JP2010106311A - Formed article with hard multilayer film and method for producing the same - Google Patents
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本発明は、自動車部品等の耐摩耗性機械部品等において、特に基材として鉄系材料に対して良好な密着性を示すと共に、優れた耐摩耗性を有するダイヤモンドライクカーボン膜を表面層とする硬質多層膜成形体、およびその製造方法に関する。 The present invention provides a surface layer made of a diamond-like carbon film that exhibits excellent adhesion to an iron-based material as a base material and has excellent wear resistance in wear-resistant machine parts such as automobile parts. The present invention relates to a molded article of a hard multilayer film and a manufacturing method thereof.
硬質カーボン膜は、一般にダイヤモンドライクカーボン（以下、ＤＬＣと記す）と呼ばれている硬質膜である。硬質カーボンはその他にも、硬質非晶質炭素、無定形炭素、硬質無定形型炭素、ｉ−カーボン、ダイヤモンド状炭素等、様々な呼称があるが、これらの用語は明確に区別されていない。 The hard carbon film is a hard film generally called diamond-like carbon (hereinafter referred to as DLC). In addition, hard carbon has various names such as hard amorphous carbon, amorphous carbon, hard amorphous carbon, i-carbon, diamond-like carbon, etc., but these terms are not clearly distinguished.
このような用語が用いられるＤＬＣの本質は、構造的にはダイヤモンドとグラファイトが混ざり合った両者の中間構造を有するものであり、ダイヤモンドと同等に硬度が高く、耐摩耗性、固体潤滑性、熱伝導性、化学安定性等に優れることから、例えば、金型・工具類、耐摩耗性機械部品、研磨材、摺動部材、磁気・光学部品等の保護膜として利用されつつある。こうしたＤＬＣ膜を形成する方法として、スパッタリング法やイオンプレーティング法等の物理的蒸着（以下、ＰＶＤと記す）法、および化学的蒸着（以下、ＣＶＤと記す）法等が採用されているが、通常ＤＬＣ膜は膜形成時に極めて大きな内部応力が発生し、また高い硬度およびヤング率を持つ反面、変形能が極めて小さいことから、基材との密着性が弱く、剥離しやすい等の欠点を持っている。 The essence of DLC in which such terms are used is structurally an intermediate structure in which diamond and graphite are mixed, and has the same hardness as diamond, wear resistance, solid lubricity, heat Because of its excellent conductivity and chemical stability, it is being used as a protective film for molds / tools, wear-resistant mechanical parts, abrasives, sliding members, magnetic / optical parts, and the like. As a method for forming such a DLC film, a physical vapor deposition (hereinafter referred to as PVD) method such as a sputtering method or an ion plating method, a chemical vapor deposition (hereinafter referred to as CVD) method, or the like is employed. In general, DLC films generate extremely large internal stress during film formation, and have high hardness and Young's modulus, but their deformability is extremely small, so they have weaknesses such as poor adhesion to the substrate and easy peeling. ing.
基材との密着性を改良する手段として、（１）膜応力を制御する方法、（２）基材と炭素膜の間に中間層を設ける方法の２つが挙げられる。しかしながら、これらの技術では、以下に示す問題があり、改善されることが望まれているのが実情である。まず、上記（１）の方法では、基本的には基材とＤＬＣ膜を組織および機械的特性において両者の中間的な層を持つ層をもって糊付け層として結合するという観点から、その中間層として硬質の脆性材料を含むものを採用するものであるが、上記ＰＶＤ法やＣＶＤ法によって成膜されたＤＬＣ膜における巨大な内部応力によって、特に数μｍにおよぶ厚膜を形成した場合やダイヤモンド成分の多い硬度４０ＧＰａをこえるような硬い膜を形成した場合には、密着性不良の問題は顕著である。 As means for improving the adhesion to the substrate, there are two methods: (1) a method for controlling the film stress, and (2) a method for providing an intermediate layer between the substrate and the carbon film. However, these techniques have the following problems, and it is actually desired to be improved. First, in the method of (1), basically, the intermediate layer and the DLC film are hard as an intermediate layer from the viewpoint of bonding a layer having an intermediate layer between the two in terms of structure and mechanical properties. However, when the DLC film formed by the PVD method or the CVD method has a large internal stress, a thick film having a thickness of several μm is formed, or there is a large amount of diamond components. When a hard film having a hardness exceeding 40 GPa is formed, the problem of poor adhesion is significant.
この問題に対して、スクラッチ試験において５０Ｎ以上の密着性を示すＤＬＣ膜を最表面層とするＤＬＣ硬質多層膜成形体がが知られている（特許文献１参照）。この技術はＤＬＣ膜を最表面層とし、基材と最表面層の間の中間層として、Ｗ、Ｔａ、ＭｏおよびＮｂからなる群から選択される１種類以上の金属元素と炭素を含む非晶質層からなる最表面層側の第２層からなる２層構造としたＤＬＣ硬質多層膜成形体に関するものである。そして、こうした膜構造を有するＤＬＣ硬質多層膜成形体では、ＷＣ−Ｃｏ等の超硬合金製基材に対するＤＬＣ膜の良好な密着性が提示されている。しかしながら、この技術においても以下のような解決すべき問題があった。 In order to solve this problem, there is known a DLC hard multilayer film molded body having a DLC film having an adhesion of 50 N or more in a scratch test as an outermost surface layer (see Patent Document 1). This technique uses a DLC film as the outermost surface layer, and an amorphous layer containing one or more metal elements selected from the group consisting of W, Ta, Mo, and Nb and carbon as an intermediate layer between the base material and the outermost surface layer. The present invention relates to a DLC hard multilayer film molded body having a two-layer structure composed of a second layer on the outermost surface layer side composed of a porous layer. And in the DLC hard multilayer film molding having such a film structure, good adhesion of the DLC film to a substrate made of a cemented carbide such as WC-Co is presented. However, this technique also has the following problems to be solved.
上記技術は、基本的にＷＣ−Ｃｏ基材等の超硬合金を基材として使用する場合を想定しており、上記ＷＣ−Ｃｏ系超硬合金およびＳｉやＡｌ２Ｏ３等の絶縁材を基材として用いた場合には、上記中間層は基材との良好な密着性を確保できたのであるが、高速度工具鋼のような鉄系材料を基材として用いた場合には、上記中間層と基材の相性が必ずしも良好であるとは限らず、中間層と基材の間で密着性が悪くなり、ＤＬＣ膜の剥離が生じやすいという問題があった。また、耐摩耗性に優れる最上層ＤＬＣ膜の成膜条件の最適化が行なわれておらず、改善の余地があった。 The above technology basically assumes the case where a cemented carbide such as a WC-Co substrate is used as a substrate, and the WC-Co based cemented carbide and an insulating material such as Si or Al 2 O 3 are used. When used as a base material, the intermediate layer was able to ensure good adhesion with the base material, but when an iron-based material such as high-speed tool steel was used as the base material, The compatibility between the intermediate layer and the substrate is not always good, and there is a problem that the adhesion between the intermediate layer and the substrate is deteriorated and the DLC film is easily peeled off. Further, the film forming conditions of the uppermost DLC film having excellent wear resistance have not been optimized, and there is room for improvement.
