JP4578382B2 - Hard coating and hard coating tool - Google Patents
Hard coating and hard coating tool Download PDFInfo
- Publication number
- JP4578382B2 JP4578382B2 JP2005309223A JP2005309223A JP4578382B2 JP 4578382 B2 JP4578382 B2 JP 4578382B2 JP 2005309223 A JP2005309223 A JP 2005309223A JP 2005309223 A JP2005309223 A JP 2005309223A JP 4578382 B2 JP4578382 B2 JP 4578382B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- coating
- hard
- hard coating
- wear resistance
- 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.)
- Active
Links
Description
本願発明は、耐摩耗性及び耐熱性が要求される切削工具、金型、軸受け、ダイス、ロール及び内燃機関部品等の耐熱部材などの表面に被覆する硬質皮膜と硬質皮膜を被覆した被覆工具に関する。 TECHNICAL FIELD The present invention relates to a hard tool for coating a surface of a cutting tool, a die, a bearing, a die, a roll, and a heat-resistant member such as an internal combustion engine component that requires wear resistance and heat resistance, and a coated tool coated with the hard coat. .
被覆工具等の耐摩耗性を向上させることを目的として硬質皮膜をコーティングする技術が開示されている。特許文献１は、硬質皮膜の組成式が（ＡｌａＭｂ）１００−ｃＸｃで示され、Ｍ成分の選択肢から、Ｎｂ、Ｃｒが存在することが開示されている。特許文献２は、Ａｌ、Ｃｒ、Ｓｉの窒化物からなる皮膜が開示されている。特許文献３は、（ＡｌＣｒ）（ＮＢＣＯ）の組成を有する硬質皮膜が開示されている。特許文献４は、（ＡｌＴｉＮｂＳｉ）（ＯＮ）の組成を有する硬質皮膜が開示されている。 A technique for coating a hard film for the purpose of improving the wear resistance of a coated tool or the like is disclosed. Patent Document 1 discloses that the composition formula of the hard coating is (Al a M b ) 100-c X c , and Nb and Cr are present from the choice of the M component. Patent Document 2 discloses a film made of a nitride of Al, Cr, or Si. Patent Document 3 discloses a hard film having a composition of (AlCr) (NBCO). Patent Document 4 discloses a hard film having a composition of (AlTiNbSi) (ON).
本願発明の課題は、（ＡｌＣｒ）Ｎ系皮膜又は（ＡｌＣｒＳｉ）Ｎ系皮膜よりも高硬度で耐酸化性に優れ、同時に熱応力が作用する環境下においても安定して優れた耐摩耗性、密着強度を発揮し、高温における強度・靱性を高めた硬質皮膜又は該硬質皮膜を被覆した被覆工具を提供することである。 The problem of the present invention is that it has higher hardness and better oxidation resistance than (AlCr) N-based coatings or (AlCrSi) N-based coatings, and at the same time has stable and excellent wear resistance and adhesion even in an environment where thermal stress acts. The object is to provide a hard coating that exhibits strength and has improved strength and toughness at high temperatures, or a coated tool coated with the hard coating.
本発明の硬質皮膜は、基材表面に被覆する硬質皮膜であって、この硬質皮膜は、（Ａｌ１−ｘ−ｙＮｂｘＣｒｙ）の窒化物からなるＡｌ必須硬質皮膜（但し、ｘ及びｙは夫々原子比率を示し、０．０４＜ｘ＜０．４０、０．０６＜ｙ＜０．４０及び０．１０＜ｘ＋ｙ＜０．５０を満足する。）と、（ＳｉｕＴｉ１−ｕ）の窒化物からなるＳｉ必須硬質皮膜（但し、ｕは原子比率を示し、０．０４＜ｕ＜０．８０を満足する。）とを積層した構造を有し、Ａｌ必須硬質皮膜の膜厚とＳｉ必須硬質皮膜の膜厚との総膜厚を１００％としたとき、Ａｌ必須硬質皮膜の膜厚比が１０％以上９９％未満であることを特徴とする。
上記の構成を採用することにより、高硬度で耐酸化性に優れ、また同時に熱応力が作用する環境下においても安定して優れた耐摩耗性及び密着強度を発揮する硬質皮膜を提供することができる。
また、該硬質皮膜を工具等へ被覆することにより優れた耐摩耗性を発揮するため、好適である。
The hard film of the present invention is a hard film that coats the surface of a substrate, and this hard film is an Al essential hard film made of a nitride of (Al 1-xy Nb x Cr y ) (provided that x and y represents an atomic ratio, and satisfies 0.04 <x <0.40, 0.06 <y <0.40, and 0.10 <x + y <0.50), and (Si u Ti 1− a film of an Al essential hard film having a structure in which an Si essential hard film (where u represents an atomic ratio and satisfies 0.04 <u <0.80) is formed of a nitride of u ) When the total film thickness of the thickness and the film thickness of the Si essential hard coating is 100%, the Al essential hard coating thickness ratio is 10% or more and less than 99% .
