JP2000144376A - Film excellent in sliding characteristic - Google Patents
Film excellent in sliding characteristicInfo
- Publication number
- JP2000144376A JP2000144376A JP10328220A JP32822098A JP2000144376A JP 2000144376 A JP2000144376 A JP 2000144376A JP 10328220 A JP10328220 A JP 10328220A JP 32822098 A JP32822098 A JP 32822098A JP 2000144376 A JP2000144376 A JP 2000144376A
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- hard coating
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- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、耐摩耗性、耐焼
き付き性及び耐酸化性に優れ、摩擦係数の低い、すなわ
ち、摺動特性の高い皮膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film having excellent abrasion resistance, seizure resistance and oxidation resistance and having a low friction coefficient, that is, a high sliding property.
【０００２】[0002]
【従来の技術】従来、自動車のエンジン、各種機械等の
摺動部に利用される部品には、その摺動特性を高めるた
めの表面処理が行われてきた。この摺動特性は、耐摩耗
性、耐焼き付き性、耐酸化性、摩擦性によって決定され
る。これらの性質をトータルで向上させるために、部品
表面を窒化処理、メッキ処理、溶射処理、物理的蒸着法
による改質又は被覆等が試みられてきた。例えば、特公
平１−５２４７１号公報、特開平６２−１２０４７１号
公報に、物理的蒸着法による表面被覆は、優れた摺動特
性を示すことが開示されている。2. Description of the Related Art Hitherto, parts used for sliding parts of automobile engines, various machines and the like have been subjected to a surface treatment for improving the sliding characteristics. The sliding characteristics are determined by abrasion resistance, seizure resistance, oxidation resistance, and friction. In order to improve these properties in total, attempts have been made to perform nitriding, plating, thermal spraying, modification or coating by physical vapor deposition, etc. on the component surface. For example, Japanese Patent Publication No. 1-52471 and Japanese Patent Application Laid-Open No. 62-120471 disclose that a surface coating by a physical vapor deposition method exhibits excellent sliding characteristics.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、最近
は、摺動部材の使用条件がさらに過酷になっており、物
理的蒸着法による表面被覆の摺動特性の向上をさらに図
る必要がある。However, recently, the use conditions of the sliding member have become more severe, and it is necessary to further improve the sliding characteristics of the surface coating by a physical vapor deposition method.
【０００４】物理的蒸着法により得られるＣｒの窒化物
からなる表面皮膜は、耐焼き付き性が高いものの、硬度
が十分でないため、耐摩耗性が十分でない。さらに、Ａ
ｌの窒化物ほどの耐酸化性を有さない。また、物理的蒸
着法により得られるＡｌの窒化物からなる表面皮膜は、
耐酸化性が高いものの、耐焼き付き性や耐摩耗性が十分
でない。さらに、物理的蒸着法により得られるＴｉの窒
化物からなる表面皮膜は、耐焼き付き性、耐摩耗性及び
耐酸化性のいずれも十分でない。さらにまた、物理的蒸
着法により得られるＶの窒化物からなる表面皮膜は、耐
焼き付き性及び耐摩耗性が高いものの、耐酸化性が十分
でない。[0004] A surface coating made of a nitride of Cr obtained by a physical vapor deposition method has high seizure resistance, but does not have sufficient hardness and thus has insufficient wear resistance. Furthermore, A
It does not have the oxidation resistance of the nitride of l. In addition, the surface film made of Al nitride obtained by the physical vapor deposition method,
Although oxidation resistance is high, seizure resistance and abrasion resistance are not sufficient. Further, the surface film made of Ti nitride obtained by the physical vapor deposition method is not satisfactory in all of seizure resistance, abrasion resistance and oxidation resistance. Furthermore, a surface coating made of V nitride obtained by a physical vapor deposition method has high seizure resistance and abrasion resistance, but does not have sufficient oxidation resistance.
【０００５】また、特開平８−３１２７７９号公報や特
開平８−２１２７７９号公報には、Ｃｒの窒化物の結晶
成長の形態の異なる二層を交互に積層させて、欠け発生
を抑制したり、Ｃｒの窒化物の配向性を制御して耐欠け
性を向上させることが開示されている。In Japanese Patent Application Laid-Open Nos. 8-31779 and 8-212779, two layers having different forms of crystal growth of Cr nitride are alternately laminated to suppress chipping, It is disclosed that the orientation of a Cr nitride is controlled to improve chipping resistance.
【０００６】ところが、摺動特性のさらなる向上は、耐
摩耗性、耐焼き付き性若しくは耐酸化性の向上、又は摩
擦係数の低減化のうちの一部のみを図るのでは不十分
で、それら全ての向上又は低減化を図る必要がある。However, further improvement of the sliding properties is not sufficient if only a part of the improvement of the wear resistance, the seizure resistance or the oxidation resistance, or the reduction of the friction coefficient is insufficient. It is necessary to improve or reduce it.
【０００７】そこで、この発明は、耐摩耗性、耐焼き付
き性及び耐酸化性を向上、並びに、摩擦係数の低減化と
いう全ての摺動特性の向上を図る皮膜を提供することを
目的とする。Accordingly, an object of the present invention is to provide a coating which improves wear resistance, seizure resistance and oxidation resistance, and improves all sliding characteristics such as reduction of friction coefficient.
【０００８】[0008]
【課題を解決するための手段】この発明は、Ｃｒ、Ｔ
ｉ、Ａｌ、Ｖの窒化物うち少なくとも２種の金属窒化物
から構成される複合体であり、この複合体が示すＸ線回
折ピークであって、上記複合体を構成するそれぞれの金
属窒化物の（１１１）面及び（２００）面のＸ線回折ピ
ーク間に生じるＸ線回折ピークの強さ（Ｉ(111) 及びＩ
(200) ）の強度比Ｉ(111) ／Ｉ(200) が３〜６とするこ
とにより上記の課題を解決するものである。According to the present invention, Cr, T
a composite composed of at least two kinds of metal nitrides of i, Al, and V nitrides, and an X-ray diffraction peak of the composite, which is a peak of each metal nitride constituting the composite. X-ray diffraction peak intensities (I (111) and I (111) and I ) generated between the (111) plane and the (200) plane
The above problem is solved by setting the intensity ratio I (111) / I (200) of (200)) to 3 to 6.
