JP2011173244A - Lamination film covering member and method of producing the same - Google Patents

Lamination film covering member and method of producing the same Download PDF

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JP2011173244A
JP2011173244A JP2010036828A JP2010036828A JP2011173244A JP 2011173244 A JP2011173244 A JP 2011173244A JP 2010036828 A JP2010036828 A JP 2010036828A JP 2010036828 A JP2010036828 A JP 2010036828A JP 2011173244 A JP2011173244 A JP 2011173244A
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film
nitrogen
chromium
containing chromium
solid lubricant
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JP5530751B2 (en
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Yuichiro Shimizu
雄一郎 清水
Masahiro Kitamura
征寛 北村
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Dowa Thermotech Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a lamination film covering member which is excellent in wear resistance and adhesion property, improves sliding characteristics to reduce attacking properties to a counter member, and prevents the damage of a substrate even in a severe environment, and also to provide a method of producing the lamination film covering member at a low cost. <P>SOLUTION: A plurality of chromium films 2 and a plurality of nitrogen-containing chromium films 3 are alternately and continuously formed in this order on the substrate 1 and, thereafter, a film 4 made of solid lubricant is formed on the outermost surface of the nitrogen-containing chromium films 3. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、積層皮膜被覆部材およびその製造方法に関し、特に、基材上に硬質皮膜として窒素含有クロム皮膜が形成された部材およびその製造方法に関する。   The present invention relates to a laminated film-coated member and a method for producing the same, and more particularly to a member having a nitrogen-containing chromium film formed as a hard film on a substrate and a method for producing the same.

従来、耐摩耗性や耐焼き付き性が必要とされる自動車などの摺動部品や機械部材の他、高面圧下で使用される金型などの表面に、スパッタリングなどの物理的蒸着によって窒素含有クロム皮膜を形成して、耐摩耗性や耐焼き付き性を向上させる方法が知られている（例えば、特許文献１参照）。また、自動車などの摺動部品の摺動面に、ＰＶＤ法によりダイヤモンドライクカーボンの下層膜を形成した後に、ＣＶＤ法によりダイヤモンドライクカーボンの上層膜を形成することによって、耐久性が高く且つ摩擦係数が低いダイヤモンドライクカーボン皮膜を形成する方法も提案されている（例えば、特許文献２参照）。   Conventionally, nitrogen-containing chromium is produced by physical vapor deposition such as sputtering on the surfaces of sliding parts and machine parts such as automobiles that require wear resistance and seizure resistance, as well as dies used under high surface pressure. A method of forming a film to improve wear resistance and seizure resistance is known (see, for example, Patent Document 1). In addition, a diamond-like carbon lower layer film is formed by a PVD method on a sliding surface of a sliding part such as an automobile, and then a diamond-like carbon upper layer film is formed by a CVD method. A method of forming a diamond-like carbon film having a low thickness has also been proposed (see, for example, Patent Document 2).

特開平１１−２１７６６６号公報（段落番号０００８−００１０）JP 11-217666 A (paragraph number 0008-0010) 特開２００９−１６７５１２号公報（段落番号００１４−００１９）JP 2009-167512 A (paragraph number 0014-0019)

しかし、従来の方法では、自動車などの摺動部品、機械部材、金型などの表面に要求される耐磨耗性、密着性、摺動特性などの全てを満足する硬質皮膜として表面処理皮膜を単純な系で形成するのは困難であり、硬質皮膜としての能力を最大限に発揮させるためには、硬質皮膜を形成する基材の強化や、基材の表面形状の調整などが必須であった。   However, in the conventional method, the surface-treated film is used as a hard film that satisfies all of the wear resistance, adhesion, and sliding characteristics required for the surfaces of sliding parts such as automobiles, machine parts, and dies. It is difficult to form with a simple system, and in order to maximize its capability as a hard coating, it is essential to reinforce the substrate on which the hard coating is formed and to adjust the surface shape of the substrate. It was.

また、特許文献１などに記載された窒素含有クロム皮膜は、アモルファス構造を有するために化学的に安定で耐磨耗性および密着性に優れているが、硬質皮膜であるが故の相手部材への攻撃性や、過酷環境下における硬質皮膜の破壊時の基材（母材）の損傷の問題がある。   In addition, the nitrogen-containing chromium film described in Patent Document 1 and the like has an amorphous structure, and thus is chemically stable and excellent in wear resistance and adhesion, but is a hard film. There is a problem of damage to the base material (base material) at the time of destruction of the hard coating in a severe environment.

また、特許文献２などに記載されたダイヤモンドライクカーボン皮膜は、耐久性が高く且つ摩擦係数が低いが、基材との密着性や、皮膜の破壊時の基材の損傷の問題があり、また、製造工程が複雑で製造コストが高いという問題がある。   In addition, the diamond-like carbon film described in Patent Document 2 has high durability and a low coefficient of friction, but there are problems of adhesion to the base material and damage to the base material when the film is broken. The manufacturing process is complicated and the manufacturing cost is high.

したがって、本発明は、このような従来の問題点に鑑み、耐磨耗性および密着性に優れ、摺動特性を向上させて相手部材への攻撃性を低下させることができ、過酷環境下においても基材の損傷を防止することができる、積層皮膜被覆部材およびその積層皮膜被覆部材を低コストで製造する方法を提供することを目的とする。   Therefore, in view of such a conventional problem, the present invention is excellent in wear resistance and adhesion, can improve the sliding characteristics and can reduce the aggression to the mating member, in a harsh environment Another object of the present invention is to provide a multilayer coating member and a method for producing the multilayer coating member at a low cost, which can prevent damage to the substrate.

