JP3934136B2 - Hard film coating member and coating method thereof - Google Patents
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Description
本発明は、表面に硬質皮膜を被覆した部材に関する。該部材としては、切削工具、金型、軸受け、ダイス、ロールなど高硬度が要求される耐摩耗工具等がある。また、該硬質皮膜の被覆方法に関する。 The present invention relates to a member whose surface is coated with a hard film. Examples of the member include wear-resistant tools that require high hardness such as cutting tools, dies, bearings, dies, and rolls. The present invention also relates to a method for coating the hard film.
硬質皮膜被覆部材については、皮膜硬度、基体密着性、耐酸化性の改善を目的とした以下の特許文献１から８の技術が開示されている。
特許文献１は、Ｓｉを含有した（ＴｉＳｉ）（ＣＮ）皮膜を開示している。（ＴｉＳｉ）（ＣＮ）は極めて高硬度を有するものの、同時に硬質皮膜内の残留圧縮応力が過剰であり、被覆基体との密着性が悪く、（ＴｉＳｉ）（ＣＮ）単一層のみでは切削工具として十分な性能を示さない。
特許文献２は、金属成分のみの原子％が、Ａｌ：４０％越え７５％以下、残Ｔｉで構成される窒化物、炭窒化物、酸窒化物、酸炭窒化物の何れかを、母材表面直上に被覆し、その直上に高硬度を有するＳｉを含有する皮膜を被覆することにより、切削性能を改善した硬質皮膜切削工具を開示している。この改善によれば、高硬度を有するＳｉ含有硬質皮膜の剥離を低減させ切削性能は改善される。しかし、耐摩耗性を改善させるために、皮膜硬度を向上させる場合、又は高硬度を有するＳｉ含有皮膜の膜構成比率を増加させると、膜内部の残留圧縮応力の影響で、剥離が発生し易くなり、耐摩耗性を逆に低下させる結果となる。従って、皮膜構成層の１部を高硬度化しているに過ぎず、また皮膜の高硬度化にも限界があり、十分な耐摩耗性の改善には至ってはいない。
特許文献３は、Ｓｉを含有した硬質皮膜において、金属成分のみの原子％で、Ｓｉが１０％以上６０％以下、Ｂ、Ａｌ、Ｖ、Ｃｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗの１種または２種以上で１０％未満、残りＴｉで構成される窒化物、炭窒化物、酸窒化物、酸炭窒化物のいずれかで、Ｓｉ３Ｎ４及びＳｉが独立した相として化合物中に存在せしめることにより、Ｓｉ含有皮膜の高硬度化が開示されている。
特許文献４は、Ｓｉを含有した硬質皮膜においてＳｉの含有濃度が相対的に高い結晶粒と相対的に低い結晶粒とを含有する組成偏析多結晶体で構成した事例を開示している。この改善は、Ｓｉ含有皮膜の高硬度化を追求した結果、従来硬質皮膜に比べ、高硬度化が達成されたものの、層全体としても検討が不十分であり、高硬度化に伴い剥離や異常摩耗が発生し易くなり、皮膜の高硬度化による耐摩耗性改善効果には限界がある。
特許文献５は、硬質皮膜をナノオーダーで積層する手段による皮膜の高硬度化を開示している。４ａ、５ａ、６ａ族金属元素或いはＡｌ、Ｓｉの窒化物、酸化物、炭化物、炭窒化物、ホウ化物の中から選んだ１つ以上の化合物と、４ａ、５ａ、６ａ族金属元素及びＡｌ、Ｓｉのうち、２種の金属元素の合金の窒化物、酸化物、炭化物、炭窒化物及び／若しくはホウ化物を積層周期０．４ｎｍ〜５０ｎｍで積層し、全体の膜厚を０．５〜１０μｍとした構成の硬質皮膜である。
特許文献６は、周期律表４ａ、５ａ、６ａ族元素、Ａｌ、Ｓｉ、およびＢから選択される１種以上の元素（第１元素）と、Ｂ、Ｃ、Ｎ、およびＯから選択される１種以上の元素（第２元素）とを主成分とする化合物からなり、互いに異なる組成を有する少なくとも２種の化合物層であって、厚さ方向に元素の組成（ａｔ％）が変化する組成変調層とを含み、該化合物層と前記組織変調層とが周期的に積層されてなり、且つ、前記組成変調層において結晶格子が歪みながら連続していることを特徴とする積層体を開示している。しかし、上記の特許文献５、６に記載の技術においては、硬質皮膜の高硬度化が計られているものの、密着強度に関する対策が十分ではない。
特許文献７は、組成式：（Ｔｉ１−（Ｘ＋Ｙ）ＡｌＸ ＳｉＹ）Ｎ（但し、原子比で、Ｘは０．４０〜０．６５、Ｙ：０．０５〜０．１５）と組成式：（ＴＩ１-ＹＳｉＹ）Ｎ（但し、原子比で、Ｙ：０．０５〜０．１５）を０．０１〜０．１μｍの積層周期で積層することにより、硬質皮膜の強度及び靭性不足によるチッピングを抑制する技術を開示している。
特許文献８は、ＴｉＳｉの窒化物、炭化物、炭窒化物、酸窒化物及び炭酸窒化物から選択された１種の化合物からなる第一の膜と、Ｔｉ、Ｃｒ及びＴｉＣｒから選択された１種の金属Ｍの窒化物、炭化物、炭窒化物、酸窒化物及び炭酸窒化物から選択された１種の化合物からなる第２の膜とを夫々１層以上交互に積層し、各層厚が夫々０．５ｎｍ以上５０ｎｍ以下で構成する技術を開示している。
特許文献９は、炭化タングステン基超硬合金基体または炭窒化チタン系サーメット基体の表面に、ＡｌとＴｉとＳｉの複合窒化物層からなる硬質被覆層を０．５〜１５μｍの全体平均層厚で物理蒸着してなる表面被覆超硬合金製切削工具において、上記硬質被覆層が、層厚方向にそって、Ａｌ最高含有点とＴｉ最高含有点とが所定間隔をおいて交互に繰り返し存在し、かつ前記Ａｌ最高含有点から前記Ｔｉ最高含有点、前記Ｔｉ最高含有点から前記Ａｌ最高含有点へＡｌ及びＴｉ含有量が夫々連続的に変化する成分濃度分布構造を有し、更に、上記Ａｌ最高含有点が、組成式：（Ａｌ１−（Ｘ＋Ｚ）ＴｉＸＳｉＺ）Ｎ（但し、原子比で、Ｘは０．０５〜０．２５、Ｚは０．０５〜０．１５）、上記Ｔｉ最高含有を満足し、かつ隣り合う上記Ａｌ最高含有点とＴｉ最高含有点の間隔が、０．０１〜０．１μｍであること、点が、組成式：（Ｔｉ１−（Ｙ＋Ｚ）ＡｌＹＳｉＺ）Ｎ（但し、原子比で、Ｙは０．０５〜０．２５、Ｚは０．０５〜０．１５）とする高速重切削条件で硬質被覆層が耐摩耗性を発揮する表面被覆超硬合金製切削工具を開示している。しかし、上記の特許文献７から８に記載の手法においては、硬質皮膜間の接合強度、密着強度が十分ではなく、硬質皮膜の高硬度化にも限界があり耐摩耗性の改善が十分ではない。
With respect to the hard coating member, the following Patent Documents 1 to 8 for the purpose of improving coating hardness, substrate adhesion, and oxidation resistance are disclosed.
Patent Document 1 discloses a (TiSi) (CN) film containing Si. Although (TiSi) (CN) has extremely high hardness, the residual compressive stress in the hard coating is excessive at the same time, and the adhesion to the coated substrate is poor, so that only a single layer of (TiSi) (CN) is sufficient as a cutting tool Does not show good performance.
Patent Document 2 discloses that any one of nitride, carbonitride, oxynitride, and oxycarbonitride in which atomic percent of only a metal component is Al: more than 40% and 75% or less and remaining Ti is used as a base material A hard coating cutting tool with improved cutting performance is disclosed by coating directly on the surface and coating a coating containing Si having high hardness directly on the surface. According to this improvement, peeling of the Si-containing hard film having a high hardness is reduced and the cutting performance is improved. However, in order to improve the wear resistance, when the film hardness is increased, or when the film composition ratio of the Si-containing film having a high hardness is increased, peeling is likely to occur due to the effect of residual compressive stress inside the film. This results in a decrease in wear resistance. Therefore, only a part of the coating layer is hardened, and there is a limit to the high hardness of the coating, so that sufficient wear resistance has not been improved.
Patent Document 3 discloses that in a hard film containing Si, the atomic percentage of only the metal component, Si is 10% or more and 60% or less, B, Al, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, One or more of W and less than 10% of the remaining Ti, nitride, carbonitride, oxynitride, oxycarbonitride composed of the remaining Ti, Si3N4 and Si as independent phases in the compound Increasing the hardness of a Si-containing film by making it exist is disclosed.
Patent Document 4 discloses an example in which a hard coating containing Si is composed of a composition segregated polycrystal containing a crystal grain having a relatively high Si content and a crystal grain having a relatively low content. As a result of pursuing higher hardness of the Si-containing coating, this improvement has achieved higher hardness compared to the conventional hard coating, but the entire layer is not fully studied, and peeling and abnormalities are accompanied by higher hardness. Wear tends to occur, and there is a limit to the effect of improving the wear resistance by increasing the hardness of the coating.
Patent Document 5 discloses increasing the hardness of a film by means of laminating a hard film on the nano order. One or more compounds selected from 4a, 5a, 6a group metal elements or Al, Si nitrides, oxides, carbides, carbonitrides, borides, 4a, 5a, 6a group metal elements and Al, Of Si, nitrides, oxides, carbides, carbonitrides and / or borides of alloys of two metal elements are laminated with a lamination period of 0.4 nm to 50 nm, and the total film thickness is 0.5 to 10 μm. This is a hard film having the structure as described above.
Patent Document 6 is selected from one or more elements (first elements) selected from the periodic table 4a, 5a, 6a group elements, Al, Si, and B, and B, C, N, and O A composition comprising at least two compound layers having different compositions from each other, the composition comprising at least two kinds of elements (second element) as a main component, wherein the composition (at%) of the element varies in the thickness direction. Disclosed is a laminate comprising a modulation layer, wherein the compound layer and the tissue modulation layer are periodically laminated, and the crystal lattice is continuous while being distorted in the composition modulation layer. ing. However, in the techniques described in Patent Documents 5 and 6 described above, although the hardness of the hard coating is increased, measures for adhesion strength are not sufficient.
Patent Document 7 describes a composition formula: (Ti1- (X + Y) AlX SiY) N (wherein, X is 0.40 to 0.65, Y: 0.05 to 0.15) and a composition formula: ( TI1-YSiY) N (however, atomic ratio Y: 0.05 to 0.15) is laminated with a lamination period of 0.01 to 0.1 μm to suppress chipping due to the strength and toughness of the hard coating. The technology to do is disclosed.
Patent Document 8 discloses a first film made of one compound selected from nitride, carbide, carbonitride, oxynitride, and carbonitride of TiSi, and one selected from Ti, Cr, and TiCr. One or more layers of each of the second films made of one compound selected from nitride, carbide, carbonitride, oxynitride, and carbonitride of the metal M are alternately stacked, and each layer has a thickness of 0. Disclosed is a technology configured with a thickness of 5 nm to 50 nm.