この密着性の改良技術として、低硬度の鉄系材料の基材にＤＬＣ膜を密着性良く被覆する技術として、比較的厚く形成しても優れた密着性を発揮させる技術（特許文献２参照）が知られている。この技術はＤＬＣを主体とする膜を最表面層とし、さらに中間層および基材を含んでおり、この基材は鉄系材料から成ると共に、上記中間層を下記（１）〜（４）の４層構造とするものである。
（１）Ｃｒおよび／またはＡｌの金属層からなる第１層
（２）Ｃｒおよび／またはＡｌの金属と、Ｗ、Ｔａ、ＭｏおよびＮｂよりなる群から選択される１種類以上の金属の混合層からなる第２層
（３）Ｗ、Ｔａ、ＭｏおよびＮｂからなる群から選択される１種類以上の金属層からなる第３層
（４）Ｗ、Ｔａ、ＭｏおよびＮｂよりなる群から選択される１種類以上の金属と炭素を含む非晶質層からなる第４層
As a technique for improving the adhesion, as a technique for coating a DLC film with good adhesion on a base material of a low hardness iron-based material, a technique for exerting excellent adhesion even when formed relatively thick (see Patent Document 2) It has been known. In this technique, a film mainly composed of DLC is used as an outermost surface layer, and further includes an intermediate layer and a base material. The base material is made of an iron-based material, and the intermediate layer is formed from the following (1) to (4). It has a four-layer structure.
(1) First layer composed of a Cr and / or Al metal layer (2) Mixed layer of Cr and / or Al metal and one or more metals selected from the group consisting of W, Ta, Mo and Nb The second layer (3) consisting of W, Ta, Mo and Nb. The third layer (4) consisting of one or more metal layers selected from the group consisting of W, Ta, Mo and Nb. A fourth layer comprising an amorphous layer containing one or more metals and carbon
特に前記第２層は、Ｃｒおよび／またはＡｌの含有量が、最表面層側に向けて段階的または連続的に減少する傾斜層を有するように構成されたものであることが好ましい。また、上記第４層は、Ｗ、Ｔａ、Ｍｏ、Ｎｂよりなる群から選択される１種類以上の金属の含有量が最表面層側に向けて段階的または連続的に減少する傾斜組成を有するように構成されたものであることが好ましい。また同様に上記第２層、上記第３層および第４層の成分であるＷ、Ｔａ、ＭｏおよびＮｂよりなる群から選択される１種類以上の金属の代わりに、ＷＣを主成分とする化合物を用いることもできる。 In particular, the second layer is preferably configured to have a gradient layer in which the content of Cr and / or Al decreases stepwise or continuously toward the outermost surface layer side. The fourth layer has a graded composition in which the content of one or more metals selected from the group consisting of W, Ta, Mo, and Nb decreases stepwise or continuously toward the outermost surface layer side. It is preferable that it is comprised as follows. Similarly, a compound containing WC as a main component instead of one or more kinds of metals selected from the group consisting of W, Ta, Mo and Nb, which are components of the second layer, the third layer and the fourth layer. Can also be used.
なお、これらのＤＬＣ膜多層成膜体を製造するに当たり、ＤＬＣ膜はアンバランスト・マグネトロン・スパッタリング（以下、ＵＢＭＳと記す）法によって形成することが好ましく、基材温度を１００〜３００℃に制御しつつ形成することが好ましい、と記載されている。
しかしながら、特許文献１および特許文献２の技術を用いた場合でも、最表面層であるＤＬＣ層の構造を最適化しない場合、ＤＬＣ層と中間層との間で、剥離が生じるという問題がある。また、密着性が良好でかつ耐摩耗性に優れるＤＬＣ膜を形成する条件を裏付ける耐摩耗性に関するデータが得られていないという問題がある。 However, even when the techniques of Patent Document 1 and Patent Document 2 are used, if the structure of the DLC layer that is the outermost surface layer is not optimized, there is a problem that peeling occurs between the DLC layer and the intermediate layer. In addition, there is a problem in that data relating to wear resistance supporting conditions for forming a DLC film having good adhesion and excellent wear resistance is not obtained.
本発明はこのような問題に対処するためになされたものであり、基材と密着性に優れる中間層と、耐摩耗性に優れる表面層であるＤＬＣ層とを備え、ＤＬＣ層最下部と中間層との間でも剥離を生じることがなく、耐摩耗性にも優れる硬質多層膜成形体、およびその製造方法を提供することを目的とする。 The present invention has been made in order to cope with such a problem, and includes an intermediate layer having excellent adhesion to the base material and a DLC layer which is a surface layer having excellent wear resistance. It is an object of the present invention to provide a hard multilayer film molded article which does not cause peeling between layers and is excellent in wear resistance, and a method for producing the same.
本発明の硬質多層膜成形体は、超硬合金材料または鉄系材料からなる基材の表面に多層の膜を形成してなる硬質多層膜成形体であって、上記多層の膜は、（１）この多層の表面層として形成される、炭素供給源として固体ターゲットのグラファイトのみを使用し、水素混入量を抑えて成膜したＤＬＣを主体とする膜と、（２）この表面層と上記基材との間に形成される、少なくともクロム（Ｃｒ）またはタングステン（Ｗ）を主体とする中間層と、（３）この中間層と上記表面層との間に形成される炭素（Ｃ）を主体とする応力緩和層とからなり、上記応力緩和層は、その硬度が上記中間層側から上記表面層側へ連続的または段階的に上昇する傾斜層であることを特徴とする。 The hard multilayer film molded body of the present invention is a hard multilayer film molded body formed by forming a multilayer film on the surface of a substrate made of a cemented carbide material or an iron-based material, and the multilayer film is (1 (2) a film composed mainly of DLC formed as a multilayer surface layer using only solid target graphite as a carbon source and suppressing the amount of mixed hydrogen; (2) the surface layer and the above-mentioned base layer An intermediate layer mainly composed of at least chromium (Cr) or tungsten (W), and (3) mainly composed of carbon (C) formed between the intermediate layer and the surface layer. The stress relaxation layer is an inclined layer whose hardness increases continuously or stepwise from the intermediate layer side to the surface layer side.
上記中間層は組成の異なる複数の層からなる構造であり、一方が上記応力緩和層と隣接する層は、他方で隣接する層の主体となる金属と、Ｃとを主体とすることを特徴とする。 The intermediate layer has a structure composed of a plurality of layers having different compositions, wherein one of the layers adjacent to the stress relaxation layer is mainly composed of a metal that is a main component of the adjacent layer and C. To do.
上記中間層が、上記基材と隣接するＷを主体とする層と、該層と一方で隣接するとともに他方で上記応力緩和層と隣接する、ＣおよびＷを主体とする層とからなる２層構造であることを特徴とする。また、上記中間層が、上記基材と隣接するＣｒを主体とする層と、該層と隣接するＷを主体とする層と、該層と一方で隣接するとともに他方で上記応力緩和層と隣接する、ＣおよびＷを主体とする層とからなる３層構造であることを特徴とする。 The intermediate layer is composed of a layer mainly composed of W adjacent to the base material, and a layer mainly composed of C and W adjacent to the layer and adjacent to the stress relaxation layer on the other side. It is a structure. In addition, the intermediate layer is adjacent to the base material mainly composed of Cr, adjacent to the layer mainly composed of W, adjacent to the layer on one side, and adjacent to the stress relaxation layer on the other side. It has a three-layer structure composed of layers mainly composed of C and W.