本発明者らは、上記課題を解決するために鋭意研究した結果、基材上にクロム皮膜を介して窒素含有クロム皮膜を形成し、この窒素含有クロム皮膜上に固体潤滑剤からなる皮膜を形成することにより、耐磨耗性および密着性に優れ、摺動特性を向上させて相手部材への攻撃性を低下させることができ、過酷環境下においても基材の損傷を防止することができる、積層皮膜被覆部材を低コストで製造することができることを見出し、本発明を完成するに至った。   As a result of diligent research to solve the above problems, the present inventors formed a nitrogen-containing chromium film on a base material via a chromium film, and formed a film made of a solid lubricant on the nitrogen-containing chromium film. By doing so, it is excellent in wear resistance and adhesion, can improve the sliding characteristics and reduce the aggressiveness to the mating member, can prevent damage to the substrate even in harsh environments, The present inventors have found that a laminated film-coated member can be produced at a low cost and have completed the present invention.

すなわち、本発明による積層皮膜被覆部材は、基材上にクロム皮膜を介して窒素含有クロム皮膜が形成され、この窒素含有クロム皮膜上に固体潤滑剤からなる皮膜が形成されていること特徴とする。また、本発明による積層皮膜被覆部材は、基材上に複数のクロム皮膜と複数の窒素含有クロム皮膜が形成され、最表面に固体潤滑剤からなる皮膜が形成されていることを特徴とする。これらの積層皮膜被覆部材において、固定潤滑剤が、フッ素系樹脂からなるのが好ましく、ポリテトラフルオロエチレンからなるのがさらに好ましい。   That is, the laminated film covering member according to the present invention is characterized in that a nitrogen-containing chromium film is formed on a substrate via a chromium film, and a film made of a solid lubricant is formed on the nitrogen-containing chromium film. . In addition, the laminated coating member according to the present invention is characterized in that a plurality of chromium coatings and a plurality of nitrogen-containing chromium coatings are formed on a substrate, and a coating made of a solid lubricant is formed on the outermost surface. In these laminated film-coated members, the fixed lubricant is preferably made of a fluororesin, more preferably polytetrafluoroethylene.

また、本発明による積層皮膜被覆部材の製造方法は、基材上にクロム皮膜を介して窒素含有クロム皮膜を形成した後、この窒素含有クロム皮膜上に固体潤滑剤を塗布して焼成することにより、窒素含有クロム皮膜上に固体潤滑剤からなる皮膜を形成することを特徴とする。また、本発明による積層皮膜被覆部材の製造方法は、基材上に複数のクロム皮膜と複数の窒素含有クロム皮膜をこの順に交互に形成した後、最表面に固体潤滑剤を塗布して焼成することにより、最表面に固体潤滑剤からなる皮膜を形成することを特徴とする。これらの積層皮膜被覆部材の製造方法において、窒素含有クロム皮膜が、クロムターゲットを使用してアルゴンガスと窒素ガスを含む雰囲気中でスパッタリングすることによって形成されるのが好ましい。また、クロム皮膜が、クロムターゲットを使用してアルゴンガス雰囲気中でスパッタリングすることによって形成されるのが好ましい。また、固定潤滑剤が、フッ素系樹脂からなるのが好ましく、ポリテトラフルオロエチレンからなるのがさらに好ましい。   Also, the method for producing a laminated coating member according to the present invention comprises forming a nitrogen-containing chromium coating on a substrate via a chromium coating, and then applying a solid lubricant on the nitrogen-containing chromium coating and firing. A film comprising a solid lubricant is formed on the nitrogen-containing chromium film. Moreover, the manufacturing method of the laminated film coating | coated member by this invention forms a several chromium film | membrane and several nitrogen-containing chromium film | membrane alternately on a base material in this order, Then, a solid lubricant is apply | coated to an outermost surface, and it bakes. Thus, a film made of a solid lubricant is formed on the outermost surface. In these production methods for laminated film-coated members, the nitrogen-containing chromium film is preferably formed by sputtering in an atmosphere containing argon gas and nitrogen gas using a chromium target. Moreover, it is preferable that a chromium film | membrane is formed by sputtering in argon gas atmosphere using a chromium target. The fixed lubricant is preferably made of a fluorine-based resin, and more preferably made of polytetrafluoroethylene.

なお、本明細書中において、「窒素含有クロム皮膜」とは、クロム皮膜中に窒素および窒化クロムの少なくとも一方が分散した皮膜をいう。   In the present specification, the “nitrogen-containing chromium film” refers to a film in which at least one of nitrogen and chromium nitride is dispersed in the chromium film.

本発明によれば、耐磨耗性および密着性に優れ、摺動特性を向上させて相手部材への攻撃性を低下させることができ、過酷環境下においても基材の損傷を防止することができる、積層皮膜被覆部材を低コストで製造することができる。この硬質被膜被覆部材は、金型、機械部品、自動車部品などに使用することができる。   According to the present invention, it is excellent in wear resistance and adhesion, can improve sliding characteristics and can reduce the attack on the mating member, and can prevent damage to the substrate even in harsh environments The laminated film covering member that can be produced can be manufactured at low cost. This hard film covering member can be used for molds, machine parts, automobile parts and the like.

本発明による積層皮膜被覆部材の実施の形態の構造を示す断面図である。It is sectional drawing which shows the structure of embodiment of the laminated film coating | coated member by this invention. 本発明による積層皮膜被覆部材の実施の形態を製造するための処理装置の概略図である。It is the schematic of the processing apparatus for manufacturing embodiment of the laminated film coating | coated member by this invention. 実施例において使用した高速ファレックス摩擦磨耗試験機の概略図である。It is the schematic of the high-speed Falex friction abrasion tester used in the Example.

以下、添付図面を参照して、本発明による積層皮膜被覆部材およびその製造方法の実施の形態について詳細に説明する。   Embodiments of a laminated film covering member and a method for manufacturing the same according to the present invention will be described below in detail with reference to the accompanying drawings.