【０００９】４種の金属窒化物の少なくとも２種を複合
させた複合体を用いるので、摺動特性を発現する耐摩耗
性、耐焼き付き性、耐酸化性、摩擦係数の各特性うち、
複合体を構成する各金属窒化物単体が有する優れた上記
特性が表出すると共に、金属窒化物単体では十分でなか
った上記特性の向上が各金属窒化物を組み合わせること
により見られる。このため、耐摩耗性、耐焼き付き性、
及び耐酸化性を向上させることができる。また、強度比
Ｉ(111) ／Ｉ(200) を上記の値とすると、皮膜が（１１
１）面に配向するので、摩擦係数の低減を図ることがで
きる。Since a composite of at least two of the four types of metal nitrides is used, abrasion resistance, seizure resistance, oxidation resistance, and friction coefficient, which exhibit sliding characteristics, are obtained.
The above-mentioned excellent properties of each metal nitride alone constituting the composite are exhibited, and the improvement of the above-mentioned properties, which was not sufficient with the single metal nitride alone, can be seen by combining each metal nitride. For this reason, wear resistance, seizure resistance,
And oxidation resistance can be improved. When the strength ratio I (111) / I (200) is set to the above value, the film becomes (11)
1) Since it is oriented in the plane, the friction coefficient can be reduced.
【００１０】[0010]
【発明の実施の形態】以下、この発明の実施形態を説明
する。Embodiments of the present invention will be described below.
【００１１】この発明にかかる硬質皮膜は、Ｃｒ、Ｔ
ｉ、Ａｌ、Ｖの窒化物うち少なくとも２種から構成され
る。組み合わせとしては、Ｃｒの窒化物（ＣｒＮ）とＴ
ｉの窒化物（ＴｉＮ）、ＣｒＮとＡｌの窒化物（Ａｌ
Ｎ）、ＣｒＮとＶの窒化物（ＶＮ）、ＴｉＮとＡｌＮ、
ＴｉＮとＶＮ、ＡｌＮとＶＮ、ＣｒＮとＴｉＮとＡｌ
Ｎ、ＣｒＮとＴｉＮとＶＮ、ＴｉＮとＡｌＮとＶＮ、Ｃ
ｒＮとＴｉＮとＡｌＮとＶＮがあげられる。そして、こ
れら複合体の耐摩耗性、耐焼き付き性及び耐酸化性の各
特性は、それぞれ単体で示す特性を比較した場合に優れ
た方の特性を示す。また、組み合わせによっては、それ
ぞれ単体で示す上記特性の向上が見られる。The hard coating according to the present invention is made of Cr, T
It is composed of at least two of i, Al and V nitrides. As a combination, Cr nitride (CrN) and T
i nitride (TiN), CrN and Al nitride (Al
N), nitrides of CrN and V (VN), TiN and AlN,
TiN and VN, AlN and VN, CrN and TiN and Al
N, CrN and TiN and VN, TiN and AlN and VN, C
rN, TiN, AlN, and VN. The respective properties of the abrasion resistance, seizure resistance and oxidation resistance of these composites show superior properties when compared with the properties shown alone. Further, depending on the combination, the above-mentioned characteristics shown individually are improved.
【００１２】すなわち、ＣｒＮとＡｌＮとの複合体は、
ＣｒＮ単体の耐焼き付き性の高さが表れると共に、Ａｌ
Ｎ単体の耐酸化性の高さが表れる。耐酸化性が高くなる
のは、ＣｒＮ表面の酸化時に強固なＡｌの酸化層がで
き、酸化の進行を食い止めることができるからである。
また、耐摩耗性は、ＣｒＮ単体とＡｌＮ単体のいずれも
十分ではないが、これらを組み合わせると、硬度が向上
するため、耐摩耗性が向上する。この硬度の原因は明ら
かではないが、一般的に標準状態である安定な六方晶の
ＡｌＮが、硬度が高いといわれるｆｃｃのＡｌＮに変形
していることや、両者が複合することでそれぞれの結晶
格子が歪み、膜内に圧縮の残留応力が発生しているため
と考えられる。That is, the composite of CrN and AlN is
The high seizure resistance of CrN alone appears, and
The high oxidation resistance of N alone appears. The reason why the oxidation resistance is high is that a strong Al oxide layer is formed when the CrN surface is oxidized, and the progress of the oxidation can be stopped.
In addition, the wear resistance of either CrN alone or AlN alone is not sufficient, but when these are combined, the hardness is improved, so that the wear resistance is improved. Although the cause of this hardness is not clear, the stable hexagonal AlN, which is generally in a standard state, is transformed into fcc AlN, which is said to have high hardness. It is considered that the lattice was distorted and compressive residual stress was generated in the film.
【００１３】ＣｒＮとＴｉＮとの複合体は、ＣｒＮ単体
の耐焼き付き性の高さが表れる。また、耐酸化性と耐摩
耗性は、ＣｒＮ単体とＴｉＮ単体のいずれも十分ではな
いが、これらを組み合わせると、いずれの特性も向上す
る。The composite of CrN and TiN exhibits high seizure resistance of CrN alone. Further, the oxidation resistance and the wear resistance are not sufficient for either CrN alone or TiN alone, but when these are combined, both characteristics are improved.
【００１４】ＣｒＮとＶＮとの複合体は、ＣｒＮ単体及
びＶＮ単体の耐焼き付き性の高さが表れる。また、ＶＮ
単体の耐摩耗性の高さが表れる。さらに、耐酸化性は、
ＣｒＮ単体とＶＮ単体のいずれも十分でないが、これら
を組み合わせると、この特性が向上する。The composite of CrN and VN exhibits high seizure resistance of CrN alone and VN alone. Also, VN
High abrasion resistance of a single unit appears. In addition, oxidation resistance
Neither CrN alone nor VN alone is sufficient, but combining them improves this characteristic.
