JPH11200012A - Hard coating excellent in wear resistance and slidability and its formation - Google Patents
Hard coating excellent in wear resistance and slidability and its formationInfo
- Publication number
- JPH11200012A JPH11200012A JP568498A JP568498A JPH11200012A JP H11200012 A JPH11200012 A JP H11200012A JP 568498 A JP568498 A JP 568498A JP 568498 A JP568498 A JP 568498A JP H11200012 A JPH11200012 A JP H11200012A
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- JP
- Japan
- Prior art keywords
- hard coating
- film
- hard
- present
- forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐摩耗性及び摺動
性に優れた硬質皮膜及びその形成方法に関し、より詳細
には、工具や摺動部材等に用いられる耐摩耗性及び摺動
性に優れた硬質皮膜及びその形成方法に関する技術分野
に属する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard coating excellent in abrasion resistance and slidability and a method for forming the same, and more particularly, to abrasion resistance and slidability used for tools and sliding members. It belongs to the technical field related to a hard coating excellent in quality and a method for forming the same.
【０００２】[0002]
【従来の技術】Ｃ、Ｃ−Ｈ、Ｃ−Ｎ、Ｃ−Ｎ−Ｈあるい
はＢ−Ｎを基礎とする硬質皮膜としては、立方晶ＢＮ
（以下、ｃＢＮという）、ダイヤモンド、ダイヤモンド
ライクカーボン（以下、ＤＬＣという）よりなる皮膜が
あり、又、最近ではダイヤモンドを上回る硬度を有する
と予想されるＣＮ系化合物皮膜がある。これらの皮膜
は、ダイヤモンドを除くとその多くがスパッタリング、
イオンプレーティング、イオンビーム蒸着等のＰＶＤ
法、或いは、熱ＣＶＤ法、プラズマＣＶＤ法、マイクロ
波ＣＶＤ法により、その合成が検討されている。しかし
ながら、これらの硬質皮膜には、皮膜形成時に大きな残
留応力が存在し（発生し）、その残留応力によって皮膜
が基板より剥離するという問題点があることが知られて
おり、又、そのために厚膜化ができないという問題点が
あり、工業的な適用が進んでいない。2. Description of the Related Art As a hard coating based on C, CH, CN, CNH or BN, cubic BN
(Hereinafter, referred to as cBN), diamond, and diamond-like carbon (hereinafter, referred to as DLC). In addition, recently, there is a CN-based compound film expected to have a hardness higher than that of diamond. Most of these films, except diamond, are sputtered,
PVD such as ion plating and ion beam evaporation
The synthesis thereof is being studied by a thermal CVD method, a plasma CVD method, or a microwave CVD method. However, it is known that these hard films have a problem that a large residual stress is present (generated) at the time of film formation, and the film is peeled off from the substrate due to the residual stress. There is a problem that the film cannot be formed, and industrial application has not been advanced.
【０００３】かかる問題点を解決することを目的とし
て、鉄基合金や超硬合金等よりなる基板材料よりも、上
記硬質皮膜との密着性に優れた物質を中間層として形成
すること、あるいは基材を硬質皮膜との密着性に優れた
物質に変更することにより、硬質皮膜の剥離を抑制しよ
うとする方法が提案されている。[0003] In order to solve such a problem, a material having better adhesion to the hard coating is formed as an intermediate layer than a substrate material made of an iron-based alloy, a cemented carbide, or the like. There has been proposed a method of suppressing exfoliation of a hard film by changing a material to a material having excellent adhesion to a hard film.
【０００４】即ち、ｃＢＮ皮膜の場合には、密着性を改
善するために４、５、６Ａ族の元素又はAlの窒化物、炭
化物を中間層として形成する方法（特開平4-120265号公
報に記載の方法）、超硬合金基材を窒化処理した後、ほ
う化処理し、その表面に硬質皮膜を形成する方法（特開
平4-124283号公報に記載の方法）、SiC を基材として使
用する方法（特開平5-39563 号公報に記載の方法）が提
示されている。ＤＬＣ皮膜の場合には、AlあるいはSiを
中間層として形成する方法が公知である（仁平他：東京
都立工業センター研究報告第25号(1996), P13 ）。That is, in the case of a cBN film, a method of forming an intermediate layer of an element belonging to Group 4, 5, 6A or a nitride or carbide of Al in order to improve the adhesion (Japanese Patent Application Laid-Open No. 4-120265). Method), a method in which a cemented carbide substrate is nitrided, then borated, and a hard film is formed on the surface (a method described in JP-A-4-124283), and SiC is used as a substrate. (A method described in JP-A-5-39563). In the case of a DLC film, a method of forming an intermediate layer of Al or Si is known (Nihei et al .: Tokyo Metropolitan Industrial Center Research Report No. 25 (1996), P13).
【０００５】また、ＣＶＤ法により硬質皮膜中にSi以外
の４Ｂ族元素を添加して硬質皮膜と基材との密着性向上
を図る方法が開示されている（特公平6-952 号公報）。
又、硬質皮膜中にTi，Zr，Cr，Nb，Mo，Hf，Ta，Ｗ等の
元素を添加することにより、硬質皮膜と基材との密着性
向上を図る方法が開示されている（特開平6-212429号公
報）。Further, a method has been disclosed in which a group 4B element other than Si is added to a hard coating by a CVD method to improve the adhesion between the hard coating and a substrate (Japanese Patent Publication No. 6-952).
Also disclosed is a method for improving the adhesion between the hard coating and the base material by adding an element such as Ti, Zr, Cr, Nb, Mo, Hf, Ta, W, etc. JP-A-6-212429).
【０００６】しかしながら、これらの方法によっても硬
質皮膜形成時の残留応力による硬質皮膜剥離という問題
点を解消し得ず、硬質皮膜の密着性は不充分であり、厚
膜化ができず、工業的使用に耐え得る硬質皮膜は得られ
ない。特に、基板に入射する粒子のエネルギーがＣＶＤ
法に比べて高いＰＶＤ法により硬質皮膜を形成する場合
には、硬質皮膜形成時の残留応力が大きくなるので、残
留応力による硬質皮膜の剥離が起こり易く、硬質皮膜の
密着性が著しく損なわれ、不充分となり、工業的使用に
耐え得る密着性及び厚さを有する硬質皮膜の形成は全く
困難である。However, even with these methods, the problem of peeling of the hard film due to the residual stress during the formation of the hard film cannot be solved, the adhesion of the hard film is insufficient, the film cannot be made thick, A hard film that can withstand use cannot be obtained. In particular, the energy of particles incident on the substrate is
When a hard coating is formed by a PVD method that is higher than the PVD method, the residual stress during the formation of the hard coating increases, so that the hard coating is easily peeled off due to the residual stress, and the adhesion of the hard coating is significantly impaired. Insufficiently, it is quite difficult to form a hard coating having an adhesion and a thickness that can withstand industrial use.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、この様な事
情に着目してなされたものであって、その目的は、前記
従来技術における硬質皮膜に比較し、硬質皮膜形成時の
残留応力による硬質皮膜剥離が生じ難く、密着性に優れ
ている硬質皮膜及びその形成方法を提供しようとするも
のである。SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and its object is to reduce the residual stress at the time of forming a hard coating, as compared with the hard coating in the prior art. An object of the present invention is to provide a hard film which hardly peels off the hard film and has excellent adhesion and a method for forming the same.