By adopting the above-mentioned configuration, it is possible to provide a hard film that exhibits high hardness and excellent oxidation resistance, and at the same time stably exhibits excellent wear resistance and adhesion strength even in an environment where thermal stress acts. it can.
In addition, it is preferable because excellent wear resistance is exhibited by coating the hard film on a tool or the like.
本願発明の硬質皮膜は、高硬度で耐酸化性に優れ、同時に硬度、ヤング率、皮膜内に残留する圧縮応力等に代表される皮膜強度が高く、熱応力が作用する環境下においても皮膜剥離を抑制し、安定して優れた耐摩耗性を発揮し、高温における強度・靱性を高めた硬質皮膜及びこれら硬質皮膜を被覆した被覆工具を提供することができる。 The hard coating of the present invention has high hardness and excellent oxidation resistance, and at the same time has high coating strength represented by hardness, Young's modulus , compressive stress remaining in the coating, etc., and even in an environment where thermal stress acts suppressed, exhibit stable and excellent abrasion resistance, it is possible to provide a coated tool coated with a hard coating and their hard film with improved strength and toughness at high temperatures.
本願発明の硬質皮膜は、（ＡｌＣｒ）Ｎ系、（ＡｌＣｒＳｉ）Ｎ系皮膜のＡｌ、Ｓｉ含有量が多い組成範囲を対象にして、皮膜強度向上に関する検討を行った。その結果、（ＡｌＣｒ）Ｎ系、（ＡｌＣｒＳｉ）Ｎ系皮膜へＮｂを最適量添加し、組成を最適化することによって、皮膜の密着強度、耐酸化性を改善できることを見出し、本願発明を完成させた。以下、本願発明の（ＡｌＣｒＮｂ）Ｎ系を皮膜Ａ、（ＡｌＣｒＮｂＳｉ）Ｎ系を皮膜Ｂと記す。
皮膜Ａ又は皮膜ＢにおけるＮｂ添加効果は、ＺｎＳ型のＡｌＮの析出を抑制することができる。皮膜硬度、ヤング率を向上させることが可能となり、優れた密着強度が得られる。Ａｌ、Ｓｉ含有量を向上させることができるため、耐酸化性に関しても良好となる。Ｎｂ添加は、酸化後に皮膜表面に形成される表面酸化物が、従来の（ＡｌＣｒ）Ｎ系、（ＡｌＣｒＳｉ）Ｎ系皮膜よりも微細構造を示し、酸素の内向拡散を抑制することができる。更に、Ｎｂは融点が１０００度以上と高く、密度が小さく、高温における強度と靭性とのバランスに優れている。即ち、Ｎｂは他の高融点金属と広い濃度領域で固溶体、化合物相をもつことができるため、これらの固溶体、化合物相とを複合化させることで高温強度と靭性に優れた特性を有することができる。例えば、析出強化型のＮｂ基合金材料のＮｂ−Ｓｉ等や、金属間化合物のＮｂ−Ａｌ系等、この他にも固溶強化型Ｎｂ基合金材料等のＮｂ系耐熱材料を硬質皮膜に存在させることが好適である。窒化Ｎｂも高温域で安定な材料として硬質皮膜に存在させることが好適である。窒化Ｎｂには、種々の元素比を有する材料が存在し、ＮｂＮ、Ｎｂ４Ｎ３、Ｎｂ２Ｎ等がある。この中でもＮｂ２Ｎは高温環境における安定性が優れている。この理由は、ＮｂとＮの原子間の結合力が高いことによるものと考えられ、高温強度と靭性に優れた特性に影響を及ぼす。