【００１５】ＴｉＮとＡｌＮとの複合体は、ＡｌＮ単体
の耐酸化性の高さが表れる。また、耐焼き付き性と耐摩
耗性は、ＴｉＮ単体とＡｌＮ単体のいずれも十分ではな
いが、これらを組み合わせると、いずれの特性も向上す
る。耐摩耗性が向上するのは、これらの複合により硬度
が増加するためと考えられる。The composite of TiN and AlN exhibits high oxidation resistance of AlN alone. In addition, the seizure resistance and the abrasion resistance are not sufficient for either TiN alone or AlN alone, but when these are combined, both characteristics are improved. It is considered that the abrasion resistance is improved because the hardness is increased by these composites.
【００１６】ＴｉＮとＶＮとの複合体は、ＶＮ単体の耐
焼き付き性及び耐摩耗性の高さが表れる。また、耐酸化
性は、ＴｉＮ単体とＶＮ単体のいずれも十分でないが、
これらを組み合わせると、この特性が向上する。The composite of TiN and VN exhibits high seizure resistance and abrasion resistance of VN alone. In addition, the oxidation resistance of both TiN alone and VN alone is not sufficient,
When these are combined, this characteristic is improved.
【００１７】ＡｌＮとＶＮとの複合体は、ＶＮ単体の耐
焼き付き性及び耐摩耗性の高さが表れる。また、ＡｌＮ
単体の耐酸化性の高さが表れる。The composite of AlN and VN exhibits high seizure resistance and abrasion resistance of VN alone. Also, AlN
The high oxidation resistance of the simple substance appears.
【００１８】ＣｒＮとＴｉＮとＡｌＮとの複合体は、Ｃ
ｒＮ単体の耐焼き付き性の高さが表れる。また、ＡｌＮ
単体の耐酸化性の高さが表れる。さらに、耐摩耗性は、
ＣｒＮ単体、ＴｉＮ単体、ＡｌＮ単体のいずれも十分で
はないが、上記の通り、ＣｒＮ単体とＡｌＮ単体との複
合により、硬度が向上するため、耐摩耗性が向上する。The complex of CrN, TiN and AlN is C
The high seizure resistance of rN alone appears. Also, AlN
The high oxidation resistance of the simple substance appears. Furthermore, the wear resistance is
Neither CrN alone, TiN alone, or AlN alone is sufficient, but as described above, the composite of CrN alone and AlN alone increases the hardness, thereby improving the wear resistance.
【００１９】ＣｒＮとＴｉＮとＶＮとの複合体は、Ｃｒ
Ｎ単体及びＶＮ単体の耐焼き付き性の高さが表れる。ま
た、ＶＮ単体の耐摩耗性の高さが表れる。さらに、耐酸
化性は、ＣｒＮ単体、ＴｉＮ単体、ＶＮ単体のいずれも
十分でないが、上記の通り、ＣｒＮ単体とＶＮ単体との
複合により、この特性が向上する。The composite of CrN, TiN and VN is Cr
The high seizure resistance of N alone and VN alone appears. In addition, the high wear resistance of the VN alone appears. Further, the oxidation resistance of any of CrN alone, TiN alone, and VN alone is not sufficient, but as described above, this characteristic is improved by the combination of CrN alone and VN alone.
【００２０】ＴｉＮとＡｌＮとＶＮとの複合体は、ＶＮ
単体の耐焼き付き性の高さが表れる。また、ＶＮ単体の
耐摩耗性の高さが表れる。さらに、ＡｌＮ単体の耐酸化
性の高さが表れる。The complex of TiN, AlN and VN is VN
The high seizure resistance of a single unit appears. In addition, the high wear resistance of the VN alone appears. Furthermore, the high oxidation resistance of AlN alone appears.
【００２１】ＣｒＮとＴｉＮとＡｌＮとＶＮとの複合体
は、ＣｒＮ単体及びＶＮ単体の耐焼き付き性の高さが表
れる。また、ＶＮ単体の耐摩耗性の高さが表れる。さら
に、ＡｌＮ単体の耐酸化性の高さが表れる。The composite of CrN, TiN, AlN, and VN exhibits high seizure resistance of CrN alone and VN alone. In addition, the high wear resistance of the VN alone appears. Furthermore, the high oxidation resistance of AlN alone appears.
【００２２】摺動特性を向上させるには、上記の耐焼き
付き性、耐摩耗性、及び耐酸性の各特性の向上以外に、
もう１つの特性である摩擦係数の低減が必要がある。こ
れは、上記の複数の金属窒化物の複合体によって形成さ
れる硬質皮膜の配向性を高めることにより行うことがで
きる。すなわち、上記複合体に対するＸ線回折ピークで
あって、上記複合体を構成するそれぞれの金属窒化物の
（１１１）面及び（２００）面のＸ線回折ピーク間に生
じるＸ線回折ピークの強さ（Ｉ(111) 及びＩ(2 00) ）の
強度比Ｉ(111) ／Ｉ(200) を３〜６とするのがよい。In order to improve the sliding characteristics, in addition to the above-mentioned improvements in the seizure resistance, abrasion resistance, and acid resistance,
It is necessary to reduce the coefficient of friction, which is another characteristic. This can be performed by increasing the orientation of the hard coating formed by the composite of the plurality of metal nitrides. That is, the intensity of the X-ray diffraction peak for the composite, which is generated between the X-ray diffraction peaks of the (111) plane and the (200) plane of each metal nitride constituting the composite. (I (111) and I (2 00)) the intensity ratio I (111) of / I (200) and preferably set to 3-6.
