JPH03291377A - Production of steel sheet having film extremely excellent in wear resistance - Google Patents
Production of steel sheet having film extremely excellent in wear resistanceInfo
- Publication number
- JPH03291377A JPH03291377A JP9314990A JP9314990A JPH03291377A JP H03291377 A JPH03291377 A JP H03291377A JP 9314990 A JP9314990 A JP 9314990A JP 9314990 A JP9314990 A JP 9314990A JP H03291377 A JPH03291377 A JP H03291377A
- Authority
- JP
- Japan
- Prior art keywords
- film
- steel sheet
- hcd
- coating
- ion plating
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 37
- 239000010959 steel Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 28
- 239000010432 diamond Substances 0.000 claims abstract description 28
- 238000007733 ion plating Methods 0.000 claims abstract description 27
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 28
- 239000010409 thin film Substances 0.000 claims description 22
- 238000005524 ceramic coating Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000919 ceramic Substances 0.000 abstract description 7
- 229910001209 Low-carbon steel Inorganic materials 0.000 abstract description 3
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 52
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 21
- 238000005299 abrasion Methods 0.000 description 12
- 230000001133 acceleration Effects 0.000 description 10
- 238000010894 electron beam technology Methods 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- -1 ceramic coating Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
この発明は、炭素鋼、ステンレス綱などの鋼板表面に、
極めて優れる耐摩耗性を有し、耐食性、密着性にも優れ
る被膜を被成する方法に関するものである。[Detailed Description of the Invention] (Industrial Application Field) This invention provides a method of applying
The present invention relates to a method of forming a coating having extremely excellent wear resistance, corrosion resistance, and adhesion.
(従来の技術)
近年、プラズマを利用したコーティング技術が著しく進
歩し、各方面でその利用が広まりつつある。かかるコー
ティング技術を利用したものとしては、たとえば磁気記
録薄膜の形成や各種耐摩耗性、耐食性コーティング、さ
らには装飾用コーティングなどが挙げられる。(Prior Art) In recent years, coating technology using plasma has made significant progress, and its use is becoming widespread in various fields. Applications of such coating techniques include, for example, the formation of magnetic recording thin films, various wear-resistant and corrosion-resistant coatings, and decorative coatings.
通常、プラズマを利用すると、金属および半金属等の蒸
発物質をイオン化又は活性化し、かつ高い運動エネルギ
ーを付与することができるため、蒸着被膜と基板との間
の密着性や膜質の良好なものが得られる。Normally, when plasma is used, it is possible to ionize or activate evaporated substances such as metals and semimetals, and to impart high kinetic energy. can get.
従来、プラズマ・コーティング法としては、マグネトロ
ンスパッタ法、E B (Electron Beam
) 十RF (Radio Frequency)法お
よびプラズマCVD法などのほか、最近では真空アーク
を利用したマルティ・アーク法やホローカソード()f
ollow CathodeDischarge、 :
単にHCDという)法によるイオンプレーティングが知
られている。Conventionally, plasma coating methods include magnetron sputtering and EB (Electron Beam).
) In addition to the RF (Radio Frequency) method and the plasma CVD method, recently the multi-arc method using a vacuum arc and the hollow cathode () f
olow CathodeDischarge, :
Ion plating using a method (simply referred to as HCD) is known.
これらの手法を利用して大面積を有する鋼板表面上に密
着性、均一性および耐食性などの緒特性に優れたセラミ
ック被膜を被成するには、イオンプレーティングやイオ
ンインプランテーション処理の際、イオン化率を向上さ
せること、鋼板への印加電圧を高くすることおよび鋼板
の温度を上げることが基本的に重要である。In order to use these methods to form a ceramic coating with excellent properties such as adhesion, uniformity, and corrosion resistance on the surface of a large steel plate, ionization is necessary during ion plating or ion implantation treatment. It is fundamentally important to improve the rate, increase the voltage applied to the steel plate, and increase the temperature of the steel plate.
このような処理を施して得たコーティング被膜は膜質、
密着性および耐食性が大幅に改善されるとはいうものの
、それでもなお充分な密着性や耐食性が得られていると
はいいがたく、またとくに十分な耐摩耗性は得られてい
ないため、その−層の改善が要望されていた。The coating film obtained through such treatment has film quality,
Although adhesion and corrosion resistance have been significantly improved, it is still difficult to say that sufficient adhesion and corrosion resistance have been obtained, and in particular, sufficient wear resistance has not been obtained. Improvements in the layers were requested.
とくにHCD方式によるイオンプレーティング処理は、
比較的イオン化率が高く、また成膜速度も大きいことか
ら、建築材等に用いる大表面積の鋼板に用いて有利であ
り、さらに耐食性や装飾性あるいは耐摩耗性の改善が期
待できることからその利用が試みられているが、現状で
は未だ、実用化までには至っていない。In particular, the ion plating process using the HCD method is
Because it has a relatively high ionization rate and a high film formation rate, it is advantageous for use in steel plates with large surface areas used for construction materials, etc. It is also useful because it can be expected to improve corrosion resistance, decorativeness, and abrasion resistance. Although attempts have been made, it has not yet been put into practical use.