図１に示すように、本発明による積層皮膜被覆部材の実施の形態は、基材１と、この基材１上に（応力緩和層としての）クロム皮膜と（硬質層としての）窒素含有クロム皮膜がこの順に交互に配置されるように形成された複数のクロム皮膜２および複数の窒素含有クロム皮膜３と、最表面の窒素含有クロム皮膜上に形成された固体潤滑剤からなる皮膜４とを備えている。   As shown in FIG. 1, an embodiment of a laminated film covering member according to the present invention includes a base material 1, a chromium film (as a stress relaxation layer) and a nitrogen-containing chromium (as a hard layer) on the base material 1. A plurality of chromium films 2 and a plurality of nitrogen-containing chromium films 3 formed so that the films are alternately arranged in this order, and a film 4 made of a solid lubricant formed on the outermost nitrogen-containing chromium film. I have.

このように、窒素含有クロム皮膜（機械的強度の高い硬質層）上にフッ素系樹脂などの固体潤滑剤からなる皮膜（低摩擦係数の層）を形成することにより、耐磨耗性および密着性に優れ、摺動特性を向上させて相手部材への攻撃性を低下させることができ、過酷環境下においても基材の損傷を防止する皮膜で被覆された積層皮膜被覆部材を製造することができる。   Thus, by forming a film (layer of low friction coefficient) made of a solid lubricant such as a fluororesin on a nitrogen-containing chromium film (hard layer with high mechanical strength), wear resistance and adhesion It is possible to improve the sliding characteristics and reduce the aggressiveness to the mating member, and it is possible to produce a laminated film coated member coated with a film that prevents damage to the base material even in a harsh environment .

すなわち、基材上に硬質で機械的な強度の高い窒素含有クロム皮膜を形成し、その上にフッ素系樹脂などの固体潤滑剤からなる低摩擦係数の皮膜を形成することにより、耐磨耗性および密着性に優れ、摺動特性を向上させて相手部材への攻撃性を低下させることができ、過酷環境下においても基材の損傷を防止することができる、積層皮膜被覆部材を製造することができる。   In other words, by forming a hard, high-strength nitrogen-containing chromium film on the substrate, and forming a low-friction coefficient film made of a solid lubricant such as fluororesin on it, it is resistant to wear. And manufacturing a laminated coating member that has excellent adhesion, can improve the sliding characteristics, can reduce the attack on the mating member, and can prevent damage to the substrate even in harsh environments Can do.

フッ素系樹脂としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、フッ化エチレンプロピレン（ＦＥＰ），テトラフルオロエチレン（ＴＦＥ）などを使用するのが好ましい。   As the fluororesin, it is preferable to use polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), tetrafluoroethylene (TFE) or the like.

積層皮膜被覆部材の耐磨耗性、耐高温酸化性、耐アルカリ性および離型性を良好にするためには、複数の窒素含有クロム皮膜の合計の厚さは、１〜３０μｍであるのが好ましく、１〜２０μｍであるのがさらに好ましく、１〜１５μｍであるのが最も好ましい。また、複数のクロム皮膜の合計の厚さは、０．０１〜１０μｍであるのが好ましく、０．１〜５μｍであるのがさらに好ましい。   In order to improve the wear resistance, high-temperature oxidation resistance, alkali resistance and releasability of the laminated film covering member, the total thickness of the plurality of nitrogen-containing chromium films is preferably 1 to 30 μm. 1 to 20 μm is more preferable, and 1 to 15 μm is most preferable. In addition, the total thickness of the plurality of chromium films is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm.

複数のクロム皮膜と複数の窒素含有クロム皮膜は、クロムターゲットを使用してスパッタリングする装置の処理室内で連続的に形成することができる。すなわち、下地層としてのクロム皮膜を形成する際には、処理室内をアルゴンガス雰囲気し、窒素含有クロム皮膜を形成する際には、処理室内をアルゴンガスと窒素ガスを含む雰囲気にして、複数のクロム皮膜と複数の窒素含有クロム皮膜を連続的に形成することができる。   The plurality of chromium films and the plurality of nitrogen-containing chromium films can be continuously formed in a processing chamber of a sputtering apparatus using a chromium target. That is, when forming a chromium film as an underlayer, an argon gas atmosphere is formed in the processing chamber, and when forming a nitrogen-containing chromium film, the processing chamber is set to an atmosphere containing argon gas and nitrogen gas, A chromium film and a plurality of nitrogen-containing chromium films can be formed continuously.

このスパッタリングは、ＤＣマグネトロンスパッタリング法によって行うことができるので、基材として使用する鋼材の焼き戻し温度（約３００℃）以下の低温で成膜することができるため、鋼材の軟化や熱歪を抑制することができ、また、他の物理的蒸着と比べて生産性が高い。また、このスパッタリングでは、イオンプレーティング法によって成膜する場合のように皮膜の材料が溶融した塊（ドロップレット）が発生しないので、平滑な表面の皮膜を形成することができる。さらに、このスパッタリングでは、クロム皮膜と窒素含有クロム皮膜を形成するため、他の材料の中間層を排除することができるので、従来のスパッタリング装置に単一のターゲットを使用して、処理室内への窒素ガスを導入のＯＮ／ＯＦＦの切り替えにより、複数のクロム皮膜と複数の窒素含有クロム皮膜を形成することができる。そのため、応力緩和層としてのクロム皮膜と硬質層としての窒素含有クロム皮膜の界面でクラックが伝播するのを防止して、高硬度を確保しながら応力緩和層により応力緩和して優れた密着性を有する窒素含有クロム皮膜を得ることができる。また、バイアス電圧を一定にしてスパッタリングを行うことができるので、皮膜の割れを防止することができ、応力緩和層を挟み込んでも硬度が低下するのを防止することができる。   Since this sputtering can be performed by the DC magnetron sputtering method, the film can be formed at a temperature lower than the tempering temperature (about 300 ° C.) of the steel material used as the base material, so that the softening and thermal strain of the steel material are suppressed. It is also more productive than other physical vapor depositions. In addition, in this sputtering, since a lump (droplet) in which the material of the film is melted does not occur as in the case of film formation by an ion plating method, a film having a smooth surface can be formed. Further, since this sputtering forms a chromium film and a nitrogen-containing chromium film, an intermediate layer of other materials can be eliminated, so that a single target is used in a conventional sputtering apparatus to enter the processing chamber. A plurality of chromium films and a plurality of nitrogen-containing chromium films can be formed by switching ON / OFF of introducing nitrogen gas. For this reason, crack propagation is prevented at the interface between the chromium film as the stress relaxation layer and the nitrogen-containing chromium film as the hard layer, and stress is relaxed by the stress relaxation layer while ensuring high hardness and excellent adhesion. The nitrogen-containing chromium film | membrane which has can be obtained. Further, since sputtering can be performed with a constant bias voltage, it is possible to prevent the film from cracking and to prevent the hardness from being lowered even if the stress relaxation layer is sandwiched.

