JP2002053946A - Hard film and wear resistant member, and manufacturing method thereof - Google Patents
Hard film and wear resistant member, and manufacturing method thereofInfo
- Publication number
- JP2002053946A JP2002053946A JP2000237443A JP2000237443A JP2002053946A JP 2002053946 A JP2002053946 A JP 2002053946A JP 2000237443 A JP2000237443 A JP 2000237443A JP 2000237443 A JP2000237443 A JP 2000237443A JP 2002053946 A JP2002053946 A JP 2002053946A
- Authority
- JP
- Japan
- Prior art keywords
- film
- oxide film
- aluminum oxide
- corundum structure
- wear
- 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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- Cutting Tools, Boring Holders, And Turrets (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、切削工具、摺動部
材、金型の如き耐摩耗部材に適用される耐摩耗性及び耐
熱性に優れた硬質皮膜に関するものであり、詳細には、
この様に耐摩耗性および耐熱性に優れた硬質皮膜を、上
記切削工具や摺動部材等の基材の特性を損なうことのな
い低温条件で形成することのできる有用な硬質皮膜とそ
の形成方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard coating excellent in wear resistance and heat resistance applied to wear-resistant members such as cutting tools, sliding members, and dies.
A useful hard coating capable of forming a hard coating excellent in wear resistance and heat resistance under low-temperature conditions without impairing the properties of the base material such as the cutting tool and the sliding member, and a method for forming the hard coating. It is about.
【０００２】尚、本発明の対象となる硬質皮膜は、上記
した様々な用途に適用できるが、以下では代表例として
切削工具に適用する場合を中心に説明を進める。[0002] The hard coating to which the present invention is applied can be applied to the various uses described above. Hereinafter, the description will be given mainly on the case where the hard coating is applied to a cutting tool as a typical example.
【０００３】[0003]
【従来の技術】一般に、優れた耐摩耗性や摺動特性が求
められる切削工具や摺動部材等においては、高速度鋼や
超硬合金等の基材表面に、物理蒸着法（以下、ＰＶＤ法
という）や化学蒸着法（以下、ＣＶＤ法という）等の方
法で、チタン窒化物やチタンアルミニウム窒化物等の硬
質皮膜を形成する方法が採用されているが、切削工具等
の刃先は切削時に１０００℃以上の高温となる場合があ
るため、特に、硬質皮膜として酸化アルミニウムを形成
して耐熱性を確保することが多い。2. Description of the Related Art Generally, in cutting tools and sliding members requiring excellent wear resistance and sliding characteristics, a physical vapor deposition (hereinafter, referred to as PVD) method is applied to the surface of a base material such as high-speed steel or cemented carbide. A method of forming a hard coating such as titanium nitride or titanium aluminum nitride by a method such as a chemical vapor deposition method (hereinafter, referred to as a CVD method) or the like is employed. Since the temperature may be as high as 1000 ° C. or more, particularly, aluminum oxide is often formed as a hard film to ensure heat resistance.
【０００４】上記酸化アルミニウムは、温度によって様
々な結晶構造をとるが、いずれも熱的に準安定状態にあ
る。しかし、切削工具の如く切削時における刃先の温度
が、常温から１０００℃以上にわたる広範囲で著しく変
動する場合、上記酸化アルミニウムの結晶構造が変化し
て、皮膜に亀裂が生じたり剥離する等の問題を生じる。
ところが、ＣＶＤ法を採用して基材温度を１０００℃以
上に高めることによって生成されるコランダム構造の酸
化アルミニウムだけは、一旦形成されると、以後、温度
に関係なく熱的に安定な構造を維持する。したがって、
切削工具等に耐熱性を付与するには、コランダム構造の
酸化アルミニウムで被覆することが非常に有効な手段と
されている。The above-mentioned aluminum oxide has various crystal structures depending on the temperature, but all are in a thermally metastable state. However, when the temperature of the cutting edge at the time of cutting, such as a cutting tool, fluctuates significantly over a wide range from room temperature to 1000 ° C. or more, the crystal structure of the aluminum oxide changes, causing problems such as cracking or peeling of the film. Occurs.
However, only the aluminum oxide having a corundum structure produced by increasing the substrate temperature to 1000 ° C. or higher by employing the CVD method, once formed, maintains a thermally stable structure regardless of the temperature thereafter. I do. Therefore,
In order to impart heat resistance to a cutting tool or the like, coating with a corundum-structured aluminum oxide is considered to be a very effective means.
【０００５】しかしながら、上述の通りコランダム構造
の酸化アルミニウムは、基材を１０００℃以上にまで加
熱しなければ形成できないため、適用できる基材が限ら
れてくる。即ち、基材の種類によっては、１０００℃以
上の高温にさらされると軟質化し、耐摩耗部材用基材と
しての適性が失われることがあるからである。However, as described above, aluminum oxide having a corundum structure cannot be formed unless the base material is heated to 1000 ° C. or higher, so that applicable base materials are limited. That is, depending on the type of the base material, the base material may be softened when exposed to a high temperature of 1000 ° C. or higher, and lose its suitability as a base material for a wear-resistant member.
【０００６】この様な問題に対し、特開平５−２０８３
２６号公報では、高硬度の（Ａｌ，Ｃｒ）2Ｏ3混合結晶
を５００℃以下で得たことが報告されている。しかしな
がら、被削材が鉄を主成分とするものである場合、前記
混合結晶皮膜の表面に存在するＣｒが、切削時に切削面
で鉄と化学反応を起こし易いため、皮膜の消耗が激しく
寿命を縮める原因となる。To solve such a problem, Japanese Patent Laid-Open Publication No.
No. 26 reports that a (Al, Cr) 2 O 3 mixed crystal of high hardness was obtained at 500 ° C. or lower. However, when the work material is mainly composed of iron, the Cr present on the surface of the mixed crystal film easily causes a chemical reaction with iron on the cut surface during cutting, so that the film is consumed greatly and the life is shortened. It causes shrinkage.
【０００７】また、O.Zywitzki，G.Hoetzschらは、高出
力(11−17ｋＷ)のパルス電源を用いて反応性スパッタリ
ングを行うことで、７５０℃以上でコランダム構造の酸
化アルミニウム皮膜が形成されることを報告している
（Surf.Coat.Technol.,86-87 (1996) 640-647）。しか
し、この方法でコランダム構造の酸化アルミニウムを得
るには、パルス電源の大型化が避けられず、また、製造
にあたっては基材温度を７５０℃以上に高めねばならな
いため、切削工具等の基材として一般的に使用される高
速度鋼が軟質化する等、基材特性が損なわれるといった
問題が生じる。Also, O. Zywitzki, G. Hoetzsch, et al. Form an aluminum oxide film having a corundum structure at 750 ° C. or more by performing reactive sputtering using a high-power (11-17 kW) pulse power supply. (Surf.Coat.Technol., 86-87 (1996) 640-647). However, in order to obtain corundum-structured aluminum oxide by this method, it is inevitable to increase the size of the pulse power supply, and since the base material temperature must be raised to 750 ° C. or more in manufacturing, it is used as a base material for cutting tools and the like. There is a problem in that the properties of the base material are impaired, such as the softening of commonly used high-speed steel.
