JP2003321764A - High wear resistance/high hardness coating superior in high-temperature oxidation resistance - Google Patents
High wear resistance/high hardness coating superior in high-temperature oxidation resistanceInfo
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- JP2003321764A JP2003321764A JP2002129512A JP2002129512A JP2003321764A JP 2003321764 A JP2003321764 A JP 2003321764A JP 2002129512 A JP2002129512 A JP 2002129512A JP 2002129512 A JP2002129512 A JP 2002129512A JP 2003321764 A JP2003321764 A JP 2003321764A
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- layer
- coating
- film
- oxidation resistance
- ion plating
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、物理蒸着法を用い
て基材上に成膜した耐高温酸化性を飛躍的に向上させた
高耐摩耗性・高硬度皮膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high abrasion resistance and high hardness coating formed by a physical vapor deposition method on a base material, which has dramatically improved high temperature oxidation resistance.
【０００２】[0002]
【従来の技術】従来イオンプレーティングに代表される
物理蒸着法を用いて基板上に高硬度皮膜を形成する技術
が開発され、ＴｉＮ皮膜はその中でも最も実用化が進ん
でおり、工具、金型、眼鏡等の装飾品等に適用されてい
る。しかし、この皮膜は５００℃以上になると、皮膜の
酸化が始まるため、高温に曝される部品、工具、金型等
には適用出来ない。そこで、この改善策として、ＴｉＡ
ｌＮ皮膜が開発され、この皮膜では約８００℃までの高
温中でも酸化が抑制され使用が可能となったが、それ以
上であると上記ＴｉＮと同様酸化による皮膜劣化で適用
が困難である。さらに高温で使用可能な皮膜として、特
開平１０−２５５６６にあるＡｌ−Ｃｒ−Ｎが考案さ
れ、この皮膜では約１０００℃までの高温での使用が可
能であるが、密着性の点で問題があり、高荷重が負荷す
る製品、部品に対しては耐摩耗性の点で課題がある。2. Description of the Related Art Conventionally, a technique for forming a high hardness coating on a substrate by using a physical vapor deposition method represented by ion plating has been developed, and the TiN coating has been most practically used among them. It is applied to ornaments such as eyeglasses. However, this film cannot be applied to parts, tools, molds, etc. exposed to high temperatures because the film starts to oxidize at temperatures above 500 ° C. Therefore, as a remedy for this, TiA
The 1N film was developed, and it was possible to use it even at high temperatures up to about 800 ° C., but if it is higher than that, it is difficult to apply due to the deterioration of the film due to oxidation like TiN. Al-Cr-N disclosed in Japanese Patent Laid-Open No. 10-25566 was devised as a coating that can be used at higher temperatures. This coating can be used at high temperatures up to about 1000 ° C., but there is a problem in terms of adhesion. However, there is a problem in terms of wear resistance with respect to products and parts subjected to high loads.
【０００３】[0003]
【発明が解決しようとする課題】本発明では、以上の従
来技術の課題を解決するため研究を進め、従来技術を飛
躍的に向上した、耐酸化性に優れかつ高耐摩耗性・高硬
度皮膜を提案するに至った。すなわち、本発明は、耐酸
化性を１０００℃以上有し、且つ、耐摩耗性が良好な高
硬度皮膜を提供することを目的とする。DISCLOSURE OF THE INVENTION In the present invention, research has been carried out to solve the above-mentioned problems of the prior art, and the conventional technology has been dramatically improved. It has excellent oxidation resistance, high wear resistance and high hardness coating. Came to propose. That is, it is an object of the present invention to provide a high hardness coating having an oxidation resistance of 1000 ° C. or higher and good wear resistance.
【０００４】[0004]
【課題を解決するための手段】本発の明耐高温酸化に優
れた高耐摩耗性・高硬度皮膜は、上記目的を達成するた
めに、被処理物の表面に形成され、Ａｌ，Ｃｒ，及びＳ
ｉを主成分とする窒化物である。上記皮膜を金属成分
は、原子％でＣｒが２０％以上７５％以下、Ｓｉが１％
以上３０％以下、残りがＡｌとすることが好ましい。ま
た、上記Ａｌ，Ｃｒ，及びＳｉを主成分とする窒化物の
皮膜ａ層と、ＴｉとＡｌを主成分とする窒化物でその金
属成分のみの原子％がＡｌが２５％以上７５％以下、残
りがＴｉであるｂ層を交互にそれぞれ１層以上形成し、
ａ層を最外層に形成することができる。さらに、上記皮
膜と基材との間にＴｉ又はＣｒの窒化物からなる層を設
けてもよい。上記皮膜の形成方法としては、アークイオ
ンプレーティング法などの物理蒸着法により形成するこ
とができる。上記皮膜は、ホブ、ピニオンカッター、ブ
ローチ等の工作機械の工具や、金型などに用いることが
できる。In order to achieve the above-mentioned object, a highly wear-resistant and high-hardness coating excellent in light and high temperature oxidation resistance of the present invention is formed on the surface of an object to be treated, and Al, Cr, And S
It is a nitride containing i as a main component. The metal component of the above coating is 20% or more and 75% or less of Cr and 1% of Si in atomic%.
It is preferable that the above is 30% or less and the balance is Al. In addition, the above-described nitride film a layer containing Al, Cr, and Si as main components, and the nitride containing Ti and Al as main components, the atomic% of only the metal component of Al is 25% or more and 75% or less, Alternately forming one or more layers b each having the remaining Ti,
The a layer can be formed as the outermost layer. Furthermore, a layer made of a nitride of Ti or Cr may be provided between the film and the base material. As a method for forming the above film, a physical vapor deposition method such as an arc ion plating method can be used. The above coating can be used for tools of machine tools such as hobs, pinion cutters, broaches, and molds.