上記多層の膜厚の合計が、０．５〜３．０μｍであることを特徴とする。また、上記硬質多層膜成形体は、ロックウェル硬さ試験機にて、１５０ｋｇの荷重によるダイヤモンド圧子の打ち込み時にできる圧痕周囲に剥離が生じない密着性を有することを特徴とする。 The total thickness of the multilayer is 0.5 to 3.0 μm. Further, the hard multilayer film molded article is characterized in that it has an adhesive property that does not cause peeling around an indentation formed when a diamond indenter is driven with a load of 150 kg by a Rockwell hardness tester.
本発明の硬質多層膜成形体の製造方法は、基材上に上記中間層を形成する中間層形成工程と、中間層上に上記応力緩和層を形成する応力緩和層形成工程と、応力緩和層上に上記表面層を形成する表面層形成工程とを有し、上記表面層形成工程は、ＵＢＭＳ法を用いて、炭素供給源として固体ターゲットのグラファイトのみを使用し、水素供給源となるスパッタリングガスは使用せずにＤＬＣを主体とする膜を形成する工程であり、上記応力緩和層形成工程は、ＵＢＭＳ法を用いて、バイアス電圧を連続的または段階的に上昇させて上記傾斜層を形成する工程であることを特徴とする。 The method for producing a hard multilayer film molded body of the present invention includes an intermediate layer forming step for forming the intermediate layer on a substrate, a stress relaxation layer forming step for forming the stress relaxation layer on the intermediate layer, and a stress relaxation layer. A surface layer forming step for forming the surface layer on the surface, wherein the surface layer forming step uses a UBMS method and uses only a solid target graphite as a carbon supply source, and a sputtering gas serving as a hydrogen supply source Is a step of forming a film mainly composed of DLC without using it, and the stress relaxation layer forming step forms the gradient layer by increasing the bias voltage continuously or stepwise using the UBMS method. It is a process.
上記応力緩和層形成工程において、上記バイアス電圧を段階的に上昇させる場合のステップ幅が５０Ｖ以下であることを特徴とする。また、上記表面層形成工程において、上記バイアス電圧を２５０Ｖ以上に印加して成膜することを特徴とする。なお、基材に対するバイアスの電位は、アース電位に対してマイナスとなるように印加しており、バイアス電圧２５０Ｖとは、アース電位に対して基材のバイアス電位が−２５０Ｖであることを示す。 In the stress relaxation layer forming step, the step width when the bias voltage is increased stepwise is 50 V or less. In the surface layer forming step, the bias voltage is applied to 250 V or more to form a film. The bias potential applied to the base material is applied so as to be negative with respect to the ground potential, and the bias voltage 250V indicates that the bias potential of the base material is −250V with respect to the ground potential.
また、上記各工程において、基材温度を１００〜３００℃に制御することを特徴とする。 Moreover, in each said process, base-material temperature is controlled to 100-300 degreeC, It is characterized by the above-mentioned.
本発明の硬質多層膜成形体は、超硬合金材料または鉄系材料からなる基材の表面に多層の膜を形成してなる硬質多層膜成形体であって、基材と密着性に優れる中間層と、炭素供給源として固体ターゲットのグラファイトのみを使用して成膜した、耐摩耗性に優れる表面層であるＤＬＣ層とを備え、中間層と表面層との間に、中間層側から表面層側に硬度が連続的または段階的に上昇する傾斜層を有するので、成形体の表面が水素含有量を低くしたＤＬＣ層となり耐摩耗性に優れるとともに、ＤＬＣ層最下部の応力緩和層（傾斜層）と中間層との間でも剥離を生じることがない。 The hard multilayer film molded body of the present invention is a hard multilayer film molded body in which a multilayer film is formed on the surface of a substrate made of a cemented carbide material or an iron-based material, and is an intermediate having excellent adhesion to the substrate. And a DLC layer, which is a surface layer having excellent wear resistance, formed using only a solid target graphite as a carbon source, and the surface from the intermediate layer side between the intermediate layer and the surface layer. Since it has a graded layer whose hardness increases continuously or stepwise on the layer side, the surface of the molded body becomes a DLC layer with a low hydrogen content and has excellent wear resistance, and a stress relaxation layer (gradient) at the bottom of the DLC layer. No peeling occurs between the layer) and the intermediate layer.
また、中間層を組成の異なる複数の層からなる構造とし、一方が応力緩和層と隣接する層を、他方で隣接する層の主体となる金属と、Ｃとを主体とすることで、この中間層と応力緩和層との間の密着性を向上できる。 In addition, the intermediate layer has a structure composed of a plurality of layers having different compositions, one of which is adjacent to the stress relaxation layer, and the other is a metal which is the main component of the adjacent layer and C. The adhesion between the layer and the stress relaxation layer can be improved.
また、硬質多層膜成形体は、ロックウェル硬さ試験機にて、１５０ｋｇの荷重によるダイヤモンド圧子の打ち込み時にできる圧痕周囲に剥離が生じない程度の優れた密着性を有する。 Further, the hard multilayer film molded article has excellent adhesion that does not cause peeling around the indentation formed when a diamond indenter is driven by a load of 150 kg with a Rockwell hardness tester.
本発明の硬質多層膜成形体の製造方法は、中間層形成工程と、応力緩和層形成工程と、表面層形成工程とを有し、上記表面層形成工程は、ＵＢＭＳ法を用いて、炭素供給源として固体ターゲットのグラファイトのみを使用し、水素供給源となるスパッタリングガスは使用せずにＤＬＣを主体とする膜を形成する工程であり、上記応力緩和層形成工程は、ＵＢＭＳ法を用いて、バイアス電圧を連続的または段階的に上昇させて上記傾斜層を形成する工程であるので、水素含有量を低くした耐摩耗性に優れるＤＬＣ層を成形体表面に形成でき、また、ＤＬＣ層最下部の応力緩和層（傾斜層）と中間層との間の密着性に優れる硬質多層膜成形体を容易に製造することができる。 The manufacturing method of the hard multilayer film molded body of the present invention includes an intermediate layer forming step, a stress relaxation layer forming step, and a surface layer forming step, and the surface layer forming step uses a UBMS method to supply carbon. It is a step of forming a film mainly composed of DLC without using a sputtering gas as a hydrogen supply source, using only a solid target graphite as a source, and the stress relaxation layer forming step uses a UBMS method. Since the gradient layer is formed by increasing the bias voltage continuously or stepwise, a DLC layer having a low hydrogen content and excellent wear resistance can be formed on the surface of the molded body. It is possible to easily produce a hard multilayer film molded article having excellent adhesion between the stress relaxation layer (gradient layer) and the intermediate layer.
また、上記応力緩和層形成工程において、バイアス電圧を段階的に変化させる場合のステップ幅を５０Ｖ以下とすることで、応力緩和層（傾斜層）の密度および硬度を細かく段階的に変化させることができ、密着性を向上させることができる。 Further, in the stress relaxation layer forming step, the density and hardness of the stress relaxation layer (gradient layer) can be changed finely and stepwise by setting the step width when the bias voltage is changed stepwise to 50 V or less. And adhesion can be improved.