【０００８】現在、汎用されている切削工具では、耐摩
耗性等を付与するため、基材表面にチタンの窒化物や炭
化物、炭窒化物等からなる皮膜を形成し、該皮膜上に前
記コランダム構造の酸化アルミニウムを形成している。
さらに近年では、チタンとアルミニウムの複合窒化皮膜
（以下、ＴｉＡｌＮと記す）が、より優れた耐摩耗性を
示すことから、前記チタンの窒化物や炭化物、炭窒化物
等からなる皮膜に代わって切削工具等に適用されつつあ
る。[0008] At present, a cutting tool that is widely used forms a film made of titanium nitride, carbide, carbonitride or the like on the surface of a base material to impart wear resistance and the like, and the corundum is formed on the film. The structure forms aluminum oxide.
In recent years, since a composite nitride film of titanium and aluminum (hereinafter, referred to as TiAlN) shows more excellent wear resistance, cutting is performed in place of a film made of nitride, carbide, carbonitride or the like of titanium. It is being applied to tools and the like.
【０００９】しかしながら、前記ＴｉＡｌＮ皮膜は、Ｐ
ＶＤ法の一種であるアークイオンプレーディング法（以
下、ＡＩＰ法という）でしか形成することができず、一
方、前記コランダム構造の酸化アルミニウムはＣＶＤ法
でしか形成できないため、積層皮膜を得るには、ＣＶＤ
用装置とＰＶＤ用装置を用いて各々の皮膜を順次形成し
なければならず、生産効率が非常に悪い。従って、前記
コランダム構造の酸化アルミニウム、及び前記ＴｉＡｌ
Ｎ皮膜、更にその他の有用な皮膜等を、連続プロセスで
効率よく形成し得るような技術の確立が望まれている。However, the TiAlN film is made of P
Aluminum oxide having a corundum structure can be formed only by the CVD method, and can be formed only by the arc ion plating method (hereinafter, referred to as AIP method) which is a kind of the VD method. , CVD
Each film must be sequentially formed by using an apparatus for PVD and an apparatus for PVD, and the production efficiency is very poor. Therefore, the corundum-structured aluminum oxide and the TiAl
It is desired to establish a technology that can efficiently form an N film and other useful films in a continuous process.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、上記の様な
事情に鑑みてなされたものであって、その目的は、耐熱
性、耐摩耗性等に優れた硬質皮膜を、基材の特性を損な
わない低温で効率よく製造することのできる有用な方法
を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a hard coating excellent in heat resistance, abrasion resistance, etc. It is an object of the present invention to provide a useful method that can be efficiently produced at a low temperature without impairing the quality.
【００１１】[0011]
【課題を解決するための手段】本発明に係る硬質皮膜と
は、格子定数が４．７７９Å以上５．０００Å以下で膜
厚が少なくとも０．００５μmであるコランダム構造の
酸化物皮膜の一方の面に、コランダム構造の酸化アルミ
ニウム皮膜が形成されていることを要旨とするものであ
る。The hard coating according to the present invention refers to a hard coating having a lattice constant of not less than 4.779 ° and not more than 5.000 ° and a thickness of at least 0.005 μm. The gist is that an aluminum oxide film having a corundum structure is formed.
【００１２】前記酸化物皮膜の成分は、Ｃｒ2Ｏ3、（Ｆ
ｅ，Ｃｒ)2Ｏ3又は（Ａｌ，Ｃｒ）2Ｏ3のいずれかであ
ることが望ましく、該酸化物皮膜が、前記（Ｆｅ，Ｃ
ｒ)2Ｏ3である場合には（Ｆｅx，Ｃｒ(1-x))2Ｏ3（ただ
し、ｘは０≦ｘ≦０．５４）であることが好ましく、ま
た前記（Ａｌ，Ｃｒ)2Ｏ3である場合には（Ａｌy，Ｃｒ
(1-y))2Ｏ3（ただし、ｙは０≦ｙ≦０．９０）であるこ
とが好ましい。The component of the oxide film is CrTwoOThree, (F
e, Cr)TwoOThreeOr (Al, Cr)TwoOThreeAny of
Preferably, the oxide film is formed of the above (Fe, C
r)TwoOThreeIf (Fex, Cr(1-x))TwoOThree(However
And x is preferably 0 ≦ x ≦ 0.54).
(Al, Cr)TwoOThreeIf (Aly, Cr
(1-y))TwoOThree(However, y is 0 ≦ y ≦ 0.90)
Is preferred.
【００１３】更に、前記コランダム構造の酸化物皮膜の
他方の面には、中間層を介し又は介さずに、Ｔｉ、Ｃ
ｒ、Ｖよりなる群から選択される１種以上の元素とＡｌ
との複合窒化皮膜が形成され、前記中間層としては（Ａ
ｌz，Ｃｒ(1-z)）Ｎ（ただし、ｚは０≦ｚ≦０．９０）
からなる皮膜が形成されていることが好ましい。Further, on the other surface of the oxide film having the corundum structure, with or without an intermediate layer, Ti, C
at least one element selected from the group consisting of
Is formed as a composite nitride film, and (A)
l z , Cr (1-z) ) N (where z is 0 ≦ z ≦ 0.90)
It is preferable that a film consisting of
【００１４】また本発明には、上記いずれかの硬質皮膜
を、前記コランダム構造の酸化アルミニウムを表面側と
して基材上に形成した耐摩耗部材が包含される。The present invention also includes a wear-resistant member in which any one of the above hard coatings is formed on a substrate with the above-mentioned aluminum oxide having a corundum structure as a surface side.
【００１５】本発明で規定する耐摩耗部材の製法とは、
前記コランダム構造の酸化アルミニウム、酸化物皮膜、
複合窒化皮膜および必要に応じて形成される中間層を、
物理蒸着法で形成する工程を含むところに要旨を有する
ものである。また、この製法を実施するに当たり、前記
（Ａｌy，Ｃｒ(1-y)）2Ｏ3（ただし、ｙは０≦ｙ≦０．
９０）皮膜を形成するには、中間層として前記（Ａ
ｌz，Ｃｒ(1-z)）Ｎ（ただし、ｚは０≦ｚ≦０．９０）
皮膜を形成した後、その表層側の少なくとも一部を酸化
して酸化物に変えることによって形成することが好まし
く、この場合の酸化は、酸素雰囲気下で基材温度を４５
０℃以上に保持して行うことが望ましい。更に、前記コ
ランダム構造の酸化アルミニウム皮膜の形成は、基材温
度３００℃以上で行うことが好ましい。The method for producing a wear-resistant member specified in the present invention is as follows.