【０００５】[0005]
【発明の実施の形態】以下、本実施の形態による耐酸化
性に優れかつ高耐摩耗性・高硬度皮膜について図面を参
照しながら説明する。初めに本発明がなされた経緯につ
いて説明すると以下のとおりである。ＴｉＡｌＮ皮膜
は、高温大気中で使用されると８００℃程度で皮膜が酸
化され皮膜強度及び密着性が低下する。この酸化状態を
分析すると、皮膜成分のＡｌ及びＴｉが酸化されてお
り、特にＴｉの酸化物は非常にポーラスであるため酸素
の進入が容易であり厚くなる。このため、上述の皮膜強
度及び密着性が低下し、皮膜の剥離に繋がる。一方、Ａ
ｌＣｒＮ皮膜はこの点を改善した皮膜であり、ポーラス
で厚く形成するＴｉ成分に代えＣｒとし、酸素の進入を
防止し酸化皮膜を極薄く生成させこの酸化層によりその
後の酸化を防止することにより、耐酸化性を向上してい
る。しかしこの皮膜は、Ａｌ，Ｃｒの酸化物の密着性が
低いため、高荷重が負荷する例えば工具に使用した場合
剥離が生じ耐摩耗性の点で問題がある。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a coating film excellent in oxidation resistance and having high wear resistance and high hardness according to the present embodiment will be described with reference to the drawings. First, the background of the present invention will be described as follows. When the TiAlN film is used in a high temperature atmosphere, the film is oxidized at about 800 ° C. and the film strength and adhesiveness are deteriorated. Analysis of this oxidation state shows that Al and Ti of the film components are oxidized, and in particular, the oxide of Ti is very porous, so that oxygen easily enters and becomes thick. For this reason, the above-mentioned film strength and adhesion are lowered, which leads to peeling of the film. On the other hand, A
The lCrN film is a film in which this point has been improved. Cr is used in place of the Ti component that is formed to be porous and thick, and the invasion of oxygen is prevented, an oxide film is formed extremely thin, and the subsequent oxidation is prevented by this oxide layer. Has improved oxidation resistance. However, since this coating has low adhesion to oxides of Al and Cr, when it is used in a tool under a high load, for example, peeling occurs and there is a problem in wear resistance.
【０００６】これらの現象を基に本発明では、酸素の進
入を防止するすなわち耐酸化性を高めるため、Ａｌ，Ｃ
ｒ，Ｓｉの窒化物とし、これにより結晶の微細化を図
り、高温酸化雰囲気に曝された場合、生成する酸化物が
Ａｌ，Ｃｒ，Ｓｉ複合酸化皮膜となり酸素の進入を防止
すると共に、非常に緻密な複合酸化皮膜であるため密着
性が著しく向上することを見出した。Based on these phenomena, in the present invention, in order to prevent entry of oxygen, that is, to enhance oxidation resistance, Al and C are used.
When it is a nitride of r and Si, the crystal is made finer by this, and when it is exposed to a high temperature oxidizing atmosphere, the generated oxide becomes an Al, Cr, Si composite oxide film to prevent the ingress of oxygen and to It was found that the adhesion is remarkably improved due to the dense composite oxide film.
【０００７】図１は、その耐酸化性に優れかつ高耐摩耗
性・高硬度皮膜を基材表面に形成するためのアークイオ
ンプレーティング装置１を示す。このアークイオンプレ
ーティング装置１は、大気と気密なケーシング２を設
け、その天井部には、ターゲット３を配設し、ケーシン
グ２の室内１２にはテーブル状のホルダー７が配設され
ている。ホルダー７は、回転軸９を介してモータ８と連
結され、ホルダー７はその周方向に回転が可能である。
そして、ターゲット３とホルダー７間には、直流電源１
１が接続され、ターゲット３は電源１１の＋側と接続さ
れ、ホルダー７は電源１１の−側に接続されている。ケ
ーシング２の室内１２には、室内１２を真空にするため
の真空ポンプ４が制御バルブ１３を介して接続され、ま
た、室内１２の不活性ガスを供給するためのアルゴンの
ガス源５が制御バルブ１４を介して接続され、さらに、
室内１２に窒素を供給するための窒素ガス源６が制御バ
ルブ１５を介して接続されている。FIG. 1 shows an arc ion plating apparatus 1 for forming a highly wear-resistant and high-hardness coating having excellent oxidation resistance on the surface of a substrate. This arc ion plating apparatus 1 is provided with a casing 2 that is airtight to the atmosphere, a target 3 is provided on the ceiling of the casing 2, and a table-shaped holder 7 is provided inside a chamber 12 of the casing 2. The holder 7 is connected to the motor 8 via the rotation shaft 9, and the holder 7 can rotate in the circumferential direction.
The DC power supply 1 is provided between the target 3 and the holder 7.
1 is connected, the target 3 is connected to the + side of the power source 11, and the holder 7 is connected to the − side of the power source 11. A vacuum pump 4 for evacuating the room 12 is connected to the room 12 of the casing 2 through a control valve 13, and an argon gas source 5 for supplying an inert gas in the room 12 is a control valve. Connected via 14,
A nitrogen gas source 6 for supplying nitrogen to the room 12 is connected via a control valve 15.