この理由として、
1)鋼板とセラミック被膜との密着性が良好であること
、
2) 大表面積に均一にセラミック被膜をコーティング
できること、
3) セラミック被膜の膜質が良好であること、4)耐
摩耗性、耐食性に優れていること、5)大表面積の鋼板
上に高速成膜ができがっ、良好なプラズマ雰囲気下でコ
ーティングが行えること、
などが要求されるが、従来のHCD法では上記のような
条件を十分に満足することはできなかったがらである。The reasons for this are: 1) good adhesion between the steel plate and the ceramic coating, 2) ability to uniformly coat a large surface area with the ceramic coating, 3) good quality of the ceramic coating, and 4) wear resistance. , excellent corrosion resistance, and 5) the ability to form a film at high speed on a steel plate with a large surface area and the ability to perform coating in a favorable plasma atmosphere. However, it was not possible to fully satisfy these conditions.
これとは別に、最近アーク放電法を用いたイオンプレー
ティング法による表面処理#4#Iiについてその物性
に関する検討が行われ、鋼板との界面に異種金属をドラ
イブレーティングして二層被膜とすると単層被膜に比較
して著しい耐食性の改善が認められたことが報告されて
いる。(影近博、木部洋、安谷屋武志、苗村博、原富啓
:鉄と綱、72(1986)、 51309参照)、一
方特開昭62−99458号公報には、1.OXl0−
’Torr以下の高真空雰囲気中でイオンプレーティン
グを施して第1層のめっき層を形成させる工程とその被
膜上に第1層とは異なる材質のめっき層を形成させる方
法が開示さている。しかしながら、かかるイオンプレー
ティング法は真空中の雰囲気圧力を1.OXl0−’T
orr以下の高真空とする必要があるため、実際の工業
的規模での工程に採用するには問題があった。Separately, studies have recently been conducted on the physical properties of surface treatment #4#Ii by the ion plating method using the arc discharge method. It has been reported that a significant improvement in corrosion resistance was observed compared to layer coatings. (Refer to Hiroshi Kagechika, Hiroshi Kibe, Takeshi Ayasuya, Hiroshi Naemura, and Hiroshi Haratomi: Tetsu to Tsuna, 72 (1986), 51309). On the other hand, JP-A-62-99458 states: 1. OXl0-
A process of forming a first plating layer by performing ion plating in a high vacuum atmosphere of 'Torr or less, and a method of forming a plating layer of a material different from the first layer on the coating are disclosed. However, such ion plating method reduces the atmospheric pressure in vacuum to 1. OXl0-'T
Since it is necessary to create a high vacuum of less than orr, there is a problem in applying it to an actual industrial scale process.
さらにごく最近、ステンレス鋼板に、硝酸電解処理後、
プラズマCVDによって5iO1または5iJaのコー
ティングを施す(橋本ら: CAMP −l5IJ。Furthermore, very recently, after nitric acid electrolytic treatment, stainless steel plates have been
A coating of 5iO1 or 5iJa is applied by plasma CVD (Hashimoto et al.: CAMP-l5IJ.
Vol、 1 (1988)、 P426および特開昭
63−62860号公報参照)と耐食性が向上すること
が報告れさている。Vol. 1 (1988), P426 and JP-A No. 63-62860) and corrosion resistance is reported to be improved.
しかしながらこの方法は、ドライブレーティング処理の
前に通常イオンボンバード処理を施すので、鋼板表面に
おける電解処理効果が消失し、さらにステンレス鋼板表
面上に不動態被膜が形成されるために鋼板とセラミック
被膜との間の密着性が劣化するなど、実際の生産工程で
採用するにはまだ解決すべき多くの問題を残していた。However, since this method usually performs ion bombardment treatment before dry rating treatment, the electrolytic treatment effect on the surface of the steel sheet disappears, and furthermore, a passive film is formed on the surface of the stainless steel sheet, which causes the bond between the steel sheet and the ceramic coating. There were still many problems that needed to be resolved before it could be used in actual production processes, such as poor adhesion between the two.
(発明が解決しようとするm!り
発明者は、上記従来技術の問題の解決策として、さきに
蒸発物質の移動経路に工夫を加えたHCD法の利用によ
る耐食性および密着性に優れるセラミック被膜をそなえ
る鋼板の製造方法を、特願昭63−203924号明細
書において提案した。(What the invention is trying to solve!) As a solution to the problems of the prior art described above, the inventor has developed a ceramic coating with excellent corrosion resistance and adhesion by using the HCD method, which has a modified transfer route for evaporated substances. A method for manufacturing such a steel plate was proposed in Japanese Patent Application No. 63-203924.
しかじなら、この方法では、耐摩耗性に関する高度な要
求に対し、必ずしも十分とは言えなかった。However, this method was not necessarily sufficient to meet the high requirements regarding wear resistance.
したがって、この発明は、大表面積の炭素鋼板やステン
レス鋼板に、耐摩耗性に極めて優れ、かつ、耐食性およ
び密着性にも優れる被膜を有利に形成する方法について
提案することを目的とする。Therefore, an object of the present invention is to propose a method for advantageously forming a coating having extremely excellent wear resistance, corrosion resistance, and adhesion on a large surface area carbon steel plate or stainless steel plate.