【０００８】[0008]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明に係る硬質皮膜及びその形成方法は、請求
項１記載の硬質皮膜、請求項２〜３記載の硬質皮膜の形
成方法としており、それは次のような構成としたもので
ある。即ち、請求項１記載の硬質皮膜は、Ｃ，Ｃ−Ｈ，
Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの何れかを基礎とする硬質
皮膜であって、前記皮膜中にFe，Co，Ni，Cuよりなる群
から選択される１種又は２種以上の元素を0.1 〜30at％
含有してなることを特徴とする耐摩耗性及び摺動性に優
れた硬質皮膜である（第１発明）。In order to achieve the above object, a hard coating according to the present invention and a method for forming the same are provided by a hard coating according to claim 1 and a method for forming a hard coating according to claims 2 to 3. It has the following configuration. That is, the hard coating according to claim 1 is C, CH,
A hard coating based on any one of CN, CNH, and BN, wherein one or more selected from the group consisting of Fe, Co, Ni, and Cu in the coating. Element of 0.1 to 30at%
A hard coating excellent in wear resistance and slidability characterized by containing (first invention).
【０００９】請求項２記載の硬質皮膜の形成方法は、F
e，Co，Ni，Cuよりなる群から選択される１種又は２種
以上の元素とＣ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎ
の何れか１種とを含有する固体状蒸発源を用い、アーク
イオンプレーティング法により、Fe，Co，Ni，Cuよりな
る群から選択される１種又は２種以上の元素を0.1 〜30
at％含有する、Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−
Ｎの何れかを基礎とする硬質皮膜を基材表面に形成する
ことを特徴とする耐摩耗性及び摺動性に優れた硬質皮膜
の形成方法である（第２発明）。The method for forming a hard coating according to claim 2 is characterized in that
one, two or more elements selected from the group consisting of e, Co, Ni, and Cu, and C, CH, CN, CNH, and BN
One or two or more elements selected from the group consisting of Fe, Co, Ni and Cu by an arc ion plating method using a solid evaporation source containing any one of
at%, C, CH, CN, CNH, B-
This is a method for forming a hard coating excellent in abrasion resistance and slidability, characterized by forming a hard coating based on any one of N on the surface of a substrate (second invention).
【００１０】請求項３記載の硬質皮膜の形成方法は、F
e，Co，Ni，Cuよりなる群から選択される１種又は２種
以上の元素を電子ビームにより蒸発させると共に、Ｃ，
Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの何れか１種を含
有するイオンビームを照射することにより、Fe，Co，N
i，Cuよりなる群から選択される１種又は２種以上の元
素を0.1 〜30at％含有する、Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−
Ｎ−Ｈ，Ｂ−Ｎの何れかを基礎とする硬質皮膜を基材表
面に形成することを特徴とする耐摩耗性及び摺動性に優
れた硬質皮膜の形成方法である（第３発明）。The method for forming a hard coating according to claim 3 is characterized in that
One or more elements selected from the group consisting of e, Co, Ni, and Cu are evaporated by an electron beam, and C,
By irradiating an ion beam containing any one of C—H, C—N, C—N—H, and B—N, Fe, Co, N
C, C—H, C—N, C— containing 0.1 to 30 at% of one or more elements selected from the group consisting of i and Cu
This is a method for forming a hard coating excellent in wear resistance and slidability, characterized by forming a hard coating based on either NH or BN on the surface of a substrate (third invention). .
【００１１】[0011]
【発明の実施の形態】本発明は例えば次のようにして実
施する。アークイオンプレーティング用の固体状蒸発源
として、Fe，Co，Ni，Cuよりなる群から選択される１種
又は２種以上の元素（以下、本発明に係る添加元素とい
う）とＣ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの何れ
か１種（以下、硬質皮膜基礎成分という）とを含有する
固体状蒸発源を用い、アークイオンプレーティング法に
より、硬質皮膜を基材表面に形成する。このとき、固体
状蒸発源における本発明に係る添加元素と硬質皮膜基礎
成分との配合割合は、形成される硬質皮膜中における本
発明に係る添加元素の割合が0.1 〜30at％となるように
する。このようにすると、本発明に係る硬質皮膜を基材
表面に形成することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is implemented, for example, as follows. As a solid evaporation source for arc ion plating, one or more elements selected from the group consisting of Fe, Co, Ni, and Cu (hereinafter, referred to as additive elements according to the present invention) and C, C- H, C—N, C—N—H, and B—N (hereinafter, referred to as “hard coating basic component”) are used to form a hard coating by an arc ion plating method using a solid evaporation source. Formed on the substrate surface. At this time, the mixing ratio of the additive element according to the present invention and the hard film basic component in the solid evaporation source is such that the ratio of the additive element according to the present invention in the formed hard film is 0.1 to 30 at%. . By doing so, the hard coating according to the present invention can be formed on the surface of the substrate.
【００１２】本発明に係る硬質皮膜は、前述のように、
Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの何れかを基
礎とする硬質皮膜であって、前記皮膜中にFe，Co，Ni，
Cuよりなる群から選択される１種又は２種以上の元素を
0.1 〜30at％含有してなることを特徴とする耐摩耗性及
び摺動性に優れた硬質皮膜である。即ち、本発明に係る
硬質皮膜は、硬質皮膜基礎成分を基礎とする硬質皮膜で
あって、この皮膜中に本発明に係る添加元素を0.1 〜30
at％含有してなるものである（第１発明）。[0012] The hard coating according to the present invention, as described above,
A hard coating based on any one of C, CH, CN, CNH, and BN, wherein Fe, Co, Ni,
One or more elements selected from the group consisting of Cu
A hard coating excellent in wear resistance and slidability, characterized by containing 0.1 to 30 at%. That is, the hard coating according to the present invention is a hard coating based on a hard coating basic component, in which the additive element according to the present invention is contained in an amount of 0.1 to 30.
at% (first invention).
【００１３】上記本発明に係る添加元素は、硬質皮膜形
成時に生じる硬質皮膜の固有応力を大幅に低減させ、そ
のため硬質皮膜の残留応力を著しく低減させ、ひいては
残留応力による硬質皮膜剥離を抑制し、硬質皮膜の密着
性を著しく向上させる作用がある。従って、本発明に係
る硬質皮膜は、前記従来技術における硬質皮膜に比較
し、硬質皮膜形成時の残留応力による硬質皮膜剥離が極
めて生じ難く、密着性に著しく優れている。[0013] The additive element according to the present invention significantly reduces the intrinsic stress of the hard film generated during the formation of the hard film, thereby significantly reducing the residual stress of the hard film, and further suppressing the hard film peeling due to the residual stress. It has the effect of significantly improving the adhesion of the hard coating. Therefore, the hard coating according to the present invention is very hard to peel off the hard coating due to the residual stress during the formation of the hard coating, and is extremely excellent in adhesion, as compared with the hard coating in the above-mentioned conventional technology.