【０００８】本実施形態では、ターゲット３はＡｌ，Ｃ
ｒ，Ｓｉからなり、また、基板１０はＳＫＨ−５１を用
いた。そして、ホルダー７上に基板１０を載置し、制御
バルブ１３〜１５のうち、初めに制御バルブ１３，１４
を開き、室内１２にアルゴンガスを供給するとともに、
室内１２を真空引きする。真空引きが完了し、室内１２
がアルゴン雰囲気になったら、モータ８によりホルダー
７を回転させる。次いで、遮断バルブ１３，１４を閉じ
てターゲット３とホルダー７間に直流電圧を印加させ
て、プラズマを発生して室内１２温度を上昇させる。室
内１２温度が一定温度に達したときに、制御バルブ１５
を開き窒素ガス源６から室内１２へ窒素を供給してアー
ク放電を生じさせる。これにより、基板１０の表面に耐
高温酸化に優れた高耐摩耗性・高硬度皮膜が形成され
る。このような高耐摩耗性・高硬度皮膜は、ホブ、ピニ
オンカッター、ブローチ、金型などの工具や、眼鏡など
の装飾品に使用することができる。In this embodiment, the target 3 is made of Al, C.
The substrate 10 was SKH-51. Then, the substrate 10 is placed on the holder 7, and of the control valves 13 to 15, the control valves 13 and 14 are first
Open and supply argon gas to the room 12,
The chamber 12 is evacuated. Vacuuming is completed, and indoor 12
When is in an argon atmosphere, the holder 7 is rotated by the motor 8. Next, the shutoff valves 13 and 14 are closed and a DC voltage is applied between the target 3 and the holder 7 to generate plasma and raise the temperature of the room 12. When the temperature in the room 12 reaches a certain temperature, the control valve 15
Is opened to supply nitrogen from the nitrogen gas source 6 to the room 12 to generate arc discharge. As a result, a high wear-resistant and high-hardness coating excellent in high temperature oxidation resistance is formed on the surface of the substrate 10. Such a high wear-resistant and high-hardness coating can be used for tools such as hobs, pinion cutters, broaches, dies, and decorative items such as eyeglasses.
【０００９】[0009]
【実施例】アークイオンプレーティング装置により各種
合金ターゲットを用い、ＳＫＨ−５１基材上に膜厚４μ
ｍの皮膜２０を成膜した。成膜条件は表１に示すとおり
とした。そして、生成した皮膜のヌープ硬度を、室温で
荷重０．２４５Ｎで測定した。また、白金上に表１の条
件で同様に膜厚４μｍ成膜し、示差熱分析装置を用い、
空気気流中（１Ｌ／ｍｉｎ．），１０Ｋ／ｍｉｎ．の昇
温速度で１２００℃までの酸化による質量変化を測定
し、皮膜の酸化重量増加率を求めた。各実施例のＡｌ，
Ｃｒ，Ｓｉの組成と、比較例及び従来例の測定結果は以
下の通りである。[Example] Using an alloy target of various types by an arc ion plating device, a film thickness of 4 μm was formed on a SKH-51 substrate.
A film 20 of m was formed. The film forming conditions were as shown in Table 1. Then, the Knoop hardness of the formed film was measured at room temperature under a load of 0.245N. In addition, a film having a thickness of 4 μm was similarly formed on platinum under the conditions shown in Table 1, and using a differential thermal analyzer,
In air flow (1 L / min.), 10 K / min. The change in mass due to oxidation up to 1200 ° C. was measured at the heating rate of 1, and the rate of increase in oxidized weight of the film was determined. Al of each example,
The composition of Cr and Si and the measurement results of the comparative example and the conventional example are as follows.
【００１０】[0010]
【表１】
［実施例１］ターゲットに、Ａｌ：７９％、Ｃｒ：２０
％、Ｓｉ：１％のものを用い、アークイオンプレーティ
ングを行った。その結果、図２に示すようなコーティン
グ層ａを得た。コーティング層ａの酸化重量増加率は４
％であり、硬さは、２７００（Ｈｋ）であった。
［実施例２］ターゲットに、Ａｌ：５０％、Ｃｒ：２０
％、Ｓｉ：３０％のものを用い、アークイオンプレーテ
ィングを行った。その結果、生成したコーティング層ａ
の酸化重量増加率は２％であり、硬さは、２７５０（Ｈ
ｋ）であった。（図２参照）
［実施例３］ターゲットに、Ａｌ：２４％、Ｃｒ：７０
％、Ｓｉ：１％のものを用い、アークイオンプレーティ
ングを行った。その結果、コーティング層ａの酸化重量
増加率は４％であり、硬さは、２７５０（Ｈｋ）であっ
た。（図２参照）
［実施例４］ターゲットに、Ａｌ：２０％、Ｃｒ：７５
％、Ｓｉ：５％のものを用い、アークイオンプレーティ
ングを行った。その結果、コーティング層ａの酸化重量
増加率は２％であり、硬さは、２７００（Ｈｋ）であっ
た。（図２参照）
［実施例５］ターゲットに、Ａｌ：３０％、Ｃｒ：４０
％、Ｓｉ：３０％のものを用い、アークイオンプレーテ
ィングを行った。その結果、コーティング層ａの酸化重
量増加率は２％であり、硬さは、２９５０（Ｈｋ）であ
った。（図２参照）
［実施例６］ターゲットに、Ａｌ：４４％、Ｃｒ：４６
％、Ｓｉ：１０％のものを用い、アークイオンプレーテ
ィングを行った。その結果、コーティング層ａの酸化重
量増加率は２％であり、硬さは、３０００（Ｈｋ）であ
った。（図２参照）
［比較例７］ターゲットに、Ａｌ：８５％、Ｃｒ：５
％、Ｓｉ：１０％のものを用い、アークイオンプレーテ
ィングを行った。その結果、酸化重量増加率は１０％で
あり、硬さは、２３００（Ｈｋ）であった。
［比較例８］ターゲットに、Ａｌ：１０％、Ｃｒ：８０
％、Ｓｉ：１０％のものを用い、アークイオンプレーテ
ィングを行った。その結果、酸化重量増加率は１５％で
あり、硬さは、２２００（Ｈｋ）であった。
［従来例９］ターゲットに、Ｔｉ：５３％、Ａｌ：４７
％のものを用い、アークイオンプレーティングを行っ
た。その結果、酸化重量増加率は２２％であり、硬さ
は、２７００（Ｈｋ）であった。
上記の各実施例、比較例及び従来例の結果をまとめて表
２に示す。[Table 1] [Example 1] As a target, Al: 79% and Cr: 20
%, Si: 1%, and arc ion plating was performed. As a result, a coating layer a as shown in FIG. 2 was obtained. The oxidation weight increase rate of the coating layer a is 4
%, And the hardness was 2700 (Hk). [Example 2] As targets, Al: 50%, Cr: 20
%, Si: 30%, arc ion plating was performed. As a result, the generated coating layer a
The oxidative weight increase rate is 2% and the hardness is 2750 (H
k). (See FIG. 2) [Example 3] Target: Al: 24%, Cr: 70