(!III!!!を解決するための手段)発明者は、上
記の問題を解決すべく鋭意研究を重ねた結果、所期した
目的の達成のためには、上記した)ICD方式を用いた
イオンプレーティングの実施に際し、密着性の良好なC
rまたはTiなどの下地金属被覆と、CrまたはTiの
セラミック被膜およびダイヤモンド薄膜の組合せを活用
することが極めてを効であるとの知見を得た。(Means for solving !III!!!) As a result of intensive research to solve the above problem, the inventor found that in order to achieve the intended purpose, the above-mentioned) ICD method was used. C with good adhesion when performing ion plating
It has been found that it is extremely effective to utilize a combination of a base metal coating such as r or Ti, a ceramic coating of Cr or Ti, and a diamond thin film.
すなわちこの発明は、HCD方式によるイオンプレーテ
ィング処理によって、鋼板表面に金属被膜を被成し、つ
いでこの被膜上にCr、もしくはTiの炭化物、窒化物
、又は炭窒化物などのセラミック被膜を被成し、さらに
該セラミック被膜表面に、HCD方式によるビームを照
射すると同時に、先端を電気的に加熱した活性化ノズル
から炭化水素と水素の混合ガスを供給して、該セラミッ
ク被膜上にダイヤモンド薄膜を被成することを特徴とす
る耐摩耗性の極めて優れる被膜をそなえる鋼板の製造方
法である。That is, this invention forms a metal film on the surface of a steel plate by ion plating treatment using the HCD method, and then forms a ceramic film such as Cr or Ti carbide, nitride, or carbonitride on this film. Furthermore, the surface of the ceramic coating is irradiated with a beam using the HCD method, and at the same time, a mixed gas of hydrocarbon and hydrogen is supplied from an activation nozzle whose tip is electrically heated to coat the ceramic coating with a diamond thin film. This is a method for producing a steel plate having a coating with extremely excellent wear resistance.
ここに、金属被膜はCr、 Tiが好適であり、膜厚は
金属被膜、セラミック被膜およびダイヤモンド薄膜、共
に各々0.01μ−から5μ−の範囲とすることが好ま
しく、炭化水素と水素の混合比は体積比で、水素工に対
し炭化水素を0.05〜0.5の範囲にすることが望ま
しい。Here, the metal coating is preferably Cr or Ti, and the thickness of each of the metal coating, ceramic coating, and diamond thin film is preferably in the range of 0.01 μ- to 5 μ-, and the mixing ratio of hydrocarbon and hydrogen is is a volume ratio of hydrocarbon to hydrogen, which is preferably in the range of 0.05 to 0.5.
(作 用)
この発明では、極めて優れる耐摩耗性を有し、耐食性、
密着性にも優れる被膜を有する鋼板を得るための条件と
して、
鋼板表面にダイヤモンド薄膜を被成するに先立ち、下地
層として金属被膜を被成し、さらにその金属被膜の上に
セラミックを被成すること、金属被膜、セラミック被膜
、ダイヤモンド薄膜の被成にはHCD方式によるイオン
プレーティングを用いること、
などが肝要である。(Function) This invention has extremely excellent wear resistance, corrosion resistance,
In order to obtain a steel sheet with a film that has excellent adhesion, prior to forming a diamond thin film on the surface of the steel sheet, a metal film is formed as a base layer, and a ceramic is further formed on top of the metal film. In addition, it is important to use ion plating using the HCD method for depositing metal coatings, ceramic coatings, and diamond thin films.
以下、この発明を具体的に説明する。This invention will be specifically explained below.
低炭素鋼板あるいはステンレス鋼板を用いて、冷延を含
む再結晶焼鈍を行なった後、綱板表面を研削あるいは研
磨処理を施して清浄にし、)fcD方式によるイオンプ
レーティング処理により、鋼板上に密着性の良好なCr
、 Ti等の金属を厚さ0.01μMから5μ鋼の範囲
で被成させ、その上に、CrN 。After performing recrystallization annealing including cold rolling using a low carbon steel plate or stainless steel plate, the steel plate surface is cleaned by grinding or polishing, and then adhered to the steel plate by ion plating using the fcD method. Cr with good properties
, Ti, etc. is coated with a thickness ranging from 0.01 μM to 5 μM steel, and then CrN is deposited on top of it.
CrC,TiN、 TiC及びTi (C,N)等のセ
ラミック被膜を厚さ0.01μ■から5μmの範囲で被
成させ、さらにその上にダイヤモンド被膜を厚さ0.0
1μmから5μ糟の範囲で被成させることが好ましい。A ceramic film such as CrC, TiN, TiC and Ti (C,N) is formed to a thickness of 0.01 μm to 5 μm, and then a diamond film is further applied to a thickness of 0.0 μm.
It is preferable to form the coating with a thickness in the range of 1 μm to 5 μm.
ここに金属被膜、セラミック被膜、およびダイヤモンド
薄膜の各膜厚は、0.01 a m未満では目的とする
効果が得られず、5μ−を趨えると高硬度のため、引張
り、圧縮、あるいは衝撃に対して薄膜がわれやすく、ま
た必要以上に厚くすることは経済性にも劣ることになる
。したがって5μ顛以下が好ましい。If the thickness of each of the metal coating, ceramic coating, and diamond thin film is less than 0.01 am, the desired effect will not be obtained, and if it exceeds 5 μm, the hardness will be high, so it will not be able to withstand tension, compression, or impact. However, the thin film tends to break easily, and making it thicker than necessary is also uneconomical. Therefore, the thickness is preferably 5 μm or less.