【００２３】複数の金属窒化物の複合体からなる硬質皮
膜のＸ線回折ピークは、選択されたそれぞれの金属窒化
物の結晶格子構造をｆｃｃ型と見なした場合の同じ面同
士の面間隔の中間位置に観察されるピークが含まれる。
つまり、例えば、ＣｒＮとＴｉＮの複合体の場合は、ｆ
ｃｃ−ＣｒＮの（１１１）面とｆｃｃ−ＴｉＮの（１１
１）面の面間隔の中間位置にピーク（Ｐ(111) ）が観察
される。このときに観察されるピークは、金属窒化物同
士の結晶格子が一致するためによるものか、両者がｎｍ
レベルで複合しているために、両者の面からの回折線が
干渉したためと考えられる。また、（２００）面につい
ても同様に、ｆｃｃ−ＣｒＮの（２００）面とｆｃｃ−
ＴｉＮの（２００）面の面間隔の中間位置にピーク（Ｐ
(200) ）が観察される。摩擦係数は、結晶格子構造の配
向性が高いほど低減するので、結晶構造をｆｃｃと見な
した場合の（１１１）面に起因するピークＰ(111) の強
度Ｉ(111) と（２００）面に起因するピークＰ(200) の
強度Ｉ(200) との強度比Ｉ(111) ／Ｉ(200) を３〜６と
すると、上記複合体からなる硬質皮膜の（１１１）面へ
の配向性が高まるので好ましい。上記強度比が３未満だ
と、上記複合体からなる硬質皮膜の（１１１）面への配
向性が低下するので、摩擦係数の低減に繋がりにくい場
合がある。また、上記強度比が６を超えてもよいが、製
造効率の点から上記強度比は６で十分である。The X-ray diffraction peak of a hard coating composed of a composite of a plurality of metal nitrides is determined by the distance between planes of the same plane when the crystal lattice structure of each selected metal nitride is regarded as fcc type. Includes peaks observed at intermediate positions.
That is, for example, in the case of a composite of CrN and TiN, f
(111) plane of cc-CrN and (11) plane of fcc-TiN
1) A peak (P (111) ) is observed at an intermediate position between the planes. The peak observed at this time may be due to the coincidence of the crystal lattices of the metal nitrides,
It is considered that the diffraction at both levels interfered with each other due to the compounding at the level. Similarly, the (200) plane and the (200) plane of fcc-CrN
The peak (P
(200) ) is observed. Since the coefficient of friction decreases as the orientation of the crystal lattice structure increases, the intensity I (111) and (200) plane of the peak P (111) due to the (111) plane when the crystal structure is regarded as fcc. When the intensity ratio I (111) / I (200) 3-6 of the intensity I (200) of the peak P (200) due to the orientation of the (111) plane of the hard film composed of the complex Is preferred because the If the strength ratio is less than 3, the orientation of the hard coating composed of the composite to the (111) plane will be reduced, and it may be difficult to reduce the friction coefficient. Further, the above-mentioned intensity ratio may exceed 6, but from the viewpoint of manufacturing efficiency, the above-mentioned intensity ratio is sufficient.
【００２４】Ｐ(111) 及びＰ(200) のピーク位置は、上
記複合体によって異なる。具体的には、ＣｒＮとＡｌＮ
との複合体の場合は、Ｐ(111) は、２．３７〜２．４０
Åに見られ、Ｐ(200) は、２．０６〜２．０７Åに見ら
れる。The peak positions of P (111) and P (200) differ depending on the complex. Specifically, CrN and AlN
In the case of the complex with, P (111) is 2.37 to 2.40.
And P (200) is found between 2.06 and 2.07 °.
【００２５】ＣｒＮとＴｉＮとの複合体の場合は、Ｐ
(111) は、２．３９〜２．４５Åに見られ、Ｐ
(200) は、２．０６〜２．１３Åに見られる。In the case of a composite of CrN and TiN, P
(111) is found between 2.39 and 2.45 °
(200) is found at 2.06 to 2.13 °.
【００２６】ＣｒＮとＶＮとの複合体の場合は、Ｐ
(111) は、２．３８〜２．４０Åに見られ、Ｐ
(200) は、２．０６〜２．０７Åに見られる。In the case of a composite of CrN and VN, P
(111) is found between 2.38 and 2.40 °
(200) is found between 2.06 and 2.07 °.
【００２７】ＴｉＮとＡｌＮとの複合体の場合は、Ｐ
(111) は、２．３７〜２．４５Åに見られ、Ｐ
(200) は、２．０６〜２．１３Åに見られる。In the case of a composite of TiN and AlN, P
(111) is found between 2.37 and 2.45 °,
(200) is found at 2.06 to 2.13 °.
【００２８】ＴｉＮとＶＮとの複合体の場合は、Ｐ
(111) は、２．３８〜２．４５Åに見られ、Ｐ
(200) は、２．０６〜２．１３Åに見られる。In the case of a composite of TiN and VN, P
(111) is found between 2.38 and 2.45 ° and P
(200) is found at 2.06 to 2.13 °.
【００２９】ＡｌＮとＶＮとの複合体の場合は、Ｐ
(111) は、２．３７〜２．３９Åに見られ、Ｐ
(200) は、２．０６〜２．０７Åに見られる。In the case of a complex of AlN and VN, P
(111) is found between 2.37 and 2.39Å
(200) is found between 2.06 and 2.07 °.
【００３０】ＣｒＮとＴｉＮとＡｌＮとの複合体、Ｃｒ
ＮとＴｉＮとＶＮとの複合体、ＴｉＮとＡｌＮとＶＮと
の複合体、または、ＣｒＮとＴｉＮとＡｌＮとＶＮとの
複合体の場合は、Ｐ(111) は、２．３７〜２．４０Åに
見られ、Ｐ(200) は、２．０６〜２．１３Åに見られ
る。A composite of CrN, TiN and AlN;
In the case of a complex of N and TiN and VN, a complex of TiN and AlN and VN, or a complex of CrN, TiN, AlN and VN, P (111) is 2.37 to 2.40 °. And P (200) is found between 2.06 and 2.13 °.
【００３１】この発明にかかる上記複合体からなる硬質
皮膜の構造は、各種の構造を採用することができる。例
えば、図１に示すように、基材１の表面に、上記の硬質
皮膜を構成する各金属窒化物２、３が交互に積み重ねら
れて積層体４を形成したものがあげられる。図１では、
２種の金属窒化物の積み重ねであるが、３種又は４種の
金属窒化物の積層体４であってもよい。Various structures can be adopted as the structure of the hard coating composed of the composite according to the present invention. For example, as shown in FIG. 1, a laminate 4 is formed by alternately stacking the respective metal nitrides 2 and 3 constituting the hard coating on the surface of the substrate 1. In FIG.