In Patent Document 9, a hard coating layer composed of a composite nitride layer of Al, Ti, and Si is formed on the surface of a tungsten carbide base cemented carbide substrate or a titanium carbonitride cermet substrate with an overall average layer thickness of 0.5 to 15 μm. In the surface-coated cemented carbide cutting tool formed by physical vapor deposition, the hard coating layer is repeatedly present along the layer thickness direction with Al highest content points and Ti highest content points alternately with a predetermined interval, And a component concentration distribution structure in which Al and Ti contents continuously change from the highest Al content point to the highest Ti content point, from the highest Ti content point to the highest Al content point, respectively, Containing point is composition formula: (Al1- (X + Z) TiXSiZ) N (however, in atomic ratio, X is 0.05 to 0.25, Z is 0.05 to 0.15), satisfying the above-mentioned highest Ti content And the above A The interval between the highest content point and the highest Ti content point is 0.01 to 0.1 μm, and the point is the composition formula: (Ti1- (Y + Z) AlYSiZ) N (wherein the atomic ratio, Y is 0.05 -0.25, Z is 0.05-0.15) The surface coating cemented carbide cutting tool with which a hard coating layer exhibits abrasion resistance on high-speed heavy cutting conditions is disclosed. However, in the methods described in Patent Documents 7 to 8, the bonding strength and adhesion strength between the hard coatings are not sufficient, and there is a limit in increasing the hardness of the hard coatings, and the improvement in wear resistance is not sufficient. .
本発明は、Ｓｉ含有皮膜を著しく高硬度化させても、剥離や異常摩耗が発生し難く、硬質皮膜全体の高硬度化と同時に耐剥離性に優れ、過酷な摩耗環境において、耐摩耗性の要求される部材等に最適な硬質皮膜を提供し、更にこの硬質皮膜を被覆した硬質皮膜被覆部材及びその被覆方法を提供することが課題である。 The present invention makes it difficult for peeling and abnormal wear to occur even when the hardness of the Si-containing film is remarkably increased, and is excellent in peeling resistance at the same time as increasing the hardness of the entire hard film. It is an object to provide a hard coating optimal for a required member and the like, and further to provide a hard coating coated member coated with the hard coating and a coating method thereof.
本発明は、基体に、物理蒸着法により組成が異なる複数層の硬質皮膜を積層した硬質皮膜被覆部材において、該硬質皮膜は基体表面に被覆される最下層と、硬質皮膜の最表面に被覆される最上層と、該最下層と該最上層とに接する中間積層部とを有し、該最下層は、Ａｌ、Ｔｉ、Ｃｒ、Ｓｉ、Ｎｂから選択される１種以上の金属元素からなる窒化物主体の硬質皮膜であり、該最上層は、金属元素のみの原子％で、Ｓｉが１０％以上、３０％以下を含有し、非金属成分として、Ｎ、Ｃ、Ｏ、Ｂの少なくとも１種以上を含有する少なくとも非晶質相を含有し、硬度が４０ＧＰａ以上、８０ＧＰａ未満の高硬度な硬質皮膜であり、該中間積層部は、金属元素としてＡｌ及びＳｉを含有し、残部Ｔｉ、Ｃｒ、Ｎｂ、Ｚｒ、Ｗから選択される１種以上の金属元素からなる窒化物、ホウ窒化物又は炭窒化物の何れかが主体の積層部であり、該積層部はＡ層とＢ層とが交互に積層され、夫々層厚方向にＡｌ含有量が、金属元素のみの原子％で、該Ａ層は、５％以上、３０％未満の層であり、該Ｂ層は、３０％以上、６０％未満の層であり、該Ａ層と該Ｂ層との層厚さは夫々０．５ｎｍ以上、２０ｎｍ未満であり、且つ、該Ａ層と該Ｂ層との含有組成に周期構造を有することを特徴とする硬質皮膜被覆部材である。本構成を採用して中間積層部に高硬度を有するＳｉ含有皮膜を用いることにより、皮膜全体を高硬度化することを可能とし、同時に積層する硬質皮膜が夫々優れた密着強度を有した状態で構成される。そのため、２層間の剥離が起こり難く、高硬度を有しながら耐剥離性、耐チッピング性に優れ、異常摩耗が発生し難く、優れた耐摩耗性を発揮することができる。更に、本発明に重要な点は、高硬度を有するＳｉ含有皮膜を硬質皮膜に被覆する場合において、最適な層構造を有していることである。皮膜の剥離や異常摩耗を著しく抑制することを可能にして、優れた耐摩耗性を発揮する硬質皮膜被覆部材を提供することができる。
The present invention relates to a hard coating member in which a plurality of hard coatings having different compositions are stacked on a substrate by physical vapor deposition, and the hard coating is coated on the lowermost layer coated on the substrate surface and on the outermost surface of the hard coating. An uppermost layer, and an intermediate laminated portion in contact with the lowermost layer and the uppermost layer, and the lowermost layer is nitrided of one or more metal elements selected from Al, Ti, Cr, Si, and Nb It is a hard film mainly composed of an object, and the uppermost layer contains at least one element of N, C, O, and B as a non-metallic component, containing at least 10% and not more than 30% of Si with only an atomic% of a metal element. It is a high hardness hard film containing at least an amorphous phase containing the above and having a hardness of 40 GPa or more and less than 80 GPa, and the intermediate laminated portion contains Al and Si as metal elements, and the balance Ti, Cr, One or more selected from Nb, Zr, W It is a laminated part mainly composed of nitride, boronitride or carbonitride composed of a genus element, and the laminated part is formed by alternately laminating A layers and B layers, each having an Al content in the layer thickness direction. The layer A is a layer of 5% or more and less than 30%, and the layer B is a layer of 30% or more and less than 60%, and the A layer and the B layer. the layer thickness of a respectively 0.5nm or more, 20 nm less der is, and a hard-coated member according to claim Rukoto that having a periodic structure containing composition with the a layer and the B layer. By adopting this configuration and using a Si-containing film having high hardness in the intermediate laminated part, it is possible to increase the hardness of the entire film, and at the same time, the hard film to be laminated has excellent adhesion strength. Composed. Therefore, peeling between two layers hardly occurs, and while having high hardness, it has excellent peeling resistance and chipping resistance, hardly causes abnormal wear, and can exhibit excellent wear resistance. Furthermore, an important point in the present invention is that it has an optimum layer structure when a hard film is coated with a Si-containing film having a high hardness. It is possible to remarkably suppress peeling of the film and abnormal wear, and it is possible to provide a hard film-coated member that exhibits excellent wear resistance.
本発明の硬質皮膜を被覆した部材において、該中間積層部の金属元素組成は（ＡｌＸＳｉＹＭＺ）で示され、但し、ＭはＴｉ、Ｃｒ、Ｎｂ、Ｚｒ、Ｗから選択される少なくとも１種から成り、Ｘ、Ｙ、Ｚは夫々原子％を示し、該Ａ層は、５≦Ｘ＜３０、５≦Ｙ≦３０、６０≦Ｚ≦８５、Ｘ＋Ｙ＋Ｚ＝１００であり、該Ｂ層は、３０≦Ｘ＜５５、１≦Ｙ≦１５、４０≦Ｚ≦７０、Ｘ＋Ｙ＋Ｚ＝１００であることを特徴とする硬質皮膜被覆部材であることが好ましい。更により好ましくは、該Ａ層は、１０≦Ｘ≦２５、１０≦Ｙ≦２０、６５≦Ｚ≦８０、Ｘ＋Ｙ＋Ｚ＝１００であり、該Ｂ層は、２５＜Ｘ≦４７、１≦Ｙ＜１０、５０≦Ｚ＜６５、Ｘ＋Ｙ＋Ｚ＝１００である。また、該Ａ層と該Ｂ層とは、少なくともＳｉ及びＡｌの相互拡散層であり、結晶格子が連続していることが好ましい。更に、該中間積層部のＳｉ含有量が層厚方向に異なり、表層側になる程Ｓｉ含有量の多いことが好ましい。
本発明の硬質皮膜において、該最上層の層厚さＴＴＨμｍが、０．１≦ＴＴＨ＜５、該中間積層部の層厚さＭＴＨμｍが、０．１≦ＭＴＨ＜５、該最下層の厚さ層ＢＴＨμｍが、０．０１≦ＢＴＨ＜３、であること、更により好ましくは、ＴＴＨ≧ＭＴＨ≧ＢＴＨ、となることである。
本発明の硬質皮膜において、該最上層、該中間積層部、該最下層の夫々の硬度をＴＨＡ、ＭＨＡ、ＢＨＡとすると、ＴＨＡ≧ＭＨＡ≧ＢＨＡ、であること、また該最上層、該中間積層部、該最下層の夫々の弾性係数をＴＥＬ、ＭＥＬ、ＢＥＬとすると、ＴＥＬ≦ＭＥＬ≦ＢＥＬ、であること、ナノインデンテーションによる硬度測定により求めた該最上層、該中間積層部、該最下層の夫々の弾性回復率（％）をＴＲ、ＭＲ、ＢＲとすると、ＴＲ≧ＭＲ≧ＢＲ、であること、更に該中間積層部の弾性回復率ＭＲ（％）が、３０＜ＭＲ＜３８となることが好ましい。
本発明の硬質皮膜において、該最上層は酸素を含有し、最表面から膜厚方向に１００ｎｍ以内の深さ領域で酸素濃度の最大値を有することが好ましい。本発明の硬質皮膜を被覆した部材は、エンドミル又はドリルであることが好ましい。
In the member coated with the hard film of the present invention, the metal element composition of the intermediate laminated portion is represented by (Al X Si Y M Z ), where M is at least selected from Ti, Cr, Nb, Zr, and W 1 type, X, Y, Z each represents atomic%, the A layer is 5 ≦ X <30, 5 ≦ Y ≦ 30, 60 ≦ Z ≦ 85, X + Y + Z = 100, and the B layer is 30 ≦ X < 55 , 1 ≦ Y ≦ 15, 40 ≦ Z ≦ 70, and X + Y + Z = 100 are preferable. Even more preferably, the A layer is 10 ≦ X ≦ 25, 10 ≦ Y ≦ 20, 65 ≦ Z ≦ 80, X + Y + Z = 100, and the B layer is 25 <X ≦ 47 , 1 ≦ Y <10. , 50 ≦ Z <65 and X + Y + Z = 100. Further, the A layer and the B layer are at least Si and Al mutual diffusion layers, and it is preferable that the crystal lattice is continuous. Furthermore, it is preferable that the Si content of the intermediate laminated portion is different in the layer thickness direction and that the Si content increases as it becomes closer to the surface layer side.
In the hard coating of the present invention, the layer thickness TTH μm of the uppermost layer is 0.1 ≦ TTH <5, the layer thickness MTH μm of the intermediate laminated portion is 0.1 ≦ MTH <5, and the thickness of the lowermost layer. The layer BTH μm is 0.01 ≦ BTH <3, and even more preferably, TTH ≧ MTH ≧ BTH.
In the hard film of the present invention, if the hardness of each of the uppermost layer, the intermediate laminated portion, and the lowermost layer is THA, MHA, and BHA, THA ≧ MHA ≧ BHA, and the uppermost layer, the intermediate laminated layer. The uppermost layer, the intermediate laminated portion, and the lowermost layer determined by hardness measurement by nanoindentation, where TEL ≦ MEL ≦ BEL When each elastic recovery of (%) TR, MR, and BR, it is, TR ≧ MR ≧ BR, further elastic recovery of the intermediate stacking portion MR (%), the 30 <MR <38 It is preferable.
In the hard film of the present invention, it is preferable that the uppermost layer contains oxygen and has a maximum oxygen concentration in a depth region within 100 nm from the outermost surface in the film thickness direction. The member coated with the hard coating of the present invention is preferably an end mill or a drill.
本発明の硬質皮膜被覆部材に被覆する方法は、物理蒸着法を採用し、該物理蒸着法はスパッタリング法及び／又はアーク放電式イオンプレーティング（以下、ＡＩＰと言う。）法であることが好ましい。更に好ましい被覆方法は、該硬質皮膜の被覆時に使用する金属製ターゲット材の組成が、該最上層被覆用と該最下層被覆用とで異なり、該中間積層部の被覆時は該最上層被覆用のターゲット材を装着した蒸着源と、該最下層被覆用のターゲット材を装着した蒸着源とを同時に稼動して被覆する方法を用いることが好ましい。 The method for coating the hard coating member of the present invention employs a physical vapor deposition method, and the physical vapor deposition method is preferably a sputtering method and / or an arc discharge ion plating (hereinafter referred to as AIP) method. . A more preferable coating method is that the composition of the metal target material used at the time of coating the hard coating is different between the top layer coating and the bottom layer coating, and the intermediate layered portion is coated at the top layer coating. It is preferable to use a method in which a vapor deposition source equipped with the target material and a vapor deposition source equipped with the target material for lowermost layer coating are simultaneously operated and coated.