本発明による積層皮膜被覆部材の実施の形態は、例えば、図２に示す処理装置１０を使用して製造することができる。この処理装置１０は、真空処理室１２と、この真空処理室１２内を減圧して真空にするための真空ポンプ１４と、真空処理室１２内の底部の中心部に配設された回転テーブル１６と、この回転テーブル１６上に治具１８を介して載置された被処理部材として基材２０と、この基材２０を取り囲むように配置された蒸発源としてのターゲット２２と、これらのターゲット２２の各々に接続された直流のスパッタ電源２４と、回転テーブル１６に接続された直流のイオンボンバードおよびバイアス電源２６と、真空処理室１２内にアルゴンガスおよび窒素ガスを導入するためのガス導入パイプ２８とを備えている。以下、この処理装置１０を使用して、本発明による積層皮膜被覆部材の実施の形態を製造する方法について説明する。   The embodiment of the laminated film covering member according to the present invention can be manufactured using, for example, the processing apparatus 10 shown in FIG. The processing apparatus 10 includes a vacuum processing chamber 12, a vacuum pump 14 for reducing the pressure in the vacuum processing chamber 12 to form a vacuum, and a rotary table 16 disposed at the center of the bottom of the vacuum processing chamber 12. A substrate 20 as a member to be processed placed on the turntable 16 via a jig 18; a target 22 as an evaporation source disposed so as to surround the substrate 20; and these targets 22 A DC sputtering power source 24 connected to each of these, a DC ion bombard and bias power source 26 connected to the rotary table 16, and a gas introduction pipe 28 for introducing argon gas and nitrogen gas into the vacuum processing chamber 12. And. Hereinafter, a method for producing an embodiment of a laminated coating member according to the present invention using this processing apparatus 10 will be described.

（イオンボンバード処理工程）
まず、処理装置１０のターゲット２２としてクロムターゲットを使用し、真空ポンプ１４を作動させて真空処理室１２内を真空排気した後、ガス導入パイプ２８を介して真空処理室１２内にアルゴンガスを導入して真空処理室１２内をアルゴンガス雰囲気にして、イオンボンバード処理を行って、基材２０の表面を活性化する。 (Ion bombarding process)
First, a chromium target is used as the target 22 of the processing apparatus 10, the vacuum pump 14 is operated to evacuate the vacuum processing chamber 12, and then argon gas is introduced into the vacuum processing chamber 12 through the gas introduction pipe 28. Then, the inside of the vacuum processing chamber 12 is made an argon gas atmosphere, and ion bombarding is performed to activate the surface of the substrate 20.

（クロム皮膜形成工程）
次に、アルゴンガスの導入を一旦停止し、真空処理室１２内を真空排気した後、ガス導入パイプ２８を介して真空処理室１２内にアルゴンガスを導入して真空処理室１２内をアルゴンガス雰囲気にする。その後、ターゲット２２にスパッタ電源２４の所定の電圧を印加して、ターゲット２２の近傍にグロー放電（低温プラズマ）を生じさせる。これにより、放電領域内のアルゴンガスがイオン化してターゲット２２に高速で衝突し、この衝突によってターゲット２２からクロム原子が叩き出され、このクロム原子が基材２０の表面に叩き付けられて、基材２０の表面に応力緩和層としてのクロム皮膜が形成される。 (Chromium film formation process)
Next, the introduction of the argon gas is temporarily stopped, the inside of the vacuum processing chamber 12 is evacuated, and then the argon gas is introduced into the vacuum processing chamber 12 through the gas introduction pipe 28 so that the inside of the vacuum processing chamber 12 is argon gas. Make the atmosphere. Thereafter, a predetermined voltage of the sputtering power supply 24 is applied to the target 22 to cause glow discharge (low temperature plasma) in the vicinity of the target 22. As a result, the argon gas in the discharge region is ionized and collides with the target 22 at a high speed. As a result of this collision, chromium atoms are struck out from the target 22, and the chrome atoms are struck against the surface of the substrate 20. A chromium film as a stress relaxation layer is formed on the surface of 20.

（窒素含有クロム皮膜形成工程）
次に、真空処理室１２内を真空排気した後、ガス導入パイプ２８を介して真空処理室１２内にアルゴンガスと窒素ガスを導入して真空処理室１２内をアルゴンガスと窒素ガスの雰囲気にする。その後、ターゲット２２にスパッタ電源２４の所定の電圧を印加して、ターゲット２２の近傍にグロー放電（低温プラズマ）を生じさせる。これにより、放電領域内のアルゴンガスがイオン化してターゲット２２に高速で衝突し、この衝突によってターゲット２２からクロム原子が叩き出され、このクロム原子が真空処理室１２内の雰囲気中の窒素原子とともに基材２０上のクロム皮膜の表面に叩き付けられて、基材２０上のクロム皮膜の表面に窒素を含有するクロム皮膜（硬質層）が形成される。 (Nitrogen-containing chromium film forming process)
Next, after evacuating the inside of the vacuum processing chamber 12, argon gas and nitrogen gas are introduced into the vacuum processing chamber 12 through the gas introduction pipe 28, and the inside of the vacuum processing chamber 12 is brought to an atmosphere of argon gas and nitrogen gas. To do. Thereafter, a predetermined voltage of the sputtering power supply 24 is applied to the target 22 to cause glow discharge (low temperature plasma) in the vicinity of the target 22. As a result, the argon gas in the discharge region is ionized and collides with the target 22 at a high speed, and this collision expels chromium atoms from the target 22, and these chromium atoms together with nitrogen atoms in the atmosphere in the vacuum processing chamber 12. A chromium film (hard layer) containing nitrogen is formed on the surface of the chromium film on the substrate 20 by being struck against the surface of the chromium film on the substrate 20.