皮膜Ａ又は皮膜ＢにおけるＮｂ含有量であるｘ値は、原子比率で、０．０４＜ｘ＜０．４０とする。ｘ値が０．０４以下の場合、ヤング率が小さく添加効果が確認されず耐摩耗性の改善には至らなかった。ｘ値が０．４０以上の場合、硬度と耐熱性改善には至らなかった。好ましいｘ値は、０．０５以上、０．２５未満である。
皮膜Ａ又は皮膜ＢにおけるＣｒ含有量であるｙ値は、０．０６＜ｙ＜０．４０とする。ｙ値が０．０６以下の場合、皮膜硬度が低く耐摩耗性に乏しい。ｙ値が、０．４０以上の場合、ヤング率即ち皮膜強度が低く、耐剥離性に乏しい。Ｃｒの一部を、Ｍｏ、Ｗで置換しても良い。
皮膜ＢにおけるＳｉ含有量であるｚ値は、０≦ｚ＜０．２０とする。Ｓｉ添加は皮膜の高硬度化、耐酸化性の改善の観点から、含有することが好ましい。しかし、ｚ値が０．２０以上の場合、耐酸化性を示すものの、皮膜硬度、ヤング率が低く耐摩耗性が十分ではない。
皮膜Ａ又は皮膜ＢにおけるＡｌ含有量は残り、すなわち（１−ｘ−ｙ−ｚ）値で表す。この時の（ｘ＋ｙ＋ｚ）値の範囲は、０．１０＜ｘ＋ｙ＋ｚ＜０．５０とする。従って、Ａｌ含有量は、０．５０以上、０．９０以下である。Ａｌ含有量が０．５０未満の場合、皮膜硬度、耐酸化性が十分ではない。Ａｌ含有量が０．９０を超える場合、皮膜硬度が低く耐摩耗性に乏しい。好ましいＡｌ含有量としては、皮膜硬度と耐酸化性の観点から０．５５以上、０．７５未満である。
皮膜Ａ又は皮膜Ｂは、Ａｌ、Ｓｉの含有量のバランスから基材の直上に被覆する場合は、ＦＣＣ単一相から構成されることが好ましい。ＦＣＣと六方晶の混合相、非晶質相を含む場合も優れた耐酸化特性を示し、耐熱性が要求される部材等への被覆においてもその効果を発揮する。ＦＣＣ相の場合は、Ｘ線回折において（１１１）面又は（２００）面に最大強度を示す場合が好適である。
For the hard coating of the present invention, studies were made on improving the coating strength in the composition range where the Al and Si contents of the (AlCr) N-based and (AlCrSi) N-based coatings are large. As a result, it was found that the adhesion strength and oxidation resistance of the coating can be improved by adding the optimum amount of Nb to the (AlCr) N-based and (AlCrSi) N-based coatings and optimizing the composition, thereby completing the present invention. It was. Hereinafter, the (AlCrNb) N system of the present invention is referred to as coating A, and the (AlCrNbSi) N system is referred to as coating B.