また、上記表面層形成工程において、バイアス電圧を最終的に２５０Ｖ以上に印加して成膜することで、Ａｒ等の希ガスイオンのアシスト効果を高めて、基材との衝突エネルギーを増大させることにより、緻密で高硬度な耐摩耗性に優れるＤＬＣ膜を形成することができる。 In the surface layer forming step, the bias voltage is finally applied to 250 V or more to form a film, thereby enhancing the assist effect of rare gas ions such as Ar and increasing the collision energy with the substrate. Thus, a DLC film having high density and high hardness and excellent wear resistance can be formed.
また、上記製造方法において、基材温度を１００〜３００℃に制御することで、基材に対する多層膜の密着性を向上させることができる。 Moreover, in the said manufacturing method, the adhesiveness of the multilayer film with respect to a base material can be improved by controlling base-material temperature to 100-300 degreeC.
ＤＬＣ膜からなる表面層の密着性と耐摩耗性とに優れる硬質多層膜成形体を得るべく鋭意検討の結果、基材と密着性に優れる中間層を選定し、かつ表面層であるＤＬＣ膜に優れた耐摩耗性を付与するために成膜条件を選定し、特に、ＤＬＣ層形成時の基材に対するバイアス電圧を連続的または段階的に変化させてＤＬＣ層最下部にＤＬＣの密度および硬度が連続的または段階的に変化する応力緩和層（傾斜層）を形成することで、中間層最上部と、ＤＬＣ層最下部の応力緩和層（傾斜層）との間の密着性が向上し、剥離を防止できることを見出した。本発明はこのような知見に基づきなされたものである。 As a result of intensive studies to obtain a hard multilayer film molded article having excellent adhesion and wear resistance of the surface layer made of DLC film, an intermediate layer excellent in adhesion with the substrate was selected, and the DLC film as the surface layer was selected. In order to provide excellent wear resistance, the film forming conditions are selected. In particular, the density and hardness of the DLC at the bottom of the DLC layer are changed by continuously or stepwise changing the bias voltage with respect to the substrate when forming the DLC layer. By forming a stress relaxation layer (gradient layer) that changes continuously or stepwise, the adhesion between the uppermost part of the intermediate layer and the stress relaxation layer (gradient layer) at the bottom of the DLC layer is improved, and peeling It was found that can be prevented. The present invention has been made based on such findings.
本発明の硬質多層膜成形体を図面に基づいて説明する。図１は本発明の硬質多層膜成形体の構成を示す断面図である。図１に示すように、本発明の硬質多層膜成形体１は、基材２の表面に多層の膜を形成してなり、この多層の膜は、（１）表面層５として形成される、炭素供給源として固体ターゲットのグラファイトのみを使用し、水素混入量を抑えたＤＬＣを主体とする膜と、（２）表面層５と基材２との間に形成される、少なくともＣｒまたはＷを主体とする中間層３と、（３）中間層３と表面層５との間に形成される応力緩和層４とからなる。 The hard multilayer film molded product of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing the configuration of the hard multilayer film molded article of the present invention. As shown in FIG. 1, the hard multilayer film molded article 1 of the present invention is formed by forming a multilayer film on the surface of a base material 2, and this multilayer film is formed as (1) a surface layer 5. A film mainly composed of DLC using only a solid target graphite as a carbon supply source and suppressing the amount of hydrogen contamination, and (2) at least Cr or W formed between the surface layer 5 and the substrate 2 It consists of an intermediate layer 3 as a main component, and (3) a stress relaxation layer 4 formed between the intermediate layer 3 and the surface layer 5.
基材２としては、超硬合金材料または鉄系材料からなる基材であれば用いることができる。超硬合金材料としては機械的特性が最も優れるＷＣ−Ｃｏ系合金の他に、切削工具として、耐酸化性を向上させた、ＷＣ−ＴｉＣ−Ｃｏ系合金、ＷＣ−ＴａＣ−Ｃｏ系合金、ＷＣ−ＴｉＣ−ＴａＣ−Ｃｏ系合金等を挙げることができる。鉄系材料としては炭素工具鋼、高速度工具鋼、合金工具鋼、ステンレス鋼、軸受鋼、快削鋼等を挙げることができる。本発明では、安価な鉄系材料を基材に用いた場合でも、ＤＬＣに相当する硬質多層膜成形体を製造することができる。 As the base material 2, any base material made of a cemented carbide material or an iron-based material can be used. In addition to the WC-Co alloy with the most excellent mechanical properties as a cemented carbide material, the WC-TiC-Co alloy, WC-TaC-Co alloy, and WC have improved oxidation resistance as cutting tools. -TiC-TaC-Co based alloy and the like. Examples of the iron-based material include carbon tool steel, high speed tool steel, alloy tool steel, stainless steel, bearing steel, free cutting steel and the like. In the present invention, even when an inexpensive iron-based material is used as a base material, a hard multilayer film molded body corresponding to DLC can be produced.
中間層３は、組成の異なる複数の層からなる構造であり、図１では３ａ〜３ｃの３層構造を例示している。例えば、基材２の表面にＣｒを主体とする層３ｃを形成し、その上にＷを主体とする層３ｂを形成し、その上にＷおよびＣを主体とする層３ａを形成する。図１では３層構造を例示したが、中間層３は、必要に応じて、これ以下または以上の数の層からなるものであってもよい。 The intermediate layer 3 has a structure composed of a plurality of layers having different compositions, and FIG. 1 illustrates a three-layer structure of 3a to 3c. For example, the layer 3c mainly composed of Cr is formed on the surface of the substrate 2, the layer 3b mainly composed of W is formed thereon, and the layer 3a mainly composed of W and C is formed thereon. Although the three-layer structure is illustrated in FIG. 1, the intermediate layer 3 may be composed of a number of layers equal to or less than this, if necessary.
応力緩和層４に隣接する層３ａは、他方で隣接する層３ｂの主体となる金属と、炭素とを主体することで、中間層３と応力緩和層４との間の密着性を向上できる。例えば、層３ａがＷとＣとを主体とする場合、Ｗを主体とする中間層３ｂ側からＣを主体とする応力緩和層４側に向けて、Ｗの含有量を減少させ、一方、Ｃの含有量を増加させる（組成傾斜）ことで、より密着性の向上が図れる。 The layer 3a adjacent to the stress relaxation layer 4 can improve the adhesion between the intermediate layer 3 and the stress relaxation layer 4 by mainly including the metal that is the main component of the adjacent layer 3b and carbon. For example, when the layer 3a is mainly composed of W and C, the content of W is decreased from the intermediate layer 3b side mainly composed of W toward the stress relaxation layer 4 side mainly composed of C, while C By increasing the content of (composition gradient), the adhesion can be further improved.
応力緩和層４は、Ｃを主体とし、その硬度が中間層３側から表面層５側へ連続的または段階的に上昇する傾斜層である。具体的には、ＵＢＭＳ法においてグラファイト製ターゲットを用い、基材に対するバイアス電圧を連続的または段階的に上昇させて成膜することで得られるＤＬＣ傾斜層である。硬度が連続的または段階的に上昇するのは、ＤＬＣ構造におけるグラファイト構造（ＳＰ２）とダイヤモンド構造（ＳＰ３）との構成比率が、バイアス電圧の上昇により後者に偏っていくためである。 The stress relaxation layer 4 is an inclined layer whose main component is C and whose hardness increases continuously or stepwise from the intermediate layer 3 side to the surface layer 5 side. Specifically, it is a DLC gradient layer obtained by forming a film by using a graphite target in the UBMS method and increasing the bias voltage with respect to the substrate continuously or stepwise. The reason why the hardness increases continuously or stepwise is that the constituent ratio of the graphite structure (SP 2 ) and the diamond structure (SP 3 ) in the DLC structure is biased toward the latter as the bias voltage increases.