つぎに、このダイヤモンド薄膜の被成方法について、そ
の−例を、圧力勾配のHCD法を用いたダイヤモンド薄
膜製造装置の模式図第1図により説明を加える。すなわ
ちHCDガンlから、電極2゜3、!m磁石を用いてH
CDのプラズマビームラ発生させ、基板8の背後に設け
た永久磁石9を用いて、5の点線で示すような高プラズ
マ電子流を基板8の表面上に照射する。一方ノズルの先
端が電気的に加熱された活性化ノズル10を用いて例え
ばCLとH2の混合ガスのイオン化を促進させて、基板
表面上に供給しダイヤモンド薄膜を被成させるものであ
る。Next, an example of the method for forming a diamond thin film will be explained with reference to FIG. 1, which is a schematic diagram of a diamond thin film manufacturing apparatus using a pressure gradient HCD method. That is, from the HCD gun l, electrodes 2°3,! H using m magnet
A CD plasma beam beam is generated, and a permanent magnet 9 provided behind the substrate 8 is used to irradiate the surface of the substrate 8 with a high plasma electron flow as shown by the dotted line 5. On the other hand, an activation nozzle 10 whose tip is electrically heated is used to promote ionization of a mixed gas of, for example, CL and H2, and the ionized gas is supplied onto the substrate surface to form a diamond thin film.
ここに、上記装置においてダイヤモンド薄膜を得る条件
としては、HCDガンの電圧、電流条件は、それぞれ電
圧: IOVから100V、電流: 200Aから30
0OAの範囲が、また、活性化ノズル先端の電気的加熱
条件は、電圧:20vから60V 、電流=10^から
5OAの範囲が好ましく、この条件によりガスのイオン
化が促進される。また、炭化水素、CI(4,Cfh及
びCH,等の少なくとも1種と水素との混合比は、体積
比で水素1に炭化水素は0.05〜0.5の範囲が望ま
しく、ガス流量は300cc/sinから3000cc
10+inの範囲が望ましい。Here, as conditions for obtaining a diamond thin film in the above apparatus, the voltage and current conditions of the HCD gun are as follows: voltage: IOV to 100V, current: 200A to 30V, respectively.
The electrical heating conditions at the tip of the activation nozzle are preferably in the range of voltage: 20V to 60V, current = 10^ to 5OA, and the ionization of the gas is promoted under these conditions. In addition, the mixing ratio of at least one of hydrocarbons, CI (4, Cfh, CH, etc.) and hydrogen is preferably in the range of 0.05 to 0.5 by volume of hydrogen to 1 part of hydrocarbon, and the gas flow rate is 300cc/sin to 3000cc
A range of 10+in is desirable.
ここに、炭化水素と水素の混合比が体積比で水素1に対
し炭化水素0.05未満では濃度が薄く効果が不十分で
あり、0.5を超えるとCの成分が過剰となり炉内を汚
すため、0.5以下が望ましい。Here, if the mixing ratio of hydrocarbon and hydrogen is less than 0.05 hydrocarbon to 1 hydrogen by volume, the concentration will be low and the effect will be insufficient, and if it exceeds 0.5, the C component will be excessive and the inside of the furnace will be To prevent staining, a value of 0.5 or less is desirable.
つぎに、この発明の基礎となった実験結果について説明
する。Next, the experimental results that formed the basis of this invention will be explained.
C: 0.049wtχ、Si : 0.18wLχ、
Mn : 0.3211tX、Cr : 17.1wt
X、 P : 0.018wtχ、S : 0.00
4wtχを含有する2、2■厚のステンレス鋼熱延板を
、0.25■厚に冷間圧延し、ついで750℃の不活性
雰囲気中で再結晶焼鈍を施したのち、下記のa、b、c
。C: 0.049wtχ, Si: 0.18wLχ,
Mn: 0.3211tX, Cr: 17.1wt
X, P: 0.018wtχ, S: 0.00
A 2.2-inch thick hot-rolled stainless steel plate containing 4wtχ was cold-rolled to a thickness of 0.25-inch, and then recrystallized annealed in an inert atmosphere at 750°C, followed by the following a and b. ,c
.
d、e、f及びgに示す7種類の手法によって鋼板表面
上にそれぞれの被膜を被成した。Each film was formed on the surface of the steel plate using seven methods shown in d, e, f, and g.
記
a、エレクトロンビーム(単にEBという)走査により
Tiを蒸発させ、これをRF (Radio Freq
uency)コイルを用いてイオン化してTiN被膜(
1,0pyi厚)を被成するいわゆるEB + RF法
にて成膜を行った。なお処理条件は、真空度3 X 1
0−’Torr、EB (ピアス式)の照射条件は、加
速電圧: 60KV、加速電流:5鵬^とし、N2ガス
イオン化のためのRFの電力は1000縁とした。Note a. Ti is evaporated by electron beam (simply referred to as EB) scanning, and then RF (Radio Freq)
ionization using a TiN coating (
The film was formed by the so-called EB + RF method, which coats the film with a thickness of 1.0 pyi. The processing conditions are vacuum degree 3 x 1
The irradiation conditions for 0-'Torr and EB (pierce type) were as follows: acceleration voltage: 60KV, acceleration current: 5p^, and RF power for N2 gas ionization was 1000V.