本発明は、Ｓｉ含有皮膜を著しく高硬度化させても、剥離や異常摩耗が発生し難く、硬質皮膜全体の高硬度化と同時に耐剥離性に優れ、過酷な摩耗環境において、耐摩耗性の要求される部材等に最適な硬質皮膜を提供し、更にこの硬質皮膜を被覆した硬質皮膜被覆部材及びその被覆方法を提供することが可能となった。例えば、過酷な摩耗環境において耐摩耗性の要求される高速切削加工等の工具部材に適用した場合、硬質皮膜全体の剥離が起こり難く、高硬度を有しながら耐剥離性、耐チッピング性に優れ異常摩耗が発生し難く、優れた耐摩耗性を発揮する硬質皮膜被覆工具部材を提供することが可能となった。 The present invention makes it difficult for peeling and abnormal wear to occur even when the hardness of the Si-containing film is remarkably increased, and is excellent in peeling resistance at the same time as increasing the hardness of the entire hard film. It has become possible to provide an optimum hard coating for a required member and the like, and further to provide a hard coating covering member coated with this hard coating and a coating method thereof. For example, when applied to a tool member such as high-speed cutting that requires wear resistance in harsh wear environments, the entire hard coating is unlikely to peel off and has excellent peel resistance and chipping resistance while having high hardness. It has become possible to provide a hard film-coated tool member that hardly causes abnormal wear and exhibits excellent wear resistance.
本発明は、硬質皮膜の層構造が重要である。図１に本発明における硬質皮膜の積層構造の概略図を示す。本発明の硬質皮膜の層構造は、基体に物理蒸着法により組成が異なる複数層の硬質皮膜を積層しており、硬質皮膜は基体表面に被覆される最下層と、硬質皮膜の最表面に被覆される最上層と、最下層と最上層とに接する中間積層部とから構成される。高硬度を有する最上層が存在しない場合には、優れた耐摩耗効果を発揮することができず、中間積層部が存在しない場合には、最上層の過剰な残留応力により、剥離や異常摩耗が発生し、同様に耐摩耗性の改善には至らない。また、最下層が存在せず、中間積層部だけしか存在しない場合、最上層の残留応力を吸収することができず、剥離や異常摩耗が先行した摩耗状態となり、耐摩耗性の改善には至らないのである。
本発明の最下層は、Ａｌ、Ｔｉ、Ｃｒ、Ｓｉ、Ｎｂから選択される１種以上の金属元素からなる窒化物主体の硬質皮膜とすることが必要である。これより、最上層の応力緩和層として有効に作用することと伴に、中間積層部との密着強度に優れる。
次に、本発明の最上層は、金属元素のみの原子％で、Ｓｉが１０％以上、３０％以下を含有し、非金属成分として、Ｎ、Ｃ、Ｏ、Ｂの少なくとも１種以上を含有する少なくとも非晶質相を含有し、硬度が４０ＧＰａ以上、８０ＧＰａ未満の高硬度な硬質皮膜である。Ｓｉ含有量が１０％以上、３０％以下とし、非金属成分として、Ｎ、Ｃ、Ｏ、Ｂの少なくとも１種以上を含有する少なくとも非晶質相が存在する場合、高硬度を有する硬質皮膜が得られる。Ｓｉが１０％未満、又は３０％を超えて大きい場合、耐摩耗性を発揮するための硬度達成が不十分である。Ｓｉ含有量が本発明規定の範囲であり、非晶質相を含有する場合、皮膜が高硬度化する。最上層の皮膜硬度は、４０ＧＰａ以上、８０ＧＰａ未満であることが必要である。最上層の硬度が４０ＧＰａ未満の場合、耐摩耗性改善効果が確認できない。また硬度が８０ＧＰａ以上の場合、最下層及び中間積層部を改善しても、剥離や、剥離による異常摩耗の発生を抑制することができない。
本発明の中間積層部は、金属元素としてＡｌ及びＳｉを含有し、残部Ｔｉ、Ｃｒ、Ｎｂ、Ｚｒ、Ｗから選択される１種以上の金属元素からなる窒化物、ホウ窒化物又は炭窒化物の何れかが主体の積層部であり、この積層部はＡ層とＢ層とが交互に積層され、夫々層厚方向にＡｌ含有量が、金属元素のみの原子％で、Ａ層は、５％以上、３０％未満の層であり、Ｂ層は、３０％以上、６０％未満の層であり、Ａ層とＢ層との層厚さは夫々０．５ｎｍ以上、２０ｎｍ未満である。この条件を満たす事によって、最下層と最上層との硬度、密着性、強度のバランスが最適となる。ここで、Ａ層は、金属元素のみの原子％で、５％以上３０％未満であることが必要である。５％未満の場合、Ａ層とＢ層との密着強度が十分ではない。一方、３０％以上の場合、中間積層部の硬度が低下する傾向にあり、強度が十分でない。またＢ層は、３０％以上、６０％未満であることが必要である。３０％未満となる場合、中間積層部の皮膜硬度が低下する傾向にあり、強度が十分ではない。６０％以上となる場合、Ａ層との密着強度が十分ではない。更に、Ａ層とＢ層との各層の厚さが０．５ｎｍ以上、２０ｎｍ未満の範囲で交互に積層されることが必要である。Ａ層とＢ層とを交互に積層することにより、中間積層部が高硬度化され、最下層並びに最上層との密着強度及び硬質皮膜全体の強度のバランスが最適となる。また、中間積層部の上層側に最上層を被覆することにより、最上層の硬度が向上することも本発明において重要である。
上記に述べた様に、最下層と中間積層部とから構成される硬質皮膜を被覆することにより、この上層側に、硬度が４０ＧＰａ以上、８０ＧＰａ未満の高硬度な硬質皮膜を最上層として被覆しても、剥離や異常摩耗を著しく抑制することが可能である。
In the present invention, the layer structure of the hard coating is important. FIG. 1 shows a schematic diagram of a laminated structure of hard coatings in the present invention. The layer structure of the hard coating of the present invention is that a substrate is formed by laminating a plurality of hard coatings having different compositions by physical vapor deposition, and the hard coating is coated on the lowermost layer coated on the substrate surface and on the outermost surface of the hard coating. The uppermost layer is formed, and an intermediate laminated portion in contact with the lowermost layer and the uppermost layer. When the uppermost layer having high hardness does not exist, an excellent wear resistance effect cannot be exhibited, and when the intermediate laminated portion does not exist, peeling or abnormal wear is caused by excessive residual stress of the uppermost layer. Occurs and does not lead to improved wear resistance as well. In addition, when there is no lowermost layer and only the intermediate layered portion exists, the residual stress of the uppermost layer cannot be absorbed, resulting in a wear state preceded by peeling or abnormal wear, leading to improved wear resistance. There is no.
The lowermost layer of the present invention is required to be a nitride-based hard coating composed of one or more metal elements selected from Al, Ti, Cr, Si, and Nb. As a result, it effectively acts as the uppermost stress relaxation layer and has excellent adhesion strength with the intermediate laminated portion.
Next, the uppermost layer of the present invention contains only 10% or more and 30% or less of Si, and contains at least one or more of N, C, O, and B as nonmetallic components. It is a hard film having at least an amorphous phase and having a hardness of 40 GPa or more and less than 80 GPa. When the Si content is 10% or more and 30% or less, and there is at least an amorphous phase containing at least one of N, C, O, and B as a nonmetallic component, a hard film having high hardness is formed. can get. When Si is less than 10% or more than 30%, the achievement of hardness for exhibiting wear resistance is insufficient. When the Si content is within the range specified in the present invention and an amorphous phase is contained, the film becomes harder. The film hardness of the uppermost layer needs to be 40 GPa or more and less than 80 GPa. When the hardness of the uppermost layer is less than 40 GPa, the effect of improving the wear resistance cannot be confirmed. Further, when the hardness is 80 GPa or more, even if the lowermost layer and the intermediate laminated portion are improved, it is not possible to suppress peeling and occurrence of abnormal wear due to peeling.
The intermediate laminated portion of the present invention contains nitride and boronitride or carbonitride containing Al and Si as metal elements and the balance of one or more metal elements selected from Ti, Cr, Nb, Zr, and W. Any one of the above is a main laminated portion, and in this laminated portion, the A layer and the B layer are alternately laminated, and the Al content is atomic% of only the metal element in the layer thickness direction, respectively. % And less than 30%, the B layer is 30% and less than 60%, and the layer thicknesses of the A and B layers are 0.5 nm and less than 20 nm, respectively. By satisfying this condition, the balance of hardness, adhesion and strength between the lowermost layer and the uppermost layer is optimal. Here, the A layer needs to be 5% or more and less than 30% by atomic% of only the metal element. If it is less than 5%, the adhesion strength between the A layer and the B layer is not sufficient. On the other hand, when it is 30% or more, the hardness of the intermediate laminated portion tends to decrease, and the strength is not sufficient. The B layer needs to be 30% or more and less than 60%. When it is less than 30%, the film hardness of the intermediate laminated portion tends to decrease, and the strength is not sufficient. When it is 60% or more, the adhesion strength with the A layer is not sufficient. Furthermore, it is necessary that the thicknesses of the A layer and the B layer are alternately stacked in a range of 0.5 nm or more and less than 20 nm. By alternately laminating the A layer and the B layer, the intermediate laminated portion is increased in hardness, and the balance between the adhesion strength with the lowermost layer and the uppermost layer and the strength of the entire hard coating becomes optimum. It is also important in the present invention that the hardness of the uppermost layer is improved by coating the uppermost layer on the upper layer side of the intermediate laminated portion.
As described above, by covering the upper layer with a hard film composed of the lowermost layer and the intermediate laminated portion, a hard film having a hardness of 40 GPa or more and less than 80 GPa is coated as the uppermost layer. However, it is possible to remarkably suppress peeling and abnormal wear.