The Nb addition effect in the film A or the film B can suppress the precipitation of ZnS-type AlN. The film hardness and Young's modulus can be improved, and excellent adhesion strength can be obtained. Since the Al and Si contents can be improved, the oxidation resistance is also improved. When Nb is added, the surface oxide formed on the surface of the film after oxidation exhibits a finer structure than conventional (AlCr) N-based and (AlCrSi) N-based films, and can suppress inward diffusion of oxygen. Further, Nb has a high melting point of 1000 ° C. or higher, a low density, and an excellent balance between strength and toughness at high temperatures. That is, Nb can have a solid solution and a compound phase in a wide concentration range with other refractory metals. Therefore, by combining these solid solution and compound phase, Nb has excellent properties at high temperature strength and toughness. it can. For example, precipitation hardened Nb-based alloy materials such as Nb-Si, intermetallic compounds such as Nb-Al, and other Nb-based heat-resistant materials such as solid solution strengthened Nb-based alloy materials are present in the hard coating. Is preferable. Nb nitride is also preferably present in the hard coating as a stable material at high temperatures. Nb nitride includes materials having various element ratios, such as NbN, Nb 4 N 3 , and Nb 2 N. Among these, Nb 2 N is excellent in stability in a high temperature environment. The reason for this is considered to be due to the high bonding force between the Nb and N atoms, which affects the properties excellent in high-temperature strength and toughness.
X value which is Nb content in the film A or the film B is an atomic ratio, and 0.04 <x <0.40. When the x value was 0.04 or less, the Young's modulus was small and the effect of addition was not confirmed, and the wear resistance was not improved. When the x value was 0.40 or more, the hardness and heat resistance were not improved. A preferable x value is 0.05 or more and less than 0.25.
The y value that is the Cr content in the coating A or the coating B is 0.06 <y <0.40. When the y value is 0.06 or less, the film hardness is low and the wear resistance is poor. When the y value is 0.40 or more, the Young's modulus, that is, the film strength is low, and the peel resistance is poor. A part of Cr may be replaced with Mo or W.
The z value, which is the Si content in the coating B , is 0 ≦ z <0.20. Si addition is preferably contained from the viewpoint of increasing the hardness of the film and improving the oxidation resistance. However, when the z value is 0.20 or more, although the oxidation resistance is exhibited, the film hardness and Young's modulus are low and the wear resistance is not sufficient.
The Al content in the coating A or the coating B is the rest, that is, expressed by a (1-xyz) value. The range of (x + y + z) values at this time is 0.10 <x + y + z <0.50. Therefore, the Al content is 0.50 or more and 0.90 or less. When the Al content is less than 0.50, the film hardness and oxidation resistance are not sufficient. When the Al content exceeds 0.90, the film hardness is low and the wear resistance is poor. The preferable Al content is 0.55 or more and less than 0.75 from the viewpoint of film hardness and oxidation resistance.
The coating A or coating B is preferably composed of an FCC single phase in the case of coating directly on the substrate from the balance of the contents of Al and Si. Even when it contains a mixed phase of FCC and hexagonal crystal and an amorphous phase, it exhibits excellent oxidation resistance characteristics, and also exhibits its effect in coating on a member or the like that requires heat resistance. In the case of the FCC phase, it is preferable that the maximum intensity is shown on the (111) plane or the (200) plane in X-ray diffraction.