【００１４】この詳細を以下に説明する。The details will be described below.
【００１５】硬質皮膜の殆どは前述の如くＰＶＤ法や各
種ＣＶＤ法により形成される。これらのＰＶＤ法やＣＶ
Ｄ法は気相からの蒸着法である。通常、かかる気相から
の蒸着法により形成される皮膜に発生する残留応力は、
成膜時の温度上昇による基板と皮膜との熱膨張率差に起
因する熱応力と、皮膜自身が有している固有応力とに分
類される。Most of the hard coating is formed by the PVD method or various CVD methods as described above. These PVD methods and CV
Method D is a vapor deposition method from the gas phase. Usually, the residual stress generated in the film formed by the vapor deposition method from the gas phase is as follows:
It is classified into a thermal stress caused by a difference in thermal expansion coefficient between the substrate and the film due to a rise in temperature during film formation, and an intrinsic stress of the film itself.
【００１６】硬質皮膜基礎成分（Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，
Ｃ−Ｎ−Ｈ，Ｂ−Ｎの１種）を基礎とする硬質皮膜の場
合には、硬質皮膜自身が有している固有応力による残留
応力の占める割合が圧倒的に大きく、硬質皮膜自身の固
有応力に起因する残留応力が支配的である。そのため、
基板として硬質皮膜の熱膨張率に近い熱膨張率を有する
基板、例えばセラミック等を用いても、残留応力を低減
させることは困難である。従って、残留応力を低減させ
るためには、硬質皮膜形成時に生じる硬質皮膜の固有応
力を緩和し、低減させることが必要である。Hard film basic components (C, CH, CN,
In the case of a hard coating based on C—N—H or BN), the ratio of the residual stress due to the intrinsic stress of the hard coating itself is overwhelmingly large, and The residual stress caused by the intrinsic stress is dominant. for that reason,
Even if a substrate having a coefficient of thermal expansion close to the coefficient of thermal expansion of the hard film, such as a ceramic, is used as the substrate, it is difficult to reduce the residual stress. Therefore, in order to reduce the residual stress, it is necessary to relax and reduce the intrinsic stress of the hard coating generated during the formation of the hard coating.
【００１７】本発明者らは、かかる硬質皮膜の固有応力
を低減させて残留応力を低減させ、それにより硬質皮膜
の剥離を防止し、密着性を向上させることを目的とし
て、鋭意研究を重ねた。その結果、硬質皮膜基礎成分
（Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの１種）を
基礎とする硬質皮膜を形成する際に、硬質皮膜中に前記
本発明に係る添加元素（Fe，Co，Ni，Cuよりなる群から
選択される１種又は２種以上の元素）を0.1 〜30at％含
有させることにより、硬質皮膜形成時に生じる硬質皮膜
の固有応力を大幅に低減させ、そのため硬質皮膜の残留
応力を著しく低減させ、ひいては残留応力による硬質皮
膜剥離を抑制し、硬質皮膜の密着性を著しく向上させる
ことができ、従って、前記従来技術における硬質皮膜に
比較し、硬質皮膜形成時の残留応力が著しく小さく、硬
質皮膜形成時の残留応力による硬質皮膜剥離が極めて生
じ難く、密着性に著しく優れた硬質皮膜が得られること
を見出した。The present inventors have conducted intensive studies for the purpose of reducing the intrinsic stress of such a hard coating to reduce the residual stress, thereby preventing peeling of the hard coating and improving the adhesion. . As a result, when forming a hard coating based on a hard coating basic component (one of C, CH, CN, CNH and BN), the present invention is incorporated into the hard coating. 0.1 to 30 at% of the additive element (1 or 2 or more elements selected from the group consisting of Fe, Co, Ni, and Cu) related to To significantly reduce the residual stress of the hard coating, and thereby suppress the peeling of the hard coating due to the residual stress, thereby significantly improving the adhesion of the hard coating. It has also been found that the residual stress at the time of forming the hard film is extremely small, the hard film is hardly peeled off due to the residual stress at the time of forming the hard film, and a hard film having extremely excellent adhesion can be obtained.
【００１８】本発明は以上のような新規知見に基づき完
成されたものであり、本発明に係る硬質皮膜は、前述の
如く、硬質皮膜基礎成分（Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ
−Ｈ，Ｂ−Ｎの１種）を基礎とする硬質皮膜であって、
この皮膜中に本発明に係る添加元素（Fe，Co，Ni，Cuよ
りなる群から選択される１種又は２種以上の元素）を0.
1 〜30at％含有してなるものとしている。従って、本発
明に係る硬質皮膜は、前記従来技術における硬質皮膜に
比較し、硬質皮膜形成時の残留応力が著しく小さく、硬
質皮膜形成時の残留応力による硬質皮膜剥離が極めて生
じ難く、密着性に著しく優れている。The present invention has been completed on the basis of the above-described new findings. As described above, the hard coating according to the present invention comprises a hard coating basic component (C, CH, CN, CN). N
-H, BN).
In this film, an additive element (one or more elements selected from the group consisting of Fe, Co, Ni, and Cu) according to the present invention is added in an amount of 0.
It is assumed to contain 1-30at%. Therefore, the hard coating according to the present invention has a remarkably small residual stress at the time of forming the hard coating as compared with the hard coating according to the related art, and hardly peels off the hard coating due to the residual stress at the time of forming the hard coating. Notably better.
【００１９】ここで、硬質皮膜中での本発明に係る添加
元素の含有量を0.1 〜30at％としているのは、0.1 at％
未満にすると硬質皮膜形成時の残留応力の低減の程度が
小さくて不充分であり、ひいては硬質皮膜の密着性が低
下して不充分となり、一方、30at％超にすると硬質皮膜
の硬さが低下し、硬質皮膜の耐摩耗性が低下して不充分
となり、硬質皮膜として有するべき基本特性が損なわれ
るからである。The reason why the content of the additive element according to the present invention in the hard coating is 0.1 to 30 at% is that 0.1 at%
If the amount is less than the above, the degree of reduction of the residual stress during the formation of the hard film is small and inadequate, and the adhesion of the hard film is reduced and becomes insufficient. On the other hand, if the amount exceeds 30 at%, the hardness of the hard film decreases. However, the abrasion resistance of the hard coating decreases and becomes inadequate, and the basic properties that the hard coating should have are impaired.
【００２０】上記本発明に係る添加元素の含有量につい
ては、0.1 〜10at％とすることが望ましい。それは、10
〜30at％の場合には硬質皮膜の耐摩耗性が不充分とはな
らないものの、硬質皮膜の耐摩耗性が比較的低下する傾
向にあり、これに対し、0.1〜10at％の場合は硬質皮膜
の耐摩耗性が低下する程度が小さく、殆ど低下せず、硬
質皮膜の耐摩耗性がより優れているからである。The content of the additional element according to the present invention is desirably 0.1 to 10 at%. It is 10
In the case of up to 30 at%, the wear resistance of the hard coating does not become insufficient, but the wear resistance of the hard coating tends to relatively decrease, whereas in the case of 0.1 to 10 at%, the wear resistance of the hard coating is reduced. This is because the degree to which the wear resistance is reduced is small and hardly reduced, and the wear resistance of the hard coating is more excellent.
