JPH04106359U - Parts coated with hard carbon film - Google Patents
Parts coated with hard carbon filmInfo
- Publication number
- JPH04106359U JPH04106359U JP1350291U JP1350291U JPH04106359U JP H04106359 U JPH04106359 U JP H04106359U JP 1350291 U JP1350291 U JP 1350291U JP 1350291 U JP1350291 U JP 1350291U JP H04106359 U JPH04106359 U JP H04106359U
- Authority
- JP
- Japan
- Prior art keywords
- iron
- titanium
- layer
- carbon film
- hard carbon
- 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
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 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 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910001096 P alloy Inorganic materials 0.000 claims abstract description 5
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910000640 Fe alloy Inorganic materials 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007733 ion plating Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- GPWDPLKISXZVIE-UHFFFAOYSA-N cyclo[18]carbon Chemical compound C1#CC#CC#CC#CC#CC#CC#CC#CC#C1 GPWDPLKISXZVIE-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
(57)【要約】
【目的】優れた密着強度を有する硬質カーボン膜を被覆
した鉄を主成分とする金属部品を提供すること。
【構成】鉄を主成分とする(鉄合金)基台の表面に中間
層を介して硬質カーボン膜を被覆した部品上に、基台側
から順に鉄あるいはニッケルリン合金からなる層、鉄あ
るいはニッケルとチタンとの合金層、鉄あるいはニッケ
ルとチタンとの炭化物層、チタンの炭化物層、チタンの
炭化物とカーボンとの混合物層となるように組成が連続
的に変化している中間層とこの中間層上に被覆した硬質
カーボン膜で構成する。
【効果】鉄を主成分とする金属製部品に密着性良く硬質
カーボン膜を被覆することが可能となり、硬質カーボン
膜の特性を充分にいかした耐摩耗部品など、実用域での
多方面への展開が可能となる。
(57) [Summary] [Purpose] To provide a metal part whose main component is iron and which is coated with a hard carbon film having excellent adhesion strength. [Structure] On a part whose main component is iron (iron alloy), the surface of the base is coated with a hard carbon film through an intermediate layer, and then from the base side, layers of iron or nickel-phosphorus alloy, iron or nickel An intermediate layer whose composition changes continuously, such as an alloy layer of iron or nickel and titanium, a carbide layer of iron or nickel and titanium, a carbide layer of titanium, and a mixture layer of titanium carbide and carbon, and this intermediate layer. It consists of a hard carbon film coated on top. [Effect] It is now possible to coat metal parts whose main component is iron with a hard carbon film with good adhesion, which can be used in many practical applications such as wear-resistant parts that fully utilize the characteristics of the hard carbon film. Expansion is possible.
Description
【0001】0001
本考案は気相合成法による硬質カーボン膜を被覆した部品に関する。 The present invention relates to parts coated with a hard carbon film produced by vapor phase synthesis.
【0002】0002
硬質カーボン膜は1970年代後半から英国で研究されはじめたi−カーボン と俗称される超硬質炭素膜であり、炭素原子の結合状態に長周期の結晶性が見ら れず、アモルファスシリコンと類似の結合状態を有するものと考えられている。 また、その物性にはダイヤモンドのそれと類似点が多く、その特性(高硬度、耐 摩耗性、潤滑性、絶縁性、耐薬品性)から工具をはじめとし、各種機械、電子部 品への保護コーティング、あるいは機能性デバイスへの応用が期待されている。 この膜の形成方法は試料基板を加熱せず、比較的高真空、たとえば0.1Tor r以下で炭化水素ガスをプラズマ分解する気相合成法が主なものである。 The hard carbon film is i-carbon, which began to be researched in the UK in the late 1970s. This is an ultra-hard carbon film, commonly known as a carbon film with long-period crystallinity in the bonding state of carbon atoms. It is thought that it has a bonding state similar to that of amorphous silicon. In addition, its physical properties have many similarities with those of diamond, and its characteristics (high hardness, durability, Abrasion resistance, lubricity, insulation, chemical resistance), tools, various machines, electronic parts, etc. It is expected to be applied as a protective coating for products or as a functional device. This film formation method does not heat the sample substrate and is performed under a relatively high vacuum, for example 0.1 Torr. The main method is a gas phase synthesis method in which hydrocarbon gas is subjected to plasma decomposition at temperatures below r.