表面層５は、応力緩和層４の延長で形成されるＤＬＣを主体とする膜であり、特に、構造中の水素含有量を低減したＤＬＣ膜である。水素含有量を低減させたことで、耐摩耗性が向上する。このようなＤＬＣ膜を形成するためには、例えばＵＢＭＳ法を用いて、スパッタリング処理に用いる原料およびスパッタリングガス中に水素および水素を含む化合物を混入させない方法を用いる。 The surface layer 5 is a film mainly composed of DLC formed by extension of the stress relaxation layer 4, and in particular, a DLC film with a reduced hydrogen content in the structure. Abrasion resistance is improved by reducing the hydrogen content. In order to form such a DLC film, for example, a method in which hydrogen and a compound containing hydrogen are not mixed into a raw material used for the sputtering process and a sputtering gas by using the UBMS method is used.
応力緩和層４および表面層５の成膜法に関して、ＵＢＭＳ法を用いる場合を例示したが、硬度を連続的または段階的に変化させることができる成膜法であれば、その他公知の成膜法を採用することができる。 The case of using the UBMS method has been exemplified for the film formation method of the stress relaxation layer 4 and the surface layer 5, but any other known film formation method can be used as long as the film thickness can be changed continuously or stepwise. Can be adopted.
硬質多層膜成形体１において、中間層３と、応力緩和層４と、表面層５とからなる多層の膜厚の合計が０．５〜３．０μｍとすることが好ましい。膜厚の合計が０．５ｍ未満であれば、耐摩耗性および機械的強度に劣り、３．０μｍをこえると剥離し易くなるので好ましくない。 In the hard multilayer film molded body 1, the total thickness of the multilayer composed of the intermediate layer 3, the stress relaxation layer 4, and the surface layer 5 is preferably 0.5 to 3.0 μm. If the total film thickness is less than 0.5 m, the abrasion resistance and mechanical strength are inferior, and if it exceeds 3.0 μm, it tends to peel off, which is not preferable.
硬質多層膜成形体１は、その密着性が、ロックウェル硬さ試験機にて、１５０ｋｇの荷重によるダイヤモンド圧子の打ち込み時にできる圧痕周囲に剥離が生じない程度であることが好ましい。ここで、「圧痕周囲に剥離が生じない」とは、例えば、図３（ａ）に示すような状態をいう。 It is preferable that the adhesiveness of the hard multilayer film molded body 1 is such that no peeling occurs around the indentation formed when the diamond indenter is driven with a load of 150 kg by a Rockwell hardness tester. Here, “there is no peeling around the indentation” means, for example, a state as shown in FIG.
本発明の硬質多層膜成形体の製造方法は、（１）基材２上に中間層３を形成する中間層形成工程と、（２）中間層３上に応力緩和層４を形成する応力緩和層形成工程と、（３）応力緩和層４上に表面層５を形成する表面層形成工程とからなる。各工程において、密着性を向上させるために、基材温度を１００〜３００℃に制御して各層の被膜を形成させることが好ましい。基材や被膜を形成された基材の温度が１００℃未満であれば、膜の緻密化が進行し難い。また、３００℃をこえるとＤＬＣ層がダメージを受けるので好ましくない。 The method for producing a hard multilayer film molded body of the present invention includes (1) an intermediate layer forming step of forming an intermediate layer 3 on a substrate 2 and (2) stress relaxation of forming a stress relaxation layer 4 on the intermediate layer 3. A layer forming step and (3) a surface layer forming step of forming the surface layer 5 on the stress relaxation layer 4. In each step, in order to improve adhesion, it is preferable to form a coating of each layer by controlling the substrate temperature to 100 to 300 ° C. If the temperature of the substrate or the substrate on which the film is formed is less than 100 ° C., the densification of the film is difficult to proceed. Further, if the temperature exceeds 300 ° C., the DLC layer is damaged, which is not preferable.
（１）中間層形成工程は、ＣｒやＷを主体とする中間層を形成する工程であり、成膜法は特に限定されないが、以下の各層の形成を連続して行なえることから、ＵＢＭＳ法を採用し、ターゲットを逐次取り替えて中間層３、応力緩和層４、表面層５を連続して成膜することが好ましい。なお、ＵＢＭＳ法において、組成傾斜（２種）の中間層を形成する場合は、ターゲットを２種類用い、それぞれのターゲットに印加するスパッタ電力を調整することで組成比を傾斜できる。 (1) The intermediate layer forming step is a step of forming an intermediate layer mainly composed of Cr or W, and the film forming method is not particularly limited. However, since the following layers can be formed continuously, the UBMS method is used. It is preferable that the intermediate layer 3, the stress relaxation layer 4, and the surface layer 5 are successively formed by successively changing the target. In the UBMS method, when forming an intermediate layer having two composition gradients (two types), the composition ratio can be tilted by using two types of targets and adjusting the sputtering power applied to each target.
（２）応力緩和層形成工程は、ＵＢＭＳ法においてグラファイト製ターゲットを用い、基材に対するバイアス電圧を連続的または段階的に上昇させて応力緩和層（傾斜層）４を形成する工程である。この工程において、バイアス電圧を段階的に変化させる場合のステップ幅を５０Ｖ以下（例えば、２５Ｖ、５０Ｖ）とすることが好ましい。ステップ幅を５０Ｖ以下とすることで、応力緩和層４の密度および硬度を細かく段階的に変化でき密着性を向上させることができる。ステップ幅が５０Ｖをこえると、密着性に劣り応力緩和層内での剥離が起こる等のおそれがある。 (2) The stress relaxation layer forming step is a step of forming the stress relaxation layer (gradient layer) 4 by using a graphite target in the UBMS method and increasing the bias voltage with respect to the substrate continuously or stepwise. In this step, it is preferable that the step width when changing the bias voltage stepwise is 50 V or less (for example, 25 V, 50 V). By setting the step width to 50 V or less, the density and hardness of the stress relaxation layer 4 can be finely changed stepwise and the adhesion can be improved. If the step width exceeds 50 V, the adhesion is inferior and peeling in the stress relaxation layer may occur.
（３）表面層形成工程は、ＵＢＭＳ法を用いて、炭素供給源として固体ターゲットのグラファイトのみを使用し、メタン（ＣＨ4）等の水素供給源となるスパッタリングガスは使用せずにＤＬＣを主体とする膜を形成する工程である。スパッタリングガスとしては、Ｈｅ、Ａｒ、Ｘｅ等の希ガスを用いることができる。希ガス成分は単独でも、２種類以上を混合して用いてもよい。この工程では、基材に対するバイアス電圧を２５０Ｖ以上に印加して成膜することが好ましい。バイアス電圧を２５０Ｖ以上とすることで、Ａｒ等の希ガスイオンのアシスト効果が高まり、基材との衝突エネルギーを増大させることにより、緻密で高硬度な耐摩耗性に優れるＤＬＣ膜を形成できる（後述の表２および図４参照）。 (3) The surface layer forming step uses UBMS method, using only graphite as a solid target as a carbon source, and mainly using DLC without using a sputtering gas as a hydrogen source such as methane (CH 4 ). Is a step of forming a film. As the sputtering gas, a rare gas such as He, Ar, or Xe can be used. The rare gas components may be used alone or in combination of two or more. In this step, it is preferable to form a film by applying a bias voltage to the substrate to 250 V or higher. By setting the bias voltage to 250 V or more, the assist effect of rare gas ions such as Ar is enhanced, and by increasing the collision energy with the base material, a dense and high hardness DLC film excellent in wear resistance can be formed ( (See Table 2 and FIG. 4 below).
