JP2006207691A - Hard film coated sliding member - Google Patents
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- JP2006207691A JP2006207691A JP2005020496A JP2005020496A JP2006207691A JP 2006207691 A JP2006207691 A JP 2006207691A JP 2005020496 A JP2005020496 A JP 2005020496A JP 2005020496 A JP2005020496 A JP 2005020496A JP 2006207691 A JP2006207691 A JP 2006207691A
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本願発明は、冷間加工、引き抜き加工、押し出し加工、冷間鍛造、圧縮加工、曲げ加工、絞り加工、せん断加工等に使用される金型や内燃機関に使用されるエンジン部品であるカム、ピストンリング、内燃機関の過給圧制御用部品等の硬質皮膜被覆摺動部材に関する。 The present invention relates to a mold or a engine used for an internal combustion engine or a die used for cold working, drawing, extrusion, cold forging, compression, bending, drawing, shearing, etc. The present invention relates to a hard film-coated sliding member such as a ring and a supercharging pressure control component for an internal combustion engine.
自動車のエンジン部品、各種機械部品などの摺動部には摺動特性にすぐれた表面処理を形成し、部材の長寿命化が図られている。物理的蒸着法によりＴｉＮ、ＴｉＣ、ＣｒＮ等の硬質皮膜を被覆することにより、耐摩耗性及び耐焼付性を改善する検討が行われ、これに関する技術が以下の特許文献１、２に開示されている。
特許文献１は、Ｃｒ−Ｎ系、Ｃｒ−Ｎ−Ｏ系、Ｃｒ−Ｂ−Ｎ系、Ｃｒ−Ｂ−Ｎ−Ｏ系、Ｔｉ−Ｎ系の硬質皮膜を被覆したピストンリングの技術が開示されている。
特許文献２は、構成元素の原子比でクロム：珪素：窒素＝１：０．０５〜１．２：０．１〜１．２の範囲から成る組成を有し、かつ少なくとも窒化クロムと窒化珪素が存在する皮膜を基体に被覆したことを特徴とする摺動材料が開示されている。Ｃｒ系皮膜に珪素を添加することにより、高硬度化が達成され、耐摩耗性の改善に貢献する。しかし、硬質皮膜が脆くなってしまうことに加え、潤滑性の改善が十分ではなく、焼き付きが発生する場合や相手材の攻撃性が高くなってしまう等の課題を有する。
Surface treatments with excellent sliding characteristics are formed on sliding parts such as automobile engine parts and various machine parts in order to extend the life of the members. Studies have been made to improve wear resistance and seizure resistance by coating a hard film such as TiN, TiC, CrN, etc. by physical vapor deposition, and techniques related thereto are disclosed in the following Patent Documents 1 and 2. Yes.
Patent Document 1 discloses the technology of a piston ring coated with a hard coating of Cr—N, Cr—N—O, Cr—B—N, Cr—B—N—O, or Ti—N. ing.
Patent Document 2 has a composition of chromium: silicon: nitrogen = 1: 0.05 to 1.2: 0.1 to 1.2 in terms of atomic ratio of constituent elements, and at least chromium nitride and silicon nitride. There is disclosed a sliding material characterized in that a substrate is coated with a film in which is present. By adding silicon to the Cr-based film, high hardness is achieved, which contributes to improvement of wear resistance. However, in addition to the hard film becoming brittle, the lubricity is not sufficiently improved, and there are problems such as occurrence of seizure and increased attack of the counterpart material.
本願発明は硬質皮膜被覆摺動部材において、耐摩耗性、潤滑特性に優れ、更に硬質皮膜内の残留圧縮応力が低減させて硬質皮膜の厚膜化を可能にし、過酷な摺動環境下においても部材の摩耗、焼き付き、相手材の攻撃性を低減させることのできる硬質皮膜被覆部材を提供することである。 The invention of the present application is a hard coating coated sliding member, which has excellent wear resistance and lubrication characteristics, and further reduces the residual compressive stress in the hard coating, enabling a thick coating of the hard coating, even under severe sliding environments It is an object of the present invention to provide a hard coating member that can reduce the wear, seizure, and aggressiveness of a mating member.
本願発明は、硬質皮膜が被覆された硬質皮膜被覆摺動部材において、該硬質皮膜の少なくとも１層は（Ｃｒ（１００−α）Ｓｉα）（Ｎ（１００−γ−η）ＢγＧη）で示され、但し、α、γ、ηは原子％を表し、金属成分のみの原子％を１００及び非金属成分の原子％を１００としたとき、０＜α≦４．７６、０≦γ＜４５、０≦η≦５５を満たし、ＧはＣ、Ｏ、Ｓから選択される少なくとも１種以上を有し、該硬質皮膜はＳｉ含有量の濃度変調を有していること、を特徴とする硬質皮膜被覆摺動部材である。上記の構成を採用することにより、耐摩耗性、潤滑特性に優れ、更に硬質皮膜内の残留圧縮応力が低減させて硬質皮膜の厚膜化を可能にし、過酷な摺動環境下においても部材の摩耗、焼き付き、相手材の攻撃性を低減させることを可能とする硬質皮膜被覆部材を提供することが可能となる。 The present invention relates to a hard film-coated sliding member coated with a hard film, wherein at least one layer of the hard film is (Cr (100-α) Si α ) (N (100-γ-η) B γ G η ). Where α, γ, and η represent atomic percent, where 0 <α ≦ 4.76, 0 ≦ γ <, where atomic percent of the metal component alone is 100 and atomic percent of the nonmetallic component is 100. 45, 0 ≦ η ≦ 55, G has at least one selected from C, O, and S, and the hard coating has a concentration modulation of Si content. It is a hard film-coated sliding member. By adopting the above configuration, it has excellent wear resistance and lubrication characteristics, and further reduces the residual compressive stress in the hard coating, enabling thick coating of the hard coating, and even in severe sliding environments It is possible to provide a hard coating member that can reduce wear, seizure, and aggressiveness of the counterpart material.