Aluminum oxide of the corundum structure, oxide film,
The composite nitride film and the optional intermediate layer
The present invention has a gist in including a step of forming by a physical vapor deposition method. Further, in carrying out this process, the (Al y, Cr (1- y)) 2 O 3 ( however, y is 0 ≦ y ≦ 0.
90) To form a film, (A)
l z , Cr (1-z) ) N (where z is 0 ≦ z ≦ 0.90)
After the film is formed, it is preferable to form the film by oxidizing at least a part of the surface layer side to convert it to an oxide.
It is desirable to carry out the process while maintaining the temperature at 0 ° C. or higher. Further, the formation of the aluminum oxide film having a corundum structure is preferably performed at a substrate temperature of 300 ° C. or higher.
【００１６】[0016]
【発明の実施の形態】本発明者らは、前述した様な状況
の下で、コランダム構造の酸化アルミニウムを、被覆す
べき基材の特性を損ねない低温で形成することのできる
方法について鋭意研究を進めた。その結果、結晶構造が
酸化アルミニウムと同じコランダム構造であり且つ特定
の格子定数を有する物質を、酸化物皮膜として予め形成
しておけば、低温条件下であっても、該酸化物皮膜上に
コランダム構造の酸化アルミニウムを容易に形成できる
ことを見出した。以下、本発明のポイントである上記酸
化物皮膜、および優れた特性を付与する他の有用な皮膜
について詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have intensively studied a method for forming aluminum oxide having a corundum structure at a low temperature without impairing the properties of a substrate to be coated under the above-described circumstances. Advanced. As a result, if a substance having a crystal structure of the same corundum structure as aluminum oxide and a specific lattice constant is formed in advance as an oxide film, corundum can be formed on the oxide film even at a low temperature. It has been found that aluminum oxide having a structure can be easily formed. Hereinafter, the above oxide film, which is the point of the present invention, and other useful films that impart excellent properties will be described in detail.
【００１７】＜酸化物皮膜＞被覆する酸化アルミニウム
と同じコランダム結晶構造を有し、かつ格子定数が酸化
アルミニウムに近い物質として、Ｃｒ2Ｏ3、Ｆｅ2Ｏ3、
（Ｆｅ，Ｃｒ）2Ｏ3、（Ｃｒ，Ａｌ）2Ｏ3が挙げられ
る。そこで、これら種々の酸化物皮膜上に酸化アルミニ
ウムを形成したところ、該酸化物の格子定数が、４．７
７９〜５．０００Åの範囲内にある場合には、比較的低
い温度条件（例えば３００℃〜７００℃）でもコランダ
ム構造の酸化アルミニウムが形成されるのに対し、コラ
ンダム構造の酸化物皮膜であっても、格子定数が上記範
囲を外れる場合は、コランダム構造の酸化アルミニウム
が形成されないことが分かった。<Oxide film> As a substance having the same corundum crystal structure as aluminum oxide to be coated and having a lattice constant close to that of aluminum oxide, Cr 2 O 3 , Fe 2 O 3 ,
(Fe, Cr) 2 O 3 and (Cr, Al) 2 O 3 . Then, when aluminum oxide was formed on these various oxide films, the lattice constant of the oxide was 4.7.
When the temperature is in the range of 79 to 5.000 °, aluminum oxide having a corundum structure is formed even under a relatively low temperature condition (for example, 300 ° C. to 700 ° C.). It was also found that when the lattice constant was out of the above range, aluminum oxide having a corundum structure was not formed.
【００１８】即ち、酸化物皮膜の格子定数が５．０００
Åを超える場合には、被覆する酸化アルミニウムの格子
定数とのずれが大きくなるため、コランダム構造の酸化
アルミニウムが形成されにくく、立方晶構造等の如きコ
ランダム構造以外の構造が形成される。従って酸化物皮
膜の格子定数は、５．０００Å以下に抑える必要があ
り、４．９８２Å以下にすることが好ましい。That is, the lattice constant of the oxide film is 5,000.
If Å is exceeded, the deviation from the lattice constant of the aluminum oxide to be coated becomes large, so that aluminum oxide having a corundum structure is not easily formed, and a structure other than the corundum structure such as a cubic structure is formed. Therefore, the lattice constant of the oxide film must be suppressed to 5.000 ° or less, and is preferably set to 4.982 ° or less.
【００１９】尚、酸化物皮膜としてＦｅとＣｒの複合酸
化物を用いる場合、Ｆｅの組成比が０．５４を超える
と、上記複合酸化物の格子定数が５．０００Åを超え、
該酸化物皮膜上にコランダム構造のみからなる酸化アル
ミニウムを形成できなくなる。従って、酸化物皮膜とし
てＦｅとＣｒの複合酸化物を用いる場合には、組成式
（Ｆｅx，Ｃｒ(1-x)）2Ｏ3において、ｘを０≦ｘ≦０．
５４、より好ましくは０≦ｘ≦０．３０の範囲とすべき
である。When a composite oxide of Fe and Cr is used as the oxide film, if the composition ratio of Fe exceeds 0.54, the lattice constant of the composite oxide exceeds 5.000 °,
Aluminum oxide having only a corundum structure cannot be formed on the oxide film. Therefore, in the case of using a composite oxide of Fe and Cr as an oxide film, the composition formula (Fe x, Cr (1- x)) In 2 O 3, the x 0 ≦ x ≦ 0.
54, more preferably 0 ≦ x ≦ 0.30.
【００２０】次に、酸化物皮膜の格子定数の下限を４．
７７９Åに規定した理由について述べる。Next, the lower limit of the lattice constant of the oxide film is set to 4.
The reason specified in 779 ° will be described.
【００２１】Ｃｒ2Ｏ3とＦｅ2Ｏ3の格子定数は、共にＡ
ｌ2Ｏ3の格子定数よりも大きいため、Ａｌ2Ｏ3の格子定
数に近い格子定数のより小さな酸化物皮膜を得るには、
ＣｒとＡｌの複合酸化物またはＦｅとＡｌの複合酸化物
とすればよい。しかしながら、ＦｅとＡｌの複合酸化物
は、スピネル構造となって純粋なコランダム構造が形成
されないため、本発明の酸化物皮膜には適さない。The lattice constants of Cr 2 O 3 and Fe 2 O 3 are both A
To obtain a smaller oxide film having a lattice constant close to the lattice constant of Al 2 O 3 because it is larger than the lattice constant of l 2 O 3 ,
A composite oxide of Cr and Al or a composite oxide of Fe and Al may be used. However, the composite oxide of Fe and Al has a spinel structure and does not form a pure corundum structure, and thus is not suitable for the oxide film of the present invention.