【0003】0003
しかしながら、この方法ではたとえばステンレス鋼やSK鋼などの鉄を主成分 とする材料上に硬質カーボン膜を直接密着性良く被覆することは困難であり、前 処理として基台と硬質カーボン膜との間に密着改善のための中間層を必要とする 。 この中間層としてシリコン、ゲルマニウムなどの周期率表第4族元素(特開昭 59ー143498)あるいはチタニウム、ジルコニウム、ハフニウム等の炭化 物層、窒化物層等を中間層に用いる方法が提案されているが、これらの中間層は 硬質カーボン膜との密着性には優れているものの鉄を主成分とする材料との密着 性は劣るため、外部からの衝撃によって剥離を生じることがあり、いまだ充分な 効果は得られていない。 However, with this method, for example, stainless steel or SK steel, which mainly consists of iron, It is difficult to directly coat a hard carbon film with good adhesion on the material to be used. As a treatment, an intermediate layer is required between the base and the hard carbon film to improve adhesion. . As this intermediate layer, silicon, germanium, and other Group 4 elements of the periodic table (Japanese Patent Application Publication No. 59-143498) or carbonization of titanium, zirconium, hafnium, etc. Methods have been proposed in which a material layer, a nitride layer, etc. are used as an intermediate layer, but these intermediate layers are Although it has excellent adhesion with hard carbon films, it does not adhere well with materials whose main component is iron. Due to its inferior properties, it may peel off due to external impact, and it is still not fully developed. No effect has been obtained.
【0004】 本考案の目的は優れた密着強度を有する硬質カーボン膜を被覆した鉄を主成分 とする金属部品を提供することである。0004 The purpose of this invention is to use iron as a main component coated with a hard carbon film that has excellent adhesion strength. Our objective is to provide metal parts that meet the following requirements.
【0005】[0005]
上記目的のため本考案においては、鉄を主成分とする基台の表面に中間層を介 して硬質カーボン膜を被覆した部品において、中間層を基台側から順に鉄あるい はニッケルリン合金からなる層、鉄あるいはニッケルとチタンとの合金層、鉄あ るいはニッケルとチタンとの炭化物層、チタンの炭化物層、チタンの炭化物とカ ーボンとの混合層となるように中間層の組成が連続的に変化するような構造とし た。 For the above purpose, in this invention, an intermediate layer is interposed on the surface of the base whose main component is iron. For parts coated with a hard carbon film, the intermediate layer is coated with iron or steel in order from the base side. is a layer made of nickel phosphorous alloy, a layer made of iron or an alloy of nickel and titanium, and a layer made of iron or nickel and titanium. Rui is a carbide layer of nickel and titanium, a carbide layer of titanium, and a carbide layer of titanium and carbon. The structure is such that the composition of the intermediate layer changes continuously so that it becomes a mixed layer with carbon. Ta.
【0006】[0006]
【実施例1】 以下、図面を用いて本考案の実施例を説明する。第1図は本考案による硬質カ ーボン膜を被覆したステンレス鋼製部品の一部分を示す断面図である。ステンレ ス鋼製部品1上に、ステンレス鋼製部品1側から順次鉄からなる層3と鉄とチタ ンとの合金層4と鉄とチタンとの炭化物層5とチタンの炭化物層6とチタンの炭 化物とカーボンの混合層7となるように連続的に組成が変化している中間層2と 硬質カーボン膜8とを積層する構造とする。中間層2はチタンと鉄の両者の蒸着 源を備えている反応性イオンプレーティング法によって形成され、イオンプレー ティング装置内を10-5Torrに真空排気後、アルゴンガスを導入し、電子 ビームで鉄を蒸発させ、鉄からなる層3を形成し、その後、チタンをその蒸発量 を徐々に増加させながら蒸発させ、チタンと鉄からなる合金層4を形成する。次 にエチレンガスを徐々に導入しながら、チタンと鉄からなる炭化物層5を形成す る 。次に鉄の蒸発量を下げながら、イオンプレーティングを続け、チタンの炭化物 層6を形成しする。その後、さらにエチレン流量を増加させることによってチタ ンの炭化物とカーボンの混合層7を形成する。以上の操作は連続的に行うことが 望ましい。その後、以下の条件でプラズマCVD法によって硬質カーボン膜8を 形成する。Embodiment 1 An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view showing a portion of a stainless steel component coated with a hard carbon film according to the present invention. On the stainless steel part 1, from the side of the stainless steel part 1, a layer 3 made of iron, an alloy layer 4 of iron and titanium, a carbide layer 5 of iron and titanium, a carbide layer 6 of titanium, and a carbide of titanium are formed. The structure is such that an intermediate layer 2 whose composition changes continuously and a hard carbon film 8 are laminated to form a carbon mixed layer 7. The intermediate layer 2 is formed by the reactive ion plating method, which is equipped with vapor deposition sources for both titanium and iron. After the ion plating apparatus is evacuated to 10 - 5 Torr, argon gas is introduced, and iron is deposited using an electron beam. is evaporated to form a layer 3 made of iron, and then titanium is evaporated while gradually increasing its evaporation amount to form an alloy layer 4 made of titanium and iron. Next, while gradually introducing ethylene gas, a carbide layer 5 made of titanium and iron is formed. Next, ion plating is continued while reducing the amount of iron evaporated to form a titanium carbide layer 6. Thereafter, a mixed layer 7 of titanium carbide and carbon is formed by further increasing the ethylene flow rate. It is desirable to perform the above operations continuously. Thereafter, a hard carbon film 8 is formed by plasma CVD under the following conditions.
