably 100 V to 500 V. When the article is heated prior to the formation of the coating film, if the heating is performed by ion irradiation, it is performed by using Cr ions to ionize C.
The electric field that accelerates r is a voltage value of 500 V to 2000
V is preferable, and more preferably 800 V to 1500
It is V. When heating with Cr ions, Cr
Evaporation and ionization may be performed under vacuum.
【００１３】ＣｒＮ被膜層の形成には金属Ｃｒを蒸発源
として用い、窒素の供給源としての反応性ガスには
Ｎ2、ＮＨ3または窒素を含んだ有機化合物、例えば（Ｃ
Ｈ3）3Ｎなどが使用できる。反応性ガスの圧力は、用い
るガスの種類により異なるが、一般に１０-3〜１０1Tor
rの範囲内で適宜選択すれば良い。Metal Cr is used as an evaporation source for the formation of the CrN coating layer, and N 2 or NH 3 or an organic compound containing nitrogen, such as (C
H 3) 3 N and the like can be used. The pressure of the reactive gas varies depending on the type of gas used, but is generally 10 −3 to 10 1 Tor.
It may be appropriately selected within the range of r.
【００１４】ＣｒＮの被膜層を形成した金属物品の加熱
は不活性雰囲気下、酸化性雰囲気下いずれでも良い。加
熱温度は５００〜１５００℃であるが、好ましくは７０
０〜１０００℃である。加熱温度が５００℃より低いと
ＣｒＮの被膜層の結晶子径が１００Å以上にならず、ま
た、１５００℃を超えると数分間の加熱でＣｒＮ被膜層
の大部分が酸化クロムとなってしまう。加熱時間は加熱
温度によるが、１分以上であれば良い。The heating of the metal article on which the CrN coating layer is formed may be performed in either an inert atmosphere or an oxidizing atmosphere. The heating temperature is 500 to 1500 ° C, preferably 70
It is 0 to 1000 ° C. If the heating temperature is lower than 500 ° C., the crystallite diameter of the CrN coating layer does not exceed 100 Å, and if it exceeds 1500 ° C., most of the CrN coating layer becomes chromium oxide by heating for several minutes. The heating time depends on the heating temperature, but may be 1 minute or more.
【００１５】[0015]
実施例 ・・・ 大きさ１７×１７×２ｍｍ、ビッカー
ス硬度Ｈｖ＝８５０のＳＫＨ５１高速度鋼のテストピー
スを基板とし、Ｃｒカソードを備えたカソードアーク方
式のイオンプレーティング装置を用いて本発明の被膜構
造を形成した。装置反応容器内の所定位置に基板をセッ
トした後、反応容器内を１０-5Torrまで真空排気した。Example ... A coating of the present invention using a cathodic arc type ion plating apparatus having a test piece of SKH51 high-speed steel having a size of 17 × 17 × 2 mm and a Vickers hardness of Hv = 850 as a substrate and a Cr cathode. The structure formed. After setting the substrate at a predetermined position in the reaction vessel of the apparatus, the inside of the reaction vessel was evacuated to 10 −5 Torr.
【００１６】次に基板に１０００Ｖのバイアス電圧を印
加し、Ｃｒカソードよりアーク放電を生起させた。この
時アーク放電電流は６０Ａであった。赤外放射温度計に
より基板の表面温度を監視しながらこのアーク放電を５
分間続け、Ｃｒを蒸発、イオン化させた。アーク放電中
最大４５０℃まで基板表面温度の上昇が認められた。さ
らに、バイアス電圧を４００Ｖまで下げ、Ｃｒカソード
への電圧印加を停止し、反応容器内に窒素ガスを導入
し、容器内の圧力が３×１０-2Torrを保つように窒素ガ
スを流しながらＴｉカソードに１時間電圧を印加した。
このときアーク放電電流は８０Ａであった。これにより
ＣｒＮの被膜層が形成された。Next, a bias voltage of 1000 V was applied to the substrate to cause arc discharge from the Cr cathode. At this time, the arc discharge current was 60A. This arc discharge is monitored while monitoring the surface temperature of the substrate with an infrared radiation thermometer.
Continuing for a minute, Cr was evaporated and ionized. A rise in the substrate surface temperature was recognized up to 450 ° C during arc discharge. Further, the bias voltage was lowered to 400 V, the voltage application to the Cr cathode was stopped, nitrogen gas was introduced into the reaction vessel, and Ti gas was supplied while flowing nitrogen gas so that the pressure in the vessel was kept at 3 × 10 -2 Torr. A voltage was applied to the cathode for 1 hour.
At this time, the arc discharge current was 80A. As a result, a CrN coating layer was formed.
【００１７】ＣｒＮの被膜層形成後の基板は、ビッカー
ス硬度Ｈｖが１８００で、外観は金属光沢を有する銀白
色であった。形成されたＣｒＮ被膜の結晶子径を測定し
たところ、８４Åであった。次に、この基板を横型管状
電気炉を用いて窒素気流中８２０℃で１分間で加熱し、
冷却後炉から取り出し、本発明の被膜構造を形成した。
加熱処理後のＣｒＮの被膜層の結晶子径は１２４Åであ
った。ここで、ＣｒＮ被膜層の結晶子径は、被膜層をＸ
線回折測定して得られた回折パターン中の、ＣｒＮの
（２２０）面のピークの半値幅より算出した。The substrate on which the CrN coating layer was formed had a Vickers hardness Hv of 1800 and was silver white in appearance with metallic luster. The crystallite diameter of the formed CrN coating was measured and found to be 84Å. Next, this substrate was heated for 1 minute at 820 ° C. in a nitrogen stream using a horizontal tubular electric furnace,
After cooling, it was taken out of the furnace and the coating structure of the present invention was formed.