%, Si: 1%, and arc ion plating was performed. As a result, the rate of increase in oxidized weight of the coating layer a was 4%, and the hardness was 2750 (Hk). (See FIG. 2) [Example 4] Target: Al: 20%, Cr: 75
%, Si: 5%, and arc ion plating was performed. As a result, the oxidation weight increase rate of the coating layer a was 2%, and the hardness was 2700 (Hk). (See FIG. 2) [Example 5] As a target, Al: 30%, Cr: 40
%, Si: 30%, arc ion plating was performed. As a result, the rate of increase in oxidized weight of the coating layer a was 2%, and the hardness was 2950 (Hk). (See FIG. 2) [Example 6] Al: 44%, Cr: 46 as a target
%, Si: 10%, and arc ion plating was performed. As a result, the rate of increase in oxidized weight of the coating layer a was 2%, and the hardness was 3000 (Hk). (See FIG. 2) [Comparative Example 7] Al: 85%, Cr: 5 as a target
%, Si: 10%, and arc ion plating was performed. As a result, the rate of increase in oxidized weight was 10% and the hardness was 2300 (Hk). [Comparative Example 8] As a target, Al: 10%, Cr: 80
%, Si: 10%, and arc ion plating was performed. As a result, the rate of increase in oxidized weight was 15% and the hardness was 2200 (Hk). [Conventional Example 9] Target: Ti: 53%, Al: 47
%, And arc ion plating was performed. As a result, the rate of increase in oxidized weight was 22% and the hardness was 2700 (Hk). The results of each of the above Examples, Comparative Examples and Conventional Example are summarized in Table 2.
【００１１】[0011]
【表２】
ここで、Ｓｉの役割に着目すると、結晶の微細化の点で
密着性に対し大きく影響を与え、金属成分のみの原子％
で１％以上３０％以下で効果を発揮する。１％未満であ
ると、密着性が不十分であり、３０％を超えると皮膜が
もろくなり、衝撃に対し弱くなり剥離の原因となる。さ
らに、Ｃｒ量については、金属成分のみの原子％で２０
％以上７５％以下で効果を発揮する。２０％未満である
と硬さが低下し、７５％を超えると耐酸化性が劣化す
る。よって、上記各実施例１〜６において、本発明皮膜
は耐酸化性に優れ、硬さも高いことが判明した[Table 2] Here, focusing on the role of Si, it has a great influence on the adhesion in terms of crystal miniaturization.
The effect is exhibited at 1% or more and 30% or less. If it is less than 1%, the adhesion is insufficient, and if it exceeds 30%, the coating becomes brittle and weak against impact, causing peeling. Further, regarding the amount of Cr, the atomic percentage of the metal component alone is 20
%, The effect is exhibited at 75% or less. If it is less than 20%, the hardness decreases, and if it exceeds 75%, the oxidation resistance deteriorates. Therefore, in each of the above Examples 1 to 6, it was found that the coating of the present invention has excellent oxidation resistance and high hardness.
【００１２】次に、他の実施例として、上記のアークイ
オンプレーティング装置により、各種合金ターゲットを
用い、超硬（ＴＨ−１０）基材上に膜厚４μｍ成膜し
た。成膜条件は表１に示すとおりとした。基材／コーテ
ィング層間の窒化物皮膜の膜厚は１．０μｍとした。こ
の場合の総厚さは５μｍである。その後、アルミナボー
ル（φ６）を使用したボールオンディスク摩耗試験を実
施し耐摩耗性を評価した。試験条件は、荷重５Ｎ、すべ
り速度１００ｍ／ｓ、摺動距離３００ｍ、室温、無潤滑
である。摩耗量の測定は、摩耗試験後のコーティング層
の摩耗深さ及び摩耗幅を測定することにより行った。各
実施例の各種合金ターゲットの組成（原子％）は以下の
通りである。なお、下記の実施例１６〜１９及び実施例
２２，２３は、２種の２層以上の皮膜（コーティング
層）を作成し、実施例２０、２２はＴｉ窒化物の皮膜を
基材１０表面に形成させてからコーティング層を形成し
た。また、実施例２１，２３は、Ｃｒ窒化物の皮膜を基
材１０の表面に形成させてからコーティング層を形成し
た。Next, as another example, a film having a thickness of 4 .mu.m was formed on a cemented carbide (TH-10) substrate by using the above-mentioned arc ion plating device and various alloy targets. The film forming conditions were as shown in Table 1. The film thickness of the nitride film between the base material and the coating layer was 1.0 μm. The total thickness in this case is 5 μm. Then, a ball-on-disk abrasion test using alumina balls (φ6) was performed to evaluate abrasion resistance. The test conditions are a load of 5 N, a sliding speed of 100 m / s, a sliding distance of 300 m, room temperature, and no lubrication. The amount of wear was measured by measuring the wear depth and wear width of the coating layer after the wear test. The composition (atomic%) of each alloy target of each example is as follows. In addition, the following Examples 16 to 19 and Examples 22 and 23 form two or more types of coatings (coating layers), and Examples 20 and 22 apply a Ti nitride coating to the surface of the substrate 10. After being formed, a coating layer was formed. Further, in Examples 21 and 23, a coating film of Cr nitride was formed on the surface of the base material 10 and then the coating layer was formed.