Although two types of metal nitrides are stacked, a stacked body 4 of three or four types of metal nitrides may be used.
【００３２】また、図２に示すように、基材１の表面
に、上記の硬質皮膜を構成する各金属窒化物５、６がそ
れぞれ粒状であり、これらが複合して粒状複合体７を形
成したものがあげられる。図２では、２種の金属窒化物
の複合であるが、３種又は４種の金属窒化物の粒状複合
体７であってもよい。As shown in FIG. 2, the metal nitrides 5 and 6 constituting the hard coating are granular on the surface of the base material 1 and are combined to form a granular composite 7. What you did. In FIG. 2, a composite of two types of metal nitrides is used, but a granular composite 7 of three or four types of metal nitrides may be used.
【００３３】さらに、上記の硬質皮膜を構成する各原料
金属の合金を用いて合金窒化物としたものを用いること
ができる。これは、この合金窒化物単独で硬質皮膜を形
成してもよく、また、これを上記積層体４や粒状複合体
７の一構成成分として供与してもよい。Further, an alloy nitride obtained by using an alloy of each raw material metal constituting the above-mentioned hard coating can be used. In this case, the alloy nitride alone may form a hard coating, or the hard coating may be provided as a component of the laminate 4 or the granular composite 7.
【００３４】上記積層体４を形成する場合、その一層あ
たりの膜厚は、１〜６００ｎｍとするのがよい。この範
囲を外れると、２種以上の金属窒化物を積層したときに
表れる上記の特性の向上が観察されない場合が生じる。When the above-mentioned laminated body 4 is formed, it is preferable that the thickness of one layer is 1 to 600 nm. If the ratio is out of this range, there may be a case where the above-described improvement in the characteristics, which appears when two or more metal nitrides are laminated, is not observed.
【００３５】また、上記粒子複合体７を形成する場合、
形成される各粒子の粒径は、０．４〜６００ｎｍとする
のがよい。この範囲を外れると、２種以上の金属窒化物
を複合したときに表れる上記の特性の向上が観察されな
い場合が生じる。When forming the particle composite 7,
The particle size of each formed particle is preferably 0.4 to 600 nm. If the ratio is out of this range, there may be a case where the above-described improvement in the characteristics which is exhibited when two or more metal nitrides are combined is not observed.
【００３６】なお、これらの場合、上記の特性を表出さ
せるため、２種以上の金属窒化物の添加率が異なっても
よい。In these cases, the addition ratio of two or more metal nitrides may be different in order to exhibit the above characteristics.
【００３７】上記の上記複合体からなる硬質皮膜、すな
わち、積層体４又は粒状複合体７の全体の膜厚は、１ｎ
ｍ〜３０μｍがよい。１ｎｍ未満では、上記の特性が観
察されない場合がある。また、３０μｍを超えてもよい
が、上記の特性のさらなる向上はあまり見られないの
で、３０μｍで十分である。The hard coating made of the above composite, that is, the total thickness of the laminate 4 or the granular composite 7 is 1 n
m to 30 μm is preferred. If it is less than 1 nm, the above characteristics may not be observed. Although it may exceed 30 μm, further improvement of the above-mentioned properties is hardly seen, so that 30 μm is sufficient.
【００３８】上記の積層体４又は粒状複合体７は、基材
１との密着力を高めたり、配向性を制御する目的等によ
り、基材１と積層体４又は粒状複合体７との間に１層以
上の中間層を設けることが可能である。また、摺動特性
をより高めたり、強度を強めたり、配向性を制御するた
め、上記の金属窒化物以外の物質を積層したり、粒状で
複合したり、積層体４又は粒状複合体７の表面に上記の
他物質からなる層をコーティングすることが可能であ
る。The laminate 4 or the granular composite 7 is provided between the substrate 1 and the laminate 4 or the granular composite 7 for the purpose of increasing the adhesion to the substrate 1 or controlling the orientation. May be provided with one or more intermediate layers. In addition, in order to further enhance the sliding characteristics, increase the strength, or control the orientation, a material other than the above-described metal nitride is laminated, composited in a granular form, laminated 4 or granular composite 7. It is possible to coat the surface with a layer made of the other substance described above.
【００３９】上記の複合体からなる硬質皮膜、すなわ
ち、積層体４又は粒状複合体７は、各種の材料からなる
工具や部品の表面に被覆することができる。この材料と
しては、超硬合金、サーメット、セラミックス、鉄系合
金、アルミニウム合金等があげられる。上記超硬合金と
しては、ＷＣを主成分とするＷＣ基超硬合金等があげら
れる。上記セラミックスとしては、炭化ケイ素、窒化ケ
イ素、窒化アルミニウム、アルミナ、窒化ホウ素、炭化
ホウ素、ガラス、ダイヤモンド等があげられる。上記鉄
系合金としては、高速度鋼、ステンレス鋼、ＳＫＤ等が
あげられる。The hard coating made of the above-mentioned composite, that is, the laminate 4 or the granular composite 7 can be coated on the surface of tools and components made of various materials. Examples of this material include cemented carbide, cermet, ceramics, iron-based alloy, and aluminum alloy. Examples of the cemented carbide include a WC-based cemented carbide mainly composed of WC. Examples of the ceramics include silicon carbide, silicon nitride, aluminum nitride, alumina, boron nitride, boron carbide, glass, and diamond. Examples of the iron-based alloy include high-speed steel, stainless steel, and SKD.
【００４０】また、上記の工具や部品としては、切削工
具、機械部品、摺動部品等があげられる。これらの中で
も、切削工具、金型部品、内燃機関部品に適応させる
と、十分な効果が発揮できる。The above tools and parts include cutting tools, mechanical parts, sliding parts and the like. Among them, when applied to cutting tools, mold parts, and internal combustion engine parts, a sufficient effect can be exhibited.