【００２１】硬質皮膜基礎成分（Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，
Ｃ−Ｎ−Ｈ，Ｂ−Ｎの１種）を基礎とする硬質皮膜と
は、硬質皮膜基礎成分を主成分として含有してなる硬質
皮膜、換言すれば、マトリックスが硬質皮膜基礎成分よ
りなる硬質皮膜のことである。例えば、Ｃ−Ｈを基礎と
する硬質皮膜とはマトリックスがＣとＨとからなる硬質
皮膜のこと、Ｂ−Ｎを基礎とする硬質皮膜とはマトリッ
クスがＢとＮとからなる硬質皮膜のことである。The hard coating basic components (C, CH, CN,
The hard coating based on one of C—N—H and BN) is a hard coating containing a hard coating basic component as a main component, in other words, a hard coating in which a matrix is composed of a hard coating basic component. It is a film. For example, a hard coating based on CH is a hard coating in which the matrix is composed of C and H, and a hard coating based on BN is a hard coating in which the matrix is composed of B and N. is there.
【００２２】ところで、本発明に係る硬質皮膜と、前記
従来技術における硬質皮膜の中の特公平6-952 号公報に
記載の硬質皮膜や特開平6-212429号公報に記載の硬質皮
膜とは、密着性向上を目的として硬質皮膜中に該皮膜成
分以外の元素を添加する（含有させる）点において類似
し、共通している。しかしながら、本発明に係る硬質皮
膜と上記公報に記載の硬質皮膜とは、添加元素の種類が
相違し、そのため、添加元素の作用の仕方、即ち、添加
元素による硬質皮膜の固有応力の緩和（低減）のメカニ
ズムが異なり、本発明に係る硬質皮膜は上記公報に記載
の硬質皮膜に比較して硬質皮膜の固有応力の緩和の程度
が極めて大きく、残留応力が著しく小さくなる点におい
て顕著に相違する。この詳細を以下説明する。Incidentally, the hard coating according to the present invention and the hard coating described in JP-B-6-952 or the hard coating described in JP-A-6-212429 among the hard coatings in the prior art described above are as follows: They are similar and common in that elements other than the film components are added (contained) to the hard film for the purpose of improving adhesion. However, the hard coating according to the present invention and the hard coating described in the above-mentioned publication differ in the kind of the additive element, and therefore, the way of action of the additional element, that is, the relaxation (reduction) of the intrinsic stress of the hard coating due to the additional element. 2), the hard coating according to the present invention is significantly different from the hard coating described in the above publication in that the degree of relaxation of the intrinsic stress of the hard coating is extremely large and the residual stress is significantly reduced. The details will be described below.
【００２３】先ず、本発明に係る硬質皮膜と特開平6-21
2429号公報に記載の硬質皮膜とを比較すると、前者での
添加元素はFe，Co，Ni，Cuの１種以上であり、後者での
添加元素はTi，Zr，Cr，Nb，Mo，Hf，Ta，Ｗ（以下、Ti
等という）であるので、両者の添加元素の種類は明らか
に相違する。First, the hard coating according to the present invention and JP-A-6-21
Compared with the hard coating described in Japanese Patent No. 2429, the additive element in the former is at least one of Fe, Co, Ni, and Cu, and the additive element in the latter is Ti, Zr, Cr, Nb, Mo, Hf , Ta, W (hereinafter, Ti
Etc.), the types of the added elements are clearly different.
【００２４】この後者の公報記載の硬質皮膜での添加元
素は、硬質皮膜基礎成分であるＣ、Ｂ、Ｎとの反応性が
比較的高く、炭化物、ほう化物、窒化物、或いは、これ
らの複合化合物を形成し易いので、硬質皮膜中に化合物
として存在していると考えられる。かかる化合物は比較
的硬度が高く、ヤング率が大きいので、硬質皮膜のヤン
グ率があまり低下せずに大きく、そのため、固有応力の
緩和効果が小さい。The additional elements in the hard coating described in the latter publication have relatively high reactivity with the hard coating basic components C, B, and N, and include carbides, borides, nitrides, or composites thereof. Since the compound is easily formed, it is considered that the compound exists in the hard coating. Such a compound has a relatively high hardness and a large Young's modulus, so that the Young's modulus of the hard film is large without being reduced so much, and the effect of relaxing the intrinsic stress is small.
【００２５】これに対して、前者の本発明に係る硬質皮
膜での添加元素は、Ｃ、Ｂ、Ｎとの反応性が低いので、
硬質皮膜中に単体の金属に近い状態で存在していると考
えられる。かかる状態の金属は、硬質皮膜のマトリック
スを構成するｃＢＮ、ＤＬＣ、ＣＮ系化合物等に比べて
硬度が低く、又、前記の如き化合物よりも著しく硬度が
低く、ヤング率が小さいので、硬質皮膜のヤング率が低
下して小さくなり、そのため、固有応力の緩和効果が極
めて高い。そのため、本発明に係る硬質皮膜は特開平6-
212429号公報に記載の硬質皮膜に比較して硬質皮膜の固
有応力の緩和の程度が極めて大きく、残留応力が著しく
小さくなる。On the other hand, since the former additive element in the hard coating according to the present invention has low reactivity with C, B and N,
It is considered that the hard coating exists in a state close to a single metal. The metal in such a state has a lower hardness than cBN, DLC, CN-based compounds, etc. constituting the matrix of the hard coating, and also has a significantly lower hardness and a lower Young's modulus than the above-mentioned compounds, so that The Young's modulus decreases and decreases, and therefore, the effect of relaxing the intrinsic stress is extremely high. Therefore, the hard coating according to the present invention is disclosed in
Compared with the hard coating described in 212429, the degree of relaxation of the intrinsic stress of the hard coating is extremely large, and the residual stress is significantly reduced.
【００２６】尚、硬質皮膜のヤング率が低下すると、固
有応力が緩和されて残留応力が小さくなるのは、残留応
力はヤング率に反比例して小さくなるからである。即
ち、硬質皮膜の形成時に皮膜に弾性歪みが生じて残った
場合に残留応力が発生する。この残留応力は残った弾性
歪みとヤング率との積の値に相当する。従って、残留応
力はヤング率に反比例して小さくなり、ヤング率が低下
すると残留応力が小さくなるのである。When the Young's modulus of the hard coating decreases, the intrinsic stress is relaxed and the residual stress decreases. This is because the residual stress decreases in inverse proportion to the Young's modulus. That is, when an elastic strain occurs in the hard coating and the hard coating remains, a residual stress is generated. This residual stress corresponds to the product of the remaining elastic strain and the Young's modulus. Therefore, the residual stress decreases in inverse proportion to the Young's modulus, and the lower the Young's modulus, the smaller the residual stress.
【００２７】次に、本発明に係る硬質皮膜と特公平6-95
2 号公報に記載の硬質皮膜とを比較すると、前者での添
加元素はFe，Co，Ni，Cuの１種以上であり、後者での添
加元素はSi以外の４Ｂ族元素（Ge，Sn等）であるので、
両者の添加元素の種類は明らかに相違する。Next, the hard film according to the present invention and
Comparing with the hard coating described in Japanese Patent Publication No. 2, the additive element in the former is one or more of Fe, Co, Ni, and Cu, and the additive element in the latter is a group 4B element other than Si (Ge, Sn, etc.). ), So
The types of the added elements are obviously different.