【００１３】［実施例１０］ターゲットに、Ａｌ：７９
％、Ｃｒ：２０％、Ｓｉ：１％のものを用い、アークイ
オンプレーティングを行った。その結果、コーティング
層ａを得た。コーティング層ａの摩耗深さは０．２５
（μｍ）であり、摩耗幅は０．２５（ｍｍ）であった。
（図２参照）
［実施例１１］ターゲットに、Ａｌ：５０％、Ｃｒ：２
０％、Ｓｉ：３０％のものを用い、アークイオンプレー
ティングを行った。その結果、摩耗深さは０．２２（μ
ｍ）であり、摩耗幅は０．２６（ｍｍ）であった。（図
２参照）
［実施例１２］ターゲットに、Ａｌ：２４％、Ｃｒ：７
０％、Ｓｉ：１％のものを用い、アークイオンプレーテ
ィングを行った。その結果、摩耗深さは０．２３（μ
ｍ）であり、摩耗幅は０．２５（ｍｍ）であった。（図
２参照）
［実施例１３］ターゲットに、Ａｌ：２０％、Ｃｒ：７
５％、Ｓｉ：５％のものを用い、アークイオンプレーテ
ィングを行った。その結果、摩耗深さは０．２３（μ
ｍ）であり、摩耗幅は０．２５（ｍｍ）であった。（図
２参照）
［実施例１４］ターゲットに、Ａｌ：３０％、Ｃｒ：４
０％、Ｓｉ：３０％のものを用い、アークイオンプレー
ティングを行った。その結果、摩耗深さは０．２０（μ
ｍ）であり、摩耗幅は０．２２（ｍｍ）であった。（図
２参照）
［実施例１５］ターゲットに、Ａｌ：４４％、Ｃｒ：４
６％、Ｓｉ：１０％のものを用い、アークイオンプレー
ティングを行った。その結果、摩耗深さは０．１９（μ
ｍ）であり、摩耗幅は０．２０（ｍｍ）であった。（図
２参照）
［実施例１６］図３に示すように、第１番目の層ａとし
てターゲットに、Ａｌ：４４％、Ｃｒ：４６％、Ｓｉ：
１０％のものを用い、第２番目の層としてｂ層に、Ｔ
ｉ：５３％、Ａｌ：４７％のものを用い、アークイオン
プレーティングを行った。ａ層とｂ層は各々１層であ
る。その結果、摩耗深さは０．２５（μｍ）であり、摩
耗幅は０．２４（ｍｍ）であった。なお、２種のコーテ
ィング層を２層以上に形成する場合は、ａ層を最外層に
配置する（以下、同様）。
［実施例１７］図４に示すように、第１番目の層として
ａ層に、Ａｌ：４４％、Ｃｒ：４６％、Ｓｉ：１０％の
ものを用い、第２番目の層としてｂ層に、Ｔｉ：５３
％、Ａｌ：４７％のものを用い、アークイオンプレーテ
ィングを行った。ａ層とｂ層は各々互い違いに５層宛、
併せて１０層形成した。その結果、摩耗深さは０．２３
（μｍ）であり、摩耗幅は０．２４（ｍｍ）であった。
［実施例１８］第１番目の層としてａ層に、Ａｌ：４４
％、Ｃｒ：４６％、Ｓｉ：１０％のものを用い、第２番
目の層としてｂ層に、Ｔｉ：７５％、Ａｌ：２５％のも
のを用い、アークイオンプレーティングを行った。ａ層
とｂ層は各々互い違いに５層宛である。その結果、摩耗
深さは０．２０（μｍ）であり、摩耗幅は０．２１（ｍ
ｍ）であった。（図４参照）
［実施例１９］第１番目の層としてａ層に、Ａｌ：４４
％、Ｃｒ：４６％、Ｓｉ：１０％のものを用い、第２番
目の層としてｂ層に、Ｔｉ：２５％、Ａｌ：７５％のも
のを用い、アークイオンプレーティングを行った。ａ層
とｂ層は各々互い違いに５層宛である。その結果、摩耗
深さは０．２１（μｍ）であり、摩耗幅は０．２２（ｍ
ｍ）であった。（図４参照）
［実施例２０］図５に示すように、予め基材にＴｉ窒化
物を形成した後、ターゲットに、Ａｌ：４４％、Ｃｒ：
４６％、Ｓｉ：１０％のものを用い、アークイオンプレ
ーティングを行った。その結果、摩耗深さは０．２０
（μｍ）であり、摩耗幅は０．２３（ｍｍ）であった。
［実施例２１］予め基材にＣｒ窒化物を形成した後、タ
ーゲットに、Ａｌ：４４％、Ｃｒ：４６％、Ｓｉ：１０
％のものを用い、アークイオンプレーティングを行っ
た。その結果、摩耗深さは０．２０（μｍ）であり、摩
耗幅は０．２３（ｍｍ）であった。（図５参照）
［実施例２２］図６に示すように、予め基材にＴｉ窒化
物を形成した後、第１番目の層としてａ層に、Ａｌ：４
４％、Ｃｒ：４６％、Ｓｉ：１０％のものを用い、第２
番目の層としてｂ層に、Ｔｉ：５３％、Ａｌ：４７％の
ものを用い、アークイオンプレーティングを行った。ａ
層とｂ層は各々互い違いに５層宛である。その結果、摩
耗深さは０．１５（μｍ）であり、摩耗幅は０．１９
（ｍｍ）であった。
［実施例２３］予め基材にＣｒ窒化物を形成した後、第
１番目の層としてａ層に、Ａｌ：４４％、Ｃｒ：４６
％、Ｓｉ：１０％のものを用い、第２番目の層としてｂ
層に、Ｔｉ：５３％、Ａｌ：４７％のものを用い、アー
クイオンプレーティングを行った。ａ層とｂ層は各々互
い違いに５層宛である。その結果、摩耗深さは０．１７
（μｍ）であり、摩耗幅は０．１９（ｍｍ）であった。
（図６参照）
［比較例２４］ターゲットに、Ａｌ：８５％、Ｃｒ：５
％、Ｓｉ：１０％のものを用い、アークイオンプレーテ
ィングを行った。その結果、摩耗深さは０．６０（μ
ｍ）であり、摩耗幅は０．５０（ｍｍ）であった。
［比較例２５］ターゲットに、Ａｌ：１０％、Ｃｒ：８
０％、Ｓｉ：１０％のものを用い、アークイオンプレー
ティングを行った。その結果、摩耗深さは０．７０（μ
ｍ）であり、摩耗幅は０．５２（ｍｍ）であった。
［比較例２６］ターゲットに、Ａｌ：５１％、Ｃｒ：４
８．５％、Ｓｉ：０．５％のものを用い、アークイオン
プレーティングを行った。その結果、摩耗深さは０．５
０（μｍ）であり、摩耗幅は０．３８（ｍｍ）であっ
た。
［比較例２７］ターゲットに、Ａｌ：３０％、Ｃｒ：３
５％、Ｓｉ：３５％のものを用い、アークイオンプレー
ティングを行った。その結果、摩耗深さは０．８０（μ
ｍ）であり、摩耗幅は０．５５（ｍｍ）であった。
［従来例２８］ターゲットに、Ａｌ：４５％、Ｃｒ：５
５％のものを用い、アークイオンプレーティングを行っ
た。その結果、摩耗深さは０．５０（μｍ）であり、摩
耗幅は０．３２（ｍｍ）であった。
［従来例２９］ターゲットに、Ａｌ：５３％、Ｃｒ：４
７％のものを用い、アークイオンプレーティングを行っ
た。その結果、摩耗深さは、０．８０（μｍ）であり、
摩耗幅は０．４０（ｍｍ）であった。[Embodiment 10] A target of Al: 79
%, Cr: 20%, Si: 1%, and arc ion plating was performed. As a result, a coating layer a was obtained. The wear depth of the coating layer a is 0.25