本願発明の硬質皮膜は、θ−２θ法によるＸ線回折において測定される岩塩構造型の（２００）面にＸ線回折ピーク強度を有し、該Ｘ線回折ピーク強度の半価幅が０．５度以上、２０度以下であり、少なくともＳｉ及び／又はＢの窒化物相、酸化物相、金属相から選択される少なくとも１種以上を有していることが好ましい。本願発明の硬質皮膜は、該ＣｒＳｉ系皮膜の他に別の硬質皮膜との積層構造になっていることが好ましい。ここで他の硬質皮膜とは、４ａ、５ａ、６ａ及びＡｌ、Ｓｉから選ばれる１種以上と、Ｃ、Ｎ、Ｏ、Ｂ、Ｓから選ばれる１種以上とを有することが好ましい。該硬質皮膜の最上層は、硬質炭素膜及び／又は硬質炭素膜を含む積層皮膜であることが好ましい。或いは該硬質皮膜の最上層は、硫化物を主体とした硬質皮膜及び／又は硫化物を主体とした硬質皮膜を含む積層皮膜であることが好ましい。積層皮膜を採用する場合、該硬質皮膜の積層周期は１００ｎｍ以上、５００ｎｍ未満であることが好ましく、積層周期が０．５ｎｍ以上、３０ｎｍ未満とすることが更に好ましい。積層皮膜を採用することにより、摺動部材の寿命を大幅に改善することができる。該硬質皮膜は層厚方向に残留圧縮応力の勾配若しくは周期性を有することが好ましい。この場合、耐剥離性に有効であり硬質皮膜の厚膜化を可能にする。該硬質皮膜の最上層から膜厚方向に２００ｎｍ未満の領域で、少なくともＣ、Ｏ、Ｓ、Ｂから選ばれる１種の元素濃度が最大となることが好ましい。この場合、摺動特性を高めることができる。該硬質皮膜は、摺動部材の基体との界面に窒化層を有することが好ましい。この場合、更に部材寿命を高めることができる。該硬質皮膜は、摺動部材の基体との界面を機械的に平滑化することが好ましい。この場合、局部摩耗を低減させ、硬質皮膜を有効に活用することができる。本願発明の硬質皮膜被覆摺動部材は、金型、ピストンリング又は内燃機関の過給圧制御用部品に適用することが好ましい。この場合、摺動部材としての寿命を大幅に向上させることができる。ここで内燃機関の過給圧制御用部品としては、例えば内燃機関のターボチャージャーの制御装置用部品であるコンプレッサ、タービン及びウエイストゲート等がある。硬質皮膜の膜厚は１μｍ以上、６０μｍ未満であることが好ましく、物理的蒸着法を適用して被覆することが好ましい。特にイオンプレーティング法やスパッタ法による被覆方法が有効である。 The hard coating of the present invention has an X-ray diffraction peak intensity on the (200) plane of a rock salt structure type measured by X-ray diffraction by the θ-2θ method, and the half width of the X-ray diffraction peak intensity is 0.00. It is preferably 5 degrees or more and 20 degrees or less, and preferably has at least one selected from a nitride phase, an oxide phase, and a metal phase of at least Si and / or B. The hard coating of the present invention preferably has a laminated structure with another hard coating in addition to the CrSi-based coating. Here, the other hard coating preferably has at least one selected from 4a, 5a, 6a and Al, Si and at least one selected from C, N, O, B, S. The uppermost layer of the hard film is preferably a hard film and / or a laminated film including a hard carbon film. Alternatively, the uppermost layer of the hard film is preferably a laminated film including a hard film mainly composed of sulfide and / or a hard film mainly composed of sulfide. When a laminated film is employed, the lamination period of the hard film is preferably 100 nm or more and less than 500 nm, and the lamination period is more preferably 0.5 nm or more and less than 30 nm. By adopting the laminated film, the life of the sliding member can be greatly improved. The hard coating preferably has a residual compressive stress gradient or periodicity in the layer thickness direction. In this case, it is effective for peeling resistance and enables the hard film to be thickened. It is preferable that the concentration of at least one element selected from C, O, S, and B is maximized in a region less than 200 nm in the film thickness direction from the uppermost layer of the hard coating. In this case, sliding characteristics can be improved. The hard coating preferably has a nitride layer at the interface between the sliding member and the substrate. In this case, the member life can be further increased. It is preferable that the hard coating mechanically smoothes the interface between the sliding member and the substrate. In this case, local wear can be reduced and the hard coating can be effectively utilized. The hard film-coated sliding member of the present invention is preferably applied to a mold, a piston ring or a supercharging pressure control component for an internal combustion engine. In this case, the lifetime as a sliding member can be significantly improved. Here, the components for controlling the boost pressure of the internal combustion engine include, for example, a compressor, a turbine, a wastegate, etc., which are components for a turbocharger control device of the internal combustion engine. The film thickness of the hard coating is preferably 1 μm or more and less than 60 μm, and is preferably coated by applying a physical vapor deposition method. In particular, a coating method using an ion plating method or a sputtering method is effective.
本願発明の硬質皮膜被覆摺動部材を適用することにより、過酷な摺動環境下においても部材の摩耗、焼き付き、相手材の攻撃性を低減させることが可能となり、長寿命な硬質皮膜被覆摺動部材を提供することができた。 By applying the hard film coated sliding member of the present invention, it becomes possible to reduce the wear, seizure of the member, and the aggressiveness of the mating material even under severe sliding environment, and the long life hard film coated sliding A member could be provided.
本願発明の硬質皮膜は、硬質皮膜を最適な組成、積層構造、組織構造、機械的特性に制御することにより、課題を解決することができる。従って、本願発明の硬質皮膜の少なくとも１層は、（Ｃｒ（１００−α）Ｓｉα）（Ｎ（１００−γ−η）ＢγＧη）で示され、但し、α、γ、ηは原子％を表し、０＜α≦４．７６、０≦γ＜４５、０≦η≦５５を満たし、ＧはＣ、Ｏ、Ｓから選択される少なくとも１種以上を有する皮膜組成とする。ここで、皮膜組成式の（Ｃｒ（１００−α）Ｓｉα）は金属成分元素であり、（Ｎ（１００−γ−η）ＢγＧη）は非金属成分元素である。硬質皮膜の組成は金属成分に対する非金属成分の原子比率が必ずしも１対１であることを示すものではなく、金属成分と非金属成分を分けて記載したものである。
Ｓｉは、硬質皮膜の硬化が得られ、耐摩耗性が向上する。一方α値が４．７６を超えて大きい場合、硬質皮膜が脆化し、耐剥離性が低下する。摺動部材として機能する時の相手材への攻撃性が極めて高くなる。従って、上記範囲に限定する。ここで、相手材への攻撃性とは、例えば摺動により相手材が摩耗により擦り減る現象のことである。
γ値は０≦γ＜４５とする。Ｂ元素は硬度と潤滑性を同時に高めることができ、摺動部材の寿命向上に有効である。また、Ｓｉと同時に添加することにより、Ｓｉを単独で添加する場合よりも、更に硬質皮膜の高硬度化に有効であることも確認されている。Ｂ元素に起因する硬度の向上は、少量の場合、例えばγ＜５％においては、硬質皮膜の結晶化を促進することによる高硬度化に有効である。それ以上の場合、例えばγ≧５％の添加においては、成膜過程もしくは摩耗環境下において、ｈ−ＢＮ相の形成による潤滑効果が期待でき、潤滑性改善に有効である。しかしながら、γ≧４５％の場合は、皮膜硬度が低下し、耐摩耗性が急激に低下する場合が確認されているため不都合である。γ値の適正化によって硬度と潤滑性を同時に高めることができ、摺動部材の寿命向上に有効である。Ｂ元素に起因する硬度の向上はｃ−ＢＮ相による。また潤滑性の向上はｈ−ＢＮ相による。両者の含有比率を最適化することによって、硬度と潤滑性を同時に高めることが可能である。ｃ−ＢＮ相とｈ−ＢＮ相の含有比率は、成膜時に印加するバイアス電圧値によって制御可能である。一方、γ値が０％の場合であっても、摺動性、潤滑性や耐摩耗性の特性には満足のいく効果が得られる。
ＧはＣ、Ｏ、Ｓから選択される少なくとも１種以上を含有することによって優れた部材寿命が得られる。Ｃは、硬度と潤滑性を同時に高めることができる。Ｏは、適量であれば硬質皮膜内の残留圧縮応力低減に有効に作用する。Ｏの好ましい含有量は、２５％未満である。Ｓは、特に潤滑性を高めることができ、摺動時の相手材の摩耗を低減させる効果がある。Ｓの添加方法は、イオンプレーティング法、スパッタ法によっても添加することができる。η値は０≦η≦５５とする。η値が５５％を超えて多いい場合、耐摩耗性が急激に低下するため不都合である。
本願発明の硬質皮膜はＳｉ含有量の濃度変調の存在が必要である。濃度変調の存在により、硬質皮膜の硬度と潤滑性を同時に改善することができる。ＳｉがＣｒと固溶体相として存在する場合、皮膜硬度の上昇に伴い、潤滑特性が劣化する。しかし、濃度変調が存在することで、両特性を同時に改善することができる。具体的には、硬質皮膜の同一結晶粒内においてＳｉ濃度変調が存在する場合と、結晶粒子間でＳｉ濃度が異なる場合が存在する。特に後者の方が摺動部材の寿命改善に有効である。