本発明の硬質皮膜において、中間積層部の組成は（ＡｌＸＳｉＹＭＺ）で示され、但し、ＭはＴｉ、Ｃｒ、Ｎｂ、Ｚｒ、Ｗから選択される少なくとも１種から成り、Ｘ、Ｙ、Ｚは夫々原子％を示し、該Ａ層は、５≦Ｘ＜３０、５≦Ｙ≦３０、６０≦Ｚ≦８５、Ｘ＋Ｙ＋Ｚ＝１００であり、該Ｂ層は、３０≦Ｘ＜５５、１≦Ｙ≦１５、４０≦Ｚ≦７０、Ｘ＋Ｙ＋Ｚ＝１００であることを特徴とする硬質皮膜被覆部材であることが好ましい。更により好ましくは、該Ａ層は、１０≦Ｘ≦２５、１０≦Ｙ≦２０、６５≦Ｚ≦８０、Ｘ＋Ｙ＋Ｚ＝１００であり、該Ｂ層は、２５＜Ｘ≦４７、１≦Ｙ＜１０、５０≦Ｚ＜６５、Ｘ＋Ｙ＋Ｚ＝１００である。上記の組成範囲に調整することにより、中間積層部が高硬度化され、Ａ層とＢ層との密着強度が優れると伴に、最下層並びに最上層との密着強度にも優れ、硬質皮膜全体の強度のバランスが最適となり好ましい。
中間積層部のＡ層とＢ層とは少なくともＳｉ及びＡｌの相互拡散層であることが好ましい。この場合、特にＡ層とＢ層との密着強度、並びに、最下層及び最上層との密着強度に優れ、中間積層部の硬度を向上させると伴に、硬質皮膜全体の強度のバランスが最適となり、中間積層部にとって特に好ましい層構造の形態である。相互拡散層としての組成は、（ＡｌＸＳｉＹＭＺ）で示され、但し、ＭはＴｉ、Ｃｒ、Ｎｂ、Ｚｒ、Ｗから選択される少なくとも１種、Ｘ、Ｙ、Ｚは夫々原子％を示し、Ａ層が、１０≦Ｘ≦２５、１０≦Ｙ≦２０、６５≦Ｚ≦８０、Ｘ＋Ｙ＋Ｚ＝１００であり、Ｂ層が、２５＜Ｘ≦５５、１≦Ｙ＜１０、５０≦Ｚ＜６５、Ｘ＋Ｙ＋Ｚ＝１００であることが特に好ましい。
相互拡散層の有無は、透過型電子顕微鏡による格子像観察並びに各層のエネルギー分散型Ｘ線分光（以下、ＥＤＳと言う。）分析により確認することができる。この場合、各層を構成する金属ターゲット材の組成と、Ａ層とＢ層の組成から判断することができる。またＡ層とＢ層に相互拡散が起こらない場合は、Ａ層とＢ層で固溶体を形成していない場合である。この場合、Ａ層とＢ層は格子定数が異なり、Ｘ線回折により２種の異なるピークが存在する。
本発明の硬質皮膜において、中間積層部のＡ層とＢ層の格子が連続して成長していることが好ましい。この場合、特にＡ層とＢ層との密着強度、並びに、最下層及び最上層との密着強度に優れ、中間積層部の硬度を向上させると伴に、硬質皮膜全体の強度のバランスが最適となり、中間積層部としては好ましい層構造の形態である。本構造を確認する手法としては、透過型電子顕微鏡による格子像観察により確認することができる。
中間積層部のＳｉ含有量が層厚方向に異なり、表層側になるＳｉ含有量の多いことが好ましい。本構成により、中間積層部の密着強度、硬度並びに強度が傾斜化され、その結果として、硬質皮膜全体の密着強度、硬度並びに強度が傾斜化され、耐摩耗性を改善することができるので好ましい。
In the hard film of the present invention, the composition of the intermediate laminate portion is represented by (Al X Si Y M Z ), where M is at least one selected from Ti, Cr, Nb, Zr, and W, Y and Z each represent atomic%, the A layer has 5 ≦ X <30, 5 ≦ Y ≦ 30, 60 ≦ Z ≦ 85, and X + Y + Z = 100, and the B layer has 30 ≦ X < 55 , It is preferable that the hard film covering member is characterized in that 1 ≦ Y ≦ 15, 40 ≦ Z ≦ 70, and X + Y + Z = 100. Even more preferably, the A layer is 10 ≦ X ≦ 25, 10 ≦ Y ≦ 20, 65 ≦ Z ≦ 80, X + Y + Z = 100, and the B layer is 25 <X ≦ 47 , 1 ≦ Y <10. , 50 ≦ Z <65 and X + Y + Z = 100. By adjusting to the above composition range, the intermediate laminated part is made harder, the adhesion strength between the A layer and the B layer is excellent, and the adhesion strength between the lowermost layer and the uppermost layer is also excellent, and the entire hard coating The balance of strength is optimal and preferable.
It is preferable that the A layer and the B layer of the intermediate laminated portion are at least Si and Al interdiffusion layers. In this case, especially the adhesion strength between the A layer and the B layer, and the adhesion strength between the lowermost layer and the uppermost layer is excellent, and the balance of strength of the entire hard coating becomes optimal as the hardness of the intermediate laminated portion is improved. The layer structure is particularly preferable for the intermediate laminated portion. The composition as the interdiffusion layer is represented by (Al X Si Y M Z ), where M is at least one selected from Ti, Cr, Nb, Zr, and W, and X, Y, and Z are each atomic%. A layer is 10 ≦ X ≦ 25, 10 ≦ Y ≦ 20, 65 ≦ Z ≦ 80, X + Y + Z = 100, and B layer is 25 <X ≦ 55, 1 ≦ Y <10, 50 ≦ Z It is particularly preferred that <65, X + Y + Z = 100.
The presence or absence of the interdiffusion layer can be confirmed by observation of a lattice image with a transmission electron microscope and energy dispersive X-ray spectroscopy (hereinafter referred to as EDS) analysis of each layer. In this case, it can judge from the composition of the metal target material which comprises each layer, and the composition of A layer and B layer. The case where no mutual diffusion occurs between the A layer and the B layer is a case where no solid solution is formed between the A layer and the B layer. In this case, the A layer and the B layer have different lattice constants, and there are two different peaks due to X-ray diffraction.
In the hard coating of the present invention, it is preferable that the lattices of the A layer and the B layer in the intermediate laminated portion are continuously grown. In this case, especially the adhesion strength between the A layer and the B layer, and the adhesion strength between the lowermost layer and the uppermost layer is excellent, and the balance of strength of the entire hard coating becomes optimal as the hardness of the intermediate laminated portion is improved. The intermediate laminated portion is a preferred layer structure. As a method for confirming this structure, it can be confirmed by observing a lattice image with a transmission electron microscope.
It is preferable that the Si content of the intermediate laminated portion is different in the layer thickness direction and the Si content on the surface layer side is large. This configuration is preferable because the adhesion strength, hardness, and strength of the intermediate laminated portion are graded, and as a result, the adhesion strength, hardness, and strength of the entire hard coating are graded and the wear resistance can be improved.
本発明の硬質皮膜において、最上層のＴＴＨμｍが、０．１≦ＴＴＨ＜５、であることが好ましい。最上層が０．１μｍ未満の場合、最上層の高硬度化による耐摩耗性改善効果が確認されない場合がある。一方、最上層の層厚が５μｍ以上の場合、過剰な残留応力により、硬質皮膜の剥離や異常摩耗が発生する場合があるため好ましくない。
中間積層部のＭＴＨμｍが、０．１≦ＭＴＨ＜５、であることが好ましい。中間積層部が０．１μｍ未満の場合、最上層と最下層との密着強度、硬度、強度のバランスが悪く、耐摩耗性改善効果が発揮されない場合があるため好ましくない。
最下層のＢＴＨμｍが、０．０１≦ＢＴＨ＜３、であることが好ましい。最下層が０．０１μｍ以上未満の場合、最下層の有する効果が十分に確認されないばかりではなく、耐摩耗性が安定せず、また最下層が３μｍ以上の場合、耐摩耗効果が十分に発揮されない場合があるため、好ましくない。更に、ＴＴＨ≧ＭＴＨ≧ＢＴＨ、となることがより好ましい。本構成により、本発明の効果が最大限に発揮される層構造となる。
In the hard coating of the present invention, it is preferable that TTH μm of the uppermost layer is 0.1 ≦ TTH <5. When the uppermost layer is less than 0.1 μm, the wear resistance improving effect due to the increased hardness of the uppermost layer may not be confirmed. On the other hand, when the thickness of the uppermost layer is 5 μm or more, peeling of the hard coating or abnormal wear may occur due to excessive residual stress, which is not preferable.
The MTH μm of the intermediate laminated part is preferably 0.1 ≦ MTH <5. When the intermediate layered portion is less than 0.1 μm, the balance of adhesion strength, hardness, and strength between the uppermost layer and the lowermost layer is poor, and the effect of improving wear resistance may not be exhibited.
The BTH μm of the lowermost layer is preferably 0.01 ≦ BTH <3. When the lowermost layer is less than 0.01 μm, not only the effect of the lowermost layer is not sufficiently confirmed, but also the wear resistance is not stable, and when the lowermost layer is 3 μm or more, the wear resistance effect is not sufficiently exhibited. Since there is a case, it is not preferable. Furthermore, it is more preferable that TTH ≧ MTH ≧ BTH. With this configuration, a layer structure that maximizes the effects of the present invention is obtained.
本発明の硬質皮膜において、夫々の層の硬度であるＴＨＡ、ＭＨＡ、ＢＨＡが、ＴＨＡ≧ＭＨＡ≧ＢＨＡ、となることが好ましい。ここで言う硬度ＴＨＡ、ＭＨＡ、ＢＨＡは、押込み硬さのことであり、通常のビッカ−ス硬度等の測定方法に代表される塑性変形硬度と区別される。また、夫々の層の弾性係数であるＴＥＬ、ＭＥＬ、ＢＥＬが、ＴＥＬ≦ＭＥＬ≦ＢＥＬ、となることが好ましい。また、夫々の層の弾性回復率（％）であるＴＲ、ＭＲ、ＢＲが、ＴＲ≧ＭＲ≧ＢＲ、となることが好ましい。上記の様に、皮膜硬度、弾性係数、弾性回復率などが本発明規定の関係を示す事により、密着強度、耐摩耗性、耐剥離性のバランスが最適となり、本発明の効果が得られ易く、硬質皮膜の異常摩耗に対して効果的であり、特に好ましい層構造である。更にＭＲ（％）が、３０＜ＭＲ＜３８となることが好ましい。ＭＲが３０％以下となる場合、耐摩耗性に乏しく、一方、３８％以上となる場合、耐剥離性に乏しく異常摩耗が発生し易いためである。ここで硬度ＴＨＡ、ＭＨＡ、ＢＨＡ、弾性係数ＴＥＬ、ＭＥＬ、ＢＥＬ、の測定方法は、ナノインデンテーションによる硬度測定法により求められる。また、弾性回復率（％）は１００−［（接触深さ）／（最大荷重時の最大変位量）］により求められる。接触深さ及び最大荷重時の最大変位量はナノインデンテーション法により求められる（Ｗ．Ｃ．Ｏｌｉｖｅｒａｎｄ、Ｇ．ｍ．Ｐｈａｒｒ：Ｊ．Ｍａｔｅｒ．Ｒｅｓ．、Ｖｏｌ．７、ＮＯ．６、Ｊｕｎｅ１９９２、ｐｐ．１５６４−１５８３）。
In the hard coating of the present invention, it is preferable that THA, MHA, and BHA, which are the hardnesses of the respective layers, satisfy THA ≧ MHA ≧ BHA. The hardnesses THA, MHA, and BHA referred to here are indentation hardnesses, and are distinguished from plastic deformation hardness typified by a usual measuring method such as Vickers hardness. Moreover, it is preferable that TEL, MEL, and BEL, which are elastic coefficients of the respective layers, satisfy TEL ≦ MEL ≦ BEL. Further, it is preferable that TR, MR, and BR, which are elastic recovery rates (%) of the respective layers, satisfy TR ≧ MR ≧ BR. As described above, the film hardness, elastic modulus, elastic recovery rate, etc. show the relationship defined in the present invention, so that the balance of adhesion strength, abrasion resistance, and peel resistance is optimized, and the effects of the present invention are easily obtained. It is effective against abnormal wear of the hard film, and is a particularly preferred layer structure. Further, MR ( % ) is preferably 30 <MR <38. This is because when the MR is 30% or less, the wear resistance is poor, while when it is 38% or more, the peel resistance is poor and abnormal wear tends to occur. Here, the measurement method of hardness THA, MHA, BHA, elastic modulus TEL, MEL, BEL is determined by a hardness measurement method by nanoindentation. Further, the elastic recovery rate (%) is obtained by 100 − [(contact depth) / (maximum displacement at maximum load)]. The contact depth and the maximum displacement at the maximum load are determined by the nanoindentation method (WC Oliverand, Gm Pharr: J. Mater. Res., Vol. 7, NO. 6, June 1992, pp. 1564-1583).
最上層は酸素を含有し、最表面から膜厚方向に１００ｎｍ以内の深さ領域で酸素濃度の最大値を有することが好ましい。これにより、硬質皮膜表面への被加工物の凝着抑制に効果的である。
本発明の硬質皮膜被覆部材において、対象部材をエンドミル又はドリルとし、これに硬質皮膜を被覆した場合、特に耐摩耗性改善効果が顕著であり、工具摩耗を著しく低減させることができるため、好ましい。
The uppermost layer preferably contains oxygen and preferably has a maximum value of oxygen concentration in a depth region within 100 nm from the outermost surface in the film thickness direction. This is effective in suppressing adhesion of the workpiece to the hard coating surface.
In the hard film-coated member of the present invention, when the target member is an end mill or a drill, and this is coated with a hard film, the effect of improving wear resistance is particularly remarkable, and tool wear can be remarkably reduced, which is preferable.