【００２２】またＣｒとＡｌの複合酸化物の場合、上述
の通りＡｌの組成比が増加するにつれて格子定数は小さ
くなるが、Ａｌの組成比が０．９０を超えると、コラン
ダム構造の酸化物皮膜が高温でしか生成されなくなり、
低温ではコランダム構造以外の結晶構造が生成して純粋
なコランダム構造の酸化物皮膜が得られない。従って、
（Ａｌ0.9，Ｃｒ0.1）2Ｏ3の格子定数である４．７７９
Åを酸化物皮膜の格子定数の下限値とし、また、酸化物
皮膜としてＣｒとＡｌの複合酸化物を用いる場合には、
組成式（Ａｌy，Ｃｒ(1-y))2Ｏ3において、ｙを好まし
くは０≦ｙ≦０．９０とすることとした。In the case of a composite oxide of Cr and Al, as described above, the lattice constant decreases as the Al composition ratio increases. However, when the Al composition ratio exceeds 0.90, the oxide film having a corundum structure is formed. Is only produced at high temperatures,
At a low temperature, a crystal structure other than the corundum structure is generated, and an oxide film having a pure corundum structure cannot be obtained. Therefore,
4.779 which is a lattice constant of (Al 0.9 , Cr 0.1 ) 2 O 3
Å is the lower limit of the lattice constant of the oxide film, and when a composite oxide of Cr and Al is used as the oxide film,
Composition formula (Al y, Cr (1- y)) 2 O 3, it was decided that a preferably y and 0 ≦ y ≦ 0.90.
【００２３】本発明では、前記酸化物皮膜の膜厚を少な
くとも０．００５μｍとする必要がある。この酸化物皮
膜の膜厚が０．００５μｍより小さくなると、緻密な酸
化物皮膜が形成されず、コランダム構造のみからなる酸
化アルミニウムが形成されにくいためである。好ましく
は０．０１μｍ以上であり、より好ましくは０．０２μ
ｍ以上である。また上記膜厚が厚すぎると、切削中に皮
膜に亀裂または剥離が生じ易くなるため、１０μｍ以下
とすることが好ましく、より好ましくは５μｍ以下、更
に好ましくは３μｍ以下である。In the present invention, the oxide film needs to have a thickness of at least 0.005 μm. If the thickness of the oxide film is smaller than 0.005 μm, a dense oxide film is not formed, and it is difficult to form aluminum oxide having only a corundum structure. It is preferably 0.01 μm or more, more preferably 0.02 μm.
m or more. On the other hand, if the thickness is too large, the coating tends to crack or peel during cutting, so the thickness is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less.
【００２４】＜複合窒化皮膜＞本発明では、切削工具等
として使用する際の耐摩耗性を一層高めるため、前記酸
化物皮膜が、Ｔｉ、Ｃｒ、Ｖよりなる群から選択される
１種以上の元素とＡｌとの複合窒化皮膜の上に形成され
ていることが望ましい。<Composite Nitride Coating> In the present invention, in order to further enhance the wear resistance when used as a cutting tool or the like, the oxide coating is preferably made of at least one selected from the group consisting of Ti, Cr and V. Desirably, it is formed on a composite nitride film of element and Al.
【００２５】尚、該複合窒化皮膜の膜厚は、薄すぎると
上記効果が発揮されないため、０．５μｍ以上とするこ
とが好ましく、より好ましくは１μｍ以上である。ま
た、膜厚が厚すぎると、切削時において膜に亀裂が生じ
るため、２０μｍ以下とすることが好ましく、より好ま
しくは１０μｍ以下である。It is to be noted that the thickness of the composite nitride film is preferably 0.5 μm or more, more preferably 1 μm or more, since the above-mentioned effects are not exhibited if the thickness is too small. Further, if the film thickness is too large, cracks occur in the film at the time of cutting, so the thickness is preferably 20 μm or less, more preferably 10 μm or less.
【００２６】＜中間層＞更に、基材と上記酸化物皮膜の
間に、中間層としてＡｌとＣｒの窒化物層を設けること
によって、皮膜の密着性向上を図ることも有効である。
尚、後述するように中間層の表層部を酸化処理して、コ
ランダム構造のＡｌとＣｒの複合酸化物［（Ａｌy，Ｃ
ｒ(1-y)）2Ｏ3（ただし、ｙは０≦ｙ≦０．９０）］皮
膜を形成する場合には、前記ＡｌとＣｒの窒化物層は、
組成式（Ａｌz，Ｃｒ(1-z)）Ｎにおいて、ｚを０≦ｚ≦
０．９０とすることが好ましく、より好ましくは０≦ｚ
≦０．７５である。<Intermediate Layer> It is also effective to improve the adhesion of the film by providing a nitride layer of Al and Cr as an intermediate layer between the substrate and the oxide film.
As described later, the surface layer of the intermediate layer is oxidized to obtain a composite oxide of Al and Cr having a corundum structure [(Al y , C
r (1-y) ) 2 O 3 (where y is 0 ≦ y ≦ 0.90)] When a film is formed, the nitride layer of Al and Cr is
In the composition formula (Al z , Cr (1-z) ) N, z is 0 ≦ z ≦
0.90, more preferably 0 ≦ z
≦ 0.75.
【００２７】＜酸化アルミニウム皮膜＞コランダム構造
の酸化アルミニウムの膜厚は、０．１〜２０μｍである
ことが好ましい。前記酸化アルミニウムの膜厚が０．１
μｍ未満の場合には、例えば切削工具に適用した場合に
早期に摩耗してしまい、酸化アルミニウムの耐熱性等の
効果を発揮させることができないためであり、より好ま
しくは、０．５μｍ以上、更に好ましくは１μｍ以上で
ある。また、２０μｍを超えると、皮膜中に内部応力等
が生じて亀裂等が発生し易くなるためであり、より好ま
しくは１０μｍ以下、更に好ましくは５μｍ以下であ
る。<Aluminum oxide film> The thickness of the aluminum oxide having a corundum structure is preferably 0.1 to 20 µm. When the thickness of the aluminum oxide is 0.1
In the case of less than μm, for example, when it is applied to a cutting tool, it will be worn out early, and it is not possible to exhibit the effects such as heat resistance of aluminum oxide, more preferably 0.5 μm or more, Preferably it is 1 μm or more. On the other hand, if the thickness exceeds 20 μm, internal stress and the like are generated in the coating, and cracks and the like are likely to be generated.