各実施例および比較例に用いた基材、ＵＢＭＳ装置、スパッタリングガス、多層膜形成条件は以下のとおりである。
（１）基材；鏡面（Ｒａ=０．００５μｍ程度の）３０ｍｍ角、厚さ５ｍｍのＳＵＳ４４０Ｃ
（２）ＵＢＭＳ装置：神戸製鋼所製；ＵＢＭＳ２０２／ＡＩＰ複合装置
（３）スパッタリングガス：Ａｒガス
（４）中間層形成条件
Ｃｒ層：５×１０−３Ｐａ程度まで真空引きし、ヒータで基材を所定の温度でベーキングして、Ａｒプラズマにて基材表面をエッチング後、ＵＢＭＳ法にてＣｒ層を形成した。
Ｗ層：５×１０−３Ｐａ程度まで真空引きし、ヒータで基材を所定の温度でベーキングして、Ａｒプラズマにて基材表面をエッチング後、ＵＢＭＳ法にてＷ層を形成した。
Ｗ−Ｃ層：Ｗとグラファイトに印加するスパッタ電力を調整し、ＷとＣの組成比を傾斜させた。
（５）応力緩和層（傾斜層）形成条件
傾斜層：一定電力でスパッタし、ＤＣバイアス電圧を以下に示すステップ幅で変化させて、膜密度を傾斜させた。
バイアス電圧のステップ幅：スタートから終点のバイアス電圧までの間を、段階的に変化させる電圧の幅として、２５Ｖ、５０Ｖ、１００Ｖの３種類から選択
各ステップ維持時間：５分間
（６）最表面層形成条件
成膜時間：１８０分間
The base material, UBMS apparatus, sputtering gas, and multilayer film forming conditions used in each example and comparative example are as follows.
(1) Base material: SUS440C with a mirror surface (Ra = 0.005 μm or so) 30 mm square and 5 mm thickness
(2) UBMS device: manufactured by Kobe Steel; UBMS202 / AIP composite device (3) Sputtering gas: Ar gas (4) Intermediate layer formation condition Cr layer: vacuumed to about 5 × 10 −3 Pa, and base material with heater Was baked at a predetermined temperature, and after etching the substrate surface with Ar plasma, a Cr layer was formed by the UBMS method.
W layer: Vacuum was drawn to about 5 × 10 −3 Pa, the substrate was baked at a predetermined temperature with a heater, the substrate surface was etched with Ar plasma, and a W layer was formed by UBMS.
WC layer: The sputtering power applied to W and graphite was adjusted, and the composition ratio of W and C was inclined.
(5) Stress relaxation layer (graded layer) formation conditions Gradient layer: Sputtered at a constant power, and the DC bias voltage was changed with the step width shown below to tilt the film density.
Step width of bias voltage: Select from three types of voltage of 25V, 50V, and 100V as stepwise changing voltage width from start to end bias voltage. Each step maintaining time: 5 minutes (6) Outermost surface layer Formation conditions Film formation time: 180 minutes
実施例１〜実施例７、比較例５、比較例６および比較例８〜比較例１１
アセトンで超音波洗浄し、乾燥させた上記基板を、表１に示す中間層を上記中間層形成条件で形成した。次に、上記傾斜層形成条件の２５Ｖステップにて傾斜層を形成した。最後に表１に示すＤＬＣ層の基板バイアス電圧にて１８０分間成膜しＤＬＣ層を形成して、硬質多層膜成形体の試験片を得た。得られた試験片の膜厚を測定するとともに、この試験片を以下に示すロックウェル圧痕試験と摩耗試験に供し、密着性および耐摩耗性を評価した。結果を表１に併記する。
Examples 1 to 7, Comparative Example 5, Comparative Example 6, and Comparative Example 8 to Comparative Example 11
The intermediate layer shown in Table 1 was formed under the intermediate layer formation conditions on the substrate that had been ultrasonically cleaned with acetone and dried. Next, an inclined layer was formed by the 25V step of the inclined layer forming condition. Finally, a DLC layer was formed for 180 minutes with the substrate bias voltage of the DLC layer shown in Table 1 to form a DLC layer test piece. While measuring the film thickness of the obtained test piece, the test piece was subjected to the following Rockwell indentation test and wear test to evaluate adhesion and wear resistance. The results are also shown in Table 1.
＜ロックウェル圧痕試験＞
ダイヤモンド圧子を１５０ｋｇの荷重で試験片基材に打ち込んだ際、その圧痕周囲の剥離発生状況を観察した。観察した剥離発生状況を図３に示す評価基準により、試験片の密着性を評価した。剥離発生量が図３（ａ）に示すように軽微であれば密着性に優れると評価して「○」印を、剥離が図３（ｂ）に示すように部分的に発生している場合は密着性が劣ると評価して「△」印を、剥離が図３（ｃ）に示すように全周に発生している場合は密着性に著しく劣ると評価して「×」印を記録する。
<Rockwell indentation test>
When the diamond indenter was driven into the test piece substrate with a load of 150 kg, the state of occurrence of peeling around the indentation was observed. The adhesion of the test piece was evaluated according to the evaluation criteria shown in FIG. When the amount of peeling generated is small as shown in FIG. 3 (a), it is evaluated that the adhesiveness is excellent, and “◯” mark is shown, and peeling occurs partially as shown in FIG. 3 (b). Is evaluated as having poor adhesion, and “△” mark is recorded, and when peeling occurs all around as shown in FIG. To do.