【００２８】この特公平6-952 号公報には、「４Ｂ族元
素としてはSi以外のGe，Sn等があげられ、これらはいず
れも膜の内部応力を緩和し、金属に対する付着性をよく
する働きをする」という技術的思想が開示されている
（第２頁右欄第10〜14行目）。この中の「元素の添加に
より膜の内部応力を緩和し、付着性（密着性）をよくす
る」という技術的思想は、本発明での技術的思想と基本
的には類似している。しかしながら、この公報に記載の
硬質皮膜での添加元素は、硬質皮膜基礎成分であるＣ、
Ｂ、Ｎとの反応性が高く、炭化物、ほう化物、窒化物、
或いは、これらの複合化合物を形成し易いので、硬質皮
膜中に化合物として存在していると考えられる。かかる
化合物は硬度が比較的高く、ヤング率が大きいので、硬
質皮膜のヤング率があまり低下せずに大きく、そのた
め、固有応力の緩和効果が小さい。In Japanese Patent Publication No. 6-952, "4B group elements include Ge and Sn other than Si, all of which relax the internal stress of the film and improve the adhesion to metal. The technical idea of "work" is disclosed (page 2, right column, lines 10-14). The technical idea of "releasing the internal stress of the film by adding the element and improving the adhesion (adhesion)" is basically similar to the technical idea of the present invention. However, the additive element in the hard coating described in this publication is C, which is a hard coating basic component,
High reactivity with B, N, carbide, boride, nitride,
Alternatively, it is considered that these composite compounds are easily formed, and therefore exist as compounds in the hard coating. Such a compound has a relatively high hardness and a large Young's modulus, so that the Young's modulus of the hard coating is large without being reduced so much, and the effect of relaxing the intrinsic stress is small.
【００２９】これに対して、本発明に係る硬質皮膜での
添加元素は、前述の如く、Ｃ、Ｂ、Ｎとの反応性が低い
ことに起因して、固有応力の緩和効果が極めて高い。そ
のため、本発明に係る硬質皮膜は特公平6-952 号公報に
記載の硬質皮膜に比較して硬質皮膜の固有応力の緩和の
程度が極めて大きく、残留応力が著しく小さくなる。On the other hand, as described above, the additive element in the hard coating according to the present invention has an extremely high effect of relaxing the intrinsic stress due to the low reactivity with C, B and N. Therefore, the hard coating according to the present invention has an extremely large degree of relaxation of the intrinsic stress of the hard coating and a remarkably small residual stress as compared with the hard coating described in JP-B-6-952.
【００３０】以上の如き点において、本発明に係る硬質
皮膜は、特開平6-212429号公報記載の硬質皮膜や特公平
6-952 号公報記載の硬質皮膜とは構成及びその作用効果
が著しく相違し、これら公報記載の硬質皮膜では奏し得
ない顕著な作用効果を奏することができる。In view of the above points, the hard coating according to the present invention may be a hard coating described in Japanese Patent Application Laid-Open No.
The structure and the function and effect of the hard coating described in JP-A-6-952 are significantly different from those of the hard coating described in JP-A-6-952.
【００３１】本発明において、本発明に係る添加元素
（Fe，Co，Ni，Cuの１種以上）の中、特に、Co，Ni，Cu
は硬質皮膜基礎成分との反応性が低く、そのため硬質皮
膜の固有応力の緩和による残留応力の緩和の効果が大き
いので、Co，Ni，Cuの１種以上を選択して硬質皮膜に含
有させることが望ましい。In the present invention, among the additional elements (one or more of Fe, Co, Ni, Cu) according to the present invention, particularly, Co, Ni, Cu
Has a low reactivity with the basic components of the hard coating, and therefore has a great effect of relaxing the residual stress by relaxing the intrinsic stress of the hard coating. Therefore, select at least one of Co, Ni, and Cu to be included in the hard coating. Is desirable.
【００３２】前記硬質皮膜基礎成分としてＣ−Ｈを選択
し、本発明に係る添加元素としてCuを選択し、Ｃ−Ｈを
基礎とする硬質皮膜中にCuを含有させることが望まし
い。Ｃ−ＨとCuとは特に反応性が低く、硬質皮膜の固有
応力の緩和による残留応力の緩和の効果が特に大きくな
るからである。It is preferable that CH is selected as the hard coating basic component, Cu is selected as the additive element according to the present invention, and Cu is contained in the CH-based hard coating. This is because CH and Cu are particularly low in reactivity, and the effect of relaxing the residual stress by relaxing the intrinsic stress of the hard film becomes particularly large.
【００３３】硬質皮膜の厚みについては、特には限定さ
れるものではないが、0.1 〜５μmとするのがよい。0.1
μm 未満では、耐摩耗性の持続効果が小さくなる傾向
があり、５μm 超では、皮膜に発生する固有応力が大き
くなり、剥離しやすくなる傾向があるからである。更に
は、耐摩耗性と密着性の両立の観点より0.5 〜３μmと
することが望ましい。The thickness of the hard coating is not particularly limited, but is preferably 0.1 to 5 μm. 0.1
If it is less than μm, the effect of maintaining wear resistance tends to be small, and if it is more than 5 μm, the intrinsic stress generated in the film tends to increase, and the film tends to peel off. Further, from the viewpoint of achieving both abrasion resistance and adhesion, the thickness is preferably 0.5 to 3 μm.
【００３４】従来、残留応力による硬質皮膜の剥離、密
着性の低下という問題は、ＣＶＤ法に比べて蒸着粒子の
エネルギーが高いＰＶＤ法により硬質皮膜を形成する場
合に多く起こる問題であった。又、実用的な面よりもＰ
ＶＤ法はＣＶＤ法に比べて低温で硬質皮膜を形成し得る
ので、工業材料として多く用いられている鉄基合金等の
機械的強度を劣化させることなく、硬質皮膜を形成し得
る。これらの点から、本発明に係る硬質皮膜の形成に際
してはＰＶＤ法を適用した方が有利である。Conventionally, the problems of peeling of the hard film and lowering of adhesion due to residual stress have been problems that often occur when the hard film is formed by the PVD method in which the energy of the deposited particles is higher than that of the CVD method. In addition, P
Since the VD method can form a hard film at a lower temperature than the CVD method, the VD method can form a hard film without deteriorating the mechanical strength of an iron-based alloy or the like widely used as an industrial material. From these points, it is more advantageous to apply the PVD method when forming the hard coating according to the present invention.