【００２８】＜皮膜形成方法＞本発明の硬質皮膜は、例
えば次の様な方法で形成することができる。即ち、ＡＩ
Ｐ法とアンバランスドマグネトロンスパッタ法（以下、
ＵＢＭＳ法という）を組み合わせたＰＶＤ装置を使用
し、ＡＩＰ用固体状ターゲットとしてＴｉ−Ａｌ合金タ
ーゲット、ＵＢＭＳ法用固体状スパッタターゲットとし
てＣｒターゲットおよびＡｌターゲットを用い、順次各
々の蒸発源を作動させることによって、一連の成膜プロ
セスで、ＴｉとＡｌの複合窒化皮膜、酸化物皮膜として
酸化クロム皮膜、およびコランダム構造の酸化アルミニ
ウム皮膜を基材表面に順次層状に形成することができ
る。<Film Forming Method> The hard film of the present invention can be formed, for example, by the following method. That is, AI
P method and unbalanced magnetron sputtering method
Using a PVD apparatus combined with a UBMS method), using a Ti-Al alloy target as a solid target for AIP, a Cr target and an Al target as a solid sputter target for UBMS method, and sequentially operating the respective evaporation sources. Thus, in a series of film forming processes, a composite nitride film of Ti and Al, a chromium oxide film as an oxide film, and an aluminum oxide film having a corundum structure can be sequentially formed in layers on the substrate surface.
【００２９】また、上記Ｃｒターゲットの代わりに、ス
パッタターゲットとしてＣｒ−Ｆｅ合金ターゲットまた
はＣｒ−Ａｌ合金ターゲットを用いれば、酸化物皮膜と
して、ＣｒとＦｅの複合酸化物皮膜またはＣｒとＡｌの
複合酸化物皮膜を得ることができる。When a Cr—Fe alloy target or a Cr—Al alloy target is used as a sputtering target instead of the Cr target, a composite oxide film of Cr and Fe or a composite oxide film of Cr and Al is used as an oxide film. An object film can be obtained.
【００３０】更に前記中間層は、前記複合窒化皮膜を形
成した後に、例えばＡＩＰ法やＵＢＭＳ法等のＰＶＤ法
で、Ａｌ−Ｃｒ合金をターゲットに用いて窒素雰囲気下
で放電させることによって形成できる。Further, the intermediate layer can be formed by forming the composite nitride film and then performing a discharge in a nitrogen atmosphere using an Al-Cr alloy as a target by a PVD method such as an AIP method or a UBMS method.
【００３１】中間層として（Ａｌz，Ｃｒ(1-z)）Ｎ（た
だし、ｚは０≦ｚ≦０．９０）皮膜を形成した後、該中
間層上に、酸化物皮膜として（Ａｌy，Ｃｒ(1-y))2Ｏ3
（ただし、ｙは０≦ｙ≦０．９０）皮膜を形成する場合
には、酸素雰囲気下で基材温度を４５０℃以上に昇温し
て前記中間層の表面を酸化することで、上記（Ａｌ，Ｃ
ｒ）2Ｏ3層を、中間層表層部に容易に形成することがで
きる。前記基材温度は、好ましくは４９０℃以上であ
る。尚、基材が高速度鋼の場合には、基材温度が高すぎ
ると基材硬度が低下するため、前記酸化は５００℃以下
で行うことが好ましい。After forming an (Al z , Cr (1-z) ) N (where z is 0 ≦ z ≦ 0.90) film as an intermediate layer, (Al y , Cr (1-z) ) N is formed on the intermediate layer as an oxide film (Al y , Cr (1-y) ) 2 O 3
(However, y is 0 ≦ y ≦ 0.90) In the case of forming a film, the substrate temperature is raised to 450 ° C. or more in an oxygen atmosphere to oxidize the surface of the intermediate layer. Al, C
r) The 2 O 3 layer can be easily formed on the surface of the intermediate layer. The substrate temperature is preferably 490 ° C. or higher. When the base material is high-speed steel, if the base material temperature is too high, the base material hardness decreases. Therefore, the oxidation is preferably performed at 500 ° C. or lower.
【００３２】本発明では、上述の様にして予め酸化物皮
膜を形成しておくことによって、基材温度を好ましくは
３００℃以上にすれば、コランダム構造の酸化アルミニ
ウムを該酸化物皮膜上に形成することができるのであ
り、上記基材温度は、より好ましくは４００℃以上であ
り、更に好ましくは４５０℃以上である。In the present invention, by forming an oxide film in advance as described above, if the substrate temperature is preferably set to 300 ° C. or higher, aluminum oxide having a corundum structure is formed on the oxide film. The substrate temperature is more preferably 400 ° C. or higher, and further preferably 450 ° C. or higher.
【００３３】また、上記基材温度が高すぎると、基材が
高速度鋼の場合に軟質化する等、基材の特性を損ねるこ
ととなるので、基材温度５００℃以下で酸化アルミニウ
ム皮膜を形成することが好ましい。On the other hand, if the substrate temperature is too high, the characteristics of the substrate are impaired, such as softening when the substrate is high-speed steel. Preferably, it is formed.
【００３４】尚、前記酸化物皮膜等の成膜方法として示
したＡＩＰ法やＵＢＭＳ法は、ＰＶＤ法の一例であっ
て、本発明の硬質皮膜は、上記ＡＩＰ法やＵＢＭＳ法に
限らず、ＰＶＤ法として広く行われているいずれの方法
によっても形成され得るものである。The AIP method and the UBMS method described as the method for forming the oxide film and the like are examples of the PVD method. The hard film of the present invention is not limited to the AIP method and the UBMS method. It can be formed by any method widely used as a method.
【００３５】[0035]
【実施例】以下、実施例を挙げて本発明をより具体的に
説明するが、本発明はもとより下記実施例によって制限
を受けるものではなく、前・後記の趣旨に適合し得る範
囲で適当に変更を加えて実施することも可能であり、そ
れらはいずれも本発明の技術的範囲に含まれる。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention is not limited thereto. Modifications can be made and implemented, all of which are included in the technical scope of the present invention.
【００３６】（１）以下に示す方法で、基材上に硬質皮
膜を形成した。尚、コランダム構造の酸化アルミニウム
は、それぞれ表１に示す基材温度にて形成した。(1) A hard film was formed on a substrate by the following method. The aluminum oxide having a corundum structure was formed at a substrate temperature shown in Table 1.