The hard film of the present invention can solve the problem by controlling the hard film to an optimal composition, laminated structure, structure, and mechanical properties. Accordingly, at least one layer of the hard coating of the present invention is represented by (Cr (100-α) Si α ) (N (100-γ-η) B γ G η ), where α, γ, and η are atoms. %, 0 <α ≦ 4.76, 0 ≦ γ <45, 0 ≦ η ≦ 55, and G is a film composition having at least one selected from C, O, and S. Here, (Cr (100-α) Si α ) in the film composition formula is a metal component element, and (N (100-γ-η) B γ G η ) is a non-metal component element. The composition of the hard coating does not necessarily indicate that the atomic ratio of the nonmetallic component to the metallic component is 1: 1, but describes the metallic component and the nonmetallic component separately.
Si hardens the hard coating and improves wear resistance. On the other hand, when the α value is larger than 4.76, the hard coating becomes brittle and the peel resistance is lowered. Aggressiveness to the counterpart material when functioning as a sliding member is extremely high. Therefore, it is limited to the above range. Here, the aggressiveness to the mating material is a phenomenon in which the mating material is worn away due to wear, for example, by sliding.
The γ value is 0 ≦ γ <45. Element B can simultaneously increase hardness and lubricity, and is effective in improving the life of the sliding member. It has also been confirmed that the addition of Si at the same time is more effective in increasing the hardness of the hard coating than when adding Si alone. The improvement in hardness due to the B element is effective for increasing the hardness by promoting the crystallization of the hard film in a small amount, for example, γ <5%. In the case of more than that, for example, when γ ≧ 5% is added, a lubrication effect due to the formation of the h-BN phase can be expected in the film forming process or in a wear environment, which is effective in improving the lubricity. However, in the case of γ ≧ 45%, it is inconvenient because it has been confirmed that the film hardness decreases and the wear resistance rapidly decreases. By optimizing the γ value, the hardness and lubricity can be increased at the same time, which is effective for improving the life of the sliding member. The improvement in hardness due to the B element is due to the c-BN phase. The improvement in lubricity is due to the h-BN phase. By optimizing the content ratio of both, it is possible to simultaneously increase the hardness and lubricity. The content ratio of the c-BN phase and the h-BN phase can be controlled by the bias voltage value applied during film formation. On the other hand, even when the γ value is 0%, satisfactory effects can be obtained in terms of slidability, lubricity and wear resistance.
When G contains at least one selected from C, O, and S, an excellent member life can be obtained. C can simultaneously increase hardness and lubricity. If O is an appropriate amount, it effectively acts to reduce the residual compressive stress in the hard coating. The preferable content of O is less than 25%. S can improve lubricity in particular and has an effect of reducing wear of the mating member during sliding. The addition method of S can also be added by an ion plating method or a sputtering method. The η value is 0 ≦ η ≦ 55. If the η value exceeds 55%, it is inconvenient because the wear resistance decreases rapidly.
The hard coating of the present invention requires the presence of Si content concentration modulation. Due to the presence of concentration modulation, the hardness and lubricity of the hard coating can be improved simultaneously. When Si exists as a solid solution phase with Cr, the lubrication characteristics deteriorate as the film hardness increases. However, the presence of density modulation can improve both characteristics simultaneously. Specifically, there is a case where Si concentration modulation exists in the same crystal grain of the hard coating and a case where the Si concentration differs between crystal grains. In particular, the latter is more effective for improving the life of the sliding member.
本願発明の硬質皮膜の金属成分は、Ｃｒ、Ｓｉの他にＭ成分が含有量βとして含有され、Ｍ成分はＶ、Ｍｏ、Ｗ、Ａｌから選択される少なくとも１種以上を有し、β値は原子％で０≦β＜６０を満たすことが好ましい。Ｍは、Ｖ、Ｍｏ、Ｗ、Ａｌから選択される少なくとも１種以上を含有することによって優れた部材寿命が得られる。特にＶ、Ｍｏ、Ｗを含有した場合、摺動特性のうち、潤滑特性を高めることができるため好ましい。Ａｌを含有した場合は、耐摩耗性、耐熱性の改善に有効であるため好ましい。β値は原子％で６０％未満とする。この理由は、６０％以上含有した場合、硬質皮膜の優れた摺動性、潤滑性や耐摩耗性の特性が大きく異なり、劣るからである。これにより摺動部材としての寿命が大幅に低下してしまう。一方、β値が０％の場合であっても、摺動性、潤滑性や耐摩耗性の特性には満足のいく効果が得られる。 The metal component of the hard coating of the present invention contains M component in addition to Cr and Si as a content β, and the M component has at least one selected from V, Mo, W, and Al, and has a β value. Preferably satisfies 0 ≦ β <60 in atomic percent. When M contains at least one selected from V, Mo, W, and Al, an excellent member life can be obtained. In particular, when V, Mo, and W are contained, the lubrication characteristics can be enhanced among the sliding characteristics, which is preferable. When Al is contained, it is preferable because it is effective in improving wear resistance and heat resistance. The β value is less than 60% in atomic%. This is because when the content is 60% or more, the excellent slidability, lubricity and wear resistance characteristics of the hard coating are greatly different and inferior. Thereby, the lifetime as a sliding member will fall significantly. On the other hand, even when the β value is 0%, a satisfactory effect can be obtained in terms of slidability, lubricity and wear resistance.