さらに、上記のクロム皮膜形成工程と窒素含有クロム皮膜形成工程を繰り返して、クロム皮膜と窒素含有クロム皮膜が交互に配置されるように複数のクロム皮膜と複数の窒素含有クロム皮膜を形成する。   Furthermore, the chromium film forming step and the nitrogen-containing chromium film forming step are repeated to form a plurality of chromium films and a plurality of nitrogen-containing chromium films so that the chromium films and the nitrogen-containing chromium films are alternately arranged.

なお、上記のクロム皮膜形成工程と窒素含有クロム皮膜形成工程におけるスパッタリングでは、それぞれの皮膜の厚さを均一にするために且つ基材２０の温度をその焼戻し温度以下に維持するために、ターゲット２２と基材２０の間隔を、例えば、７０〜８０ｍｍに保持するのが好ましい。   In the sputtering in the chromium film forming process and the nitrogen-containing chromium film forming process, the target 22 is used in order to make the thickness of each film uniform and to keep the temperature of the substrate 20 below the tempering temperature. It is preferable to keep the distance between the substrate 20 and the substrate 20 at, for example, 70 to 80 mm.

（固体潤滑剤からなる皮膜形成工程）
次に、クロム皮膜と窒素含有クロム皮膜が交互に形成された基材２０を処理装置１０から取り出し、最表面の窒素含有クロム皮膜上にポリテトラフルオロエチレンなどのフッ素系樹脂などからなる固体潤滑剤をスプレーガンで噴射して所定の厚さにした後、２６０〜３４０℃の温度で０．１〜３時間程度加熱して焼成する。これにより、窒素含有クロム皮膜上に固体潤滑剤からなる皮膜が形成される。この固体潤滑剤からなる皮膜の厚さは、１〜１０μｍであるのが好ましく、１〜６μｍであるのがさらに好ましい。 (Film formation process consisting of solid lubricant)
Next, the base material 20 in which the chromium film and the nitrogen-containing chromium film are alternately formed is taken out from the processing apparatus 10, and a solid lubricant made of a fluorine-based resin such as polytetrafluoroethylene on the outermost nitrogen-containing chromium film. After spraying with a spray gun to a predetermined thickness, it is fired at a temperature of 260 to 340 ° C. for about 0.1 to 3 hours. Thereby, a film made of a solid lubricant is formed on the nitrogen-containing chromium film. The thickness of the film made of the solid lubricant is preferably 1 to 10 μm, and more preferably 1 to 6 μm.

以下、本発明による積層皮膜被覆部材およびその製造方法の実施例について詳細に説明する。   Examples of the laminated film-coated member and the method for producing the same according to the present invention will be described in detail below.

［実施例１］
まず、基材として、鋼種ＳＣＭ４１５に浸炭焼入れ焼き戻しを施した後に鏡面研磨した円柱形の直径６．５ｍｍのファビリピンを用意した。この基材をクロムターゲットを使用する処理装置（ＤＣマグネトロンスパッタリング装置）の真空処理室に入れて、到達真空度５×１０−４Ｐａ以下に真空排気した後、真空処理室内が圧力５×１０−１Ｐａのアルゴンガス雰囲気になるように制御してアルゴンガスを真空処理室内に導入し、１０００Ｖ×２Ａでイオンボンバード処理を約１８０分間施して、基材の表面を活性化した。 [Example 1]
First, as a base material, a cylindrical Fabry pin with a diameter of 6.5 mm, which was mirror-polished after carburizing, quenching and tempering the steel type SCM415, was prepared. This base material is put into a vacuum processing chamber of a processing apparatus (DC magnetron sputtering apparatus) using a chrome target and evacuated to an ultimate vacuum of 5 × 10 −4 Pa or less, and then the pressure in the vacuum processing chamber is 5 × 10 − Argon gas was introduced into a vacuum processing chamber under control of an argon gas atmosphere of 1 Pa, and ion bombarding was performed at 1000 V × 2 A for about 180 minutes to activate the surface of the substrate.

次に、アルゴンガスの導入を一旦停止し、真空処理室内を排気して真空にした後、真空処理室内の雰囲気中のアルゴンガスの分圧が０．０６１Ｐａになるようにアルゴンガスを真空処理室内に導入しながら、投入電力４ｋＷ、バイアス電圧を−１００Ｖとして、スパッタリングを３０秒間行って、基材上に厚さ約４０ｎｍのクロム皮膜（ビッカース硬度ＨＶ５００程度）を形成した（クロム皮膜形成工程）。   Next, the introduction of the argon gas is temporarily stopped, the vacuum processing chamber is evacuated and evacuated, and then the argon gas is evacuated so that the partial pressure of the argon gas in the atmosphere in the vacuum processing chamber becomes 0.061 Pa. While being introduced, the input power was 4 kW, the bias voltage was −100 V, and sputtering was performed for 30 seconds to form a chromium film having a thickness of about 40 nm (about Vickers hardness HV500) on the substrate (chromium film formation step).