(Μm) and the wear width was 0.25 (mm).
(See FIG. 2) [Embodiment 11] Target: Al: 50%, Cr: 2
Arc ion plating was performed using 0% and 30% Si. As a result, the wear depth was 0.22 (μ
m) and the wear width was 0.26 (mm). (See FIG. 2) [Example 12] A target is Al: 24%, Cr: 7
Arc ion plating was performed using 0% and 1% Si. As a result, the wear depth was 0.23 (μ
m) and the wear width was 0.25 (mm). (See FIG. 2) [Example 13] Target: Al: 20%, Cr: 7
Arc ion plating was carried out using 5% and Si: 5%. As a result, the wear depth was 0.23 (μ
m) and the wear width was 0.25 (mm). (See FIG. 2) [Example 14] As a target, Al: 30%, Cr: 4
Arc ion plating was performed using 0% and 30% Si. As a result, the wear depth was 0.20 (μ
m), and the wear width was 0.22 (mm). (Refer to FIG. 2) [Example 15] A target of Al: 44%, Cr: 4
Arc ion plating was carried out using 6% and Si: 10%. As a result, the wear depth was 0.19 (μ
m) and the wear width was 0.20 (mm). (Refer to FIG. 2) [Example 16] As shown in FIG. 3, Al: 44%, Cr: 46%, Si:
The second layer, b layer, T
Arc ion plating was carried out using i: 53% and Al: 47%. Each of the a layer and the b layer is one layer. As a result, the wear depth was 0.25 (μm) and the wear width was 0.24 (mm). When two types of coating layers are formed in two or more layers, the a layer is arranged as the outermost layer (the same applies hereinafter). [Embodiment 17] As shown in FIG. 4, as the first layer, the a layer is made of Al: 44%, Cr: 46%, Si: 10%, and as the second layer, the b layer. , Ti: 53
%, Al: 47%, arc ion plating was performed. Layers a and b are alternately addressed to 5 layers,
A total of 10 layers were formed. As a result, the wear depth is 0.23
(Μm) and the wear width was 0.24 (mm). [Embodiment 18] As the first layer, the a layer has Al: 44.
%, Cr: 46%, Si: 10%, arc ion plating was performed using a b layer as the second layer of Ti: 75%, Al: 25%. Layers a and b are alternately addressed to five layers. As a result, the wear depth was 0.20 (μm) and the wear width was 0.21 (m
m). (See FIG. 4) [Embodiment 19] The first layer is a layer, and Al: 44
%, Cr: 46%, Si: 10%, arc ion plating was performed using the second layer b layer of Ti: 25%, Al: 75%. Layers a and b are alternately addressed to five layers. As a result, the wear depth was 0.21 (μm) and the wear width was 0.22 (m
m). (See FIG. 4) [Embodiment 20] As shown in FIG. 5, after forming a Ti nitride on a base material in advance, Al: 44%, Cr:
Arc ion plating was carried out using 46% and Si: 10%. As a result, the wear depth is 0.20
(Μm) and the wear width was 0.23 (mm). [Example 21] After forming a Cr nitride on a substrate in advance, Al: 44%, Cr: 46%, Si: 10 were used as targets.