【0007】 原料ガス:メタン(以下CH4 と省略) 励起法 :高周波(13.56MHz) 励起出力:300W ガス流量:30cm3 /min. ガス圧 :0.1Torr 成膜速度:20nm/min. 処理温度:≦150℃Raw material gas: Methane (hereinafter abbreviated as CH 4 ) Excitation method: High frequency (13.56 MHz) Excitation output: 300 W Gas flow rate: 30 cm 3 /min. Gas pressure: 0.1 Torr Film formation rate: 20 nm/min. Processing temperature: ≦150℃
【0008】 以上の条件で得られた硬質カーボン膜8のビッカース硬度は5000kg/m m2 であり、X線回折、RHEED、ラマン分光スペクトルおよびフーリエ変換 赤外吸収分光法(FT−IR)などの分析結果より、アモルファス構造を有し、 膜中に水素を含有していることがわかった。The hard carbon film 8 obtained under the above conditions has a Vickers hardness of 5000 kg/m 2 and is suitable for X-ray diffraction, RHEED, Raman spectroscopy, Fourier transform infrared absorption spectroscopy (FT-IR), etc. The analysis results revealed that the film had an amorphous structure and contained hydrogen.
【0009】 本考案の実施例の効果を確認するために比較試料としてステンレス鋼製部品上 に中間層としてスパッタリングによるシリコンを用いて硬質カーボン膜を被覆し た比較試料と本考案によって得られた試料を引っかき試験によって評価した。そ の結果を表1に示す。[0009] In order to confirm the effect of the embodiment of the present invention, stainless steel parts were used as a comparison sample. coated with a hard carbon film using sputtered silicon as an intermediate layer. A comparative sample obtained by the present invention and a sample obtained by the present invention were evaluated by a scratch test. So The results are shown in Table 1.
【表1】 [Table 1]
【0010】0010
【実施例2】 第2図は本考案による硬質カーボン膜を被覆したSK鋼製部品の一部分を示す 断面図である。SK鋼製部品11上に、SK鋼製部品11側から順次ニッケルリ ン合金13とニッケルとチタンとの合金層14とニッケルとチタンとの炭化物層 15とチタンの炭化物層16とチタンの炭化物とカーボンの混合層17となるよ うに連続的に組成が変化している中間層12と硬質カーボン膜18とを積層する 構造とする。中間層12においてニッケルリン合金13は無電解メッキよって形 成される。この層はSK鋼表面の硬度をアップさせる効果がある。その後、実施 例1と同じ反応性イオンプレーティングによる方法と同様な方法によってニッケ ルとチタンの合金層14とニッケルとチタンとの炭化物層15とチタンの炭化物 層16とチタンの炭化物とカーボンの混合層17を組成が連続的に変わるように 形成し、さらに実施例2と同じ条件で硬質カーボン膜18を形成した。そして、 実施例1と同様に引っかき試験を行ったところ優れた密着強度を示すことがわか った。[Example 2] Figure 2 shows a portion of an SK steel part coated with a hard carbon film according to the present invention. FIG. Apply nickel on the SK steel part 11 in order from the SK steel part 11 side. alloy layer 13 of nickel and titanium, and carbide layer of nickel and titanium. 15, a titanium carbide layer 16, and a mixed layer 17 of titanium carbide and carbon. An intermediate layer 12 whose composition changes continuously and a hard carbon film 18 are laminated. Structure. In the intermediate layer 12, the nickel phosphorus alloy 13 is formed by electroless plating. will be accomplished. This layer has the effect of increasing the hardness of the SK steel surface. Then, carry out nickel by a method similar to the same reactive ion plating method as in Example 1. alloy layer 14 of nickel and titanium, carbide layer 15 of nickel and titanium, and carbide of titanium The composition of the layer 16 and the mixed layer 17 of titanium carbide and carbon changes continuously. Further, a hard carbon film 18 was formed under the same conditions as in Example 2. and, When a scratch test was conducted in the same manner as in Example 1, it was found that excellent adhesion strength was exhibited. It was.