b、EB定走査より、鋼板表面上にCr被膜(0,5μ
■厚)を被成させたのち、その上に、さらにTiを蒸発
させ、イオン化手段としてRFコイルを用いてTiNの
セラミック被膜(0,5μ麟厚)を被成するEB +
RF法にて成膜を行なった。ここに、第1層のCr被膜
の処理条件は真空度4 X 10−’Torr、EB
(ピアス式)の照射条件は、加速電圧: 60KV、加
速電流:5mAとし、第2層のTiN被膜の被成は、上
記と同じEB条件で、N2ガスイオン化のためのRFの
電力を1000−とした。b. From EB constant scanning, a Cr coating (0.5μ
EB+
Film formation was performed using the RF method. Here, the processing conditions for the first layer Cr film are vacuum degree 4 x 10-'Torr, EB
(Pierce type) irradiation conditions were acceleration voltage: 60KV, acceleration current: 5mA, and the second layer TiN coating was formed under the same EB conditions as above, with the RF power for N2 gas ionization being 1000- And so.
さらに、TiN被膜の上に、HCD方式によるイオンプ
レーティング装置を用いて、HCDビームをTiN被膜
を有する基板表面に照射すると同時に、ノズル先端を電
気的に加熱した活性化ノズルよりC1,とH2の混合ガ
スを供給して上記基板表面上に約0.2μ曙厚のダイヤ
モンド薄膜を被成させた。このときのHCDガンには電
圧:50v、電流: 700A、活性化ノズルには電圧
:20V、電流:40A加えた。また、CH4とH2の
混合ガスは体積比で0.5(CH4) : I rug
)とし、ガス流量は500cc/5hinとした。Furthermore, using an ion plating device using the HCD method, an HCD beam was irradiated onto the surface of the substrate having the TiN film on the TiN film, and at the same time, C1 and H2 were irradiated using an activation nozzle whose nozzle tip was electrically heated. A mixed gas was supplied to form a diamond thin film with a thickness of about 0.2 μm on the surface of the substrate. At this time, a voltage of 50 V and a current of 700 A were applied to the HCD gun, and a voltage of 20 V and a current of 40 A were applied to the activation nozzle. Also, the mixed gas of CH4 and H2 has a volume ratio of 0.5 (CH4): I rug
), and the gas flow rate was 500 cc/5 h.
c、 HCD方式によるイオンプレーティング装置を用
いて、鋼板表面上に0.5μ麟厚のTi被膜を被成後、
その上に重ねて1μ■厚のTiN被膜を被成した。この
ときのHCD方式によるイオンプレーティング処理条件
は、加速電圧=70ν、加速電流:1000A 、真空
度: 4.9 X 10−’Torrおよびバイアス電
圧:50v とした。c. After forming a Ti film with a thickness of 0.5μ on the steel plate surface using an ion plating device using the HCD method,
A TiN film with a thickness of 1 .mu.m was overlaid thereon. The conditions for the ion plating process using the HCD method at this time were acceleration voltage = 70v, acceleration current: 1000A, degree of vacuum: 4.9 x 10-' Torr, and bias voltage: 50v.
d、IIcD方式によるイオンプレーティング装置を用
いて、鋼板表面上に0.5μ■厚のCr被膜を被成後、
その上に重ねて0.5μ■厚のTiN被膜を被成した。d. After forming a Cr film with a thickness of 0.5μ■ on the surface of the steel plate using an ion plating device using the IIcD method,
A TiN film having a thickness of 0.5 .mu.m was overlaid thereon.
このときのHCD方式によるイオンプレーティング処理
条件は、加速電圧ニア0V、加速電流:1000A 、
真空度: 5.2 X 10−’Torrおよびバイア
ス電圧:50vとした。The ion plating processing conditions using the HCD method at this time were: acceleration voltage near 0V, acceleration current: 1000A,
Vacuum degree: 5.2 x 10-'Torr and bias voltage: 50v.
さらにTiN被膜の上にす、と同じ条件で約0.2μ■
厚のダイヤモンド薄膜を被成させた。Approximately 0.2μ■ under the same conditions as on the TiN film.
A thick diamond film was deposited.
e、 HCD方式によるイオンプレーティング装置を用
いて、鋼板表面上に0.5μ醜厚のCr被膜を被成後、
その上に重ねて0.5μ■厚のTiN被膜を被成した。e. After forming a Cr film with a thickness of 0.5μ on the surface of the steel plate using an ion plating device using the HCD method,
A TiN film having a thickness of 0.5 .mu.m was overlaid thereon.
このときのHCD方式によるイオンプレーティング処理
条件は、d、と同じ条件で行なった。The ion plating processing conditions using the HCD method at this time were the same as those in d.
t、)HCD方式によるイオンプレーティング装置を用
いて、鋼板表面上に0.5μ霧厚のTi被膜を被成後、
その上に重ねて1μ順厚のTiN被膜を被成した。t,) After forming a Ti film with a mist thickness of 0.5μ on the steel plate surface using an ion plating device using the HCD method,
A TiN film having a regular thickness of 1 μm was overlaid thereon.