＜摩擦試験＞
得られた試験片を、図２に示す摩擦試験機用いて摩擦試験を行なった。図２（ａ）は正面図を、図２（ｂ）は側面図を、それぞれ表す。表面粗さＲａが０．０１μｍ以下であり、ビッカース硬度Ｈｖが７８０であるＳＵＪ２焼入れ鋼を相手材７として回転軸１１に取り付け、試験片６をアーム部８に固定して所定の荷重９を図面上方から印加して、ヘルツの最大接触面圧０．５ＧＰａ、室温下、０．０５ｍ／ｓの回転速度で６０分間、相手材７を回転させたときに相手材７と試験片６との間に発生する摩擦力をロードセル１０により検出する。比摩耗量が１００×１０−１０ｍｍ３/（Ｎ・ｍ）未満の場合、耐摩耗性に優れると評価して「○」印を、１００−１０ｍｍ３/（Ｎ・ｍ）以上、３００−１０ｍｍ３/（Ｎ・ｍ）以下の場合、耐摩耗性に劣ると評価して「△」印を、３００−１０ｍｍ３/（Ｎ・ｍ）をこえる場合、耐摩耗性に著しく劣ると評価して「×」印を、それぞれ記録する。
<Friction test>
The obtained specimen was subjected to a friction test using a friction tester shown in FIG. 2A is a front view, and FIG. 2B is a side view. A SUJ2 hardened steel having a surface roughness Ra of 0.01 μm or less and a Vickers hardness Hv of 780 is attached to the rotating shaft 11 as a mating member 7, and the test piece 6 is fixed to the arm portion 8 to draw a predetermined load 9. When the mating material 7 is rotated for 60 minutes at a rotation speed of 0.05 m / s at room temperature under a maximum contact surface pressure of 0.5 GPa at a Hertz applied from above, between the mating material 7 and the test piece 6 The friction force generated in the load cell 10 is detected. When the specific wear amount is less than 100 × 10 −10 mm 3 / (N · m), it is evaluated that the wear resistance is excellent, and “◯” mark is given to 100 −10 mm 3 / (N · m) or more, 300 If it is -10 mm 3 / (N · m) or less, it is evaluated as being inferior in wear resistance, and if it exceeds “−” mark and exceeds 300 −10 mm 3 / (N · m), the wear resistance is remarkably inferior. And “x” marks are recorded respectively.
実施例８〜実施例１４
アセトンで超音波洗浄し、乾燥させた上記基板を、表１に示す中間層を上記中間層形成条件で形成した。次に、上記傾斜層形成条件の５０Ｖステップにて傾斜層を形成した。最後に表１に示すＤＬＣ層の基板バイアス電圧にて１８０分間成膜しＤＬＣ層を形成して、硬質多層膜成形体の試験片を得た。得られた試験片の膜厚を測定するとともに、この試験片を上述のロックウェル圧痕試験と摩耗試験に供し、密着性および耐摩耗性を評価した。結果を表１に併記する。
Examples 8 to 14
The intermediate layer shown in Table 1 was formed under the intermediate layer formation conditions on the substrate that had been ultrasonically cleaned with acetone and dried. Next, a graded layer was formed by the 50V step of the graded layer formation conditions. Finally, a DLC layer was formed for 180 minutes with the substrate bias voltage of the DLC layer shown in Table 1 to form a DLC layer test piece. While measuring the film thickness of the obtained test piece, the test piece was subjected to the above-mentioned Rockwell indentation test and wear test to evaluate the adhesion and wear resistance. The results are also shown in Table 1.
比較例１および比較例３
Ａｒ１００体積部に対してメタンガスを表１に示す割合でスパッタリングガスとして併用したこと以外は実施例１と同様の処理および評価を実施した。結果を表１に併記する。
Comparative Example 1 and Comparative Example 3
The same treatment and evaluation as in Example 1 were performed except that methane gas was used as a sputtering gas in a proportion shown in Table 1 with respect to 100 parts by volume of Ar. The results are also shown in Table 1.
比較例２
アセトンで超音波洗浄し、乾燥させた上記基板を、表１に示す中間層を上記中間層形成条件で形成した。次に、上記傾斜層形成条件の１００Ｖステップにて傾斜層を形成した。最後に表１に示すＤＬＣ層の基板バイアス電圧にて１８０分間成膜しＤＬＣ層を形成して、硬質多層膜成形体の試験片を得た。得られた試験片の膜厚を測定するとともに、この試験片を上述のロックウェル圧痕試験と摩耗試験に供し、密着性および耐摩耗性を評価した。結果を表１に併記する。
Comparative Example 2
The intermediate layer shown in Table 1 was formed under the intermediate layer formation conditions on the substrate that had been ultrasonically cleaned with acetone and dried. Next, an inclined layer was formed at a step of 100 V under the inclined layer forming conditions. Finally, a DLC layer was formed for 180 minutes with the substrate bias voltage of the DLC layer shown in Table 1 to form a DLC layer test piece. While measuring the film thickness of the obtained test piece, the test piece was subjected to the above-mentioned Rockwell indentation test and wear test to evaluate the adhesion and wear resistance. The results are also shown in Table 1.
比較例４
アセトンで超音波洗浄し、乾燥させた上記基板を、表１に示す中間層を上記中間層形成条件で形成した。次に、表１に示すＤＬＣ層の基板バイアス電圧にて１８０分間成膜しＤＬＣ層を形成して、硬質多層膜成形体の試験片を得た。得られた試験片の膜厚を測定するとともに、この試験片を上述のロックウェル圧痕試験と摩耗試験に供し、密着性および耐摩耗性を評価した。結果を表１に併記する。
Comparative Example 4
The intermediate layer shown in Table 1 was formed under the intermediate layer formation conditions on the substrate that had been ultrasonically cleaned with acetone and dried. Next, a DLC layer was formed by forming a DLC layer for 180 minutes at the substrate bias voltage of the DLC layer shown in Table 1 to obtain a test piece of a hard multilayer film molded body. While measuring the film thickness of the obtained test piece, the test piece was subjected to the above-mentioned Rockwell indentation test and wear test to evaluate the adhesion and wear resistance. The results are also shown in Table 1.
比較例７
アセトンで超音波洗浄し、乾燥させた上記基板を試験片とした。得られた試験片の膜厚を測定するとともに、この試験片を上述のロックウェル圧痕試験と摩耗試験に供し、密着性および耐摩耗性を評価した。結果を表１に併記する。
Comparative Example 7
The substrate that had been ultrasonically cleaned with acetone and dried was used as a test piece. While measuring the film thickness of the obtained test piece, the test piece was subjected to the above-mentioned Rockwell indentation test and wear test to evaluate the adhesion and wear resistance. The results are also shown in Table 1.