The crystallite diameter of the CrN coating layer after the heat treatment was 124Å. Here, the crystallite diameter of the CrN coating layer is X
It was calculated from the half width of the peak of the CrN (220) plane in the diffraction pattern obtained by the line diffraction measurement.
【００１８】比較例 ・・・ 加熱処理温度を４００℃
とした他は、実施例と同様の方法で被膜構造を形成し
た。ＣｒＮの被膜層の結晶子径は８７Åであった。Comparative Example: Heat treatment temperature is 400 ° C.
A film structure was formed in the same manner as in the example except that. The crystallite diameter of the CrN coating layer was 87Å.
【００１９】次に、加熱処理前の基板と、８２０℃で加
熱処理後の基板とを、１０％の塩酸溶液に浸漬して腐食
による重量変化を調べ、耐食性を比較した。基板は片面
の被膜形成面のみ現れるようにし、残りの面はテープに
よりマスキングした。基板の腐食が進行するほど基板の
重量減少量は大きく、耐食性に劣ることになる。加熱処
理前の基板では、浸漬時間２００時間で重量減少量は
５．８ｍｇ、３００時間で１１．０ｍｇ、５００時間で
１９．２ｍｇであった。一方、本発明の方法による加熱
処理後の基板は、１０００時間浸漬した後も重量減少量
は０．０ｍｇであった。Next, the substrate before the heat treatment and the substrate after the heat treatment at 820 ° C. were dipped in a 10% hydrochloric acid solution and the weight change due to the corrosion was examined to compare the corrosion resistance. The substrate was formed so that only one surface on which the film was formed was exposed, and the remaining surface was masked with tape. As the corrosion of the substrate progresses, the weight reduction amount of the substrate increases and the corrosion resistance deteriorates. The weight loss of the substrate before the heat treatment was 5.8 mg after 200 hours of immersion, 11.0 mg after 300 hours, and 19.2 mg after 500 hours. On the other hand, the substrate after the heat treatment by the method of the present invention had a weight loss of 0.0 mg even after being immersed for 1000 hours.
【００２０】[0020]
【発明の効果】本発明によると、従来のＣｒＮ被膜と比
較してより耐食性に優れた被膜が得られ、従来より高耐
食性を有する金属物品を製造することができる。EFFECTS OF THE INVENTION According to the present invention, a coating having more excellent corrosion resistance than that of a conventional CrN coating can be obtained, and a metal article having higher corrosion resistance than conventional can be manufactured.
Claims (2)
し、該ＣｒＮの被膜層の結晶子径が１００Å以上である
ことを特徴とする耐食性被膜付き金属物品。1. A metal article with a corrosion resistant coating, comprising a CrN coating layer on the surface of the metal article, wherein the CrN coating layer has a crystallite diameter of 100 Å or more.
グ法によりＣｒＮの被膜層を形成した後、該金属物品を
５００〜１５００℃にて加熱することを特徴とする、請
求項１記載の耐食性被膜付き金属物品の製造方法。2. The corrosion resistant coating according to claim 1, wherein a CrN coating layer is formed on the surface of the metal article by an ion plating method, and the metal article is heated at 500 to 1500 ° C. Of manufacturing a metal article with an adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15007292A JPH05320872A (en) | 1992-05-19 | 1992-05-19 | Metallic article with corrosion resistant coating film and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15007292A JPH05320872A (en) | 1992-05-19 | 1992-05-19 | Metallic article with corrosion resistant coating film and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05320872A true JPH05320872A (en) | 1993-12-07 |
Family
ID=15488912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15007292A Pending JPH05320872A (en) | 1992-05-19 | 1992-05-19 | Metallic article with corrosion resistant coating film and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05320872A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100389959B1 (en) * | 2001-03-12 | 2003-07-02 | 한국기계연구원 | A Method of Forming Cr/Cr-X Layer for Corrosion Resistance |
| JP2008098183A (en) * | 1999-09-17 | 2008-04-24 | Matsushita Electric Ind Co Ltd | Polymer electrolyte fuel cell |
| JP2011006777A (en) * | 2009-05-22 | 2011-01-13 | Hirotaka Tanabe | Method for producing ceramics coating material |
-
1992
- 1992-05-19 JP JP15007292A patent/JPH05320872A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008098183A (en) * | 1999-09-17 | 2008-04-24 | Matsushita Electric Ind Co Ltd | Polymer electrolyte fuel cell |
| KR100389959B1 (en) * | 2001-03-12 | 2003-07-02 | 한국기계연구원 | A Method of Forming Cr/Cr-X Layer for Corrosion Resistance |
| JP2011006777A (en) * | 2009-05-22 | 2011-01-13 | Hirotaka Tanabe | Method for producing ceramics coating material |
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