皮膜Ａ又は皮膜Ｂは、単一層、積層膜において優れた耐摩耗性を示す。その他、優れた特性を有する機能皮膜との積層をすることも可能であり、好ましい形態である。皮膜Ａ又は皮膜Ｂと積層する、優れた特性を有する皮膜Ｃは、（ＳｉｕＭｅ１−ｕ）の窒化物、炭化物、硼化物、酸化物、硫化物から選択される１種以上もしくはこれらの固溶体からなり、但し、ＭｅはＣｒ、Ｔｉ、Ａｌ、Ｎｂ、Ｙから選択される１種以上、ｕは原子比率を示し、０．０４＜ｕ＜０．８０、を満足する。この皮膜Ｃは、本願発明の皮膜Ａ又は皮膜Ｂよりも、高硬度、耐酸化性に優れる。皮膜Ａ又は皮膜Ｂと、皮膜Ｃとは特に優れた密着強度を有するため、その相互作用により優れた耐摩耗性を発揮する。
皮膜ＣのＳｉ含有量であるｕ値は、０．０４＜ｕ＜０．８０、とする。ｕ値が０．０４以下の場合は、単一層の場合に比べ、耐摩耗性を改善するには至らない。ｕ値が０．８以上の場合は、皮膜硬度の低下が著しく、その効果が顕著に確認できない。
皮膜Ａ又は皮膜Ｂと皮膜Ｃとを積層する場合の最適な積層構造は、硬質皮膜の総膜厚を１としたとき、皮膜Ａ又は皮膜Ｂが１０％以上、９９％未満である。この範囲であれば、積層する効果が顕著になり優れた耐摩耗性を発揮することができる。皮膜Ａが６０％以上、９９％未満の場合、残留圧縮応力が比較的低く耐チッピング性を重視した切削工具の中でも、特に多刃エンドミル、汎用エンドミル、ドリル、インサート工具に最適である。皮膜Ａが１０％以上、６０％未満の場合、残留圧縮応力が比較的高く、耐クラック性を重視した切削工具の中でも、特にボールエンドミルに最適である。皮膜Ａが１０％以上、９９％未満とは、２層以上積層することが可能であり、上記範囲の中で積層することも本発明に含まれる。具体的には、２層以上、３０００層未満の積層構造が、耐摩耗性の観点から好ましい範囲である。
皮膜Ｃは、高い皮膜硬度、残留圧縮応力を有する場合、硬質皮膜の最表層に被覆されることが好ましい積層構造である。皮膜Ｃ以外にも、例えば密着強化層として、ＴｉＮ、ＣｒＮ、（ＴｉＡｌ）Ｎ、（ＡｌＣｒ）Ｎ等、また摩擦を低減するために硬質皮膜の表層に硬質炭素膜等を被覆する場合等は、本発明の効果を損なわない範囲であれば本発明の効果が確認され、使用分野に応じて適宜変更を施すことができる。
本発明の硬質皮膜は、特に耐熱性に優れ、耐摩耗性に優れることから切削工具へ被覆するとにより、その効果が顕著に確認できる。本願発明の硬質皮膜の被覆方法に関しては、特に限定するものではないが物理蒸着法による被覆が好ましい。物理蒸着法の中でも特にアーク放電式イオンプレーティング（以下、ＡＩＰと記す。）法、スパッタリング（以下、ＳＰと記す。）法が好適である。以下、本願発明を実施例に基づいて説明する。
Film A or film B exhibits excellent wear resistance in a single layer or laminated film. In addition, it is also possible to laminate with a functional film having excellent characteristics, which is a preferred form. The film C having excellent characteristics laminated with the film A or the film B is one or more selected from nitrides, carbides, borides, oxides and sulfides of (Si u Me 1-u ), or these It consists of a solid solution, where Me is one or more selected from Cr, Ti, Al, Nb, and Y, u indicates an atomic ratio, and satisfies 0.04 <u <0.80. This film C is higher in hardness and oxidation resistance than the film A or film B of the present invention. Since the coating A or the coating B and the coating C have particularly excellent adhesion strength, they exhibit excellent wear resistance due to their interaction.
The u value, which is the Si content of the film C, is 0.04 <u <0.80. When the u value is 0.04 or less, the wear resistance cannot be improved as compared with the case of a single layer. When the u value is 0.8 or more, the film hardness is remarkably lowered, and the effect cannot be remarkably confirmed.
The optimum laminated structure in the case of laminating the film A or the film B and the film C , when the total film thickness of the hard film is 1, the film A or the film B is 10% or more and less than 99%. If it is this range, the effect to laminate | stack will become remarkable and the outstanding abrasion resistance can be exhibited. When the coating A is 60% or more and less than 99%, the cutting force with relatively low residual compressive stress and importance for chipping resistance is particularly suitable for a multi-blade end mill, a general-purpose end mill, a drill, and an insert tool. When the film A is 10% or more and less than 60%, the residual compressive stress is relatively high, and it is particularly suitable for a ball end mill among cutting tools that place importance on crack resistance. When the film A is 10% or more and less than 99%, it is possible to laminate two or more layers, and laminating within the above range is also included in the present invention. Specifically, a laminated structure of 2 layers or more and less than 3000 layers is a preferable range from the viewpoint of wear resistance.