このときの)HCD方式によるイオンプレーティング処
理条件は、加速電圧:68V、加速電流:1000A
、真空度: 6 Xl0−’Torrおよびバイアス電
圧: 50Vとした。The ion plating processing conditions using the HCD method at this time were: acceleration voltage: 68V, acceleration current: 1000A.
, degree of vacuum: 6 Xl0-'Torr, and bias voltage: 50V.
さらにTiN被膜の上にHCD方式によるイオンプレー
ティング装置を用いて、HCDビームを、TiN被膜を
有する基板表面に照射すると同時に、ノズル先端を電気
的に加熱した活性化ノズルよりCH,とH2の混合ガス
を供給して、上記基板表面上に約0.2μ■厚のダイヤ
モンド薄膜を被成させた。このときのHCDガンには電
圧:50v、電流: 100OA、活性化ノズルには電
圧:50v、電流=2OAを加えた。また、CH,とH
2の混合ガスは体積比で0.5(C)!、) : 1
(H2)とし、ガス流量は500 cc/winとした
。Furthermore, using an ion plating device using the HCD method, the HCD beam is irradiated onto the surface of the substrate having the TiN film on the TiN film, and at the same time, CH and H2 are mixed from an activated nozzle whose nozzle tip is electrically heated. Gas was supplied to form a diamond thin film with a thickness of about 0.2 .mu.m on the surface of the substrate. At this time, a voltage of 50 V and a current of 100 OA were applied to the HCD gun, and a voltage of 50 V and a current of 2 OA were applied to the activation nozzle. Also, CH, and H
The volume ratio of the mixed gas in step 2 is 0.5 (C)! , ) : 1
(H2), and the gas flow rate was 500 cc/win.
g、HCD方式によるイオンプレーティング装置を用い
て、鋼板表面上に0.5μ顛厚のCr被膜を被成後、そ
の上に重ねて0.3μ■厚のTiN被膜を被成した。g. Using an ion plating device using the HCD method, a 0.5 μm thick Cr film was formed on the surface of the steel plate, and then a 0.3 μm thick TiN film was overlaid thereon.
このときのHCD方式によるイオンプレーティング条件
はf、と同条件とした。The ion plating conditions using the HCD method at this time were the same as f.
さらにTiN被膜の上にf、と同じ条件でダイヤモンド
薄膜を被成した。Furthermore, a diamond thin film was formed on the TiN film under the same conditions as f.
上述の各処理によって得た被膜を有する鋼板について、
耐食性、密着性および耐摩耗性について調べた結果を表
1に示す。Regarding the steel plate having the coating obtained by each of the above-mentioned treatments,
Table 1 shows the results of examining corrosion resistance, adhesion, and abrasion resistance.
ここに 摩耗試験方法においては、試験前のコーティン
グ表面の色差と摩耗試験後のコーティング表面の色差を
測定し、その色差変化をΔε値であられした。In the abrasion test method, the color difference on the coating surface before the test and the color difference on the coating surface after the abrasion test were measured, and the change in color difference was expressed as a Δε value.
表1から明らかなように、鋼板表面に下から順に金属被
膜(Cr、 Ti)、セラミック被膜(TiN)、及び
最外層にダイヤモンド薄膜を被成した試料、b。As is clear from Table 1, sample b was coated with a metal coating (Cr, Ti), a ceramic coating (TiN), and a diamond thin film as the outermost layer on the steel plate surface in this order from the bottom.
d、f及びgは耐摩耗性が極端に向上していることが注
目される。特に耐摩耗性の良否を示すΔE値は0.2か
ら0.3とダイヤモンド薄膜を被成しなかった試料a、
c、eの3.0から7.0に比較して1/10から1/
35と大巾に向上する。It is noteworthy that d, f, and g have extremely improved wear resistance. In particular, the ΔE value, which indicates the quality of wear resistance, was 0.2 to 0.3, and sample a, which was not coated with a diamond thin film,
1/10 to 1/ compared to 3.0 to 7.0 for c and e.
35, a huge improvement.
また、bを除く、d、f及びg試料は、耐食性、密着性
共に優れているが、ダイヤモンド薄膜があっても、金属
被膜、セラミック被膜をHCD方式で行なわなかったb
試料は耐食性で劣っている。In addition, except for b, samples d, f, and g have excellent corrosion resistance and adhesion, but even with the diamond thin film, metal coating and ceramic coating were not done using the HCD method.
The sample has poor corrosion resistance.
このように、耐摩耗性が顕著に向上し、しかも耐食性、
密着性にも優れる被膜の被成は、コーティング方法、セ
ラミックの膜質などにも起因するが、セラミック被膜上
に硬度の高いダイヤモンド薄膜を被成させることにより
耐摩耗性が大巾に改善されることが明らかである。In this way, wear resistance is significantly improved, and corrosion resistance and
The formation of a film with excellent adhesion is due to factors such as the coating method and the quality of the ceramic film, but wear resistance can be greatly improved by forming a thin diamond film with high hardness on the ceramic film. is clear.