本発明の硬質皮膜を物理蒸着法により被覆する場合は、スパッタリング法及び／又はＡＩＰ法により被覆した硬質皮膜被覆部材は、特に硬質皮膜が高硬度で密着強度に優れ、剥離及び異常摩耗抑制に優れ、本発明の効果が得られ易い。
上記硬質皮膜をスパッタリング法及び／又はＡＩＰ法により被覆し、被覆方法において、硬質皮膜の被覆時に使用する金属製ターゲット材の組成は、最上層被覆用と最下層被覆用とが異なり、中間積層部の被覆時は最上層被覆用のターゲット材を装着した蒸着源と、最下層被覆用のターゲット材を装着した蒸着源とを同時に稼動して被覆することである。この被覆方法を採用することにより、優れた耐摩耗性を発揮することができる硬質皮膜被覆部材を得ることができる。上記被覆方法の１例として、まず最下層の被覆について、最下層構成元素からなる金属製ターゲット１による被覆を行い、次に最上層構成元素からなる金属製ターゲット２による放電を開始し、金属ターゲット１と金属ターゲット２とにより同時に中間積層部を被覆する。次に、金属ターゲット１による被覆を停止し、金属ターゲット２により最上層を被覆するのである。以下、本発明を実施例に基づいて説明するが、本発明は実施例に限定されるものではない。
When the hard film of the present invention is coated by physical vapor deposition, the hard film coated member coated by the sputtering method and / or AIP method is particularly hard and has high adhesion and excellent adhesion strength, and excellent peeling and abnormal wear suppression. The effect of the present invention is easily obtained.
The hard coating is coated by sputtering and / or AIP. In the coating method, the composition of the metal target material used when coating the hard coating is different between the uppermost layer coating and the lowermost layer coating. During the coating, the vapor deposition source equipped with the target material for the uppermost layer coating and the vapor deposition source equipped with the target material for the lowermost layer coating are simultaneously operated and coated. By adopting this coating method, it is possible to obtain a hard film-coated member capable of exhibiting excellent wear resistance. As an example of the above-described coating method, the lowermost layer coating is first coated with the metal target 1 made of the lowermost layer constituent element, and then the discharge with the metal target 2 made of the uppermost layer constituent element is started. 1 and the metal target 2 simultaneously cover the intermediate laminated portion. Next, the coating with the metal target 1 is stopped, and the uppermost layer is coated with the metal target 2. EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example.
（実施例１）
本発明の硬質皮膜の被覆には、ＡＩＰ装置を用いた。図２に装置の概略図を示し、構成並びに被覆方法を述べる。装置構成は、減圧容器３と絶縁された複数のアーク放電式蒸発源４、５、６、７、基体ホルダー８よりなる。蒸発源４から７に硬質皮膜の金属成分となるターゲット１及び２を装着し、各蒸発源に所定の電流を供給してターゲット１及び２上でアーク放電を行い、金属ターゲット成分を蒸発しイオン化させ、減圧容器３と基体ホルダー８との間に負に印加したバイアス電圧により、基体９に被覆した。基体９は回転機構１０を有しており、１回転／分から１５回転／分の範囲で回転させた。即ち、ターゲット１の前面に基体９が対向した場合にターゲット１を含有した硬質皮膜が被覆され、ターゲット２の前面に基体９が対向した場合にターゲット２を含有した硬質皮膜が被覆される。この時、夫々のターゲット材成分を含有した窒化物を形成する場合は、窒素ガスを導入しながら放電した。
本発明の硬質皮膜特性を評価するために、組成が質量％で、Ｃｏ含有量１３．５％、残りＷＣ及び不可避不純物からなる超硬合金を用いて、ＪＩＳ規格ＳＮＧＡ４３２のインサートを製作した。この基体を脱脂洗浄し、基体ホルダー８に装填した。減圧容器３に設置された加熱用ヒーターにより、基体は５５０℃に加熱され、この状態を３０分間保持することにより加熱及び脱ガス処理を行った。続いて、減圧容器３にＡｒガスを導入し、減圧容器３に設置された熱フィラメントにより、Ａｒのイオン化を行った。基体に印加したバイアス電圧により、基体をＡｒイオンによるクリーニング処理を３０分間行った。ここで、硬質皮膜への炭素、酸素、窒素、硼素成分の添加方法は、反応ガスであるＮ２ガス、ＣＨ４ガス、Ｃ２Ｈ２ガス、Ａｒガス、Ｏ２ガス、ＣＯガス等から目的の皮膜組成が得られるようにガス種を選択し、被覆工程時に減圧容器３へ導入することによって可能である。また予め金属ターゲットに添加することによっても可能である。
Example 1
An AIP apparatus was used for coating the hard film of the present invention. FIG. 2 shows a schematic diagram of the apparatus, and the configuration and covering method will be described. The apparatus configuration includes a plurality of arc discharge evaporation sources 4, 5, 6, 7 and a substrate holder 8 that are insulated from the decompression vessel 3. Evaporation sources 4 to 7 are equipped with targets 1 and 2, which are metal components of the hard coating, and a predetermined current is supplied to each evaporation source to cause arc discharge on targets 1 and 2, thereby evaporating and ionizing the metal target components. Then, the substrate 9 was coated with a negative bias voltage applied between the decompression vessel 3 and the substrate holder 8. The substrate 9 has a rotation mechanism 10 and was rotated in the range of 1 to 15 rotations / minute. That is, when the substrate 9 is opposed to the front surface of the target 1, the hard coating containing the target 1 is coated, and when the substrate 9 is opposed to the front surface of the target 2, the hard coating containing the target 2 is coated. At this time, when forming a nitride containing each target material component, discharge was performed while introducing nitrogen gas.
In order to evaluate the hard film characteristics of the present invention, a JIS standard SNGA432 insert was manufactured using a cemented carbide having a composition of mass%, a Co content of 13.5%, the remaining WC and inevitable impurities. The substrate was degreased and cleaned and loaded into the substrate holder 8. The substrate was heated to 550 ° C. by a heating heater installed in the decompression vessel 3, and this state was maintained for 30 minutes for heating and degassing. Subsequently, Ar gas was introduced into the decompression vessel 3, and Ar was ionized by a hot filament installed in the decompression vessel 3. The substrate was cleaned with Ar ions for 30 minutes by a bias voltage applied to the substrate. Here, the method of adding carbon, oxygen, nitrogen, and boron components to the hard film is to obtain the desired film composition from N2 gas, CH4 gas, C2H2 gas, Ar gas, O2 gas, CO gas, etc., which are reaction gases. It is possible to select the gas species and introduce it into the decompression vessel 3 during the coating process. It is also possible to add to the metal target in advance.
本発明例１の硬質皮膜に使用したターゲット材は、粉末法で作成した金属製ターゲットである。本発明例１は、最下層被覆用ターゲット材１として、組成が原子％で、Ａｌ５５Ｔｉ４５を、アーク放電式蒸発源４、６に装着した。最上層被覆用ターゲット材２として、Ｔｉ７５Ｓｉ２５を、アーク放電式蒸発源５、７に装着した。
第１に、ターゲット材１を装着した蒸発源に２５Ｖ、１００Ａの電力を供給し、負バイアス電圧を５０Ｖ、反応ガス圧力を４Ｐａ、被覆基体温度を５００℃とし、基体ホルダー８を３回転／分とし、基体表面に約２００ｎｍの窒化物膜を被覆した。この時のターゲット材１の組成がＡｌ５５Ｔｉ４５であるのに対し、硬質皮膜組成における金属成分の組成は、Ａｌ５２Ｔｉ４８の窒化物であった。この硬質皮膜は本発明例１の最下層である。
第２に、中間積層部を、ターゲット材１を装着した蒸発源に２５Ｖ、１００Ａの電力を供給し、ターゲット材２を装着した蒸発源に２０Ｖ、６０Ａの電力を供給した。この状態で、ターゲット材１、２を装着した全ての蒸着源を同時に稼動させ窒化膜の被覆を開始した。そして、窒化膜の成膜条件を連続的に変化させていった。即ち、ターゲット材２を装着した蒸発源に供給する電流を被覆時間の経過と伴に６０Ａから段階的に１００Ａまで増加させ、同時にターゲット材１を装着した蒸発源の電流を被覆時間の経過と伴に１００Ａから段階的に６０Ａまで変化させて被覆を行った。被覆の間は、基体にはパルスバイアス電圧を印加した。その条件は負バイアス電圧を６０Ｖ、正バイアス電圧を１０Ｖ、周波数を２０ｋＨｚ、振幅を負側に８０％、正側に２０％、とした。全圧力は６Ｐａ、基体温度は５２５℃とし、被覆基体を保持する冶具は、６回転／分で回転させ、ターゲット材１、２の２種のターゲットから放出される夫々の窒化物の中間積層部を約１３００ｎｍ被覆した。
第３に、最上層を、ターゲット材１を装着した蒸発源への電力供給を止め、成膜条件を段階的に変化させた。パルスバイアス電圧の条件は、負バイアス電圧を８０Ｖ、正バイアス電圧を０Ｖ、周波数を１０ｋＨｚ、振幅を負側に９５％、正側に５％、とした。全圧力を５Ｐａ、基体温度を５００℃、基体回転数を３回転／分に設定変更し、ターゲット材２による窒化物ベースの皮膜を約１５００ｎｍ被覆した。第１〜第３の工程により得られた試料を本発明例１とした。本発明例１による硬質皮膜の中間積層部の層厚、皮膜構造、組成、結晶構造を確認した。オージェ電子分光（以下、ＡＥＳと言う。）分析により、マクロ領域における膜厚深さ方向の組成分析と、透過型電子顕微鏡（以下、ＴＥＭと言う。）によるナノ領域の解析を行った。
ＡＥＳ分析によるマクロ領域の膜厚深さ方向の組成分析方法について述べる。使用した装置は、ＰＨＩ社製６７０Ｘｉ型、走査型ＡＥＳ装置であり、加速電圧１０ｋＶ、試料電流１５ｎＡ、電子線プローブ径を０．１μｍ以下に設定し、Ａｒイオン銃により試料をエッチングしながら、マクロ領域の膜厚深さ方向の組成分析を行った。図３に、本発明例１の硬質皮膜について、ＡＥＳ分析によるマクロ領域の膜厚深さ方向の組成分析結果を示す。図３より本発明例１の硬質皮膜は、中間積層部のＳｉ含有量が層厚方向に異なり、表面側になる程Ｓｉ含有量が多くなっていることを確認した。中間積層部に約５０ｎｍから１００ｎｍの層厚で組成が異なっていることも確認できた。このような比較的大きな組成の異なる層厚の変化は、成膜装置におけるターゲット配置に影響を受けるものである。これは、皮膜の硬度等の性能を傾斜させることが可能である。このように、中間積層部に約５０ｎｍから１００ｎｍの層厚で組成が変調した層が存在する場合であっても、この組成が変調した層の中にＡ層とＢ層とから構成される０．５ｎｍ以上２０ｎｍ未満の積層部が存在すれば本発明の効果は発揮されるのである。
The target material used for the hard film of Example 1 of the present invention is a metal target prepared by a powder method. In Invention Example 1, as the lowermost layer covering target material 1, Al55Ti45 having a composition of atomic% was mounted on the arc discharge evaporation sources 4 and 6. Ti75Si25 was attached to the arc discharge evaporation sources 5 and 7 as the target material 2 for covering the uppermost layer.
First, power of 25 V and 100 A is supplied to the evaporation source on which the target material 1 is mounted, the negative bias voltage is 50 V, the reaction gas pressure is 4 Pa, the coated substrate temperature is 500 ° C., and the substrate holder 8 is rotated 3 times / minute. And a nitride film of about 200 nm was coated on the surface of the substrate. The composition of the target material 1 at this time was Al55Ti45, whereas the composition of the metal component in the hard film composition was Al52Ti48 nitride. This hard film is the lowermost layer of Example 1 of the present invention.