【００３５】ＰＶＤ法には、スパッタリング法、イオン
プレーティング法、イオンビーム法等がある。この中
で、イオンプレーティング法の１種であるアークイオン
プレーティング法（AIP 法）は、蒸発源として固体状蒸
発源を使用することから、蒸発源の取り扱いが容易であ
り、又、他の成膜方法に比べて成膜速度が非常に速く、
蒸着原子のイオン化率が高いことから、基板との密着性
に優れた皮膜が得られるという特徴を有している。又、
本発明に係る硬質皮膜の如くＢ、Ｃ、Ｎと金属元素を含
む硬質皮膜を形成するに際して、Ｂ、Ｃ、Ｎと金属元素
との化合物あるいは混合物を蒸発源として使用すること
が可能であるため、安定した組成制御が可能である。こ
れらの点より、本発明に係る硬質皮膜の形成に際して
は、本発明に係る添加元素（Fe，Co，Ni，Cuの１種以
上）と硬質皮膜基礎成分（Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ
−Ｈ，Ｂ−Ｎの１種）とを含有する固体状蒸発源を用
い、アークイオンプレーティング法により、本発明に係
る硬質皮膜を基材表面に形成することが望ましい（第２
発明）。The PVD method includes a sputtering method, an ion plating method, an ion beam method and the like. Among them, the arc ion plating method (AIP method), which is a kind of ion plating method, uses a solid evaporation source as an evaporation source, so that the evaporation source can be easily handled. The deposition rate is very fast compared to the deposition method,
Since the ionization rate of vapor-deposited atoms is high, a film having excellent adhesion to a substrate can be obtained. or,
When forming a hard coating containing B, C, N and a metal element as in the hard coating according to the present invention, a compound or a mixture of B, C, N and a metal element can be used as an evaporation source. In addition, stable composition control is possible. From these points, when forming the hard coating according to the present invention, the additive element (at least one of Fe, Co, Ni, and Cu) according to the present invention and the hard coating basic components (C, CH, CN) are used. , C-N
-H, BN), and the hard coating according to the present invention is desirably formed on the surface of the base material by an arc ion plating method using a solid-state evaporation source (second type).
invention).
【００３６】尚、上記アークイオンプレーティング法に
用いる固体状蒸発源としては、電気伝導性を有すること
が必要であり、電気伝導性の高い方がよい。上記硬質皮
膜基礎成分の中、Ｃは電気伝導性が高く金属と同程度で
ある。かかる点からすると、Ｃを多量に含む固体状蒸発
源を用いることが望ましい。The solid evaporation source used in the arc ion plating method needs to have electric conductivity, and the higher the electric conductivity, the better. Among the above basic components of the hard coating, C has a high electric conductivity and is comparable to a metal. From this point, it is desirable to use a solid evaporation source containing a large amount of C.
【００３７】ＰＶＤ法の中でイオンビーム法はアークイ
オンプレーティング法に比べて、成膜速度は低いが、成
膜時に基板に入射するイオンのエネルギーを均一に且つ
高エネルギー側まで制御することが可能であるので、合
成イオンエネルギー領域が狭い場合にイオンビーム法の
方が有利となる場合がある。又、含有させる金属イオン
を電子ビームにより蒸着をして含有させるので、皮膜の
基板に近い側では金属濃度を高くし、皮膜の表面側では
金属濃度を低くし得て傾斜機能的な皮膜を形成すること
が可能である。従って、本発明に係る硬質皮膜の形成に
際し、合成イオンエネルギー領域が狭い場合や、傾斜機
能的な皮膜を得ようとする場合等には、本発明に係る添
加元素（Fe，Co，Ni，Cuの１種以上）を電子ビームによ
り蒸発させると共に、硬質皮膜基礎成分（Ｃ，Ｃ−Ｈ，
Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの１種）を含有するイオン
ビームを照射することにより、本発明に係る硬質皮膜を
基材表面に形成することが望ましい（第３発明）。In the PVD method, the ion beam method has a lower film forming speed than the arc ion plating method, but can control the energy of ions incident on the substrate at the time of film formation uniformly and to a higher energy side. Because it is possible, the ion beam method may be more advantageous when the synthetic ion energy region is narrow. In addition, since metal ions to be contained are deposited by electron beam deposition, the metal concentration can be increased on the side of the film close to the substrate, and the metal concentration can be reduced on the surface side of the film, forming a functionally graded film. It is possible to Therefore, when forming the hard coating according to the present invention, when the synthetic ion energy region is narrow, or when trying to obtain a functionally gradient coating, etc., the additive element (Fe, Co, Ni, Cu) according to the present invention is used. Or more) is evaporated by an electron beam, and the hard film basic components (C, CH,
It is desirable to form the hard coating according to the present invention on the surface of the base material by irradiating an ion beam containing one of CN, CNH and BN (third invention).
【００３８】[0038]
【実施例】（実施例１）表１に示す方法により表１に示
す組成のＤＬＣ膜（ダイヤモンドライクカーボン膜）を
基板上に形成した。EXAMPLES Example 1 A DLC film (diamond-like carbon film) having the composition shown in Table 1 was formed on a substrate by the method shown in Table 1.
【００３９】即ち、ターゲットとして固体炭素ターゲッ
ト中に本発明に係る添加元素を混入させたものを用い、
スパッタリング法により、本発明の実施例１に係るＤＬ
Ｃ膜を形成した（No.1〜4)。又、固体状蒸発源として固
体炭素と本発明に係る添加元素との混合物を用い、AIP
法（アークイオンプレーティング法）により、本発明の
実施例１に係るＤＬＣ膜を形成した（No.5〜9 、12〜1
5) 。又、本発明に係る添加元素を電子ビームにより蒸
発させると共にＣを含有するイオンビームを照射すると
いうイオンビーム法（：IB＋EB法）により、本発明の実
施例１に係るＤＬＣ膜を形成した(No.10〜11）。更に
は、比較のために比較例１に係るＤＬＣ膜として、添加
元素を含有させないＤＬＣ膜、及び、Cr，Ti又はGeを含
有するＤＬＣ膜を形成した（No.17 〜20) 。That is, a target obtained by mixing the additive element according to the present invention into a solid carbon target is used as the target.
DL according to Example 1 of the present invention by sputtering
A C film was formed (Nos. 1 to 4). Further, using a mixture of solid carbon and the additive element according to the present invention as a solid evaporation source, AIP
The DLC films according to Example 1 of the present invention were formed by a method (arc ion plating method) (Nos. 5 to 9, 12 to 1).
Five) . Further, the DLC film according to Example 1 of the present invention was formed by an ion beam method (IB + EB method) in which the additive element according to the present invention was evaporated with an electron beam and irradiated with an ion beam containing C (No. .10-11). For comparison, a DLC film containing no additional element and a DLC film containing Cr, Ti or Ge were formed as DLC films according to Comparative Example 1 (Nos. 17 to 20).