本願発明の硬質皮膜は、岩塩構造型の（２００）面にＸ線回折ピーク強度を有し、Ｘ線回折ピーク強度の半価幅が、０．５度以上、２０度以下であることが好ましい。ピーク強度はθ−２θ法によるＸ線回折測定により得られる。（２００）面にＸ線回折ピーク強度得られ、半価幅が０．５度以上、２０度以下の範囲内に結晶構造を制御することにより、残留圧縮応力のバランスと結晶粒径に依存する皮膜硬度のバランスが最適となる。
本願発明の硬質皮膜は、少なくともＳｉ及び／又はＢの窒化物相、酸化物相、金属相から選択される少なくとも１種以上を有することが好ましい。窒化物相、酸化物相、金属相の有無は、例えばＸ線光電子分光分析において確認することができる。硬質皮膜中のＳｉ及び／又はＢが窒化物相として存在する場合、硬度と潤滑性を同時に改善に有効である。また窒化物相に加えて、酸化物相としても存在する場合、特に潤滑性の低減に有効である。窒化物相と酸化物相とが共存する場合が特に好ましい。これに加えて金属相も共存する場合、硬質皮膜内の残留圧縮応力の低減に特に有効である。
The hard coating of the present invention preferably has an X-ray diffraction peak intensity on the (200) plane of the rock salt structure type, and the half width of the X-ray diffraction peak intensity is preferably 0.5 degrees or more and 20 degrees or less. . The peak intensity is obtained by X-ray diffraction measurement by the θ-2θ method. The X-ray diffraction peak intensity is obtained on the (200) plane, and the crystal structure is controlled within a range where the half width is not less than 0.5 degrees and not more than 20 degrees, thereby depending on the balance of residual compressive stress and the crystal grain size The balance of film hardness is optimal.
The hard coating of the present invention preferably has at least one selected from a nitride phase, an oxide phase, and a metal phase of at least Si and / or B. The presence or absence of a nitride phase, an oxide phase, or a metal phase can be confirmed, for example, by X-ray photoelectron spectroscopy. When Si and / or B in the hard coating exists as a nitride phase, it is effective for improving the hardness and lubricity at the same time. Further, when it is present as an oxide phase in addition to the nitride phase, it is particularly effective for reducing lubricity. The case where the nitride phase and the oxide phase coexist is particularly preferable. In addition to this, when a metal phase coexists, it is particularly effective for reducing the residual compressive stress in the hard coating.
本願発明の硬質皮膜は組成の異なる硬質皮膜を積層することにより、更に特性を向上させることができる。他の硬質皮膜は、金属成分として４ａ、５ａ、６ａ及びＡｌ、Ｓｉから選ばれる１種以上と、Ｃ、Ｎ、Ｏ、Ｂ、Ｓから選ばれる１種以上とを有する。ここでの特性の向上とは、例えば基体と硬質皮膜との密着強度を高めることである。これには、ＣｒやＴｉ等の窒化物皮膜を採用し、比較的硬度の高いＳｉ含有皮膜との積層構造によって実現することができる。耐摩耗性を改善する場合は、Ｔｉ、Ａｌ、Ｃｒ、Ｚｒ、Ｓｉ、Ｎｂ、Ｍｏ、Ｈｆ、Ｗ等の窒化物、又は炭窒化物と比較的硬度の高いＳｉ含有皮膜との積層構造によって実現することができる。硬質皮膜全体の残留圧縮応力を低減する場合には、金属リッチ層を用いることが有効である。 The characteristics of the hard coating of the present invention can be further improved by laminating hard coatings having different compositions. Another hard film has 1 or more types chosen from 4a, 5a, 6a and Al, Si as a metal component, and 1 or more types chosen from C, N, O, B, and S. The improvement of the characteristics here means, for example, increasing the adhesion strength between the substrate and the hard film. This can be realized by adopting a nitride film such as Cr or Ti and a laminated structure with a relatively hard Si-containing film. Abrasion resistance is improved by a laminated structure of nitrides such as Ti, Al, Cr, Zr, Si, Nb, Mo, Hf, and W, or carbonitrides and a relatively hard Si-containing coating. can do. In order to reduce the residual compressive stress of the entire hard coating, it is effective to use a metal rich layer.
本願発明の硬質皮膜の最上層に硬質炭素皮膜を被覆すること及び／又は硬質炭素皮膜を含んだ積層皮膜とすることが、摺層部材の長寿命化に有効である。硬質炭素皮膜は摩擦係数が低く結晶粒径が微細であり、本願発明の硬質皮膜との密着強度にも優れている。最上層において硬質炭素皮膜及び／又は硬質炭素皮膜を含む積層皮膜とすることが、潤滑特性を高めることに有効であり、摺動時の相手材の摩耗量低減に有効に作用するため好ましい。 Covering the hard carbon film on the uppermost layer of the hard film of the present invention and / or forming a laminated film containing the hard carbon film is effective for extending the life of the sliding layer member. The hard carbon film has a low coefficient of friction and a fine crystal grain size, and is excellent in adhesion strength with the hard film of the present invention. It is preferable to use a hard carbon film and / or a laminated film containing a hard carbon film in the uppermost layer because it is effective for improving the lubrication characteristics and effectively acts to reduce the wear amount of the counterpart material during sliding.
本願発明の硬質皮膜の最上層に硫化物を主体とした硬質皮膜を被覆すること及び／又は硫化物を主体とした硬質皮膜を含む積層皮膜とすることも、摺動部材の長寿命化に有効である。硫化物を主体とした硬質皮膜は、摩擦係数が低く結晶粒径が微細であり、本願発明の硬質皮膜との密着強度にも優れている。最上層において硫化物を主体とした硬質皮膜を含む積層皮膜とすることが、潤滑特性を高めることに有効であり、摺動時の相手材の摩耗量低減に有効に作用するため、好ましい。 It is also effective to extend the life of the sliding member by covering the uppermost layer of the hard film of the present invention with a hard film mainly composed of sulfide and / or a laminated film including a hard film mainly composed of sulfide. It is. A hard film mainly composed of sulfide has a low friction coefficient and a fine crystal grain size, and is excellent in adhesion strength with the hard film of the present invention. A laminated film including a hard film mainly composed of sulfide in the uppermost layer is preferable because it is effective in improving the lubrication characteristics and effectively acts in reducing the wear amount of the counterpart material during sliding.
本願発明の硬質皮膜の積層周期を１００ｎｍ以上、５００ｎｍ未満とすることにより、硬質皮膜全体の残留圧縮低減し、硬質皮膜の厚膜化において密着性を確保すること及び摺動部材の長寿命化に有効であり好ましい。 By setting the laminating cycle of the hard coating of the present invention to 100 nm or more and less than 500 nm, the residual compression of the entire hard coating is reduced, ensuring adhesion in thickening the hard coating and extending the life of the sliding member. Effective and preferred.