【００３７】表１に示すＮｏ．１〜２９および３１〜
４４では、図１に概略例示するようなＰＶＤ成膜装置に
て硬質皮膜を形成した。即ち、ＡＩＰ用ターゲットとし
てＴｉ−Ａｌ合金ターゲット６、ＵＢＭＳ用ターゲット
としてＣｒターゲット４およびＡｌターゲット５をセッ
トし、試料保持台３上に、基材２として超硬合金チップ
（SNGN120408）または高速度鋼チップをセットし、チャ
ンバ１内の排気８を行って真空状態にした後、以下の各
皮膜の形成を各々のガス７を導入して行った。No. 1 shown in Table 1 1-29 and 31-
At 44, a hard coating was formed using a PVD film forming apparatus as schematically illustrated in FIG. That is, a Ti—Al alloy target 6 is set as an AIP target, a Cr target 4 and an Al target 5 are set as UBMS targets, and a cemented carbide chip (SNGN120408) or a high-speed steel After the chip was set and the chamber 1 was evacuated 8 to create a vacuum, the following films were formed by introducing each gas 7.
【００３８】即ち、チャンバ１内を窒素ガス雰囲気と
し、Ｔｉ−Ａｌ合金ターゲット６を用いて、ＡＩＰ法で
膜厚３μｍの窒化チタンアルミニウム硬質皮膜を形成
し、続いてＣｒターゲット４を用い、アルゴンと酸素の
混合ガス雰囲気下にてＵＢＭＳ法で酸化クロム皮膜を形
成した。更に、Ａｌターゲット５を用い、アルゴンと酸
素の混合ガス雰囲気下にてＵＢＭＳ法で酸化アルミニウ
ム膜を形成した。That is, a 3 μm-thick titanium aluminum nitride hard film is formed by the AIP method using a Ti—Al alloy target 6 in a nitrogen gas atmosphere in the chamber 1, and subsequently, using a Cr target 4, A chromium oxide film was formed by a UBMS method in an atmosphere of a mixed gas of oxygen. Further, using an Al target 5, an aluminum oxide film was formed by a UBMS method in a mixed gas atmosphere of argon and oxygen.
【００３９】尚、酸化物皮膜として（Ａｌ，Ｃｒ）2Ｏ3
皮膜や（Ｆｅ，Ｃｒ）2Ｏ3皮膜を形成する場合には、Ｃ
ｒターゲット４に代えて、Ａｌ−Ｃｒ合金ターゲット、
Ｆｅ−Ｃｒ合金ターゲットを用いた。As the oxide film, (Al, Cr) 2 O 3
When forming a film or (Fe, Cr) 2 O 3 film,
an Al—Cr alloy target instead of the r target 4,
An Fe-Cr alloy target was used.
【００４０】また、Ｎｏ．３３、３４および３９では、
複合窒化皮膜（窒化チタンアルミニウム硬質皮膜）を設
けず、基材表面に直接、酸化物皮膜を形成した。In addition, No. In 33, 34 and 39,
An oxide film was formed directly on the substrate surface without providing a composite nitride film (titanium aluminum nitride hard film).
【００４１】表１に示すＮｏ．３０、４５、４６、４
８および４９では、図２に概略例示するようなＰＶＤ成
膜装置にて硬質皮膜を形成した。即ち、ＡＩＰ用ターゲ
ットとして、Ｔｉ−Ａｌ合金ターゲット６およびＣｒ−
Ａｌ合金ターゲット９、ＵＢＭＳ用ターゲットとしてＡ
ｌターゲット５をセットし、試料保持台３上に、基材２
として超硬合金チップ（SNGN120408）または高速度鋼チ
ップをセットし、チャンバ１内の排気８を行って真空状
態にした後、以下の各皮膜の形成を各々のガス７を導入
して行った。No. 1 shown in Table 1. 30, 45, 46, 4
In Nos. 8 and 49, a hard coating was formed using a PVD film forming apparatus as schematically illustrated in FIG. That is, the Ti—Al alloy target 6 and the Cr—
Al alloy target 9, A as UBMS target
l Set the target 5 and place the substrate 2 on the sample holder 3.
, A cemented carbide tip (SNGN120408) or a high-speed steel tip was set, and the inside of the chamber 1 was evacuated 8 to make a vacuum state, and then the following films were formed by introducing each gas 7.
【００４２】即ち、チャンバ１内を窒素ガス雰囲気と
し、Ｔｉ−Ａｌ合金ターゲット６を用いて、ＡＩＰ法で
膜厚３μｍの窒化チタンアルミニウム硬質皮膜を形成
し、続いてＣｒ−Ａｌ合金ターゲット９を用い、窒素雰
囲気下にてＡＩＰ法で窒化クロムアルミニウム膜を形成
した。その後、前記皮膜の形成された基材を装置内に保
ったまま、酸素雰囲気下にて４５０℃で酸化してＡｌと
Ｃｒの複合酸化物皮膜を形成した。次に、アルゴンと酸
素の混合ガス雰囲気下Ａｌターゲット５を用い、ＵＢＭ
Ｓ法で酸化アルミニウム皮膜を形成した。尚、上記窒化
クロムアルミニウム膜の膜厚は、いずれも０．５μｍで
あった。That is, a 3 μm thick titanium aluminum nitride hard film is formed by the AIP method using a Ti—Al alloy target 6 in a nitrogen gas atmosphere in the chamber 1, and then using a Cr—Al alloy target 9. A chromium aluminum nitride film was formed by an AIP method under a nitrogen atmosphere. Thereafter, while keeping the substrate on which the film was formed in the apparatus, the substrate was oxidized at 450 ° C. in an oxygen atmosphere to form a composite oxide film of Al and Cr. Next, UBM was performed using an Al target 5 under a mixed gas atmosphere of argon and oxygen.
An aluminum oxide film was formed by the S method. The thickness of each of the chromium aluminum nitride films was 0.5 μm.
【００４３】また、Ｎｏ．４７では、図２に例示すよう
な装置のチャンバ１内に、更にＦｅ−Ｃｒ合金ターゲッ
トを設け、上記と同様にして窒化チタンアルミニウム硬
質皮膜および窒化クロムアルミニウム皮膜を形成した
後、アルゴンと酸素の混合ガス雰囲気下にて、ＵＢＭＳ
法で鉄とクロムの複合酸化物皮膜を形成し、その後上記
と同様にして酸化アルミニウム皮膜を形成した。In addition, No. At 47, an Fe—Cr alloy target was further provided in the chamber 1 of the apparatus as illustrated in FIG. 2, and a titanium aluminum nitride hard film and a chromium aluminum nitride film were formed in the same manner as described above. UBMS under mixed gas atmosphere
A composite oxide film of iron and chromium was formed by a method, and then an aluminum oxide film was formed in the same manner as above.