【0011】[0011]
以上の実施例から明らかなように、本考案によれば鉄を主成分とする金属製部 品に密着性良く硬質カーボン膜を被覆することが可能となり、硬質カーボン膜の 特性を充分に生かした耐摩耗部品など、実用域での多方面への展開が可能となる 。 As is clear from the above embodiments, according to the present invention, metal parts whose main component is iron. It is now possible to coat the product with a hard carbon film with good adhesion. It will be possible to develop it in many fields in practical applications, such as wear-resistant parts that fully utilize its characteristics. .
【図1】本考案の実施例1における硬質カーボン膜を被
覆したステンレス鋼製部品の模式断面図である。FIG. 1 is a schematic cross-sectional view of a stainless steel component coated with a hard carbon film in Example 1 of the present invention.
【図2】本考案の実施例2における硬質カーボン膜を被
覆したSK鋼製部品の模式断面図である。FIG. 2 is a schematic cross-sectional view of an SK steel component coated with a hard carbon film in Example 2 of the present invention.
1 ステンレス鋼製部品 2 中間層 3 鉄からなる層 4 鉄とチタンとの合金層 5 鉄とチタンとの炭化物層 6 チタンの炭化物層 7 チタンの炭化物とカーボンの混合層 8 硬質カーボン膜 11 SK鋼製部品 12 中間層 13 ニッケルリン合金 14 ニッケルとチタンとの合金層 15 ニッケルとチタンとの炭化物層 16 チタンの炭化物層 17 チタンの炭化物とカーボンの混合層 18 硬質カーボン膜 1 Stainless steel parts 2 Middle class 3 Layer made of iron 4 Alloy layer of iron and titanium 5 Carbide layer of iron and titanium 6 Titanium carbide layer 7 Mixed layer of titanium carbide and carbon 8 Hard carbon film 11 SK steel parts 12 Middle class 13 Nickel phosphorus alloy 14 Nickel and titanium alloy layer 15 Carbide layer of nickel and titanium 16 Titanium carbide layer 17 Mixed layer of titanium carbide and carbon 18 Hard carbon film
Claims (1)
介して硬質カーボン膜を被覆した部品において、中間層
が基台側から順に鉄あるいはニッケルリン合金からなる
層、鉄あるいはニッケルとチタンとの合金層、鉄あるい
はニッケルとチタンとの炭化物層、チタンの炭化物層、
チタンの炭化物とカーボンとの混合物層となるように中
間層の組成が連続的に変化していることを特徴とする硬
質カーボン膜を被覆した部品。Claim 1: A component in which the surface of a base whose main component is iron is coated with a hard carbon film via an intermediate layer, in which the intermediate layer consists of layers consisting of iron or nickel phosphorus alloy, iron or nickel phosphorus alloy in order from the base side. alloy layer of iron or nickel and titanium, carbide layer of iron or nickel and titanium, carbide layer of titanium,
A part coated with a hard carbon film, characterized in that the composition of the intermediate layer changes continuously so that it becomes a mixture layer of titanium carbide and carbon.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1350291U JPH04106359U (en) | 1991-02-19 | 1991-02-19 | Parts coated with hard carbon film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1350291U JPH04106359U (en) | 1991-02-19 | 1991-02-19 | Parts coated with hard carbon film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04106359U true JPH04106359U (en) | 1992-09-14 |
Family
ID=31901500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1350291U Pending JPH04106359U (en) | 1991-02-19 | 1991-02-19 | Parts coated with hard carbon film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04106359U (en) |
-
1991
- 1991-02-19 JP JP1350291U patent/JPH04106359U/en active Pending
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