【００４１】上記の複合体からなる硬質皮膜、すなわ
ち、積層体４又は粒状複合体７の作製は、イオンプレー
ティング、真空アーク放電蒸着、スパッタリング等の物
理的蒸着法で行うことができる。これらは、成膜温度が
高くならないため、鉄系合金等において比較的低温で生
じる結晶構造の変態を抑制することができる。The hard coating made of the above composite, that is, the laminate 4 or the granular composite 7 can be produced by a physical vapor deposition method such as ion plating, vacuum arc discharge vapor deposition, and sputtering. Since the film formation temperature does not increase, the transformation of the crystal structure which occurs at a relatively low temperature in an iron-based alloy or the like can be suppressed.
【００４２】[0042]
【実施例】以下にこの発明の実施例を示す。Embodiments of the present invention will be described below.
【００４３】（実施例１）原料金属として、表１に示す
金属を使用し、真空アーク放電蒸着法によって、基材表
面に硬質皮膜を形成した。このときの硬質皮膜は、各原
料金属を交互に窒素ガス雰囲気下で蒸着させて、積層体
を形成させた。積層体中の各層の厚み及び積層体全体の
膜厚は、表１に示すとおりである。また、Ｘ線の回折ピ
ークは、ＣｕＫα線を入射Ｘ線とした回折であり、この
ピークからピーク強度比（Ｉ(111)／Ｉ(200) ）を測定
した。(Example 1) As a raw material metal, a metal shown in Table 1 was used, and a hard film was formed on the surface of a base material by a vacuum arc discharge evaporation method. At this time, the hard coating was formed by alternately depositing each raw material metal under a nitrogen gas atmosphere to form a laminate. The thickness of each layer in the laminate and the thickness of the entire laminate are as shown in Table 1. The X-ray diffraction peak was a diffraction using CuKα ray as the incident X-ray, and the peak intensity ratio (I (111) / I (200) ) was measured from this peak.
【００４４】得られた硬質皮膜の摩擦係数、摩耗量、ト
ルク低減率を下記の方法で測定した。なお、表１の皮膜
構造の欄で、「ＣｒＮ／ＴｉＮ」の「／」は、両金属窒
化物が積層構造を有することを示す。The friction coefficient, wear amount and torque reduction rate of the obtained hard coating were measured by the following methods. In the column of coating structure in Table 1, “/” in “CrN / TiN” indicates that both metal nitrides have a laminated structure.
【００４５】摩擦係数の測定 相手材としてＳＵＪ２を用い、回転速度５２ｍｍ／ｓ、
荷重１０Ｎとして、大気中又はエンジンオイル中でボー
ルオンディスク試験を行い、摩擦係数を測定した。Using SUJ2 as a material to be measured for the coefficient of friction , a rotational speed of 52 mm / s,
At a load of 10 N, a ball-on-disk test was performed in the air or in engine oil to measure the friction coefficient.
【００４６】摩耗量の測定 ピンオンディスク試験機により生じた摩耗痕の断面積を
測定し、下記の比較例１の試料１におけるＳＵＳ３０４
ｃを用いた場合の値を１０としたときの各硬質皮膜の値
を摩耗量として算出した。 Measurement of Wear Amount The cross-sectional area of a wear mark generated by a pin-on-disk tester was measured, and SUS304 of Sample 1 of Comparative Example 1 below was measured.
The value of each hard coating when the value when c was used was 10 was calculated as the amount of wear.
【００４７】トルク低減率の測定 エンジン部品のカム−シム部を基材として硬質皮膜をコ
ーティングしたときのモータリング試験におけるトルク
を測定した。このとき、下記の比較例１の試料１におけ
るＳＵＳ３０４ｃで実施した場合のトルク量からの低減
率を各硬質皮膜のトルク低減率として算出した。 Measurement of Torque Reduction Rate Torque was measured in a motoring test when a hard film was coated using the cam-shim portion of the engine component as a base material. At this time, the reduction rate from the torque amount in the case of SUS304c in Sample 1 of Comparative Example 1 described below was calculated as the torque reduction rate of each hard coating.
【００４８】[0048]
【表１】 [Table 1]
【００４９】（実施例２）原料金属として、表２に示す
金属を使用し、真空アーク放電蒸着法によって、基材表
面に硬質皮膜を形成した。このときの硬質皮膜は、別々
に用意した各原料金属をほぼ同時に窒素ガス雰囲気下で
蒸着させて、粒状複合体を形成させた。積層体全体の膜
厚は、表１に示すとおりである。Ｘ線の回折ピークは、
ＣｕＫα線を入射Ｘ線とした回折であり、このピークか
らピーク強度比（Ｉ(111) ／Ｉ(200 ) ）を、半価幅から
粒径を測定した。(Example 2) A metal film shown in Table 2 was used as a raw material metal, and a hard film was formed on the surface of a substrate by vacuum arc discharge vapor deposition. At this time, the hard coating was formed by depositing each separately prepared raw metal almost simultaneously under a nitrogen gas atmosphere to form a granular composite. The film thickness of the entire laminate is as shown in Table 1. The X-ray diffraction peak is
The diffraction was performed using CuKα rays as incident X-rays. The peak intensity ratio (I (111) / I (200 ) ) was measured from this peak, and the particle size was measured from the half width.
【００５０】得られた硬質皮膜の摩擦係数、摩耗量、ト
ルク低減率を上記の方法で測定した。なお、表２の皮膜
構造の欄で、「ＣｒＮ，ＴｉＮ」の「，」は、各金属窒
化物の粒状体が複合体を形成することを示す。The friction coefficient, abrasion loss and torque reduction rate of the obtained hard coating were measured by the above-mentioned methods. In addition, in the column of the coating structure in Table 2, “,” in “CrN, TiN” indicates that the granular material of each metal nitride forms a composite.