(実施例)
l施■1
C: 0.042wtχ、Si : 0.18wtχ、
Mn : 0.33wtχ、Cr : 17.Owt$
、P : 0.016wtχ、S : 0.015wt
χを含有する2、3 am厚のステンレス鋼熱延板を、
0.25m厚に冷間圧延し、ついで750°Cの不活性
雰囲気中で再結晶焼鈍を施したのち、前記gの条件で0
.05μ蒙厚のCr被膜を被成し、その上に0.6μm
厚のTiN被膜を被成し、さらにその上に0.3μm厚
のダイヤモンド薄膜を被成した。(Example) 1 C: 0.042wtχ, Si: 0.18wtχ,
Mn: 0.33wtχ, Cr: 17. Owt$
, P: 0.016wtχ, S: 0.015wt
A 2-3 am thick stainless steel hot-rolled plate containing χ,
After cold rolling to a thickness of 0.25 m and recrystallization annealing in an inert atmosphere at 750°C,
.. A Cr film with a thickness of 0.5 μm is formed on it, and a 0.6 μm thick Cr film is formed on it.
A thick TiN film was formed, and a 0.3 μm thick diamond thin film was further formed thereon.
かくして得られた製品の耐食性、密着性及び耐摩耗性は
いずれも良好で、特に耐摩耗性については、3000回
での色差変化ΔEが0.1と極めて良好であった。The thus obtained product had good corrosion resistance, adhesion, and abrasion resistance, and in particular, the abrasion resistance was extremely good, with a color difference change ΔE of 0.1 after 3000 cycles.
実施JLL
C: 0.045wtχ、Si : 0.029wtχ
、Mn : 0.30wtχ、P : 0.014wt
χ、S : 0.016wtXを含有する2、2 am
厚の低炭素鋼熱延板を、0.7ann厚に冷間圧延し、
ついで750°Cの再結晶焼鈍を施したのち、鋼板表面
を電界研磨により中心線平均粗さRaで0.2μMに研
磨した後、前記dの条件で0.3μ蒙厚のCr被膜を被
成し、その上に各々0.8μm厚のTiC被膜及びTi
(C,N)被膜を被成し、さらにその上に0.2μm厚
のダイヤモンド薄膜を被成した。Implemented JLL C: 0.045wtχ, Si: 0.029wtχ
, Mn: 0.30wtχ, P: 0.014wt
χ, S: 2,2 am containing 0.016wtX
A thick low carbon steel hot rolled plate was cold rolled to a thickness of 0.7 ann,
After recrystallization annealing at 750°C, the surface of the steel plate was polished to a centerline average roughness Ra of 0.2 μM by electric field polishing, and then a Cr film with a thickness of 0.3 μm was formed under the conditions of d above. On top of that, a TiC film and a TiC film each having a thickness of 0.8 μm are applied.
A (C,N) film was formed, and a 0.2 μm thick diamond thin film was further formed thereon.
かくして得られた製品の耐食性、密着性及び耐摩耗性は
いずれも良好で、特に耐摩耗性については、3000回
での色差変化ΔEが、中間のセラミック被膜がTicの
場合0.3. Ti(C,N)の場合0.4 と極めて
良好であった。The corrosion resistance, adhesion, and abrasion resistance of the thus obtained product are all good. In particular, regarding the abrasion resistance, the color difference change ΔE after 3000 cycles is 0.3. In the case of Ti(C,N), it was 0.4, which was extremely good.
夫旌貫主
C: 0.013wtχ、Si : 0.008wtχ
、Mn : 0.21wtχ、Cr : 16.7wt
χ、P : 0.009wtχ、S : 0.016w
tZを含有する2、2 m厚のステンレス鋼熱延板を、
0.20mm厚に冷間圧延し、ついで800°Cの不活
性雰囲気中で再結晶焼鈍を施したのち、前記fの条件で
0.07μ蒙厚のTiを被成し、その上に0.5μlの
TiC被膜、さらにその上に0.2μm厚のT1CN被
膜を被成後、0.2μm厚のダイヤモンド被膜を被成し
た。C: 0.013wtχ, Si: 0.008wtχ
, Mn: 0.21wtχ, Cr: 16.7wt
χ, P: 0.009wtχ, S: 0.016w
A 2.2 m thick hot rolled stainless steel plate containing tZ,
After cold rolling to a thickness of 0.20 mm and recrystallization annealing in an inert atmosphere at 800°C, a Ti film having a thickness of 0.07 μm was formed under the conditions of f above. A 5 μl TiC film was formed, and a 0.2 μm thick T1CN film was formed thereon, followed by a 0.2 μm thick diamond film.
かくして得られた製品の耐食性、密着性及び耐摩耗性は
いずれも良好で、特に耐摩耗性については、5000回
での色差変化ΔEが0.2と極めて良好であった。The thus obtained product had good corrosion resistance, adhesion, and abrasion resistance, and in particular, the abrasion resistance was extremely good, with a color difference change ΔE of 0.2 after 5000 cycles.