【００４０】このとき、目的によっては適時、雰囲気中
に水素ガスを導入し、水素化ダイヤモンドライクカーボ
ン膜にした。スパッタリング法での代表的な成膜条件と
しては、雰囲気：Arガス、Arガス圧：３ｍtorr、温度:5
00℃、RF電力:300Ｗという条件等が挙げられる。AIP 法
での代表的な成膜条件としては、アーク電流:100Ａ、基
板電圧：−300 Ｖ、基板温度:100℃という条件等が挙げ
られる。イオンビーム法（：IB＋EB法）での代表的な成
膜条件としては、炭素ガス圧：２×10-4torr、基板温
度：550 ℃、炭素イオンのエネルギー：−500 Ｖ、Ｃ蒸
着速度：100 Å／min という条件等が挙げられる。基板
には、Siウェハ或いはJIS のSKD11 相当材を鏡面研磨し
たものを用いた。At this time, hydrogen gas was appropriately introduced into the atmosphere depending on the purpose to form a hydrogenated diamond-like carbon film. Typical film forming conditions in the sputtering method are as follows: atmosphere: Ar gas, Ar gas pressure: 3 mtorr, temperature: 5
Conditions such as 00 ° C. and RF power: 300 W are mentioned. Typical film forming conditions in the AIP method include conditions such as an arc current of 100 A, a substrate voltage of −300 V, and a substrate temperature of 100 ° C. Typical film forming conditions in the ion beam method (: IB + EB method) are as follows: carbon gas pressure: 2 × 10 −4 torr, substrate temperature: 550 ° C., carbon ion energy: −500 V, C deposition rate: 100条件 / min. As the substrate, a Si wafer or a material equivalent to JIS SKD11 which was mirror-polished was used.
【００４１】このようにして得られたＤＬＣ膜（No.1〜
15、17〜20）及びSKD11 相当材(No.16）について、半
径：200 μm Ｒの半球状のダイヤコーンを用いたスクラ
ッチ試験を行い、それにより密着力の評価を行った。
又、ピンオンディスク試験を行い、それにより摺動特性
の評価を行った。このとき、ピンオンディスク試験は、
ＤＬＣ膜の中で基板にSKD11 相当材を用いたもの、及
び、SKD11 相当材(No.16）を供試し、相手材のピンには
SCM415を用い、荷重：50Ｎ、摺動速度：10mm／sec で摺
動距離：１kmになるまで摺動させ、１km摺動後の摩耗量
を測定する方法により行い、これにより耐摩耗性を評価
した。このピンオンディスク試験に供試したＤＬＣ膜の
厚みは、1.5 μm である。The DLC films thus obtained (No. 1 to No. 1)
15, 17 to 20) and a material equivalent to SKD11 (No. 16) were subjected to a scratch test using a hemispherical diamond cone having a radius of 200 μm R to thereby evaluate the adhesion.
Further, a pin-on-disk test was performed to evaluate the sliding characteristics. At this time, the pin-on-disk test
In the DLC film, SKD11 equivalent material was used for the substrate and SKD11 equivalent material (No.16) was tested.
Using SCM415, the load was 50 N, the sliding speed was 10 mm / sec, the sliding distance was 1 km, and the sliding amount was measured after 1 km sliding. The wear resistance was evaluated. . The thickness of the DLC film subjected to the pin-on-disk test was 1.5 μm.
【００４２】これらの結果を表１に示す。表１からわか
る如く、本発明の実施例１に係るＤＬＣ膜（No.1〜15）
は、比較例１に係るＤＬＣ膜（No.17 〜20）に比較し
て、著しく密着力が大きくて密着性に優れ、又、耐摩耗
性に極めて優れており、極めて優れた密着性及び耐摩耗
性を兼ね備えている。Table 1 shows the results. As can be seen from Table 1, the DLC films according to Example 1 of the present invention (Nos. 1 to 15)
Has a remarkably large adhesive force and excellent adhesion as compared with the DLC film (Nos. 17 to 20) according to Comparative Example 1, and has extremely excellent abrasion resistance. Has abrasion properties.
【００４３】本発明の実施例１に係るＤＬＣ膜（No.1〜
15）の中、No.1〜11のものは本発明に係る添加元素とし
てその中の１種のみを含有しており、No.12 〜15のもの
は本発明に係る添加元素としてその中の２種又は３種を
含有している。いずれの場合も同様に密着性及び耐摩耗
性が極めて優れている。The DLC film according to the first embodiment of the present invention (No. 1 to No. 1)
Among 15), those of Nos. 1 to 11 contain only one of them as an additive element according to the present invention, and those of Nos. 12 to 15 contain them as additive elements according to the present invention. Contains 2 or 3 types. In each case, the adhesion and the abrasion resistance are extremely excellent.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 （実施例２）表２に示す方法により表２に示す組成のＢ
Ｎ膜を基板上に形成した。[Table 2] (Example 2) B having the composition shown in Table 2 was prepared by the method shown in Table 2.
An N film was formed on the substrate.
【００４６】即ち、ターゲットとして固体ホウ素（Ｂ）
ターゲット中に本発明に係る添加元素を混入させたもの
を用い、RF（高周波）スパッタリング法により、本発明
の実施例２に係るＢＮ膜を形成した（No.21 〜24) 。
又、固体状蒸発源として固体ホウ素と本発明に係る添加
元素との混合物を用い、AIP 法により、本発明の実施例
２に係るＢＮ膜を形成した（No.31 〜34) 。又、本発明
に係る添加元素を電子ビームにより蒸発させると共にＢ
を含有するイオンビームを照射するというイオンビーム
法（：IB＋EB法）により、本発明の実施例２に係るＢＮ
膜を形成した(No.25〜30）。更には、比較のために比較
例２に係るＢＮ膜として、添加元素を含有させないＢＮ
膜（ｃＢＮ膜）を形成した（No.36)。That is, solid boron (B) is used as a target.
Using a target in which the additive element according to the present invention was mixed in a target, a BN film according to Example 2 of the present invention was formed by RF (high frequency) sputtering (Nos. 21 to 24).
Further, a BN film according to Example 2 of the present invention was formed by an AIP method using a mixture of solid boron and the additive element according to the present invention as a solid evaporation source (Nos. 31 to 34). Further, the additive element according to the present invention is evaporated by an electron beam and
BN according to Example 2 of the present invention by an ion beam method of irradiating an ion beam containing
A film was formed (Nos. 25 to 30). Further, for comparison, a BN film containing no additional element was used as the BN film according to Comparative Example 2.
A film (cBN film) was formed (No. 36).
【００４７】このとき、RFスパッタリング法はN2雰囲気
中で行い、スパッタリング時の代表的な成膜条件として
は、温度：500 ℃、N2＋Ar圧：２mtorr 、RF電力：300
Ｗという条件等が挙げられる。AIP 法での代表的な成膜
条件としては、アーク電流：100 Ａ、基板電圧：−300
Ｖ、基板温度：100 ℃という条件等が挙げられる。イオ
ンビーム法での代表的な成膜条件としては、窒素ガス
圧：２×10-4torr、基板温度：550 ℃、窒素イオンのエ
ネルギー：−500 Ｖ、Ｂ蒸着速度：100 Å／minという
条件等が挙げられる。基板には、Siウェハ或いはJIS の
SKD11 相当材を鏡面研磨したものを用いた。At this time, the RF sputtering method is performed in an N 2 atmosphere. Typical film forming conditions during sputtering include a temperature of 500 ° C., an N 2 + Ar pressure of 2 mtorr, and an RF power of 300.
And the condition of W. Typical deposition conditions for the AIP method are: arc current: 100 A, substrate voltage: -300
V, substrate temperature: 100 ° C., and the like. Typical film forming conditions in the ion beam method are as follows: nitrogen gas pressure: 2 × 10 −4 torr, substrate temperature: 550 ° C., nitrogen ion energy: −500 V, B deposition rate: 100 ° / min. And the like. Substrate can be Si wafer or JIS
Mirror-polished SKD11 equivalent material was used.