【００４４】この様にして得られた酸化アルミニウム皮
膜の結晶構造および酸化物皮膜の格子定数を薄膜Ｘ線回
折装置または透過電子顕微鏡にて同定した。また酸化ア
ルミニウム皮膜および酸化物皮膜の膜厚は、走査型電子
顕微鏡または透過電子顕微鏡を用いて測定した。更に皮
膜中の成分は、Ｘ線光電子分光法による深さ方向分析に
て測定した。その結果を表１に示す。The crystal structure of the aluminum oxide film thus obtained and the lattice constant of the oxide film were identified using a thin-film X-ray diffractometer or a transmission electron microscope. The thicknesses of the aluminum oxide film and the oxide film were measured using a scanning electron microscope or a transmission electron microscope. Furthermore, the components in the film were measured by depth analysis using X-ray photoelectron spectroscopy. Table 1 shows the results.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
【００４７】表１および表２より、Ｎｏ．１〜１３、１
５〜２０、２３、２５〜２７、３０〜３４、３７〜３
９、４１〜４３および４５〜４７は、本発明の要件を満
たしているため、結晶構造がコランダム構造のみからな
る酸化アルミニウム皮膜を得ることができた。From Tables 1 and 2, No. 1-13, 1
5-20, 23, 25-27, 30-34, 37-3
Since 9, 41 to 43 and 45 to 47 satisfy the requirements of the present invention, an aluminum oxide film having a crystal structure consisting of only a corundum structure could be obtained.
【００４８】これに対して、Ｎｏ．１４、２１、２２、
２４、２８、２９、３５、３６、４０、４４、４８およ
び４９では、コランダム構造のみからなる酸化アルミニ
ウム皮膜が得られなかった。即ち、Ｎｏ．２１、２２、
２８、４０及び４４は、酸化物皮膜の格子定数が本発明
で規定する範囲を外れているため、またＮｏ．１４、２
４、３５及び４８は、酸化物皮膜の膜厚が薄すぎるた
め、生成した酸化アルミニウム皮膜において、コランダ
ム構造以外に立方晶構造も形成される結果となった。On the other hand, no. 14, 21, 22,
With 24, 28, 29, 35, 36, 40, 44, 48 and 49, an aluminum oxide film consisting only of a corundum structure could not be obtained. That is, No. 21, 22,
Nos. 28, 40 and 44 have the lattice constants of the oxide films outside the range specified in the present invention. 14,2
In Nos. 4, 35 and 48, the thickness of the oxide film was too small, so that a cubic structure other than the corundum structure was formed in the formed aluminum oxide film.
【００４９】上述の通り、酸化物皮膜の膜厚が薄すぎる
Ｎｏ．１４、２４、３５及び４８では、形成された酸化
アルミニウムが、コランダム構造と立方晶構造の混合結
晶となったが、これを透過電子顕微鏡にて断面観察した
ところ、基材が十分に酸化物皮膜で覆われておらず、基
材表面が露出している部分に、立方晶構造の酸化アルミ
ニウムが形成していることがわかった。As described above, when the oxide film was too thin, In 14, 24, 35, and 48, the formed aluminum oxide became a mixed crystal of a corundum structure and a cubic structure. When the cross section was observed with a transmission electron microscope, the substrate was found to have a sufficient oxide film. It was found that aluminum oxide having a cubic structure was formed in portions where the base material surface was not covered with the aluminum oxide.
【００５０】更にＮｏ．２９、３６および４９は、酸化
アルミニウム皮膜の形成を、いずれも本発明で好ましい
とする温度よりも低温で行ったため、コランダム構造以
外の結晶構造が形成されたものと考えられる。Further, No. In Nos. 29, 36 and 49, since the formation of the aluminum oxide film was performed at a temperature lower than the preferable temperature in the present invention, it is considered that a crystal structure other than the corundum structure was formed.
【００５１】（２）更に、Ｎｏ．５〜１０、１４および
２９で得られたチップを用いて、以下に示す条件で丸棒
（Ｓ５０Ｃ）の旋削試験を行い、旋削によってチップに
生じたクレーター摩耗の深さを表面粗さ計を用いて測定
した。その結果を表３に示す。 被削材：Ｓ５０Ｃ 切削速度：２００ｍ／ｍｉｎ. 送り速度：０．２ｍｍ／ｓｅｃ. 切り込み：２ｍｍ 乾式（エアーブローのみ） 切削時間 １０分(2) Further, No. Using the inserts obtained in 5 to 10, 14 and 29, a turning test of a round bar (S50C) was performed under the following conditions, and the depth of crater wear generated on the insert by the turning was measured using a surface roughness meter. Measured. Table 3 shows the results. Work material: S50C Cutting speed: 200 m / min. Feeding speed: 0.2 mm / sec. Cutting depth: 2 mm Dry type (only air blow) Cutting time 10 minutes
【００５２】[0052]
【表３】 [Table 3]
【００５３】表３より、Ｎｏ．５〜１０は、コランダム
構造の酸化アルミニウムが形成されているため、摩耗量
は小さく耐摩耗性に優れていることが分かる。これに対
して、酸化アルミニウムの構造がコランダム構造以外で
あるＮｏ．１４および２９では、摩耗量が大きくなり、
耐摩耗性に劣る結果となった。As shown in Table 3, Nos. 5 to 10 show that the aluminum oxide having a corundum structure is formed, so that the wear amount is small and the wear resistance is excellent. On the other hand, in the case of No. 3 in which the structure of aluminum oxide was other than the corundum structure. In 14 and 29, the amount of wear increases,
The result was inferior wear resistance.
【００５４】[0054]
【発明の効果】本発明は以上の様に構成されており、コ
ランダム構造の酸化アルミニウムを積層する前に、コラ
ンダム構造であり且つ本発明で規定する格子定数の酸化
物皮膜を予め形成しておくことで、耐熱性、耐摩耗性等
に優れたコランダム構造の酸化アルミニウムを低温条件
下で形成することができることとなった。そして、この
様な硬質皮膜の形成方法の実現によって、多様な基材に
対して、コランダム構造の酸化アルミニウムを形成し、
優れた耐熱性、耐摩耗性等を付与できることとなった。According to the present invention, an oxide film having a corundum structure and a lattice constant specified by the present invention is formed before laminating aluminum oxide having a corundum structure. Thus, aluminum oxide having a corundum structure excellent in heat resistance, abrasion resistance and the like can be formed under low-temperature conditions. And, by realizing such a method of forming a hard coating, an aluminum oxide having a corundum structure is formed on various substrates,
Excellent heat resistance, abrasion resistance and the like can be provided.
【図１】本発明に係る硬質皮膜の形成に用いるＰＶＤ成
膜装置を例示する概略断面説明図である。FIG. 1 is a schematic sectional explanatory view illustrating a PVD film forming apparatus used for forming a hard film according to the present invention.