本願発明の硬質皮膜の積層周期を０．５ｎｍ以上、３０ｎｍ未満とすることにより、特に硬質皮膜全体の高硬度化に有効であり、耐摩耗性の改善に有効であり、より好ましい形態である。 By setting the laminating cycle of the hard coating of the present invention to 0.5 nm or more and less than 30 nm, it is particularly effective in increasing the hardness of the entire hard coating and effective in improving the wear resistance, which is a more preferable embodiment.
本願発明の硬質皮膜において、層厚方向に残留圧縮応力の勾配若しくは周期性を有した形態とすることにより、硬質皮膜の厚膜化が可能であり好ましい。残留圧縮応力が硬質皮膜の表面側ほど大きくなる様に勾配を付与した場合、硬質皮膜の耐摩耗性を改善することができる。また、層厚方向に交互に残留圧縮応力の大きい層と小さい層となるように、周期性を有した積層構造にすると、特に厚膜化したときの密着性の確保に有効である。 In the hard coating of the present invention, it is preferable to make the hard coating thicker by adopting a form having a gradient or periodicity of residual compressive stress in the layer thickness direction. When the gradient is applied so that the residual compressive stress increases toward the surface of the hard coating, the wear resistance of the hard coating can be improved. In addition, a laminated structure having periodicity so that a layer having a large residual compressive stress and a layer having a small residual compressive stress alternately in the layer thickness direction is effective in securing adhesion particularly when the film is thickened.
本願発明の硬質皮膜の最上層から膜厚方向に２００ｎｍ未満の領域で、少なくともＣ、Ｏ、Ｓ、Ｂから選ばれる１種の元素濃度が最大となることが好ましい。これにより潤滑性を高めると同時に、摺動時に相手材の攻撃性を低減させることができる。特にＣ及びＢの濃度が最大となる場合、耐摩耗性と潤滑性を高めることができる。Ｏ及びＳの濃度が最大となる場合、相手材への攻撃性を低減させることが可能である。 It is preferable that the concentration of at least one element selected from C, O, S, and B is maximized in the region of less than 200 nm in the film thickness direction from the uppermost layer of the hard coating of the present invention. As a result, the lubricity can be improved, and at the same time, the aggressiveness of the mating material can be reduced during sliding. In particular, when the concentrations of C and B are maximized, wear resistance and lubricity can be improved. When the concentrations of O and S are maximized, it is possible to reduce the aggression on the counterpart material.
本願発明の硬質皮膜と該摺動部材の基体との界面に窒化層を有する場合、該硬質皮膜の効果が発揮され易く好ましい。 When a nitride layer is provided at the interface between the hard coating of the present invention and the substrate of the sliding member, it is preferable that the effect of the hard coating is easily exhibited.
本願発明の硬質皮膜と摺動部材の基体との界面が機械的に平滑化処理されたことが好ましい。これにより摺動部材が均一に摩耗する傾向にあり、硬質皮膜の効果が発揮され易く好ましい。 The interface between the hard coating of the present invention and the base of the sliding member is preferably mechanically smoothed. As a result, the sliding member tends to wear uniformly, which is preferable because the effect of the hard coating is easily exhibited.
本願発明の硬質皮膜被覆摺動部材が金型、ピストンリング又は内燃機関の過給圧制御用部品として適用される場合、本願発明の硬質皮膜の効果が発揮される。これらは何れも摺動特性が極めて重要であり、これらの用途において最適である。本願発明の硬質皮膜の膜厚は１μｍ以上、６０μｍ未満被覆され、硬質皮膜をイオンプレーティング法やスパッタ法により被覆することで、硬質皮膜組成の制御を容易にするとともに、耐摩耗性に優れ、摺動部材の長寿命化が可能となり、好ましい。 When the hard film-coated sliding member of the present invention is applied as a mold, a piston ring or a supercharging pressure control part for an internal combustion engine, the effect of the hard film of the present invention is exhibited. In any of these, sliding characteristics are extremely important, and are optimal in these applications. The film thickness of the hard film of the present invention is 1 μm or more and less than 60 μm, and by coating the hard film by an ion plating method or a sputtering method, it is easy to control the composition of the hard film and has excellent wear resistance. This is preferable because the life of the sliding member can be extended.
本願発明の硬質皮膜について組成定量分析には、電子プローブＸ線マイクロアナリシス、オージェ電子分光法、又はＸ線光電子分光分析により決定した。硬質皮膜の結合状態の解析には、Ｘ線光電子分光分析によって行った。分析装置は、ＰＨＩ社製１６００Ｓ型Ｘ線光電子分光分析装置を用い、分析条件として、Ｘ線源はＭｇＫαを用い４００Ｗとし、分析領域は直径０．４ｍｍの円内部を分析した。試料準備は、十分に脱脂洗浄した後、真空装置内で５分間Ａｒイオンガンを用いて表面をエッチングした。処理した試料はワイドスペクトルを測定し、３０秒間エッチングした後、ナロースペクトルを測定した。ＡｒイオンガンによるエッチングレートはＳｉＯ２換算で１．９ｎｍ／分であった。半価幅の測定は、θ−２θ法によるＸ線回折によって行った。以下、実施例に基づき、本願発明を具体的に説明する。 The composition quantitative analysis of the hard coating of the present invention was determined by electron probe X-ray microanalysis, Auger electron spectroscopy, or X-ray photoelectron spectroscopy. The analysis of the bonding state of the hard film was performed by X-ray photoelectron spectroscopy. The analysis apparatus used was a 1600S type X-ray photoelectron spectroscopic analyzer manufactured by PHI, and the analysis conditions were such that the X-ray source was 400 K using MgKα, and the analysis region was analyzed inside a circle having a diameter of 0.4 mm. For sample preparation, the surface was etched using an Ar ion gun for 5 minutes in a vacuum apparatus after thoroughly degreasing and cleaning. The treated sample was measured for a wide spectrum, etched for 30 seconds, and then measured for a narrow spectrum. The etching rate by Ar ion gun was 1.9 nm / min in terms of SiO 2 . The half width was measured by X-ray diffraction by the θ-2θ method. Hereinafter, based on an Example, this invention is demonstrated concretely.