Secondly, in the intermediate laminated portion, power of 25 V and 100 A was supplied to the evaporation source on which the target material 1 was mounted, and power of 20 V and 60 A was supplied to the evaporation source on which the target material 2 was mounted. In this state, all the vapor deposition sources equipped with the target materials 1 and 2 were simultaneously operated to start the coating of the nitride film. And the film-forming conditions of the nitride film were changed continuously. That is, the current supplied to the evaporation source equipped with the target material 2 is gradually increased from 60 A to 100 A as the coating time elapses, and at the same time, the current of the evaporation source equipped with the target material 1 is increased along with the elapse of the coating time. The coating was carried out by changing from 100 A to 60 A stepwise. A pulse bias voltage was applied to the substrate during coating. The conditions were a negative bias voltage of 60 V, a positive bias voltage of 10 V, a frequency of 20 kHz, an amplitude of 80% on the negative side, and 20% on the positive side. The total pressure is 6 Pa, the substrate temperature is 525 ° C., the jig for holding the coated substrate is rotated at 6 revolutions / minute, and the intermediate laminates of the respective nitrides released from the two types of targets 1 and 2 are target materials. Was coated at about 1300 nm.
Third, for the uppermost layer, the power supply to the evaporation source on which the target material 1 was mounted was stopped, and the film formation conditions were changed stepwise. The conditions of the pulse bias voltage were as follows: the negative bias voltage was 80 V, the positive bias voltage was 0 V, the frequency was 10 kHz, the amplitude was 95% on the negative side, and 5% on the positive side. The total pressure was changed to 5 Pa, the substrate temperature was set to 500 ° C., and the rotation speed of the substrate was changed to 3 revolutions / minute. The sample obtained by the first to third steps was taken as Example 1 of the present invention. The layer thickness, film structure, composition and crystal structure of the intermediate laminated part of the hard film according to Example 1 of the present invention were confirmed. By Auger electron spectroscopy (hereinafter referred to as AES) analysis, composition analysis in the depth direction of the film thickness in the macro region and analysis of the nano region by a transmission electron microscope (hereinafter referred to as TEM) were performed.
A composition analysis method in the film thickness depth direction of the macro region by AES analysis will be described. The apparatus used is a 670Xi type, scanning AES apparatus manufactured by PHI, with an acceleration voltage of 10 kV, a sample current of 15 nA, and an electron beam probe diameter of 0.1 μm or less, while etching the sample with an Ar ion gun, Composition analysis in the direction of film thickness in the region was performed. FIG. 3 shows the result of composition analysis in the depth direction of the thickness of the macro region by AES analysis for the hard film of Example 1 of the present invention. From FIG. 3, it was confirmed that the hard coating of Example 1 of the present invention had a different Si content in the intermediate laminated portion in the layer thickness direction, and the Si content increased toward the surface side. It was also confirmed that the composition was different at a layer thickness of about 50 nm to 100 nm in the intermediate laminated portion. Such a change in layer thickness having a relatively large composition is affected by the target arrangement in the film forming apparatus. This can incline performance such as the hardness of the coating. Thus, even in the case where there is a layer whose composition is modulated with a layer thickness of about 50 nm to 100 nm in the intermediate laminated portion, the layer whose composition is modulated is composed of the A layer and the B layer. The effect of the present invention is exhibited if there is a laminated portion of 5 nm or more and less than 20 nm.
ＴＥＭによるナノ領域分析方法について説明する。組織観察に用いる試料準備の方法は、試料とダミー基板とをエポキシ樹脂を用いて接着し、切断、補強リング接着、研磨、ディンプリング、Ａｒイオンミーリングを行った。試料厚さが原子層厚さになる領域において、組織観察、格子像観察、φ１ｎｍ程度の微小部のＥＤＳ分析、微小部の電子線回折等を行い、組成及び組織構造を決定した。中間積層部の観察位置は、層厚方向における中央付近を観察した。分析装置は、日本電子製ＪＥＭ−２０１０Ｆ型の電解放射型透過型電子顕微鏡を用い、加速電圧２００ｋＶで組織観察を行った。微小部のＥＤＳ分析には、装置付属のノーラン製ＵＴＷ型Ｓｉ（Ｌｉ）半導体検出器を用いて、ナノメートルオーダーの積層膜の組成を決定した。このとき、半値幅１ｎｍの電子プローブを使用した。微小部電子線回折は、カメラ長を５０ｃｍ、ビーム径をφ１ｎｍに収束させ、ナノメートルオーダーの積層膜の結晶構造を同定した。 A nano-region analysis method using TEM will be described. As a sample preparation method used for tissue observation, a sample and a dummy substrate were bonded using an epoxy resin, and cutting, reinforcing ring bonding, polishing, dimple ringing, and Ar ion milling were performed. In the region where the sample thickness becomes the atomic layer thickness, the composition and the structure were determined by performing structure observation, lattice image observation, EDS analysis of a minute part of about φ1 nm, electron beam diffraction of the minute part, and the like. The observation position of the intermediate laminated part was observed near the center in the layer thickness direction. The analyzer used JEM-2010F type electrolytic emission transmission electron microscope manufactured by JEOL, and observed the structure at an acceleration voltage of 200 kV. For the EDS analysis of the minute part, the composition of the laminated film of nanometer order was determined using a Nolan UTW type Si (Li) semiconductor detector attached to the apparatus. At this time, an electron probe having a half width of 1 nm was used. Micro-electron beam diffraction focused the camera length to 50 cm and the beam diameter to 1 nm, and identified the crystal structure of the nanometer-order laminated film.
図４及び図５に本発明例１の走査透過電子顕微鏡法（以下、ＳＴＥＭと言う。）による皮膜組織の観察像を示す。図５は、図４とは別の視野を観察したものである。ＳＴＥＭ像は、組成によるコントラストの相違が明確に現れることから、結晶構造よりも組成の影響を考察することができる。図４、図５より、本発明例１の中間積層部は、数ナノの一定周期構造が確認され、各層の厚みが１５ｎｍ未満の積層構造となっていた。具体的な積層周期は、約４ｎｍから８ｎｍであることが確認できた。図４中の分析位置１から４、及び図５中の分析位置１から８に対応した、ＥＤＳ組成分析結果を表１に示す。 4 and 5 show observation images of the film structure by scanning transmission electron microscopy (hereinafter referred to as STEM) of Example 1 of the present invention. FIG. 5 shows a field of view different from that in FIG. The STEM image clearly shows the difference in contrast depending on the composition, so that the influence of the composition can be considered rather than the crystal structure. 4 and 5, the intermediate laminated part of Invention Example 1 was confirmed to have a constant periodic structure of several nanometers, and the thickness of each layer was a laminated structure of less than 15 nm. It was confirmed that the specific lamination period was about 4 nm to 8 nm. Table 1 shows the EDS composition analysis results corresponding to the analysis positions 1 to 4 in FIG. 4 and the analysis positions 1 to 8 in FIG.
図４の分析位置１と３とが同一層であり、分析位置２と４とが同一層である。また図５の分析位置１から４とが同一層であり、分析位置５から８とが同一層である。表１より、図４の分析位置１と３とを含む層、及び図５の分析位置１から４を含む層が中間積層部のＡ層に相当し、図４の分析位置２と４とを含む層、及び図５の分析位置５から８を含む層がＢ層に相当している。本発明例１のＡ層のＡｌ含有量は、金属元素のみの原子％で、約１０％から２０原子％に対し、Ｂ層は、約３０％から４３％であった。ここで注目すべきは、Ａ層とＢ層とは回転機構を有した基体ホルダーに設置されているため、理論的には、ターゲット材１の前面に基体ホルダーが近付いたときに、ターゲット材１成分の窒化物が被覆され、ターゲット材２前面に基体ホルダーが近付いたときに、ターゲット材２成分の窒化物が被覆されるべきである。しかし実際には、ターゲット材１成分と、ターゲット材２成分との相互拡散層となっていたことである。これは、数ナノレベルの層厚で基体に被覆された皮膜は、次の数ナノレベル層が成膜された後、若しくはその成膜中に、層間で両金属成分による相互拡散が起こっているのである。この相互拡散による層間結合が優れた層間結合強度をもたらし、中間積層部が高硬度化を有した状態で被覆されるため、その直上に最上層となる高硬度を有するＳｉ含有皮膜を被覆することを可能にし、優れた耐摩耗性を発揮するのである。
ＥＤＳ分析は、実際には試料を透過する際にビームが広がり、Ｘ線が発生する領域は更に広がると考えられるが、結果として得られている情報は２ｎｍ未満であると考えられ、２ｎｍ以上の層厚であればＥＤＳ分析による組成定量分析は可能である。また、膜厚深さ方向の情報はすべて含まれるものと考えられるが、試料厚さが原子層厚さであることより、粒子そのものの情報であると考えられる。また、一般的に試料が薄くなると得られるＸ線のカウント数が少なくなるため、定量精度は悪くなると考えられるが、精々２％未満のバラツキ範囲であった。
Analysis positions 1 and 3 in FIG. 4 are the same layer, and analysis positions 2 and 4 are the same layer. Further, analysis positions 1 to 4 in FIG. 5 are the same layer, and analysis positions 5 to 8 are the same layer. From Table 1, the layer including the analysis positions 1 and 3 in FIG. 4 and the layer including the analysis positions 1 to 4 in FIG. 5 correspond to the A layer of the intermediate laminated portion, and the analysis positions 2 and 4 in FIG. The layer including the analysis position 5 to 8 in FIG. 5 corresponds to the B layer. The Al content of the A layer of Example 1 of the present invention was about 10% to 20 atomic% in the atomic% of only the metal element, whereas the B layer was about 30% to 43%. It should be noted here that the A layer and the B layer are installed on the substrate holder having a rotation mechanism, so that theoretically, when the substrate holder comes close to the front surface of the target material 1, the target material 1 When the component nitride is coated and the substrate holder approaches the front surface of the target material 2, the nitride of the target material 2 component should be coated. However, in actuality, this is an interdiffusion layer of the target material 1 component and the target material 2 component. This is because the film coated on the substrate with a layer thickness of several nanometers causes interdiffusion between the two metal components between the layers after the next several nanometer layers are formed or during the film formation. It is. The interlayer bonding by this interdiffusion provides excellent interlayer bonding strength, and the intermediate laminated part is coated with a high hardness, so that a Si-containing film having a high hardness as the uppermost layer is coated immediately above it. And exhibits excellent wear resistance.
In the EDS analysis, the beam actually spreads when passing through the sample, and the region where X-rays are generated is considered to be further widened. However, the information obtained as a result is considered to be less than 2 nm. If it is a layer thickness, composition quantitative analysis by EDS analysis is possible. In addition, it is considered that all the information in the depth direction of the film thickness is included, but since the sample thickness is the atomic layer thickness, it is considered that the information is the particle itself. In general, the thinner the sample, the smaller the number of X-rays that can be obtained, so the accuracy of quantification is thought to be worse, but it was in the range of less than 2% at most.
図６は、図４と同一視野のＴＥＭによる観察像を示す。図６より、図４で確認された数ナノ層厚の界面は確認されず、更にＡ層とＢ層との界面の格子に連続性が認められた。この場合、特に高硬度で密着強度に優れた硬質皮膜が得られる。図７、図８は、図６の分析位置１及び２に対応した微小部電子線回折結果を示す。図７は図６の分析位置１、即ちＡ層に相当する位置の層微小部電子線回折結果を示す。図８は、図６の分析位置２、即ちＢ層に相当する位置の微小部電子線回折結果を示す。Ａ層及びＢ層の結晶構造は、ｆｃｃ構造であり、全く同じ結晶構造を示した。図９は、最上層のＳｉを多く含有したナノ領域の微小部電子線回折結果を示す。図９より最上層には非晶質相を含有していることを確認した。即ち、数ナノレベルで積層により、中間積層部のＳｉ含有皮膜は結晶質であり、一方、最上層のＳｉ含有皮膜は非晶質構造を示し、本質的に異なる特性を有していた。 FIG. 6 shows an observation image by TEM having the same field of view as FIG. From FIG. 6, the interface of several nanolayer thickness confirmed in FIG. 4 was not confirmed, and continuity was observed in the lattice at the interface between the A layer and the B layer. In this case, a hard film having a particularly high hardness and excellent adhesion strength can be obtained. 7 and 8 show the microscopic electron diffraction results corresponding to the analysis positions 1 and 2 in FIG. FIG. 7 shows a result of electron microdiffraction of the layer minute portion at the analysis position 1 in FIG. FIG. 8 shows the microscopic electron beam diffraction results at the analysis position 2 in FIG. The crystal structures of the A layer and the B layer were fcc structures, and the crystal structures were exactly the same. FIG. 9 shows a micro-electron diffraction result of a nano region containing a large amount of Si in the uppermost layer. From FIG. 9, it was confirmed that the uppermost layer contained an amorphous phase. That is, due to lamination at several nanometers, the Si-containing film in the intermediate laminated part was crystalline, while the uppermost Si-containing film exhibited an amorphous structure and had essentially different characteristics.