When the film C has high film hardness and residual compressive stress, it is a laminated structure that is preferably coated on the outermost layer of the hard film. In addition to the coating C , for example, as an adhesion strengthening layer, TiN, CrN, (TiAl) N, (AlCr) N, etc., and when a hard carbon film is coated on the surface of the hard coating to reduce friction, etc. As long as the effects of the present invention are not impaired, the effects of the present invention are confirmed, and appropriate changes can be made according to the field of use.
The effect of the hard coating of the present invention can be remarkably confirmed when it is coated on a cutting tool because it is particularly excellent in heat resistance and wear resistance. Although it does not specifically limit regarding the coating method of the hard film of this invention, Coating by the physical vapor deposition method is preferable. Among the physical vapor deposition methods, the arc discharge ion plating (hereinafter referred to as AIP) method and the sputtering (hereinafter referred to as SP) method are particularly suitable. Hereinafter, the present invention will be described based on examples.
本願発明の皮膜Ａ又は皮膜ＢをＡＩＰ法により被覆した。皮膜Ａ又は皮膜Ｂの皮膜硬度、ヤング率、耐酸化性を評価するために、試料１として、ＳＮＧＡ４３２形状、Ｃｏ含有量が１０重量％の超微粒子超硬合金、試料２として、Ｃｏ、Ｖ含有量が合計８重量％の超微粒子超硬合金製２枚刃ボールエンドミルを用いた。
本発明例１は、試料１、２を脱脂洗浄を十分に実施し、ＡＩＰ装置の容器内の冶具に配置した。冶具は３回転／分で自公転する。被覆基材温度が５００℃となるよう加熱、排気を行い、Ａｒを容器内に導入した。容器内に設けられた電極間で放電することによりＡｒのイオン化を行い、同時に基材にパルス状のバイアス電圧を印加した。イオン化されたＡｒが基材に衝突することにより基材のクリーニング、活性化処理を行った。処理後、反応ガスである窒素を容器内に導入し、全体の圧力を３．２Ｐａ、バイアス電圧−８０Ｖを印加することによって硬質皮膜を被覆した。容器内に複数配置したアーク蒸発源に設置された硬質皮膜の金属成分となるターゲットに硬質皮膜の金属成分となる合金ターゲットを設置し、夫々１５０Ａを供給し、ターゲット上で放電を開始し、硬質皮膜を約３μｍ被覆した。被覆後、基材の温度が２００℃以下になるまで冷却し、容器から取り出した。
本発明例２〜１６の皮膜Ａ又は皮膜Ｂの組成を表１に示す。表１中には、皮膜Ａ又は皮膜Ｂの組成、皮膜Ｃとの層構造の詳細について併記する。比較例１７〜１９、従来例２０〜２３に関しても表１に併記する。
The film A or film B of the present invention was coated by the AIP method. In order to evaluate the film hardness, Young's modulus , and oxidation resistance of film A or film B , as sample 1, SNGA432 shape, ultrafine cemented carbide with a Co content of 10% by weight, sample 2 , containing Co and V A two-blade ball end mill made of ultrafine particle cemented carbide with a total amount of 8% by weight was used .
In Example 1 of the present invention, samples 1 and 2 were sufficiently degreased and cleaned and placed on a jig in a container of an AIP apparatus. The jig revolves at 3 revolutions / minute. Heating and evacuation were performed so that the coating substrate temperature was 500 ° C., and Ar was introduced into the container. Ar was ionized by discharging between the electrodes provided in the container, and at the same time, a pulsed bias voltage was applied to the substrate. The substrate was cleaned and activated by the ionized Ar colliding with the substrate. After the treatment, nitrogen as a reaction gas was introduced into the vessel, and the hard film was coated by applying an overall pressure of 3.2 Pa and a bias voltage of −80V. An alloy target that is a metal component of a hard coating is installed on a target that is a metal component of a hard coating that is installed in a plurality of arc evaporation sources arranged in the container, 150A is supplied to each target, and discharge is started on the target. The film was coated about 3 μm. After coating, the substrate was cooled until the temperature of the substrate became 200 ° C. or less, and taken out from the container.
Table 1 shows the composition of coating A or coating B of Invention Examples 2 to 16 . In Table 1, the composition of film A or film B and the details of the layer structure with film C are also shown. The comparative examples 17 to 19 and conventional examples 20 to 23 are also shown in Table 1.