（実施例１）
ＣｒＳｉ系皮膜におけるＳｉ含有量とその摩耗特性を評価するために、ディスク材としてサイズ直径がφ２０ｍｍ、厚さ１０ｍｍ、材質がＳＫＤ６１相当を準備した。ディスク材の凹凸が摩擦特性に及ぼす影響を無視するために、アルミナペーストにより鏡面研摩加工し、その後５２０℃で１０時間のガス窒化処理を行った。その後、表面に形成された脆い窒化物相を除去するために、表面を約１０μｍ除去した。そして各種Ｓｉ含有量が異なるＣｒＳｉ系皮膜を被覆した。被覆方法は、脱脂洗浄を十分に行い、アーク放電式イオンプレーティング（以下、ＡＩＰと記す。）装置の容器内に固定した。
容器内の被覆基体を４５０℃に保持しながら、容器内の圧力が５×１０−４Ｐａになるまで排気を行った。容器内にＡｒガスを導入し、容器内の圧力を５×１０−１Ｐａとした。容器内の基体ホルダーに固定された被覆基体は、少なくとも２軸以上の回転機構を有している。容器内に設置された電極でＡｒのイオン化を行い、被覆基体に負バイアス電圧を印加して、被覆基体表面の活性化と酸化物等を除去した。ＡＩＰ蒸発源に設置したＣｒ金属ターゲットに電流を供給し、更に被覆基体のクリーニング処理を実施した。Ａｒの供給を止め容器内に窒素を導入し、容器内の圧力を９×１０−１Ｐａに設定し、ＡＩＰ蒸発源に設置されたＣｒＳｉ系金属ターゲットに電流を供給し、放電を開始した。この時、被覆基体には負に印加したバイアス電圧が付与し、被覆基体にＣｒＳｉ系皮膜を成膜した。被覆膜厚は５μｍに設定した。被覆したＣｒＳｉ系皮膜は何れもＳｉ含有量以外の構成は、本願請求項１の構成要素を満たしていた。ＣｒＳｉ系皮膜の摩耗特性を評価するために、ボールオンディスク型の摩耗試験を実施した。摩耗試験条件を以下に示す。評価は、摺動時間４時間後の摩擦係数、ディスク材の摩耗深さ、ボール材の摩耗深さ測定を行った。
（摩耗試験条件）
ディスク材：ＳＫＤ６１相当（直径：φ２０ｍｍ、厚さ：１０ｍｍ）
ボール材：ＦＣ２５０（ＪＩＳねずみ鋳鉄）
荷重：５０Ｎ
ボール径：φ６ｍｍ
回転半径：８ｍｍ
回転数：１００回転／分
環境設定：大気中、２００℃、潤滑無し
Example 1
In order to evaluate the Si content in the CrSi-based film and its wear characteristics, a disk material having a diameter of φ20 mm, a thickness of 10 mm, and a material equivalent to SKD61 was prepared. In order to ignore the influence of the irregularities of the disk material on the friction characteristics, mirror polishing was performed with alumina paste, and then gas nitriding treatment was performed at 520 ° C. for 10 hours. Thereafter, in order to remove the brittle nitride phase formed on the surface, the surface was removed by about 10 μm. And the CrSi type | system | group film | membrane from which various Si content differs was coat | covered. As a coating method, degreasing and washing were sufficiently performed, and fixed in an arc discharge ion plating (hereinafter referred to as AIP) apparatus container.
While maintaining the coated substrate in the container at 450 ° C., evacuation was performed until the pressure in the container reached 5 × 10 −4 Pa. Ar gas was introduced into the container, and the pressure in the container was set to 5 × 10 −1 Pa. The coated substrate fixed to the substrate holder in the container has a rotation mechanism having at least two axes. Ar ionization was performed with an electrode placed in the container, and a negative bias voltage was applied to the coated substrate to remove the activated surface of the coated substrate and oxides. A current was supplied to the Cr metal target installed in the AIP evaporation source, and the coated substrate was further cleaned. The supply of Ar was stopped, nitrogen was introduced into the container, the pressure in the container was set to 9 × 10 −1 Pa, current was supplied to the CrSi-based metal target installed in the AIP evaporation source, and discharge was started. At this time, a negatively applied bias voltage was applied to the coated substrate, and a CrSi-based film was formed on the coated substrate. The coating thickness was set to 5 μm. All of the coated CrSi-based films satisfied the constituent elements of claim 1 except for the Si content. In order to evaluate the wear characteristics of the CrSi-based film, a ball-on-disk wear test was performed. The abrasion test conditions are shown below. Evaluation was made by measuring the friction coefficient after 4 hours of sliding, the wear depth of the disk material, and the wear depth of the ball material.
(Wear test conditions)
Disk material: Equivalent to SKD61 (diameter: φ20mm, thickness: 10mm)
Ball material: FC250 (JIS gray cast iron)
Load: 50N
Ball diameter: φ6mm
Turning radius: 8mm
Rotation speed: 100 rev / min Environmental setting: In air, 200 ° C, no lubrication
摩擦係数の評価結果を図１に示す。被覆した硬質皮膜を表１、２に示す。 The evaluation results of the friction coefficient are shown in FIG. The coated hard coating is shown in Tables 1 and 2.
図１より、Ｓｉ含有量が及ぼす摩擦係数の影響は、Ｓｉを含有しない従来例２３よりも、本発明例１から３の様にＳｉを４．７６％以下の適量を含有した方が、０．５以下の低い摩擦係数を示した。一方、Ｓｉ含有量が１０％以上の比較例１７から２０は、摩擦係数が０．５を超えて大きい値を示した。本発明例の様に摩擦係数が０．５以下の場合耐溶着性にも優れ、皮膜剥離等を回避することができた。更にディスク材の摩耗深さやボール材の摩耗深さについても、何れも低い値を示し、耐摩耗性に優れる結果であった。これより、相手材の攻撃性に対しても良好であることが確認できた。以上の結果からＳｉ含有量は４．７６％以下とする必要がある。 From FIG. 1, the influence of the friction coefficient exerted by the Si content is 0% when Si is contained in an appropriate amount of 4.76% or less as in Examples 1 to 3 of the present invention rather than the conventional example 23 not containing Si. A low coefficient of friction of .5 or less was exhibited. On the other hand, Comparative Examples 17 to 20 having a Si content of 10% or more showed a large coefficient of friction exceeding 0.5. When the coefficient of friction was 0.5 or less as in the present invention example, the welding resistance was excellent, and peeling of the film could be avoided. Further, the wear depth of the disk material and the wear depth of the ball material both showed low values, and the results were excellent in wear resistance. From this, it was confirmed that it was good against the aggressiveness of the counterpart material. From the above results, the Si content needs to be 4.76% or less.