本発明例１の皮膜について、最上層、中間積層部及び最下層の夫々の層のＴＨＡ、ＭＨＡ、ＢＨＡ、ＴＥＬ、ＭＥＬ、ＢＥＬ、及びＴＲ、ＭＲ、ＢＲを各１０箇所測定した。測定結果を図１０、図１１に示す。図１０及び図１１に示すように、縦軸の硬度は、ＴＨＡ≧ＭＨＡ≧ＢＨＡの関係を示した。図１０では横軸の弾性係数ＴＥＬ、ＭＥＬ、ＢＥＬは、ＴＥＬ≦ＭＥＬ≦ＢＥＬの関係を示し、図１１では横軸の弾性回復率ＴＲ、ＭＲ、ＢＲが、ＴＲ≧ＭＲ≧ＢＲの関係を示した。上記の様な場合、硬質皮膜の構造として最適である。この理由は、Ｓｉ含有皮膜の高硬度化でき、しかも、硬質皮膜の最上層として、剥離や異常摩耗を抑制する高硬度Ｓｉ含有皮膜をバランスよく被覆することが可能となるからである。 With respect to the film of Inventive Example 1, THA, MHA, BHA, TEL, MEL, BEL, and TR, MR, and BR were measured for each of the uppermost layer, the intermediate laminated portion, and the lowermost layer. The measurement results are shown in FIGS. As shown in FIGS. 10 and 11, the hardness on the vertical axis shows a relationship of THA ≧ MHA ≧ BHA. In FIG. 10, the elastic coefficients TEL, MEL, and BEL on the horizontal axis indicate the relationship of TEL ≦ MEL ≦ BEL, and in FIG. 11, the elastic recovery rates TR, MR, and BR on the horizontal axis indicate the relationship of TR ≧ MR ≧ BR. It was. In such a case, the structure of the hard film is optimal. This is because it is possible to increase the hardness of the Si-containing coating, and to coat the high-hardness Si-containing coating that suppresses peeling and abnormal wear with a good balance as the uppermost layer of the hard coating.
（実施例２）
実施例１と略同様な手法を用い、表２に示す各種ターゲット材を用いて硬質皮膜を被覆し、皮膜の評価及び、硬質皮膜を切削工具に適用した場合の評価を行った。硬質皮膜の評価結果を表３に示し、硬質皮膜を切削工具に適用した場合の評価結果を表４に示した。
(Example 2)
Using a method substantially similar to that of Example 1, a hard coating was coated using various target materials shown in Table 2, and the coating was evaluated and evaluated when the hard coating was applied to a cutting tool. Table 3 shows the evaluation results of the hard film, and Table 4 shows the evaluation results when the hard film was applied to the cutting tool.
表２に示す蒸発源４、５、６、７には夫々所定の組成を有するターゲット材を装着し、図２の様に減圧容器に配置した。ここで、４と６及び５と７とは夫々対向して配置した。表３に最下層の組成、中間積層部のＡ層、Ｂ層、必要に応じて他層の組成、積層硬質皮膜の積層周期、相互拡散の有無、格子連続性の有無、最上層の組成、硬質皮膜表面から測定した硬度を示す。中間積層部の各層の組成は、実施例１と同様にＴＥＭ−ＥＤＳ分析により決定した。積層周期の確認は、ＳＴＥＭによる観察像から実測し、格子連続性はＴＥＭ格子像から確認した。硬度測定は、試料表面を平滑にするためにダイヤモンド粒子を含有したバフにより、５秒間平滑化処理したものを用い、ナノインデンテーションにより、押込み荷重４９ｍＮで１０点測定し、その平均値を記載した。最下層、最上層の組成は、電子プローブマイクロアナライザ（ＥＰＭＡ）分析、エネルギー分散型Ｘ線分光（ＥＤＸ）分析、又は透過型電子顕微鏡付属のＥＤＳ分析、電子エネルギー損失分光（ＥＥＬＳ）分析によっても可能であり、更に、ラザフォード後方散乱（ＲＢＳ）分析法、電子分光（ＸＰＳ）分析法、ＡＥＳ分析法等の深さ方向分析により、総合的に決定することも可能である。切削寿命評価用のエンドミルは、Ｃｏ含有量が８質量％の微粒超硬合金製、径はφ１０ｍｍの２枚刃ボールエンドミルを用いた。本発明の試料の成膜条件は、特に記載がない限り、実施例１に準ずる。 The evaporation sources 4, 5, 6, and 7 shown in Table 2 were each mounted with a target material having a predetermined composition, and placed in a vacuum container as shown in FIG. Here, 4 and 6 and 5 and 7 are arranged to face each other. In Table 3, the composition of the lowest layer, the A layer and B layer of the intermediate laminated part, the composition of other layers as required, the lamination cycle of the laminated hard film, the presence or absence of mutual diffusion, the presence or absence of lattice continuity, The hardness measured from the surface of the hard coating is shown. The composition of each layer in the intermediate laminated portion was determined by TEM-EDS analysis in the same manner as in Example 1. The stacking period was confirmed from an observation image by STEM, and lattice continuity was confirmed from a TEM lattice image. The hardness was measured using a buff containing diamond particles to smooth the surface of the sample for 5 seconds, measured by nanoindentation at 10 points with an indentation load of 49 mN, and the average value was described. . The composition of the lowermost layer and the uppermost layer is also possible by electron probe microanalyzer (EPMA) analysis, energy dispersive X-ray spectroscopy (EDX) analysis, EDS analysis with transmission electron microscope, electron energy loss spectroscopy (EELS) analysis Furthermore, it can be determined comprehensively by depth direction analysis such as Rutherford backscattering (RBS) analysis method, electron spectroscopy (XPS) analysis method, AES analysis method and the like. As the end mill for evaluating the cutting life, a two-blade ball end mill made of a fine cemented carbide having a Co content of 8% by mass and having a diameter of φ10 mm was used. The film forming conditions of the sample of the present invention are in accordance with Example 1 unless otherwise specified.
本発明の硬質皮膜被覆部材の耐摩耗性を評価するために、主な適用例としてエンドミルの性能評価を行った。評価は切削長１９０ｍにおける最大逃げ面摩耗幅を測定した。切削条件を以下に示す。
（エンドミル性能評価条件）
工具 ：超硬合金製２枚刃ボールエンドミル
被削材 ：熱間金型鋼、ＹＸＲ３３、硬さＨＲＣ５８
工具回転数：８０００回転／分
１刃当りの送り量：０．１２５ｍｍ／刃
軸方向切込み量 ：０．２ｍｍ
ピックフィード ：０．４ｍｍ
加工方法 ：乾式切削加工、底面切削、１方向ダウンカット
切削長 ：１９０ｍ
In order to evaluate the wear resistance of the hard film-coated member of the present invention, end mill performance was evaluated as a main application example. The evaluation was performed by measuring the maximum flank wear width at a cutting length of 190 m. The cutting conditions are shown below.
(End mill performance evaluation conditions)
Tool: Cemented carbide 2-flute ball end mill Work material: Hot die steel, YXR33, Hardness HRC58
Tool rotation speed: 8000 revolutions / minute Feed amount per blade: 0.125 mm / tooth Axial cutting depth: 0.2 mm
Pick feed: 0.4mm
Processing method: Dry cutting, bottom cutting, one-way down cut Cutting length: 190m
本発明例１から１４について述べる。表４に示す様に、本発明の硬質皮膜を被覆した工具は高硬度を示し、層間の密着強度に特に優れ、硬度と靭性がバランス良く構成されているため、工具の折損やチッピングが起こり難く、工具として使用した場合、格段に耐摩耗性に優れる結果となった。
本発明例１は、実施例１により作成した試料を示し、皮膜の硬度が高く、工具に適用した場合、耐摩耗性に特に優れ好ましい被覆形態である。本発明例１の様に、中間積層部の上層側に最上層を被覆することによって、高硬度を示し、耐摩耗性に優れていた。一方、従来例２６、従来例２７の様に、同一組成の最上層を被覆しても、高硬度な特性が得られず、耐摩耗性の改善は見られなかった。本発明例２は、ＡｌＣｒ系ターゲット材とＴｉＳｉ系ターゲット材を使用した場合を示す。ＴｉＡｌ系ターゲット材と同様に、耐摩耗性の改善が確認された。本発明例３は、ＡｌＣｒＳｉ系ターゲット材とＣｒＳｉ系ターゲット材を使用した場合を示す。耐摩耗性の改善が確認された。本発明例４は、蒸発源４及び蒸発源６にＡｌＴｉ系ターゲット、蒸発源５にＴｉＳｉ系ターゲット、蒸発源７にＡｌＳｉ系ターゲットを設置した場合を示す。最下層の成膜には、蒸発源４若しくは蒸発源６を用いて被覆し、中間積層部の成膜には、蒸発源５と蒸発源７とを同時に用いて被覆し、最上層の成膜には、蒸発源５を用いて被覆を行った。この場合、最上層が特に高硬度化されており、耐摩耗性が改善された。本発明例４は、ボールエンドミル以外の他の工具、例えばスクエアエンドミル、ドリルにおいても耐摩耗性の改善効果は優れていた。本発明例５、本発明例６、本発明例７は、最下層、中間積層部、最上層において夫々の膜厚の設定値が異なる場合である。何れの場合も、耐摩耗性は大幅に改善された。膜厚構成としては、特にボールエンドミルに対しては、本発明例１の膜厚設定が最も良好であった。一方、他の工具、例えばスクエアエンドミル及びドリルに関しては、本発明例７の膜厚構成が良好な耐摩耗性を示した。本発明例８は、本発明例１と同様に中間積層部のＳｉ含有量が層厚表面側方向に高くなる様に傾斜させた場合を示す。この様な処理によって最上層の硬度をより向上させることができ、耐摩耗性に特に優れていた。本発明例９は、ＡｌＴｉ系ターゲットを装着した蒸発源をＡＩＰ法、ＴｉＳｉ系ターゲットを装着した蒸発源をスパッタリング法とし、併用した場合を示す。また本発明例１０は、蒸発源にスパッタリング蒸発源を採用した場合を示す。成膜中の減圧容器内雰囲気は、ＡｒガスとＮ２ガスの雰囲気とした。ＡｒガスとＮ２ガスとの流量比は、Ａｒを９０％、Ｎ２を１０％とし、全体の圧力を０．５Ｐａに設定した。スパッタ蒸発源には９ｋＷの電力を供給した。その他の被覆条件は、実施例１に準じた。この場合もＡＩＰ法単独の場合と同様に、優れた耐摩耗性を示した。本発明例１２は、最上層の５００ｎｍ以内の範囲に酸素を含有する場合であり、耐凝着性に優れた。また、ドリルの耐摩耗性改善効果が大きかった。本発明例１２は、最上層の硬度が６２ＧＰａの場合を示す。このような高硬度膜を被覆しても、剥離や異常摩耗の発生も確認されず、耐摩耗性に優れていた。本発明例１３は、パルスバイアス電圧の条件について、負バイアス電圧を６０Ｖから２００Ｖへ増加させ、正バイアス電圧を１０Ｖ、周波数を２０ｋＨｚ、振幅を負側に８０％、正側に２０％、とした場合を示す。この時、表面から測定した硬度が７５ＧＰａと言う更に高硬度を示した。最上層にこのような高硬度の皮膜を被覆した場合でも、皮膜の密着強度は確保され、剥離や異常摩耗の発生も確認されず、耐摩耗性に優れていた。
Examples 1 to 14 of the present invention will be described. As shown in Table 4, the tool coated with the hard coating of the present invention exhibits high hardness, particularly excellent adhesion strength between layers, and is configured with a good balance between hardness and toughness, so that tool breakage and chipping are unlikely to occur. When used as a tool, the result was extremely excellent wear resistance.