図１には表１に示した、本発明例１、２、３、比較例１７、１８、従来例２０、２１、２２に対して皮膜硬度、ヤング率を測定した結果を示す。測定はナノインデンテーションによる硬度測定法を用いた。詳細は、以下の文献による方法を参照した（Ｗ．Ｃ．Ｏｌｉｖｅｒ ａｎｄ、Ｇ．Ｍ．Ｐｈａｒｒ：Ｊ．Ｍａｔｅｒ．Ｒｅｓ．，Ｖｏｌ．７，Ｎｏ．６，Ｊｕｎｅ １９９２、１５６４−１５８３）。
試料１の逃げ面を斜め５度方向に鏡面研摩した面において、最大押込み深さの１０倍以上の膜厚を有する場所を選定し、押込み荷重を４９ｍＮ、最大荷重保持時間を１秒、荷重負荷、除去速度を０．４９ｍＮ／秒の測定条件で１０点測定した。これらの測定は圧子形状の僅かな変化により、測定結果が左右される場合があるため、従来例２０の（ＴｉＡｌ）Ｎを基準試料として測定し、得られた数値を補正することが好ましい。図１より、本発明例１、２、３は、比較例１７、１８、従来例２１、２２に対して、押し込み硬さ、ヤング率が伴に高い値を示した。一方、従来例２０に対して、従来例２１、従来例２２は高硬度を示すものの、ヤング率が低く、基材との密着強度に乏しかった。比較例１７、比較例１８は、何れも皮膜硬度が従来例２０に対して低い結果となった。
FIG. 1 shows the results of measurement of film hardness and Young's modulus for Inventive Examples 1, 2, and 3, Comparative Examples 17 and 18, and Conventional Examples 20, 21, and 22 shown in Table 1. The measurement used the hardness measurement method by nanoindentation. For details, reference was made to the following literature method (WC Oliver and GM Pharr: J. Mater. Res., Vol. 7, No. 6, June 1992, 1564-1583).
On the surface of sample 1 that has been mirror-polished in the direction of 5 degrees diagonally, select a location that has a film thickness of 10 times or more of the maximum indentation depth, indentation load of 49 mN, maximum load retention time of 1 second, load load The removal rate was measured at 10 points under the measurement condition of 0.49 mN / sec. In these measurements, the measurement result may be affected by a slight change in the shape of the indenter. Therefore, it is preferable to measure (TiAl) N in Conventional Example 20 as a reference sample and correct the obtained numerical value. As shown in FIG. 1, Examples 1, 2, and 3 of the present invention showed higher values with indentation hardness and Young's modulus than Comparative Examples 17 and 18 and Conventional Examples 21 and 22. On the other hand, Conventional Example 21 and Conventional Example 22 showed high hardness compared to Conventional Example 20, but the Young's modulus was low and the adhesion strength with the substrate was poor. Comparative Example 17 and Comparative Example 18 both had lower film hardness than Conventional Example 20.