次に、真空処理室内を排気して真空にした後、真空処理室内の雰囲気中のアルゴンガスの分圧が０．０４２Ｐａになるようにアルゴンガスを真空処理室内に導入するとともに、窒素ガスの分圧が０．０５４Ｐａになるように窒素ガスを真空処理室内に導入しながら、投入電力４ｋＷ、バイアス電圧を−１００Ｖとして、スパッタリングを６０秒間行って、基材上に厚さ約８０ｎｍの窒素含有クロム皮膜を形成した（窒素含有クロム皮膜形成工程）。   Next, after evacuating and vacuuming the vacuum processing chamber, the argon gas is introduced into the vacuum processing chamber so that the partial pressure of the argon gas in the atmosphere in the vacuum processing chamber becomes 0.042 Pa, and the nitrogen gas is separated. While introducing nitrogen gas into the vacuum processing chamber so that the pressure becomes 0.054 Pa, sputtering was performed for 60 seconds with an input power of 4 kW and a bias voltage of −100 V, and a nitrogen-containing chromium having a thickness of about 80 nm on the substrate. A film was formed (nitrogen-containing chromium film forming step).

さらに、上記のクロム皮膜形成工程と窒素含有クロム形成工程を交互に繰り返して、それぞれ厚さ約４０ｎｍのクロム皮膜と厚さ約８０ｎｍの窒素含有クロム皮膜を４０層ずつ（合計８０層、全膜厚４．８μｍ）交互に形成した（窒素含有クロム皮膜形成工程）。   Further, the chromium film forming step and the nitrogen-containing chromium forming step are alternately repeated, so that 40 layers each of a chromium film having a thickness of about 40 nm and a nitrogen-containing chromium film having a thickness of about 80 nm (total 80 layers, total film thickness). 4.8 μm) alternately formed (nitrogen-containing chromium film forming step).

次に、クロム皮膜と窒素含有クロム皮膜が交互に形成された基材を処理装置から取り出し、乾式塗布焼成法に基づいて、最表面の窒素含有クロム皮膜の表面にポリテトラフルオロエチレンからなる固体潤滑剤を塗布し、３００℃で２時間程度保持して固体潤滑剤を焼成することによって、窒素含有クロム皮膜上に固体潤滑剤からなる皮膜を形成した。   Next, the base material on which the chromium film and the nitrogen-containing chromium film are alternately formed is taken out of the processing apparatus, and based on the dry coating and baking method, the surface of the outermost nitrogen-containing chromium film is solid lubricated with polytetrafluoroethylene. The coating was made of a solid lubricant on the nitrogen-containing chromium coating by applying the agent and baking the solid lubricant by holding at 300 ° C. for about 2 hours.

このようにして得られた積層皮膜被覆部材（円柱形の積層皮膜被覆ファビリピン）の表面を走査型電子顕微鏡（ＳＥＭ）で観察したところ、窒素含有クロム皮膜の全面に形成された固体潤滑剤が確認された。また、得られた積層皮膜被覆部材の断面をＳＥＭで観察したところ、厚さ２μｍ程度の固体潤滑剤の層が確認された。   Observation of the surface of the thus obtained multilayer coating member (cylindrical multilayer coating coated Fabypin) with a scanning electron microscope (SEM) confirmed the solid lubricant formed on the entire surface of the nitrogen-containing chromium coating. It was done. Moreover, when the cross section of the obtained laminated film coating | coated member was observed by SEM, the layer of the solid lubricant about 2 micrometers thick was confirmed.

また、得られた積層皮膜被覆ファビリピンの耐荷重性能および摺動特性を評価するために、図３に示すような高速ファレックス摩擦磨耗試験機の回転駆動機１１２にピン１１３により積層皮膜被覆ファビリピン１１０の上部を固定し、その側面を一対の（ＳＣＭ４１５に浸炭焼き入れ焼き戻しを施した）Ｖブロック（Ｖ溝付ブロック）１１１のＶ溝で挟み、回転駆動機１１２により積層皮膜被覆ファビリピン１１０を回転させながら、Ｖブロックに加える（図中、矢印Ｌで示す）荷重を増加して、非潤滑で摩擦磨耗試験を行った後、試験終了後の積層皮膜被覆ファビリピンとＶブロックの外観を観察した。この試験では、すべり速度を０．１ｍ／ｓとして、試験終了時の最大荷重が２００００Ｎ（試験機最大荷重）であり、摺動特性の評価として試験終了時の摩擦係数μは０．０２１であった。また、試験終了後のファビリピン（基材）の外観の観察では、焼付きや損傷などは認められず、窒素含有クロム皮膜の損傷も観察されなかった。   In addition, in order to evaluate the load bearing performance and sliding characteristics of the obtained multilayer coating coated Fabry pin, the multilayer coating coated Fabry pin 110 is connected to the rotary drive 112 of the high-speed Falex frictional wear tester as shown in FIG. The upper part of the substrate is fixed, and the side surface is sandwiched between the V-grooves of a pair of V-blocks (blocks with V-grooves SCM 415 subjected to carburizing, quenching and tempering) 111, and the multilayer coating coated Fabry pins 110 are rotated by the rotary drive 112. Then, the load applied to the V block (indicated by the arrow L in the figure) was increased, and a non-lubricated frictional wear test was performed. Then, the appearance of the laminated film-coated Fabry pins and the V block after the test was observed. In this test, the sliding speed was 0.1 m / s, the maximum load at the end of the test was 20000 N (maximum load of the testing machine), and the friction coefficient μ at the end of the test was 0.021 as an evaluation of the sliding characteristics. It was. Further, in the observation of the appearance of the fabric pin (base material) after the test was completed, no seizure or damage was observed, and no damage to the nitrogen-containing chromium film was observed.