（実施例２）
本願発明の硬質皮膜の耐焼き付き性を評価するために、表１、２に示す本発明例４から１４、比較例２１、２２、従来例２４の試験片を製作した。試験片の基体は、５ｍｍ角のＳＫＤ６１相当のものを製作し、５２０℃で１０時間のガス窒化処理を行った。表面に形成された脆い窒化物相を除去するために、試験片の表面を約１０μｍ除去した。そして各種組成が異なるＣｒＳｉ系皮膜を被覆した。被覆方法は断りの無い限り、実施例１と同様である。硬質皮膜は、必要に応じてスパッタリング蒸発源又は他の組成系ターゲットを固定したＡＩＰ蒸発源を用いた。硬質皮膜の組成、下地膜、最上層については表１、２に記載した。また何れの試験片に対しても膜厚が３０±２μｍになるようにした。得られた試験片の摩耗特性を評価するために超高圧摩擦摩耗試験機を用い、耐焼き付き性の評価を実施した。試験条件を以下に示す。
（摩擦摩耗試験条件）
摩擦速度：８ｍ／秒
摩擦面圧力：初期圧力、２ＭＰａ、３分毎に１ＭＰａづつ上昇
潤滑油：モーターオイル＃３０
油温：８０℃
相手材：ＦＣ２５０
評価方法の概略を述べる。試験片は円盤Ａの面上に摺動自在にとりつけ、ピン突起状の摺動面とした。円盤Ａは駆動装置によって所定の速度で回転させることができる。一方、ホルダーには摺動の相手材となる円盤Ｂを着脱自在に取り付けた。円盤Ｂの表面は研磨仕上げを施した。ホルダーは、注油可能な機構を有している。ホルダーは油圧装置によって円盤面と垂直方向に押し圧力も印加可能な機構を有している。ここで、試験片の円盤Ａと、摺動相手材の円盤Ｂとを相対向させた状態に設定し、この状態でホルダーに圧力を印加した。従ってこの時、試験片のピン突起状摺動面と相手材の円盤Ｂの面は圧力により接触した。この状態を初期状態として、注油を行いながら円盤Ａを所定速度で回転させた。回転によって試験片と相手材との間に発生する摩擦によってトルクが変化した。この状況をロードセル及び動歪計にて検出した。そして、トルクが急激に上昇した時点を焼き付き発生時点とみなし、評価した。また、注油はホルターの中心より４００ｍｌ／分とした。
評価結果を表３に示す。表３の数値は、従来例２４の焼付き時点の測定値、摩耗量を基準とした場合の比率として夫々耐焼付き比、耐摩耗比として示した。
(Example 2)
In order to evaluate the seizure resistance of the hard coating of the present invention, test pieces of Invention Examples 4 to 14, Comparative Examples 21 and 22, and Conventional Example 24 shown in Tables 1 and 2 were manufactured. A test piece base corresponding to 5 mm square SKD61 was manufactured, and gas nitriding treatment was performed at 520 ° C. for 10 hours. In order to remove the brittle nitride phase formed on the surface, the surface of the test piece was removed by about 10 μm. And the CrSi-type film | membrane from which various compositions differ was coat | covered. The coating method is the same as in Example 1 unless otherwise noted. As the hard coating, an AIP evaporation source in which a sputtering evaporation source or another composition target was fixed as required was used. The composition of the hard film, the base film, and the uppermost layer are shown in Tables 1 and 2. In addition, the film thickness was set to 30 ± 2 μm for any test piece. In order to evaluate the wear characteristics of the obtained specimens, an anti-seizure resistance was evaluated using an ultra-high pressure frictional wear tester. Test conditions are shown below.
(Friction and wear test conditions)
Friction speed: 8 m / sec Frictional surface pressure: Initial pressure, 2 MPa, increase by 1 MPa every 3 minutes Lubricating oil:
Oil temperature: 80 ° C
Opponent material: FC250
An outline of the evaluation method will be described. The test piece was slidably mounted on the surface of the disk A to form a pin-projection sliding surface. The disk A can be rotated at a predetermined speed by a driving device. On the other hand, a disc B serving as a sliding counterpart material was detachably attached to the holder. The surface of the disk B was polished. The holder has a mechanism capable of lubricating. The holder has a mechanism capable of applying a pressing force in a direction perpendicular to the disk surface by a hydraulic device. Here, the disk A of the test piece and the disk B of the sliding partner material were set to face each other, and pressure was applied to the holder in this state. Therefore, at this time, the pin-projection sliding surface of the test piece and the surface of the counterpart disk B were brought into contact with each other by pressure. With this state as the initial state, the disk A was rotated at a predetermined speed while lubricating. The torque was changed by the friction generated between the test piece and the counterpart material due to the rotation. This situation was detected with a load cell and a dynamic strain meter. Then, the time at which the torque increased rapidly was regarded as the time of occurrence of seizure and evaluated. Lubricating was 400 ml / min from the center of the halter.
The evaluation results are shown in Table 3. The numerical values in Table 3 are shown as the seizure resistance ratio and the wear resistance ratio, respectively, as the ratios based on the measured value and the wear amount at the time of seizure in Conventional Example 24.
表３に示す様に、本発明例４から１４の硬質皮膜は従来例２４に比べ耐焼付き比が１．２２倍から１．５５倍も優れていた。耐摩耗比も本発明例は従来例に比べ０．２８から０．５８に低減し、優れた耐摩耗性を示した。本発明例４は、ＣｒＳｉ系皮膜単層の場合である。耐焼付き性及び耐摩耗性に優れていた。本発明例５は、ＣｒＳｉ系皮膜単層に酸素を含有させた場合を示す。酸素を含有することにより、更に耐焼付き性が向上した。本発明例６は、最上層に硬質炭素膜を被覆した場合を示す。同様に優れた特性を示した。本発明例７は、ＡＩＰ蒸発源によるＣｒＳｉ系皮膜の被覆と、スパッタ法による二硫化モリブデンの被覆とを同時に行い、被覆基体の回転機構により一定の積層周期を構成しながら成膜した。更に最上層は二硫化モリブデンを被覆した。この構成によって、特に耐焼付き比を大幅に向上させることができた。本発明例８は、ＣｒＳｉ系皮膜とＣｒ系皮膜との積層皮膜の場合を示す。本発明例８においては、ＣｒＳｉ系ターゲットとＣｒターゲットを装着した２種類のＡＩＰ蒸発源を同時に放電させ、回転機構を有する被覆基体において一定の積層周期を構成しながら成膜した。これにより優れた耐焼付き性を示した。本発明例９は、ＣｒＳｉ系皮膜とＣｒ系皮膜の積層皮膜であって、その積層周期を２００ｎｍとした場合を示す。この場合も同様に優れた特性を示した。本発明例１０は、ＣｒＳｉ系ターゲットとＣｒ系ターゲットを装着した２種類のＡＩＰ蒸発源と、ＣｒＢ２セラミックス製のターゲットを装着したスパッタ蒸発源を使用し、これらを組合せて被覆した場合である。例えばＣｒＳｉ系皮膜とＣｒ系皮膜、ＣｒＳｉ系皮膜とＣｒＢ２系皮膜を同時に被覆し、一定の積層周期を構成しながら成膜した。この場合、特に優れた耐焼付き性と耐摩耗性を示した。本発明例１１は、下地層としてＣｒ系皮膜を被覆した場合を示す。この場合も耐摩耗性に優れていた。本発明例１２は、硬質皮膜最表面において酸素濃度が最大となるよう構成した場合を示す。この場合も耐摩耗性に優れていた。本発明例１３は、下地層としてＣｒ系皮膜を用い、積層皮膜はＣｒ系皮膜とＣｒＳｉ系皮膜を用いた。この場合も耐摩耗性に優れていた。本発明例１４は、下地層としてＣｒ系皮膜を用い、積層皮膜はＣｒＡｌＳｉ系皮膜とＣｒ系皮膜を用いた。この場合、耐焼付き性と同時に特に耐摩耗性に優れた特性を示した。
一方、比較例２１は、ＣｒＳｉ系皮膜の場合を示す。Ｓｉ含有量は金属元素の原子％で３０％とした。この場合、耐焼付き性並びに耐摩耗性について、有効な改善は確認されなかった。比較例２２は、ＣｒＳｉ系皮膜にＳｉ濃度変調が存在しないように構成した場合を示す。この場合、耐焼付き性並びに耐摩耗性について、有効な改善は確認されなかった。このことは、ＣｒＳｉ系皮膜内のＳｉの存在状態が重要であることを示している。ＣｒＳｉ系皮膜にＳｉ濃度変調を存在させるには、成膜工程におけるガス圧力、バイアス電圧、成膜温度、ターゲット供給電流により制御が可能である。