【００５１】[0051]
【表２】 [Table 2]
【００５２】（実施例３）原料金属として、表３に示す
金属を使用し、真空アーク放電蒸着法によって、基材表
面に硬質皮膜を形成した。このときの硬質皮膜は、各原
料金属の合金を窒素ガス雰囲気下で蒸着させて、粒状複
合体を形成させた。積層体中の粒径及び積層体全体の膜
厚は、表１に示すとおりである。また、Ｘ線の回折ピー
クは、ＣｕＫα線を入射Ｘ線とした回折であり、このピ
ークからピーク強度比（Ｉ(111) ／Ｉ(200) ）を、半価
幅から粒径を測定した。(Example 3) As a raw material metal, a metal shown in Table 3 was used, and a hard film was formed on the surface of a substrate by a vacuum arc discharge vapor deposition method. At this time, the hard coating was formed by depositing an alloy of each raw material metal under a nitrogen gas atmosphere to form a granular composite. The particle size in the laminate and the film thickness of the entire laminate are as shown in Table 1. The diffraction peak of the X-ray was a diffraction using the CuKα ray as the incident X-ray. The peak intensity ratio (I (111) / I (200) ) was measured from this peak, and the particle size was measured from the half width.
【００５３】得られた硬質皮膜の摩擦係数、摩耗量、ト
ルク低減率を上記の方法で測定した。なお、表２の皮膜
構造の欄で、「（Ｃｒ＋Ｔｉ）Ｎ」と示すのは、各原料
金属の合金を窒化したことを示す。The friction coefficient, abrasion loss and torque reduction rate of the obtained hard coating were measured by the above-mentioned methods. In the column of the coating structure in Table 2, "(Cr + Ti) N" indicates that the alloy of each raw material metal was nitrided.
【００５４】[0054]
【表３】 [Table 3]
【００５５】（比較例１）表４に示す試料からなる皮膜
を真空アーク放電蒸着法によって、基材表面に形成させ
た。Ｘ線の回折ピークは、ＣｕＫα線を入射Ｘ線とした
回折であり、このピークからピーク強度比（Ｉ(111) ／
Ｉ(200) ）を測定した。(Comparative Example 1) A coating composed of the samples shown in Table 4 was formed on the surface of a substrate by a vacuum arc discharge evaporation method. The X-ray diffraction peak is a diffraction using the CuKα ray as the incident X-ray, and the peak intensity ratio (I (111) /
I (200) ) was measured.
【００５６】得られた硬質皮膜の摩擦係数、摩耗量、ト
ルク低減率を上記の方法で測定した。なお、表１の試料
の欄で、「ＣｒＮ／ＴｉＮ」の「／」は、上記と同様の
意味を示す。The friction coefficient, abrasion loss and torque reduction rate of the obtained hard coating were measured by the above-mentioned methods. In the column of samples in Table 1, "/" in "CrN / TiN" has the same meaning as described above.
【００５７】[0057]
【表４】 [Table 4]
【００５８】（実施例４）原料金属として、表５及び表
６に示す金属を使用し、真空アーク放電蒸着法によっ
て、基材表面に硬質皮膜を形成した。このときの硬質皮
膜は、２種の原料金属の合金と残りの１種の原料金属を
交互に蒸着して積層体を形成した皮膜、３種の原料金属
を交互に蒸着して積層体を形成した皮膜、３種の原料金
属をほぼ同時に蒸着して粒状複合体を形成した皮膜のい
ずれかである。積層体全体の膜厚は、表１に示すとおり
である。なお、表５及び表６の皮膜構造の欄で、「（Ｃ
ｒ＋Ｔｉ）Ｎ／ＡｌＮ」とは、ＣｒとＴｉの合金の窒化
物とＡｌＮとの積層体であることを示す。「ＣｒＮ／Ｔ
ｉＮ／ＡｌＮ」や「ＣｒＮ、ＴｉＮ、ＡｌＮ」は、上記
と同様の意味である。Example 4 Using the metals shown in Tables 5 and 6 as raw materials, a hard film was formed on the surface of a substrate by vacuum arc discharge evaporation. At this time, the hard film is a film formed by alternately depositing an alloy of two kinds of raw material metals and the remaining one kind of raw material metal to form a laminate, and forming a laminate by alternately depositing three kinds of raw material metals. And three types of raw materials are deposited almost simultaneously to form a granular composite. The film thickness of the entire laminate is as shown in Table 1. In the column of the film structure in Tables 5 and 6, "(C
“r + Ti) N / AlN” indicates that it is a laminate of a nitride of an alloy of Cr and Ti and AlN. "CrN / T
“iN / AlN” and “CrN, TiN, AlN” have the same meaning as described above.
【００５９】Ｘ線の回折ピークは、ＣｕＫα線を入射Ｘ
線とした回折であり、このピークからピーク強度比（Ｉ
(111) ／Ｉ(200) ）を、半価幅から粒径を測定した。The diffraction peak of the X-ray was obtained by
Line, and the peak intensity ratio (I
(111) / I (200) ) was measured for the particle size from the half width.
【００６０】得られた硬質皮膜の摩擦係数、摩耗量、ト
ルク低減率を上記の方法で測定した。The friction coefficient, abrasion loss and torque reduction of the obtained hard coating were measured by the above-mentioned methods.
【００６１】[0061]
【表５】 [Table 5]
【００６２】[0062]
【表６】 [Table 6]
【００６３】結果 いずれの実施例も、比較例と比べて、摩擦係数が低減
し、摩耗量が減少すると共に、トルク低減率が向上し
た。トルク低減率の向上から、耐焼き付き性、及び耐酸
化性が向上したと判断できる。また、摩耗量が減少した
ことから、耐摩耗性が向上したと判断できる。 As a result, in each of the examples, the coefficient of friction was reduced, the amount of wear was reduced, and the torque reduction rate was improved, as compared with the comparative example. From the improvement in the torque reduction rate, it can be determined that the seizure resistance and the oxidation resistance have been improved. Further, it can be determined that the wear resistance has been improved from the decrease in the wear amount.