応力緩和層（傾斜層）を形成する際、バイアス電圧のステップ幅を５０Ｖ以下とし、表面層形成時のバイアス電圧を２５０Ｖ以上の条件で成膜した実施例１〜実施例１４の硬質多層膜成形体は、優れた耐摩耗性を示した。一方、傾斜層を形成（２５Ｖステップ）し、スパッタリングガスとしてＡｒとメタンガスとを併用した比較例１は、バイアス電圧が３００Ｖと高いにも関わらず、耐摩耗性が劣っていた。バイアス電圧が３００Ｖと高いにも関わらず、傾斜層のステップ幅を１００Ｖと広くした比較例２の場合、密着性、耐摩耗性共に劣っていた。傾斜層を形成（２５Ｖステップ）し、スパッタリングガスとしてＡｒとメタンガスとを併用し、バイアス電圧を２００Ｖとした比較例３は密着性、耐摩耗性共に劣っていた。傾斜層を設けない比較例４の場合、密着性が著しく劣っていた。中間層にＷ層とＷ−Ｃ層を用い、バイアス電圧を２００Ｖで成膜した比較例５は、密着性、耐摩耗性共に劣っていた。中間層にＷ−Ｃ層のみ使用し、傾斜層を設けた比較例６、中間層なしで傾斜層もない比較例７は密着性が著しく劣っていた。傾斜層を形成（２５Ｖステップ）し、基板バイアス電圧を１００Ｖで成膜した比較例８は耐摩耗性が著しく劣っていた。傾斜層を形成（２５Ｖステップ）し、基板バイアス電圧を２００Ｖで成膜した比較例９は耐摩耗性が劣っていた。傾斜層を形成（２５Ｖステップ）し、基板バイアス電圧を３００Ｖ、基材の温度を５０℃で成膜した比較例１０は耐摩耗性が劣っていた。ＤＬＣ傾斜層を形成（２５Ｖステップ）し、基板バイアス電圧を３００Ｖ、基材の温度を３５０℃で成膜した比較例１１は耐摩耗性が著しく劣っていた。 Hard multilayer film forming of Examples 1 to 14 in which the step width of the bias voltage was set to 50 V or less when forming the stress relaxation layer (graded layer) and the bias voltage at the time of forming the surface layer was set to 250 V or more. The body showed excellent wear resistance. On the other hand, Comparative Example 1 in which an inclined layer was formed (25 V step) and Ar and methane gas were used in combination as sputtering gas had poor wear resistance despite a high bias voltage of 300 V. In spite of the high bias voltage of 300V, in Comparative Example 2 in which the step width of the gradient layer was widened to 100V, both the adhesion and the wear resistance were inferior. In Comparative Example 3 in which an inclined layer was formed (25 V step), Ar and methane gas were used in combination as the sputtering gas, and the bias voltage was 200 V, both adhesion and wear resistance were inferior. In the case of Comparative Example 4 in which the inclined layer was not provided, the adhesion was remarkably inferior. Comparative Example 5 in which the W layer and the WC layer were used as the intermediate layer and the bias voltage was 200 V was inferior in both adhesion and wear resistance. Adhesiveness was remarkably inferior in Comparative Example 6 in which only the WC layer was used as the intermediate layer and the inclined layer was provided, and in Comparative Example 7 without the intermediate layer and without the inclined layer. In Comparative Example 8 in which the inclined layer was formed (25 V step) and the substrate bias voltage was 100 V, the wear resistance was remarkably inferior. Comparative Example 9 in which the gradient layer was formed (25 V step) and the substrate bias voltage was 200 V was inferior in wear resistance. Comparative Example 10 in which the inclined layer was formed (25 V step), the substrate bias voltage was 300 V, and the base material temperature was 50 ° C., was inferior in wear resistance. In Comparative Example 11 in which the DLC gradient layer was formed (25 V step), the substrate bias voltage was 300 V, and the base material temperature was 350 ° C., the wear resistance was extremely inferior.
また、表面層形成時のバイアス電圧と、上記摩擦試験における比摩耗量との関係を表２および図４に示す。 Table 2 and FIG. 4 show the relationship between the bias voltage when forming the surface layer and the specific wear amount in the friction test.
表２および図４に示すように、表面層（ＤＬＣ層）形成時のバイアス電圧を２５０Ｖ以上とすることで、比摩耗量を大幅に低減できることがわかる。 As shown in Table 2 and FIG. 4, it can be seen that the specific wear amount can be significantly reduced by setting the bias voltage when forming the surface layer (DLC layer) to 250 V or more.
本発明の硬質多層膜成形体は、所定の構成により基材と密着性に優れる中間層と、耐摩耗性に優れる表面層であるＤＬＣ層とを備えるので、優れた耐剥離性や耐摩耗性などが要求される軸受などの機械部品に好適に利用できる。 The hard multilayer film molded article of the present invention comprises an intermediate layer having excellent adhesion to the substrate and a DLC layer, which is a surface layer having excellent wear resistance, according to a predetermined configuration, and therefore has excellent peeling resistance and wear resistance. It can be suitably used for mechanical parts such as bearings that are required.
１ 硬質多層膜成形体
２ 基材
３ 中間層
３ａ ＷおよびＣを主体とする層
３ｂ Ｗを主体とする層
３ｃ Ｃｒを主体とする層
４ 応力緩和層（傾斜層）
５ 表面層（ＤＬＣを主体とする膜）
６ 試験片
７ 相手材
８ アーム部
９ 荷重
１０ ロードセル
１１ 回転軸
DESCRIPTION OF SYMBOLS 1 Hard multilayer film molded object 2 Base material 3 Intermediate | middle layer 3a Layer mainly composed of W and C 3b Layer mainly composed of W 3c Layer mainly composed of Cr 4 Stress relaxation layer (gradient layer)
5 Surface layer (film mainly composed of DLC)
6 Test piece 7 Counterpart 8 Arm part 9 Load 10 Load cell 11 Rotating shaft
Claims (10)
前記多層の膜は、（１）この多層の表面層として形成される、炭素供給源として固体ターゲットのグラファイトのみを使用し、水素混入量を抑えて成膜したダイヤモンドライクカーボンを主体とする膜と、（２）この表面層と前記基材との間に形成される、少なくともクロムまたはタングステンを主体とする中間層と、（３）この中間層と前記表面層との間に形成される炭素を主体とする応力緩和層とからなり、
前記応力緩和層は、その硬度が前記中間層側から前記表面層側へ連続的または段階的に上昇する傾斜層であることを特徴とする硬質多層膜成形体。 A hard multilayer film molded body in which a multilayer film is formed on the surface of a base material made of a cemented carbide material or an iron-based material,
The multilayer film is (1) a film mainly composed of diamond-like carbon formed as a multilayer surface layer using only solid target graphite as a carbon supply source and suppressing the amount of hydrogen contamination. (2) an intermediate layer mainly composed of at least chromium or tungsten formed between the surface layer and the substrate; and (3) carbon formed between the intermediate layer and the surface layer. It consists of a stress relaxation layer as the main component,
The stress relaxation layer is an inclined layer whose hardness increases continuously or stepwise from the intermediate layer side to the surface layer side.
この製造方法は、基材上に前記中間層を形成する中間層形成工程と、前記中間層上に前記応力緩和層を形成する応力緩和層形成工程と、前記応力緩和層上に前記表面層を形成する表面層形成工程とを有し、
前記表面層形成工程は、アンバランスト・マグネトロン・スパッタリング法を用いて、炭素供給源として固体ターゲットのグラファイトのみを使用し、水素供給源となるスパッタリングガスは使用せずにダイヤモンドライクカーボンを主体とする膜を形成する工程であり、
前記応力緩和層形成工程は、アンバランスト・マグネトロン・スパッタリング法を用いて、バイアス電圧を連続的または段階的に上昇させて前記傾斜層を形成する工程であることを特徴とする硬質多層膜成形体の製造方法。 A manufacturing method for manufacturing the hard multilayer film molded article according to any one of claims 1 to 6,
The manufacturing method includes an intermediate layer forming step of forming the intermediate layer on a substrate, a stress relaxation layer forming step of forming the stress relaxation layer on the intermediate layer, and the surface layer on the stress relaxation layer. A surface layer forming step to be formed,
The surface layer forming step uses an unbalanced magnetron sputtering method, uses only a solid target graphite as a carbon supply source, and mainly uses diamond-like carbon without using a sputtering gas as a hydrogen supply source. Forming a film to be
The stress relaxation layer forming step is a step of forming the inclined layer by increasing a bias voltage continuously or stepwise using an unbalanced magnetron sputtering method. Body manufacturing method.
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| EP09823652.4A EP2362000B1 (en) | 2008-10-29 | 2009-10-29 | Hard multilayer film formed body and method for manufacturing same |
| US12/998,426 US8728621B2 (en) | 2008-10-29 | 2009-10-29 | Hard multilayer film formed body and method for manufacturing same |
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