［実施例２］
クロム皮膜形成工程のスパッタリングを４５秒間行って基材上に厚さ約６０ｎｍのクロム皮膜を形成し、窒素含有クロム皮膜形成工程のスパッタリングを９０秒間行って基材上に厚さ約１２０ｎｍの窒素含有クロム皮膜を形成し、このクロム皮膜形成工程と窒素含有クロム皮膜形成工程を交互に繰り返して、それぞれ厚さ約６０ｎｍのクロム皮膜４０層と、厚さ約１２０ｎｍの窒素含有クロム皮膜３９層（合計７９層、全膜厚約７．０８μｍ）を交互に形成し、最表面のクロム皮膜の表面にポリテトラフルオロエチレンからなる固体潤滑剤を塗布した以外は、実施例１と同様の方法により、積層皮膜被覆部材を作製した。 [Example 2]
Sputtering of the chromium film forming process is performed for 45 seconds to form a chromium film having a thickness of about 60 nm on the substrate, and sputtering of the nitrogen-containing chromium film forming process is performed for 90 seconds to contain nitrogen having a thickness of about 120 nm on the substrate. A chromium film is formed, and this chromium film forming process and the nitrogen-containing chromium film forming process are alternately repeated to obtain a chromium film 40 layer having a thickness of about 60 nm and a nitrogen-containing chromium film 39 layer having a thickness of about 120 nm (79 layers in total). Layer and a total film thickness of about 7.08 μm), and a multilayer film was formed in the same manner as in Example 1 except that a solid lubricant composed of polytetrafluoroethylene was applied to the surface of the outermost chromium film. A covering member was produced.

この積層皮膜被覆部材の表面をＳＥＭで観察したところ、ほぼ全面に形成された固体潤滑剤が確認され、積層皮膜被覆部材の断面をＳＥＭで観察したところ、厚さ３μｍ程度の固体潤滑剤の層が確認された。   When the surface of this multilayer coating member was observed with an SEM, a solid lubricant formed on almost the entire surface was confirmed, and when a cross section of the multilayer coating member was observed with an SEM, a solid lubricant layer having a thickness of about 3 μm was observed. Was confirmed.

また、得られた積層皮膜被覆ファビリピンの耐荷重性能および摺動特性を実施例１と同様の方法により評価したところ、試験終了時の最大荷重は２００００Ｎであり、試験終了時の摩擦係数μは０．０２３であった。また、試験終了後のファビリピンの外観の観察では、焼付きや損傷などは認められず、積層皮膜の損傷も観察されなかった。   Further, when the load bearing performance and sliding characteristics of the obtained laminated coating coated Fabry pin were evaluated by the same method as in Example 1, the maximum load at the end of the test was 20000 N, and the friction coefficient μ at the end of the test was 0. 0.023. Further, in the observation of the appearance of the Fabry pin after the test was completed, no seizure or damage was observed, and no damage to the laminated film was observed.

［比較例１］
窒素含有クロム皮膜上に固体潤滑剤からなる皮膜を形成しなかった以外は、実施例１と同様の方法により、積層皮膜被覆部材（円柱形の積層皮膜被覆ファビリピン）を作製して、耐荷重性能および摺動特性を評価した。この試験では、試験終了時の最大荷重は５５１９Ｎ、試験終了時の摩擦係数μは０．２８２であった。また、試験終了後の外観の観察では、窒素含有クロム皮膜が破壊され、ファビリピン（基材）には塑性流動による変形が認められ、かじりや凝着も観察された。 [Comparative Example 1]
A laminated film coated member (cylindrical laminated film coated Fabry pin) was prepared by the same method as in Example 1 except that a film made of a solid lubricant was not formed on the nitrogen-containing chromium film, and the load bearing performance And the sliding characteristics were evaluated. In this test, the maximum load at the end of the test was 5519 N, and the friction coefficient μ at the end of the test was 0.282. Further, in the observation of the external appearance after completion of the test, the nitrogen-containing chromium film was broken, deformation of the Fabry pin (base material) due to plastic flow was observed, and galling and adhesion were also observed.

［比較例２］
実施例１と同様のファビリピン（鋼種ＳＣＭ４１５に浸炭焼入れ焼き戻しを施した後に鏡面研磨した円柱形の直径６．５ｍｍのファビリピン）の耐荷重性能および摺動特性を実施例１と同様の方法により評価したところ、試験終了時の最大荷重は４８３７Ｎであり、試験終了時の摩擦係数μは０．３３６であった。また、試験終了後のファビリピンの外観の観察では、塑性流動による変形が認められ、焼き付きが観察された。 [Comparative Example 2]
The load bearing performance and sliding characteristics of the same Fabry pin as in Example 1 (cylindrical type Fabry pin with a diameter of 6.5 mm, which was carburized, quenched and tempered into steel type SCM415) were evaluated by the same method as in Example 1. As a result, the maximum load at the end of the test was 4837 N, and the friction coefficient μ at the end of the test was 0.336. Further, in the observation of the appearance of the Fabry pin after the test was completed, deformation due to plastic flow was observed, and seizure was observed.

１ 基材
２ クロム皮膜
３ 窒素含有クロム皮膜
４ 固体潤滑剤からなる皮膜
１０ 処理装置
１２ 真空処理室
１４ 真空ポンプ
１６ 回転テーブル
１８ 治具
２０ 基材
２２ ターゲット
２４ スパッタ電源
２６ イオンボンバードおよびバイアス電源
２８ ガス導入パイプ
１１０ 積層皮膜被覆ファビリピン
１１１ Ｖブロック
１１２ 回転駆動機
１１３ ピン DESCRIPTION OF SYMBOLS 1 Base material 2 Chromium film | membrane 3 Nitrogen-containing chromium film | membrane 4 Film | membrane consisting of a solid lubricant 10 Processing apparatus 12 Vacuum processing chamber 14 Vacuum pump 16 Rotary table 18 Jig 20 Base material 22 Target 24 Sputter power supply 26 Ion bombard and bias power supply 28 Gas Introducing pipe 110 Laminated coating coated Fabry pin 111 V block 112 Rotating drive 113 Pin

Claims (10)