Invention Example 1 shows a sample prepared according to Example 1, has a high coating hardness, and is a preferred coating form that is particularly excellent in wear resistance when applied to a tool. As in Example 1 of the present invention, the uppermost layer was coated on the upper layer side of the intermediate laminated portion, thereby exhibiting high hardness and excellent wear resistance. On the other hand, as in Conventional Example 26 and Conventional Example 27, even when the uppermost layer having the same composition was coated, high hardness characteristics were not obtained, and no improvement in wear resistance was observed. Invention Example 2 shows the case where an AlCr-based target material and a TiSi-based target material are used. Similar to the TiAl-based target material, improvement in wear resistance was confirmed. Invention Example 3 shows a case where an AlCrSi-based target material and a CrSi-based target material are used. Improvement of wear resistance was confirmed. Inventive Example 4 shows a case where an AlTi target is installed in the evaporation source 4 and the evaporation source 6, a TiSi target is installed in the evaporation source 5, and an AlSi target is installed in the evaporation source 7. The lowermost layer is formed by using the evaporation source 4 or the evaporation source 6, and the intermediate layer is formed by simultaneously using the evaporation source 5 and the evaporation source 7, and the uppermost layer is formed. For this, the evaporation source 5 was used for coating. In this case, the uppermost layer was particularly hardened, and the wear resistance was improved. Invention Example 4 was excellent in the effect of improving wear resistance in tools other than the ball end mill, such as a square end mill and a drill. Inventive Example 5 , Inventive Example 6 , and Inventive Example 7 , the set values of the film thicknesses are different in the lowermost layer, the intermediate laminated portion, and the uppermost layer. In either case, the wear resistance was greatly improved. As the film thickness configuration, the film thickness setting of Example 1 of the present invention was the best, particularly for the ball end mill. On the other hand, with respect to other tools such as a square end mill and a drill, the film thickness configuration of Invention Example 7 showed good wear resistance. Inventive Example 8 shows a case where the Si content in the intermediate laminated portion is inclined so as to increase in the layer thickness surface side direction as in Inventive Example 1. By such treatment, the hardness of the uppermost layer can be further improved and the wear resistance is particularly excellent. Invention Example 9 shows a case where an evaporation source equipped with an AlTi-based target is an AIP method and an evaporation source equipped with a TiSi-based target is a sputtering method and used in combination. In addition, Example 10 of the present invention shows a case where a sputtering evaporation source is employed as the evaporation source. The atmosphere in the vacuum container during film formation was an atmosphere of Ar gas and N 2 gas. The flow rate ratio between Ar gas and N2 gas was 90% for Ar, 10% for N2, and the overall pressure was set to 0.5 Pa. A power of 9 kW was supplied to the sputter evaporation source. Other coating conditions were in accordance with Example 1. In this case, as in the case of the AIP method alone, excellent wear resistance was exhibited. Invention Example 12 is a case where oxygen is contained in a range of 500 nm or less of the uppermost layer, and was excellent in adhesion resistance. Moreover, the wear resistance improvement effect of the drill was great. Invention Example 12 shows a case where the hardness of the uppermost layer is 62 GPa. Even when such a high-hardness film was coated, neither peeling nor abnormal wear was confirmed, and the wear resistance was excellent. In Example 13 , the negative bias voltage was increased from 60 V to 200 V, the positive bias voltage was 10 V, the frequency was 20 kHz, the amplitude was 80% on the negative side, and 20% on the positive side. Show the case. At this time, the hardness measured from the surface showed a higher hardness of 75 GPa. Even when such a high-hardness film was coated on the uppermost layer, the adhesion strength of the film was ensured, and no occurrence of peeling or abnormal wear was confirmed, and the wear resistance was excellent.
次に比較例１４から２０について述べる。比較例の被覆条件は、実施例１より適宜条件等を変更した。比較例１４は、中間積層部のＡ層、Ｂ層ともにＡｌ含有量が金属元素のみの原子％で、４０％から５０％の範囲にあり、この影響で最上層の硬質皮膜が高硬度化されず、耐摩耗効果は確認されなかった。比較例１５は、中間積層部が存在しない場合を示す。比較例１４同様に最上層の硬質皮膜の硬度を向上させることができず、耐摩耗効果は確認されなかった。比較例１６は、中間積層部の積層周期が３０ｎｍから４０ｎｍの場合を示す。最上層の硬質皮膜の硬度が不十分であり、中間積層部の層間で相互拡散が確認されないことも影響して、耐摩耗性の改善は確認されなかった。比較例１７は、最上層の硬質皮膜のＳｉ含有量が金属元素のみの原子％で３８％となった。Ｓｉ含有量が３０％を超えたため、最上層の硬度上昇が確認されず、耐摩耗性を改善するには至らなかった。比較例１８は、最上層のＳｉ含有量が金属元素のみの原子％で３％となった。Ｓｉ含有量が１０％未満となったため、耐摩耗性改善効果は確認されなかった。比較例１９は、最上層が存在しない場合を示す。最下層、中間積層部は本発明で規定する範囲内の硬質皮膜であるが、最上層が無い場合は、耐摩耗性を改善することはできない。比較例２０は、最下層が存在しない場合を示す。中間積層部、最上層は本発明で規定する範囲内の硬質皮膜であるが、最下層が無い場合は、耐摩耗性のばらつきが大きく安定した耐摩耗性を示さないため、満足のいく結果が得られなかった。
Next, Comparative Examples 14 to 20 will be described. The coating conditions of the comparative example were changed as appropriate from Example 1. In Comparative Example 14 , the Al content of both the A layer and the B layer in the intermediate laminated portion is an atomic% of the metal element only, and is in the range of 40% to 50%. Further, the wear resistance effect was not confirmed. The comparative example 15 shows the case where an intermediate | middle laminated part does not exist. As in Comparative Example 14 , the hardness of the uppermost hard film could not be improved, and the wear resistance effect was not confirmed. Comparative Example 16 shows a case where the lamination period of the intermediate laminated part is 30 nm to 40 nm. The hardness of the uppermost hard film was insufficient, and the fact that interdiffusion was not confirmed between the layers of the intermediate laminated portion was also affected, so improvement in wear resistance was not confirmed. In Comparative Example 17 , the Si content of the uppermost hard film was 38% in terms of atomic% of only the metal element. Since the Si content exceeded 30%, the increase in hardness of the uppermost layer was not confirmed, and the wear resistance was not improved. In Comparative Example 18 , the Si content in the uppermost layer was 3% in terms of atomic% of only the metal element. Since the Si content was less than 10%, the effect of improving wear resistance was not confirmed. Comparative Example 19 shows a case where the uppermost layer does not exist. The lowermost layer and the intermediate laminated portion are hard coatings within the range defined by the present invention, but if there is no uppermost layer, the wear resistance cannot be improved. The comparative example 20 shows the case where the lowest layer does not exist. The intermediate laminated portion and the uppermost layer are hard coatings within the range specified in the present invention, but when there is no lowermost layer, the variation in wear resistance is large and stable wear resistance is not exhibited, so a satisfactory result is obtained. It was not obtained.
従来例２１から２９について述べる。従来例による被覆は、従来技術に記載された被覆条件を参考にした。従来例２１は、ＴｉＮを最下層とし、その上層側に（ＴｉＡｌ）Ｎ系皮膜を被覆した場合、従来例２２は、（ＴｉＡｌ）Ｎ皮膜の単一層の場合、従来例２３は、（ＡｌＣｒＳｉ）Ｎ系皮膜の単一層の場合、従来例２４は（ＴｉＳｉ）Ｎ系皮膜単一層の場合を示す。切削初期に硬質皮膜の剥離が認められ、最大逃げ面摩耗幅は０．２ｍｍを超えて大きくなった。従来例２５は、（ＴｉＡｌ）Ｎ系皮膜の上層側に（ＴｉＳｉ）Ｎ系皮膜を被覆した場合を示す。（ＴｉＡｌ）Ｎ系単一層の場合に比べ、耐摩耗性が改善されているものの、最大逃げ面摩耗幅は０．１９ｍｍと大きかった。従来例２６は、（ＴｉＡｌ）Ｎ系皮膜の上層側に（ＴｉＳｉ）Ｎ系皮膜を被覆した場合を示す。自己破壊を起こさない程度に負バイアス電圧を高くし、（ＴｉＳｉ）Ｎ系皮膜の硬度を向上させた場合である。ボールエンドミルによる耐摩耗性の評価では、従来例２５に比べ、多少硬度向上の効果が確認された。従来例２７は、ＴｉＮを最下層とし、その上層側に（ＴｉＳｉ）Ｎ系皮膜と（ＴｉＣｒ）Ｎ系皮膜を積層周期５ｎｍで被覆した積層皮膜の場合、従来例２８は、（ＴｉＡｌ）Ｎ系の積層皮膜の場合、従来例２９は、（ＴｉＡｌＳｉ）Ｎ系皮膜と（ＴｉＳｉ）Ｎ系皮膜の積層膜の場合を示す。何れの場合も最大逃げ面摩耗幅は０．２ｍｍを超えて大きくなった。
Conventional examples 21 to 29 will be described. The coating according to the conventional example was based on the coating conditions described in the prior art. Conventional Example 21 has TiN as the lowermost layer, and (TiAl) N-based coating is coated on the upper layer side. Conventional Example 22 is a single layer of (TiAl) N coating, and Conventional Example 23 is (AlCrSi). In the case of a single layer of N-based film, Conventional Example 24 shows the case of a single layer of (TiSi) N-based film. Peeling of the hard coating was observed at the beginning of cutting, and the maximum flank wear width was larger than 0.2 mm. Conventional Example 25 shows a case where a (TiSi) N-based coating is coated on the upper layer side of a (TiAl) N-based coating. Although the wear resistance was improved as compared with the (TiAl) N-based single layer, the maximum flank wear width was as large as 0.19 mm. Conventional Example 26 shows a case where a (TiSi) N-based coating is coated on the upper layer side of a (TiAl) N-based coating. This is a case where the negative bias voltage is increased to such an extent that self-destruction does not occur and the hardness of the (TiSi) N-based film is improved. In the evaluation of the wear resistance by the ball end mill, the effect of improving the hardness was confirmed as compared with the conventional example 25 . Conventional Example 27 is a laminated film in which TiN is the lowermost layer and (TiSi) N-based film and (TiCr) N-based film are coated on the upper layer side with a lamination period of 5 nm. Conventional Example 28 is a (TiAl) N-based film. In the case of the laminated film, Conventional Example 29 shows the case of a laminated film of a (TiAlSi) N-based film and a (TiSi) N-based film. In any case, the maximum flank wear width was larger than 0.2 mm.
１：最下層被覆用のターゲット材
２：最上層被覆用のターゲット材
３：減圧容器
４：蒸発源
５：蒸発源
６：蒸発源
７：蒸発源
８：基体ホルダー
９：基体
１０：回転機構
1: Target material for lowermost layer coating 2: Target material for uppermost layer coating 3: Depressurized container 4: Evaporation source 5: Evaporation source 6: Evaporation source 7: Evaporation source 8: Substrate holder 9: Substrate 10: Rotating mechanism
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2004
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023090620A1 (en) * | 2021-11-19 | 2023-05-25 | 한국야금 주식회사 | Cutting tool having hard coating with excellent wear resistance and toughness |
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