%, And arc ion plating was performed. As a result, the wear depth was 0.20 (μm) and the wear width was 0.23 (mm). (See FIG. 5) [Embodiment 22] As shown in FIG. 6, after a Ti nitride is formed on a base material in advance, Al: 4 is formed on the a layer as the first layer.
4%, Cr: 46%, Si: 10%, second
Arc ion plating was performed using the b layer as the second layer, which was made of Ti: 53% and Al: 47%. a
Layers b and b are alternately addressed to 5 layers. As a result, the wear depth was 0.15 (μm) and the wear width was 0.19.
(Mm). [Example 23] After forming Cr nitride on the base material in advance, Al: 44%, Cr: 46 was formed in the a layer as the first layer.
%, Si: 10%, and b as the second layer
Arc ion plating was performed using a layer of Ti: 53% and Al: 47%. Layers a and b are alternately addressed to five layers. As a result, the wear depth is 0.17
(Μm) and the wear width was 0.19 (mm).
(Refer to FIG. 6) [Comparative Example 24] As a target, Al: 85%, Cr: 5
%, Si: 10%, and arc ion plating was performed. As a result, the wear depth was 0.60 (μ
m) and the wear width was 0.50 (mm). [Comparative Example 25] As a target, Al: 10%, Cr: 8
Arc ion plating was performed using 0% and Si: 10%. As a result, the wear depth was 0.70 (μ
m) and the wear width was 0.52 (mm). [Comparative Example 26] As a target, Al: 51%, Cr: 4
Arc ion plating was performed using a material of 8.5% and Si: 0.5%. As a result, the wear depth is 0.5
It was 0 (μm) and the wear width was 0.38 (mm). [Comparative Example 27] As a target, Al: 30%, Cr: 3
Arc ion plating was performed by using 5% and Si: 35%. As a result, the wear depth was 0.80 (μ
m) and the wear width was 0.55 (mm). [Prior Art Example 28] Target: Al: 45%, Cr: 5
Arc ion plating was performed using 5%. As a result, the wear depth was 0.50 (μm) and the wear width was 0.32 (mm). [Conventional Example 29] Target: Al: 53%, Cr: 4
Arc ion plating was performed using a 7% one. As a result, the wear depth was 0.80 (μm),
The wear width was 0.40 (mm).
【００１４】各実施例１０〜２３と各比較例２４〜２７
及び従来例２８，２９の結果を表３に示すが、本発明の
皮膜は耐摩耗性に優れていることが判明した。Examples 10 to 23 and Comparative Examples 24 to 27
The results of Conventional Examples 28 and 29 are shown in Table 3, and it was found that the coating of the present invention has excellent wear resistance.
【００１５】[0015]
【表３】
密着性向上のためには、上記の窒化物の金属成分のみの
原子％でＣｒが２０％以上７５％以下、Ｓｉが１％以上
３０％以下残りＡｌからなるａ層と、ＴｉとＡｌの窒化
物の金属成分のみの原子％でＡｌが２５％以上７５％以
下、残りＴｉであるｂ層を交互に一層以上被覆し、最外
層がａ層である皮膜とすると効果が大きい。ここで、ｂ
層のＡｌが２５％未満及び７５％を超える場合は硬さ低
下による皮膜剥離の問題が生じる。さらに、上記皮膜と
基材との間にＴｉ又はＣｒの窒化物層を設けると密着性
は格段に向上する。[Table 3] In order to improve the adhesiveness, Cr is 20% or more and 75% or less, Si is 1% or more and 30% or less, and an a-layer made of Al and the nitriding of Ti and Al in atomic% of only the metal component of the above nitride It is very effective to form a coating in which at least 25% or more and 75% or less of Al is contained in atomic% of only the metal component of the material, and at least one layer of the remaining Ti is alternately coated and the outermost layer is the layer a. Where b
If the Al content of the layer is less than 25% or more than 75%, the problem of film peeling due to the decrease in hardness occurs. Further, if a Ti or Cr nitride layer is provided between the film and the base material, the adhesiveness is remarkably improved.
【００１６】以上、本発明の実施の形態について説明し
たが、本発明は、本発明の技術的思想に基づいて種々の
変形及び変更が可能である。例えば、上記コーティング
層の形成に当たっては、物理蒸着法が適用され、その金
属蒸発方法である電子銃によるもの、ホロカソードによ
るもの、スパッタリングによるもの、アーク放電による
もの等があるがこれらの方法には制約はない。Although the embodiments of the present invention have been described above, the present invention can be variously modified and changed based on the technical idea of the present invention. For example, in forming the coating layer, a physical vapor deposition method is applied, and there are metal vaporization methods such as an electron gun, a hollow cathode, a sputtering method, and an arc discharge method, but these methods are limited. There is no.
【００１７】[0017]
【発明の効果】以上のとおり、本発明皮膜は高温での耐
酸化性が優れており、且つ密着性が良好であるため耐摩
耗性も極めて良好であり、被覆した部材、製品の長寿命
化が達成できる。よって、工具、金型や眼鏡等の装飾品
の表面処理に幅広く適用が可能である。As described above, the coating film of the present invention is excellent in oxidation resistance at high temperature, and also has excellent adhesiveness because of its excellent adhesion, thus extending the service life of coated members and products. Can be achieved. Therefore, it can be widely applied to the surface treatment of ornaments such as tools, molds and glasses.
【図１】本発明の実施の形態による耐高温酸化に優れた
高耐摩耗性・高硬度皮膜を基材に形成するためのアーク
イオンプレーティング装置の概略図である。FIG. 1 is a schematic view of an arc ion plating apparatus for forming a high wear resistance and high hardness coating excellent in high temperature oxidation resistance on a base material according to an embodiment of the present invention.