基材上にクロム皮膜を介して窒素含有クロム皮膜が形成され、この窒素含有クロム皮膜上に固体潤滑剤からなる皮膜が形成されていること特徴とする、積層皮膜被覆部材。 A laminated film-coated member, wherein a nitrogen-containing chromium film is formed on a substrate via a chromium film, and a film made of a solid lubricant is formed on the nitrogen-containing chromium film. 基材上に複数のクロム皮膜と複数の窒素含有クロム皮膜が形成され、最表面に固体潤滑剤からなる皮膜が形成されていることを特徴とする、積層皮膜被覆部材。 A laminated film-coated member, wherein a plurality of chromium films and a plurality of nitrogen-containing chromium films are formed on a substrate, and a film made of a solid lubricant is formed on the outermost surface. 前記固定潤滑剤がフッ素系樹脂からなることを特徴とする、請求項１または２に記載の積層皮膜被覆部材。 The laminated coating member according to claim 1 or 2, wherein the fixed lubricant is made of a fluorine resin. 前記固定潤滑剤がポリテトラフルオロエチレンからなることを特徴とする、請求項１または２に記載の積層皮膜被覆部材。 The laminated coating member according to claim 1 or 2, wherein the fixed lubricant is made of polytetrafluoroethylene. 基材上にクロム皮膜を介して窒素含有クロム皮膜を形成した後、この窒素含有クロム皮膜上に固体潤滑剤を塗布して焼成することにより、窒素含有クロム皮膜上に固体潤滑剤からなる皮膜を形成することを特徴とする、積層皮膜被覆部材の製造方法。 After forming a nitrogen-containing chromium film on the substrate via a chromium film, a solid lubricant is applied onto the nitrogen-containing chromium film and baked to form a film made of the solid lubricant on the nitrogen-containing chromium film. A method for producing a laminated film-coated member, which is characterized in that it is formed. 基材上に複数のクロム皮膜と複数の窒素含有クロム皮膜をこの順に交互に形成した後、最表面に固体潤滑剤を塗布して焼成することにより、最表面に固体潤滑剤からなる皮膜を形成することを特徴とする、積層皮膜被覆部材の製造方法。 A plurality of chromium films and a plurality of nitrogen-containing chromium films are alternately formed on the substrate in this order, and then a solid lubricant is applied to the outermost surface and fired to form a film made of a solid lubricant on the outermost surface. A method for producing a laminated coating member, characterized in that: 前記窒素含有クロム皮膜が、クロムターゲットを使用してアルゴンガスと窒素ガスを含む雰囲気中でスパッタリングすることによって形成されることを特徴とする、請求項５または６に記載の積層皮膜被覆部材の製造方法。 The said nitrogen-containing chromium membrane | film | coat is formed by sputtering in the atmosphere containing argon gas and nitrogen gas using a chromium target, The manufacture of the laminated film coating | coated member of Claim 5 or 6 characterized by the above-mentioned. Method. 前記クロム皮膜が、クロムターゲットを使用してアルゴンガス雰囲気中でスパッタリングすることによって形成されることを特徴とする、請求項５乃至７のいずれかに記載の積層皮膜被覆部材の製造方法。 The method for producing a laminated film-coated member according to any one of claims 5 to 7, wherein the chromium film is formed by sputtering in an argon gas atmosphere using a chromium target. 前記固定潤滑剤がフッ素系樹脂からなることを特徴とする、請求項５乃至８のいずれかに記載の積層皮膜被覆部材の製造方法。 The method for producing a laminated film-coated member according to any one of claims 5 to 8, wherein the fixed lubricant is made of a fluororesin. 前記固定潤滑剤がポリテトラフルオロエチレンからなることを特徴とする、請求項５乃至８のいずれかに記載の積層皮膜被覆部材の製造方法。
The method for manufacturing a laminated film-coated member according to any one of claims 5 to 8, wherein the fixed lubricant is made of polytetrafluoroethylene.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013136510A1 (en) * 2012-03-16 2013-09-19 Ｔｐｒ株式会社 Tough film and sliding member
US20160238133A1 (en) * 2013-10-31 2016-08-18 Kabushiki Kaisha Riken Piston ring and its production method
JP2020082190A (en) * 2018-11-19 2020-06-04 Ｊｆｅスチール株式会社 Galling resistance evaluation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0740506A (en) * 1993-08-02 1995-02-10 Nippon Futsuso Kogyo Kk Corrosion preventing surface coating of metal and its method
JPH07305725A (en) * 1994-05-11 1995-11-21 Ndc Co Ltd Double layer sliding material
JP2005082822A (en) * 2003-09-05 2005-03-31 Ion Engineering Research Institute Corp Hard thick film, and method for forming the same
JP2009161813A (en) * 2008-01-07 2009-07-23 Matsuyama Giken Kk Member coated with hard film and production method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0740506A (en) * 1993-08-02 1995-02-10 Nippon Futsuso Kogyo Kk Corrosion preventing surface coating of metal and its method
JPH07305725A (en) * 1994-05-11 1995-11-21 Ndc Co Ltd Double layer sliding material
JP2005082822A (en) * 2003-09-05 2005-03-31 Ion Engineering Research Institute Corp Hard thick film, and method for forming the same
JP2009161813A (en) * 2008-01-07 2009-07-23 Matsuyama Giken Kk Member coated with hard film and production method therefor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013136510A1 (en) * 2012-03-16 2013-09-19 Ｔｐｒ株式会社 Tough film and sliding member
JPWO2013136510A1 (en) * 2012-03-16 2015-08-03 Ｔｐｒ株式会社 High toughness coating and sliding member
US9416434B2 (en) 2012-03-16 2016-08-16 Tpr Co., Ltd. High-toughness coating film and sliding member
US20160238133A1 (en) * 2013-10-31 2016-08-18 Kabushiki Kaisha Riken Piston ring and its production method
EP3064810B1 (en) 2013-10-31 2018-04-11 Kabushiki Kaisha Riken Piston ring and its production method
US10006547B2 (en) * 2013-10-31 2018-06-26 Kabushiki Kaisha Riken Piston ring and its production method
EP3064810B2 (en) † 2013-10-31 2021-03-31 Kabushiki Kaisha Riken Piston ring and its production method
JP2020082190A (en) * 2018-11-19 2020-06-04 Ｊｆｅスチール株式会社 Galling resistance evaluation method

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