【００４８】このようにして得られたＢＮ膜（No.21 〜
30、36）及びSKD11 相当材(No.35）について、実施例１
の場合と同様の方法により、密着力の評価及び摺動特性
の評価（即ち、摩耗量の測定）を行った。The thus obtained BN film (No. 21 to No. 21)
Examples 1 and 2 for 30 and 36) and SKD11 equivalent material (No. 35)
In the same manner as in the above case, the evaluation of the adhesion and the evaluation of the sliding characteristics (that is, the measurement of the wear amount) were performed.
【００４９】これらの結果を表２に示す。表２からわか
る如く、本発明の実施例２に係るＢＮ膜（No.21 〜34）
は、比較例２に係るＢＮ膜（No.36)に比較して、著しく
密着力が大きくて密着性に優れ、又、耐摩耗性に極めて
優れており、極めて優れた密着性及び耐摩耗性を兼ね備
えている。Table 2 shows the results. As can be seen from Table 2, the BN films according to Example 2 of the present invention (Nos. 21 to 34)
Has a remarkably large adhesive force and excellent adhesiveness as compared with the BN film (No. 36) according to Comparative Example 2, and is also extremely excellent in abrasion resistance. Has both.
【００５０】本発明の実施例２に係るＢＮ膜（No.21 〜
34）の中、No.21 〜30のものは本発明に係る添加元素と
してその中の１種のみを含有しており、No.31 〜34のも
のは本発明に係る添加元素としてその中の２種又は３種
を含有している。いずれの場合も同様に密着性及び耐摩
耗性が極めて優れている。The BN film according to the second embodiment of the present invention (No. 21 to No. 21)
Of the 34), those of Nos. 21 to 30 contain only one of them as an additive element according to the present invention, and those of Nos. 31 to 34 contain them as an additive element according to the present invention. Contains 2 or 3 types. In each case, the adhesion and the abrasion resistance are extremely excellent.
【００５１】[0051]
【発明の効果】本発明に係る硬質皮膜は、従来の硬質皮
膜に比べ、硬質皮膜形成時の残留応力による硬質皮膜剥
離が生じ難く、極めて密着性に優れている。従って、工
具や摺動部材等の如く耐摩耗性及び摺動性の必要な部材
の硬質皮膜として好適に用いることができ、これらの部
材の寿命の向上がはかれるようになるという効果を奏す
る。The hard coating according to the present invention is hardly peeled off by the residual stress during the formation of the hard coating, and has excellent adhesion, as compared with the conventional hard coating. Therefore, it can be suitably used as a hard film of a member requiring wear resistance and slidability, such as a tool and a sliding member, and has an effect that the life of these members can be improved.
【００５２】本発明に係る硬質皮膜の形成方法は、この
ような密着性に優れた硬質皮膜を形成することができる
という効果を奏する。The method for forming a hard film according to the present invention has an effect that a hard film having excellent adhesion can be formed.
Claims (3)
Ｎの何れかを基礎とする硬質皮膜であって、前記皮膜中
にFe，Co，Ni，Cuよりなる群から選択される１種又は２
種以上の元素を0.1 〜30at％含有してなることを特徴と
する耐摩耗性及び摺動性に優れた硬質皮膜。1. C, CH, CN, CNH, B-
A hard coating based on any one of N, wherein one or two selected from the group consisting of Fe, Co, Ni, and Cu in the coating.
A hard coating excellent in wear resistance and slidability, characterized by containing 0.1 to 30 at% of at least one kind of element.
る１種又は２種以上の元素とＣ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−
Ｎ−Ｈ，Ｂ−Ｎの何れか１種とを含有する固体状蒸発源
を用い、アークイオンプレーティング法により、Fe，C
o，Ni，Cuよりなる群から選択される１種又は２種以上
の元素を0.1 〜30at％含有する、Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，
Ｃ−Ｎ−Ｈ，Ｂ−Ｎの何れかを基礎とする硬質皮膜を基
材表面に形成することを特徴とする耐摩耗性及び摺動性
に優れた硬質皮膜の形成方法。2. One or more elements selected from the group consisting of Fe, Co, Ni, and Cu, and C, CH, CN, C-
Fe, C by arc ion plating using a solid evaporation source containing any one of NH, BN
C, CH, CN, containing 0.1 to 30 at% of one or more elements selected from the group consisting of o, Ni, and Cu.
A method for forming a hard coating excellent in wear resistance and slidability, comprising forming a hard coating based on any of CNH and BN on a substrate surface.
る１種又は２種以上の元素を電子ビームにより蒸発させ
ると共に、Ｃ，Ｃ−Ｈ，Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの
何れか１種を含有するイオンビームを照射することによ
り、Fe，Co，Ni，Cuよりなる群から選択される１種又は
２種以上の元素を0.1 〜30at％含有する、Ｃ，Ｃ−Ｈ，
Ｃ−Ｎ，Ｃ−Ｎ−Ｈ，Ｂ−Ｎの何れかを基礎とする硬質
皮膜を基材表面に形成することを特徴とする耐摩耗性及
び摺動性に優れた硬質皮膜の形成方法。3. The method of claim 1, wherein one or more elements selected from the group consisting of Fe, Co, Ni, and Cu are evaporated by an electron beam, and C, CH, CN, CNNH. , By irradiation of an ion beam containing any one of BN, 0.1 to 30 at% of one or more elements selected from the group consisting of Fe, Co, Ni, and Cu. C, CH,
A method for forming a hard coating excellent in wear resistance and slidability, comprising forming a hard coating based on any of CN, CNH, and BN on a substrate surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00568498A JP3784953B2 (en) | 1998-01-14 | 1998-01-14 | Hard coating excellent in wear resistance and sliding property and method for forming the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00568498A JP3784953B2 (en) | 1998-01-14 | 1998-01-14 | Hard coating excellent in wear resistance and sliding property and method for forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11200012A true JPH11200012A (en) | 1999-07-27 |
| JP3784953B2 JP3784953B2 (en) | 2006-06-14 |
Family
ID=11617936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00568498A Expired - Lifetime JP3784953B2 (en) | 1998-01-14 | 1998-01-14 | Hard coating excellent in wear resistance and sliding property and method for forming the same |
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| Country | Link |
|---|---|
| JP (1) | JP3784953B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4666241B2 (en) * | 1998-12-25 | 2011-04-06 | 住友電気工業株式会社 | Sliding member |
| JP2012137150A (en) * | 2010-12-27 | 2012-07-19 | Nippon Piston Ring Co Ltd | Piston ring |
-
1998
- 1998-01-14 JP JP00568498A patent/JP3784953B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4666241B2 (en) * | 1998-12-25 | 2011-04-06 | 住友電気工業株式会社 | Sliding member |
| JP2012137150A (en) * | 2010-12-27 | 2012-07-19 | Nippon Piston Ring Co Ltd | Piston ring |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3784953B2 (en) | 2006-06-14 |
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