【００６４】[0064]
【発明の効果】この発明によれば、所定の４種の金属窒
化物の少なくとも２種を複合させた複合体を用いるの
で、摺動特性を発現する耐摩耗性、耐焼き付き性、耐酸
化性、摩擦係数の各特性うち、複合体を構成する各金属
窒化物単体が有する優れた上記特性が表出すると共に、
金属窒化物単体では十分でなかった上記特性の向上が各
金属窒化物を組み合わせることにより見られる。このた
め、耐摩耗性、耐焼き付き性、及び耐酸化性を向上させ
ることができる。また、強度比Ｉ(111) ／Ｉ(200)を上
記の所定の範囲の値とすると、皮膜の（１１１）面への
配向が向上するので、摩擦係数の低減を図ることができ
る。このため、全体として、摺動特性を向上させること
ができる。According to the present invention, since a composite in which at least two of the predetermined four metal nitrides are used is used, abrasion resistance, seizure resistance, and oxidation resistance exhibiting sliding characteristics are exhibited. Among the respective characteristics of the friction coefficient, the above-mentioned excellent characteristics of each metal nitride alone constituting the composite appear,
The improvement in the above properties, which was not sufficient with the metal nitride alone, can be seen by combining each metal nitride. For this reason, wear resistance, seizure resistance, and oxidation resistance can be improved. Further, when the intensity ratio I (111) / I (200) is set to a value within the above-mentioned predetermined range, the orientation of the coating to the (111) plane is improved, so that the friction coefficient can be reduced. Therefore, the sliding characteristics can be improved as a whole.
【図１】積層体の例を示す模式図FIG. 1 is a schematic view showing an example of a laminate.
【図２】粒状複合体の例を示す模式図FIG. 2 is a schematic view showing an example of a granular composite.
１ 基材 ２ 金属窒化物 ３ 金属窒化物 ４ 積層体 ５ 金属窒化物 ６ 金属窒化物 ７ 粒状複合体 DESCRIPTION OF SYMBOLS 1 Base material 2 Metal nitride 3 Metal nitride 4 Stacked body 5 Metal nitride 6 Metal nitride 7 Granular composite
Claims (9)
くとも２種の金属窒化物から構成される複合体であり、
この複合体が示すＸ線回折ピークであって、上記複合体
を構成するそれぞれの金属窒化物の（１１１）面及び
（２００）面のＸ線回折ピーク間に生じるＸ線回折ピー
クの強さ（Ｉ(111) 及びＩ(200) ）の強度比Ｉ(111) ／
Ｉ(200) が３〜６である硬質皮膜。1. A composite comprising at least two kinds of metal nitrides of Cr, Ti, Al and V nitrides,
The intensity of the X-ray diffraction peak of the composite, which is the X-ray diffraction peak generated between the (111) and (200) X-ray diffraction peaks of each metal nitride constituting the composite ( I (111) and I (200) ) intensity ratio I (111) /
Hard coating having I (200) of 3 to 6.
金属窒化物が交互に積み重ねられて積層体を形成し、そ
の一層あたりの膜厚が１〜６００ｎｍである積層硬質皮
膜。2. A laminated hard coating having a thickness of 1 to 600 nm, wherein each of the metal nitrides constituting the hard coating according to claim 1 is alternately stacked to form a laminate.
金属窒化物が粒状で複合して粒状複合体を形成し、その
各粒子の粒径が０．４〜６００ｎｍである粒状複合硬質
皮膜。3. A granular composite hard coating in which each of the metal nitrides constituting the hard coating according to claim 1 is combined in a granular form to form a granular composite, and each particle has a particle size of 0.4 to 600 nm. .
に記載の硬質皮膜。4. The method according to claim 1, wherein the thickness is 1 nm to 30 μm.
The hard film according to the above.
ある請求項２に記載の積層硬質皮膜。5. The laminated hard coating according to claim 2, wherein the total thickness of the laminated body is 1 nm to 30 μm.
ｍである請求項３に記載の粒状複合硬質皮膜。6. The total thickness of the granular composite is from 1 nm to 30 μm.
The granular composite hard coating according to claim 3, wherein m is m.
請求項２若しくは５に記載の積層硬質皮膜、又は、請求
項３又は６に記載の粒状複合硬質皮膜のいずれかを表面
に被覆した超硬合金、サーメット、セラミックス、鉄系
合金、アルミニウム合金を用いてなる切削工具。7. The hard coating according to claim 1 or 4,
A cemented carbide, cermet, ceramics, iron-based alloy, or aluminum alloy having a surface coated with any of the laminated hard coating according to claim 2 or 5, or the granular composite hard coating according to claim 3 or 6 is used. Cutting tool.
請求項２若しくは５に記載の積層硬質皮膜、又は、請求
項３又は６に記載の粒状複合硬質皮膜のいずれかを表面
に被覆した超硬合金、サーメット、セラミックス、鉄系
合金、アルミニウム合金を用いてなる機械部品。8. The hard coating according to claim 1 or 4,
A cemented carbide, cermet, ceramics, iron-based alloy, or aluminum alloy having a surface coated with any of the laminated hard coating according to claim 2 or 5, or the granular composite hard coating according to claim 3 or 6 is used. Machine parts.
請求項２若しくは５に記載の積層硬質皮膜、又は、請求
項３又は６に記載の粒状複合硬質皮膜のいずれかを表面
に被覆した超硬合金、サーメット、セラミックス、鉄系
合金、アルミニウム合金を用いてなる摺動部品。9. The hard coating according to claim 1 or 4,
A cemented carbide, cermet, ceramics, iron-based alloy, or aluminum alloy having a surface coated with any of the laminated hard coating according to claim 2 or 5, or the granular composite hard coating according to claim 3 or 6 is used. Sliding parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10328220A JP2000144376A (en) | 1998-11-18 | 1998-11-18 | Film excellent in sliding characteristic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10328220A JP2000144376A (en) | 1998-11-18 | 1998-11-18 | Film excellent in sliding characteristic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000144376A true JP2000144376A (en) | 2000-05-26 |
Family
ID=18207794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10328220A Pending JP2000144376A (en) | 1998-11-18 | 1998-11-18 | Film excellent in sliding characteristic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000144376A (en) |
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