【図２】本発明に係る硬質皮膜の形成に用いる別のＰＶ
Ｄ成膜装置を例示する概略断面説明図である。FIG. 2 shows another PV used for forming a hard coating according to the present invention.
FIG. 3 is a schematic cross-sectional explanatory view illustrating a D film forming apparatus.
１ チャンバ ２ 基材 ３ 試料保持台 ４ Ｃｒターゲット（ＵＢＭＳ用） ５ Ａｌターゲット（ＵＢＭＳ用） ６ Ｔｉ−Ａｌ合金ターゲット（ＡＩＰ用） ７ 導入ガス（窒素、酸素、アルゴン） ８ 排気 ９ ＣｒターゲットまたはＣｒ−Ａｌ合金ターゲット
（ＡＩＰ用）Reference Signs List 1 chamber 2 base material 3 sample holder 4 Cr target (for UBMS) 5 Al target (for UBMS) 6 Ti-Al alloy target (for AIP) 7 introduction gas (nitrogen, oxygen, argon) 8 exhaust 9 Cr target or Cr -Al alloy target (for AIP)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤井 博文 兵庫県高砂市荒井町新浜２丁目３番１号 株式会社神戸製鋼所高砂製作所内 Ｆターム(参考） 3C046 FF09 FF13 FF16 FF19 FF24 FF25 4K029 AA02 AA04 BA44 BA50 BA58 BB02 BB07 BC02 BD04 BD05 CA04 CA06 DC03 DC04 DC16 DC39 DD06 EA01 EA08 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirofumi Fujii 2-3-1 Shinhama, Arai-machi, Takasago-shi, Hyogo F-term in Kobe Steel, Ltd. Takasago Works (reference) 3C046 FF09 FF13 FF16 FF19 FF24 FF25 4K029 AA02 AA04 BA44 BA50 BA58 BB02 BB07 BC02 BD04 BD05 CA04 CA06 DC03 DC04 DC16 DC39 DD06 EA01 EA08
Claims (11)
Å以下で、膜厚が少なくとも０．００５μmであるコラ
ンダム構造の酸化物皮膜の一方の面に、コランダム構造
の酸化アルミニウム皮膜が形成されていることを特徴と
する硬質皮膜。1. A lattice constant of 4.779 ° or more and 5.000 or more.
{Circle around (4)} A hard film, wherein a corundum structure aluminum oxide film is formed on one surface of a corundum structure oxide film having a film thickness of at least 0.005 μm.
ｅ，Ｃｒ)2Ｏ3又は（Ａｌ，Ｃｒ）2Ｏ3のいずれかであ
る請求項１に記載の硬質皮膜。2. The oxide film according to claim 1, wherein the component of the oxide film is Cr 2 O 3 , (F
The hard coating according to claim 1, which is any one of e, Cr) 2 O 3 and (Al, Cr) 2 O 3 .
(1-x))2Ｏ3（ただし、ｘは０≦ｘ≦０．５４）である請
求項２に記載の硬質皮膜。Wherein the (Fe, Cr) 2 O 3 is (Fe x, Cr
(1-x)) 2 O 3 ( where hard coating according to claim 2 x is 0 ≦ x ≦ 0.54).
(1-y))2Ｏ3（ただし、ｙは０≦ｙ≦０．９０）である請
求項２に記載の硬質皮膜。Wherein said (Al, Cr) 2 O 3 is (Al y, Cr
(1-y)) 2 O 3 ( where hard coating according to claim 2 y is 0 ≦ y ≦ 0.90).
の面に、中間層を介し又は介さずに、Ｔｉ、Ｃｒ、Ｖよ
りなる群から選択される１種以上の元素とＡｌとの複合
窒化皮膜が形成されている請求項１〜４のいずれかに記
載の硬質皮膜。5. A composite nitride of Al and at least one element selected from the group consisting of Ti, Cr, and V with or without an intermediate layer on the other surface of the oxide film having a corundum structure. The hard coating according to any one of claims 1 to 4, wherein the coating is formed.
（ただし、ｚは０≦ｚ≦０．９０）皮膜である請求項５
に記載の硬質皮膜。6. The method according to claim 1, wherein the intermediate layer is (Al z , Cr (1-z) ) N
(Where z is 0 ≦ z ≦ 0.90) A film.
The hard film according to the above.
前記コランダム構造の酸化アルミニウム皮膜を表面側と
して基材上に形成されていることを特徴とする耐摩耗部
材。7. The hard coating according to claim 1, wherein
A wear-resistant member, wherein the aluminum oxide film having a corundum structure is formed on a substrate with a surface side thereof.
方法であって、前記コランダム構造の酸化アルミニウ
ム、酸化物皮膜、複合窒化皮膜および必要に応じて形成
される中間層を、物理蒸着法で形成する工程を含むこと
を特徴とする耐摩耗部材の製造方法。8. The method for producing a wear-resistant member according to claim 7, wherein the corundum-structured aluminum oxide, oxide film, composite nitride film and, if necessary, an intermediate layer are formed by physical vapor deposition. A method for producing a wear-resistant member, comprising a step of forming by a method.
方法であって、前記（Ａｌz，Ｃｒ(1-z)）Ｎ（ただし、
ｚは０≦ｚ≦０．９０）皮膜を形成した後、これを酸化
して前記（Ａｌy，Ｃｒ(1-y)）2Ｏ3（ただし、ｙは０≦
ｙ≦０．９０）皮膜を形成する工程を含む請求項８に記
載の耐摩耗部材の製造方法。9. The method for manufacturing a wear-resistant member according to claim 7, wherein the (Al z , Cr (1-z) ) N (where
z is 0 ≦ z ≦ 0.90) After forming a film, it is oxidized to form the (Al y , Cr (1-y) ) 2 O 3 (where y is 0 ≦
9. The method for producing a wear-resistant member according to claim 8, comprising a step of forming a coating (y ≦ 0.90).
ム皮膜を基材温度３００℃以上で形成する請求項８また
は９に記載の耐摩耗部材の製造方法。10. The method for manufacturing a wear-resistant member according to claim 8, wherein the aluminum oxide film having a corundum structure is formed at a substrate temperature of 300 ° C. or higher.
し、ｚは０≦ｚ≦０．９０）皮膜表面の酸化を、酸素雰
囲気下にて基材温度４５０℃以上で行う請求項９に記載
の耐摩耗部材の製造方法。11. The (Al z , Cr (1-z) ) N (where z is 0 ≦ z ≦ 0.90) film surface is oxidized at a substrate temperature of 450 ° C. or higher in an oxygen atmosphere. A method for manufacturing a wear-resistant member according to claim 9.
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