【図２】本発明の実施の形態による耐高温酸化に優れた
高耐摩耗性・高硬度皮膜を基材表面に付着させた状態を
示す断面図である。FIG. 2 is a cross-sectional view showing a state in which a high wear resistance and high hardness coating excellent in high temperature oxidation resistance according to an embodiment of the present invention is attached to the surface of a base material.
【図３】２種のコーティング層を２層付着させた状態を
示す断面図である。FIG. 3 is a cross-sectional view showing a state in which two types of coating layers are attached.
【図４】２種のコーティング層を交互に１０層付着させ
た状態を示す断面図である。FIG. 4 is a cross-sectional view showing a state where 10 layers of two types of coating layers are alternately deposited.
【図５】図２の基材とコーティング層との間にＴｉ窒化
物を付着させた状態を示す断面図である。FIG. 5 is a cross-sectional view showing a state in which Ti nitride is attached between the base material and the coating layer of FIG.
【図６】図４の基材とコーティング層との間にＴｉ窒化
物を付着させた状態を示す断面図である。FIG. 6 is a cross-sectional view showing a state in which Ti nitride is attached between the base material and the coating layer of FIG.
１ アークイオンプレーティング装置 ２ ケーシング ３ ターゲット ４ 真空ポンプ ５ ガス源（Ａｒ） ６ ガス源（Ｎ2） ７ ホルダー ８ モータ ９ 回転軸 １０ 基材 １１ 電源 １３〜１５ 制御弁 ａ，ｂ 皮膜（コーティング層）1 Arc Ion Plating Device 2 Casing 3 Target 4 Vacuum Pump 5 Gas Source (Ar) 6 Gas Source (N 2 ) 7 Holder 8 Motor 9 Rotating Shaft 10 Base Material 11 Power Supply 13-15 Control Valve a, b Coating (Coating Layer) )
フロントページの続き (72)発明者 花中 勝保 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 樹神 幸夫 滋賀県栗太郡栗東町六地蔵130番地 三菱 重工業株式会社工作機械事業部内 (72)発明者 和田 佳宏 滋賀県栗太郡栗東町六地蔵130番地 三菱 重工業株式会社工作機械事業部内 (72)発明者 三崎 雅信 滋賀県栗太郡栗東町六地蔵130番地 三菱 重工業株式会社工作機械事業部内 Ｆターム(参考） 4K029 BA58 BB02 BC01 BC02 BD05 CA04 Continued front page (72) Inventor Katsuho Hananaka 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries Ltd. Hiroshima Research Center (72) Inventor Yukio Kigami 130 Rokujizo, Ritto-cho, Kurita-gun, Shiga Mitsubishi Heavy Industry Co., Ltd., Machine Tool Division (72) Inventor Yoshihiro Wada 130 Rokujizo, Ritto-cho, Kurita-gun, Shiga Mitsubishi Heavy Industry Co., Ltd., Machine Tool Division (72) Inventor Masanobu Misaki 130 Rokujizo, Ritto-cho, Kurita-gun, Shiga Mitsubishi Heavy Industry Co., Ltd., Machine Tool Division F term (reference) 4K029 BA58 BB02 BC01 BC02 BD05 CA04
Claims (6)
ｒ，及びＳｉを主成分とする窒化物であることを特徴と
する耐高温酸化に優れた高耐摩耗性・高硬度皮膜。1. Al, C formed on the surface of an object to be treated
High wear resistance and high hardness coating excellent in high temperature oxidation resistance, which is a nitride containing r and Si as main components.
が２０％以上７５％以下、Ｓｉが１％以上３０％以下、
残りがＡｌとしたことを特徴とする請求項１に記載の耐
高温酸化に優れた高耐摩耗性・高硬度皮膜。2. The above-mentioned coating is made of Cr in atomic% of only metal components.
Is 20% or more and 75% or less, Si is 1% or more and 30% or less,
The high wear resistance and high hardness coating excellent in high temperature oxidation resistance according to claim 1, wherein the remainder is Al.
る窒化物の皮膜ａ層と、ＴｉとＡｌを主成分とする窒化
物でその金属成分のみの原子％がＡｌが２５％以上７５
％以下、残りがＴｉであるｂ層を交互にそれぞれ１層以
上形成し、ａ層を最外層に形成したことを特徴とする請
求項１または２に記載の耐高温酸化に優れた高耐摩耗性
・高硬度皮膜。3. A film a layer of the nitride containing Al, Cr, and Si as the main components and a nitride containing Ti and Al as the main components, the atomic percentage of only the metal component of which is 25% or more of Al.
% Or less, and one or more b layers each having Ti as the rest are alternately formed, and the a layer is formed as the outermost layer. High wear resistance excellent in high temperature oxidation resistance according to claim 1 or 2. High-hardness coating.
窒化物からなる層を設けたことを特徴とする請求項１〜
３のいずれかに１に記載の耐高温酸化に優れた高耐摩耗
性・高硬度皮膜。4. A layer made of a nitride of Ti or Cr is provided between the film and the base material.
High wear resistance and high hardness coating excellent in high temperature oxidation resistance according to any one of 3).
とを特徴とする請求項１〜４にいずれかに記載の耐高温
酸化に優れた高耐摩耗性・高硬度皮膜。5. The high wear resistance / high hardness coating excellent in high temperature oxidation resistance according to claim 1, wherein the coating is formed by a physical vapor deposition method.
面に設けたことを特徴とする請求項１〜５にいずれか１
に記載の耐高温酸化に優れた高耐摩耗性・高硬度皮膜。6. The method according to claim 1, wherein the film is provided on a surface of a machine tool having a tool.
High wear resistance and high hardness coating excellent in high temperature oxidation resistance described in.
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