実施炎↓
C: 0.013wtχ、Si : 0.26evtX
、 Mn : 0.25wtχ、Cr : 19.3w
tχ、Mo : 3.2wtχを含有する0、7 am
厚のステンレス鋼板の上に、前記gの条件で0.5μ鋼
厚のC「を被成し、その上に0.5μm厚のCrN被膜
、さらにその上に0.2μm厚のCrC被膜を被成後、
0.15μ蒙厚のダイヤモンド被膜を被成した。かくし
て得られた製品の耐食性、密着性、耐摩耗性はいずれも
良好で、特に耐摩耗性については10,000回での色
差変化へEが0.3と極めて良好であった。Implementation flame ↓ C: 0.013wtχ, Si: 0.26evtX
, Mn: 0.25wtχ, Cr: 19.3w
tχ, Mo: 0.7 am containing 3.2wtχ
A 0.5 μm thick steel plate was coated on a 0.5 μm thick stainless steel plate under the conditions of g above, and a 0.5 μm thick CrN film was formed on top of that, and a 0.2 μm thick CrC film was further applied on top of that. After adulthood,
A 0.15 μm thick diamond coating was applied. The corrosion resistance, adhesion, and abrasion resistance of the thus obtained product were all good, and in particular, the abrasion resistance was extremely good, with E for color difference change after 10,000 cycles being 0.3.
(発明の効果)
この発明によれば、炭素鋼、ステンレス鋼などの銅板表
面にHCD方式を用いたイオンプレーティングにより、
金属被膜、セラミック被膜そして最外層にダイヤモンド
被膜を順に被成さすことにより、耐摩耗性にすぐれ、か
つ、耐食性、密着性にも優れる鋼板が得られるもので、
建築などで用いられる大表面積を有する鋼板にも好適に
用いることができ、イオンプレーティングの実用化に大
きく貢献するものである。(Effect of the invention) According to this invention, by ion plating using the HCD method on the surface of a copper plate such as carbon steel or stainless steel,
By sequentially applying a metal coating, a ceramic coating, and then a diamond coating as the outermost layer, a steel plate with excellent wear resistance, corrosion resistance, and adhesion can be obtained.
It can also be suitably used for steel plates with a large surface area used in construction, etc., and will greatly contribute to the practical application of ion plating.
【図面の簡単な説明】
第1図はこの発明の圧力勾配型のHCD法を用いたダイ
ヤモンド薄膜製造装置の模式図である。
1・・・HCDガン 2・・・第1電極3・・
・第2を極 4・・・電磁石5・・・ビーム
6・・・真空チャンバー7・・・真空吸引口
8・・・基板9・・・永久磁石 10
・・・活性化ノズル11・・・ノズル保護管 12
・・・ガス導入口第1図BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a diamond thin film manufacturing apparatus using the pressure gradient type HCD method of the present invention. 1...HCD gun 2...First electrode 3...
・Second pole 4...Electromagnet 5...Beam
6... Vacuum chamber 7... Vacuum suction port 8... Substrate 9... Permanent magnet 10
...Activation nozzle 11 ... Nozzle protection tube 12
...Gas inlet diagram 1
Claims (1)
て鋼板表面に金属被膜を被成し、ついでこの被膜上にC
r、もしくはTiの炭化物、窒化物、又は炭窒化物など
のセラミック被膜を被成し、さらに該セラミック被膜表
面に、HCD方式によるビームを照射すると同時に、先
端を電気的に加熱した活性化ノズルから炭化水素と水素
の混合ガスを供給して、該セラミ被膜上にダイヤモンド
薄膜を被成することを特徴とする耐摩耗性の極めて優れ
る被膜を有する鋼板の製造方法。1. A metal coating is formed on the surface of the steel plate by ion plating treatment using the HCD method, and then carbon is applied on this coating.
A ceramic coating such as carbide, nitride, or carbonitride of Ti or Ti is coated, and the surface of the ceramic coating is irradiated with a beam by the HCD method, and at the same time, from an activation nozzle whose tip is electrically heated. A method for manufacturing a steel plate having a coating with extremely excellent wear resistance, which comprises supplying a mixed gas of hydrocarbon and hydrogen to form a diamond thin film on the ceramic coating.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9314990A JPH03291377A (en) | 1990-04-10 | 1990-04-10 | Production of steel sheet having film extremely excellent in wear resistance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9314990A JPH03291377A (en) | 1990-04-10 | 1990-04-10 | Production of steel sheet having film extremely excellent in wear resistance |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03291377A true JPH03291377A (en) | 1991-12-20 |
Family
ID=14074481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9314990A Pending JPH03291377A (en) | 1990-04-10 | 1990-04-10 | Production of steel sheet having film extremely excellent in wear resistance |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03291377A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005500435A (en) * | 2001-06-22 | 2005-01-06 | ティッセンクルップ エレクトリカル スティール エーベーゲー ゲゼルシャフト ミット ベシュレンクテル ハフツング | Oriented electrical steel sheet with electrical insulation coating |
JP2009114525A (en) * | 2007-11-08 | 2009-05-28 | Stanley Electric Co Ltd | Plasma treatment apparatus |
-
1990
- 1990-04-10 JP JP9314990A patent/JPH03291377A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005500435A (en) * | 2001-06-22 | 2005-01-06 | ティッセンクルップ エレクトリカル スティール エーベーゲー ゲゼルシャフト ミット ベシュレンクテル ハフツング | Oriented electrical steel sheet with electrical insulation coating |
JP2009018573A (en) * | 2001-06-22 | 2009-01-29 | Thyssenkrupp Electrical Steel Gmbh | Grain-oriented electromagnetic steel sheet including electrically insulating coating |
JP2009114525A (en) * | 2007-11-08 | 2009-05-28 | Stanley Electric Co Ltd | Plasma treatment apparatus |
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