As shown in Table 3, the hard coating films of Invention Examples 4 to 14 were excellent in seizure resistance ratio by 1.22 to 1.55 times compared to Conventional Example 24. The wear resistance ratio of the present invention example was also reduced from 0.28 to 0.58 as compared with the conventional example, indicating excellent wear resistance. Invention Example 4 is a case of a CrSi-based coating single layer. Excellent seizure resistance and wear resistance. Invention Example 5 shows a case where oxygen is contained in a CrSi-based film monolayer. By containing oxygen, the seizure resistance was further improved. Invention Example 6 shows a case where a hard carbon film is coated on the uppermost layer. Similarly, excellent characteristics were exhibited. In Example 7 of the present invention, coating of the CrSi-based film with an AIP evaporation source and coating of molybdenum disulfide with a sputtering method were simultaneously performed, and the film was formed while forming a constant lamination cycle by the rotating mechanism of the coated substrate. Furthermore, the uppermost layer was coated with molybdenum disulfide. With this configuration, the seizure resistance ratio can be significantly improved. Invention Example 8 shows the case of a laminated film of a CrSi film and a Cr film. In Example 8 of the present invention, two types of AIP evaporation sources equipped with a CrSi-based target and a Cr target were discharged at the same time, and a film was formed while forming a constant lamination cycle on a coated substrate having a rotating mechanism. This showed excellent seizure resistance. Example 9 of the present invention is a laminated film of a CrSi-based film and a Cr-based film, and shows a case where the lamination period is 200 nm. In this case as well, excellent characteristics were exhibited. Example 10 of the present invention is a case where two types of AIP evaporation sources equipped with a CrSi-based target and a Cr-based target and a sputter evaporation source equipped with a CrB2 ceramic target are used and coated in combination. For example, a CrSi-based film and a Cr-based film, a CrSi-based film and a CrB2-based film were coated at the same time, and the films were formed while constituting a constant lamination cycle. In this case, particularly excellent seizure resistance and wear resistance were exhibited. Invention Example 11 shows a case where a Cr-based film is coated as an underlayer. Also in this case, the wear resistance was excellent. Invention Example 12 shows a case where the oxygen concentration is maximized on the hard coating outermost surface. Also in this case, the wear resistance was excellent. In Invention Example 13, a Cr-based film was used as the underlayer, and a Cr-based film and a CrSi-based film were used as the laminated film. Also in this case, the wear resistance was excellent. In Invention Example 14, a Cr-based film was used as the base layer, and a CrAlSi-based film and a Cr-based film were used as the laminated film. In this case, the seizure resistance and the particularly excellent wear resistance were exhibited.
On the other hand, Comparative Example 21 shows the case of a CrSi-based film. The Si content was 30% in terms of atomic percent of the metal element. In this case, effective improvement was not confirmed about seizure resistance and abrasion resistance. Comparative Example 22 shows a case where the CrSi-based film is configured so that there is no Si concentration modulation. In this case, effective improvement was not confirmed about seizure resistance and abrasion resistance. This indicates that the presence state of Si in the CrSi-based film is important. In order for Si concentration modulation to be present in the CrSi-based film, it can be controlled by gas pressure, bias voltage, film forming temperature, and target supply current in the film forming process.
（実施例３）
実施例３は、表１、２に示す本発明例１５、本発明例１６及び従来例２５の硬質皮膜を合金工具鋼製パンチ加工金型に被覆した場合である。被覆方法は、実施例２と同様な方法を採用し、膜厚は６μｍとした。パンチ加工金型の先端形状はリードフレームの打ち抜き加工を想定して幅６０μｍ、長さ１０ｍｍとした。評価には下記の加工条件で試験を行い、パンチ加工金型が規定回数の５０ｋ回のショットを打ち抜けるかどうかを評価した。
（加工条件）
加工方法：スリット打ち抜き加工
被加工材：４２Ｎｉ、板厚１５０μｍ
本発明例１５、本発明例１６は硬質皮膜の損傷が無く、規定回数の５０ｋ回のショットを打ち抜く加工が可能であった。一方、従来例２５は８ｋ回のショットを打ち抜くパンチ加工後に、被加工材の精度が大幅に劣化したため、寿命に至った。
(Example 3)
Example 3 is a case where the hard coatings of Invention Example 15, Invention Example 16 and Conventional Example 25 shown in Tables 1 and 2 were coated on a punching die made of alloy tool steel. The coating method was the same as in Example 2 and the film thickness was 6 μm. The tip shape of the punching die was 60 μm wide and 10 mm long assuming punching of the lead frame. For the evaluation, a test was performed under the following processing conditions, and it was evaluated whether the punching die could pass through the specified number of 50k shots.
(Processing conditions)
Processing method: Slit punching Work material: 42Ni, plate thickness 150μm
Invention Example 15 and Invention Example 16 had no damage to the hard film, and could be processed by punching a predetermined number of 50k shots. On the other hand, the conventional example 25 has reached the end of its service life because the accuracy of the workpiece is greatly deteriorated after punching for punching 8k shots.
Claims (15)
A hard film-coated sliding member according to any one of claims 1 to 12, wherein the hard film-coated sliding member is a supercharging pressure control component for an internal combustion engine.
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| JP2005020496A JP2006207691A (en) | 2005-01-28 | 2005-01-28 | Hard film coated sliding member |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008284642A (en) * | 2007-05-17 | 2008-11-27 | Hitachi Tool Engineering Ltd | Coated cutting tool |
| JP2012527581A (en) * | 2009-05-19 | 2012-11-08 | フェデラル−モーグル ブルシャイド ゲーエムベーハー | Sliding member |
| JP2015220328A (en) * | 2014-05-16 | 2015-12-07 | 三菱マテリアル株式会社 | Metal nitride material for thermistor, manufacturing method thereof, and film-type thermistor sensor |
-
2005
- 2005-01-28 JP JP2005020496A patent/JP2006207691A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008284642A (en) * | 2007-05-17 | 2008-11-27 | Hitachi Tool Engineering Ltd | Coated cutting tool |
| JP2012527581A (en) * | 2009-05-19 | 2012-11-08 | フェデラル−モーグル ブルシャイド ゲーエムベーハー | Sliding member |
| JP2015220328A (en) * | 2014-05-16 | 2015-12-07 | 三菱マテリアル株式会社 | Metal nitride material for thermistor, manufacturing method thereof, and film-type thermistor sensor |
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