本発明例１、２、従来例２０、２１の試料１を、高温環境下における耐酸化性能を、大気中１１００℃で各々０．２、０．５、１、３、９時間保持した後、皮膜Ａ、Ｂ、Ｃの表面を走査電子顕微鏡（以下、ＳＥＭと記す。）にて酸化物の形態を観察した。評価後の試料に関しＸ線回折（以下、ＸＲＤと記す。）を行い、皮膜Ａ又は皮膜Ｂ、超硬基材の酸化について確認した。
図２〜図６より、上記酸化環境化において超硬合金基材は複雑な複数の酸化物を形成していることが確認される。即ち、これらの酸化物が形成される場合、硬質皮膜の耐酸化性が乏しいことを示す。従来例２０の表面は、０．２時間保持後で、（ＡｌＴｉ）Ｎ皮膜がほぼ消滅しており、酸化した超硬合金基材が剥き出しになっていた。従来例２１は、１時間保持後、巨大な酸化物が硬質皮膜表面に形成され、図６から、超硬合金の基材表面には硬質皮膜はほぼ消滅しており、酸化した超硬合金基材であると考えられる複数のピークが確認された。
図７、図８より、本発明例１は９時間保持後、皮膜Ａ表面に酸化物を形成した。図９、図１０より、本発明例２は９時間保持後も皮膜Ｂ表面は微細な表面構造をしており、大幅に酸化特性が改善された。これらの結果から（ＡｌＣｒ）Ｎ系、（ＡｌＣｒＳｉ）Ｎ系皮膜にＮｂを添加することにより、高温環境下における耐酸化性が大幅に改善されることがわかった。これらは何れもＡｌ含有量一定化で評価した結果であることから、Ｎｂ添加による効果である。
Samples 1 of Invention Examples 1 and 2 and Conventional Examples 20 and 21 were kept at 1100 ° C. in the atmosphere for 0.2, 0.5, 1, 3 , and 9 hours, respectively. The form of the oxide was observed on the surfaces of the coatings A, B, and C with a scanning electron microscope (hereinafter referred to as SEM). The sample after the evaluation was subjected to X-ray diffraction (hereinafter referred to as XRD), and the film A or film B and the oxidation of the cemented carbide substrate were confirmed.
2 to 6, it is confirmed that the cemented carbide base material forms a plurality of complex oxides in the oxidation environment. That is, when these oxides are formed, the oxidation resistance of the hard film is poor. The surface of Conventional Example 20 had the (AlTi) N film almost disappeared after being held for 0.2 hours , and the oxidized cemented carbide base material was exposed. In Conventional Example 21, after holding for 1 hour, a huge oxide is formed on the surface of the hard film, and from FIG. 6, the hard film almost disappears on the surface of the base material of the cemented carbide, and the oxidized cemented carbide base Several peaks considered to be the material were confirmed.
7 and 8, Example 1 of the present invention formed an oxide on the surface of the coating A after being held for 9 hours. 9 and 10, Example 2 of the present invention had a fine surface structure on the surface of the coating B even after being held for 9 hours, and the oxidation characteristics were greatly improved. From these results, it was found that by adding Nb to the (AlCr) N-based and (AlCrSi) N-based coatings , the oxidation resistance under a high temperature environment is greatly improved. Since these are the results of evaluation with the Al content being made constant, the effect is due to the addition of Nb.
試料２の切削試験を以下に示す。切削工具の逃げ面摩耗幅が０．１ｍｍに達した切削長又は著しく不安定な加工状態、例えば火花発生、異音、加工面のむしれ、焼け等などの状態に達した時点における切削長を切削寿命として表１中に示した。１０ｍ未満の切削寿命は切り捨てて表記した。
（切削条件）
切削方法：高速仕上げ加工
被削材：マルテンサイト系ステンレス鋼（ＨＲＣ５２）
切り込み：軸方向、１．０ｍｍ、径方向、０．２ｍｍ
主軸回転数：２０ｋｍｉｎ−１
テーブル送り：４ｍ／ｍｉｎ
切削油：無し、ドライ切削（エアーブロー）
The cutting test of Sample 2 is shown below. The cutting length when the flank wear width of the cutting tool has reached 0.1 mm or the extremely unstable machining state, for example, the occurrence of sparks, abnormal noise, flaking of the machining surface, burning, etc. The cutting life is shown in Table 1. The cutting life of less than 10 m was rounded down.
(Cutting conditions)
Cutting method: High-speed finishing Work material: Martensitic stainless steel (HRC52)
Cutting: axial direction, 1.0 mm, radial direction, 0.2 mm
Spindle speed: 20kmin- 1
Table feed: 4m / min
Cutting oil: None, dry cutting (air blow)
表１より、切削工具における耐摩耗性の評価結果、本発明例は、従来例、比較例に比べ、耐摩耗性に優れる結果となった。本発明例１から３は、耐摩耗評価においても剥離が著しく抑制され、従来例２１、２２に対して飛躍的に切削寿命を向上させることができた。Ｎｂを添加することにより、ヤング率の低下を抑制でき、密着強度を大幅に改善することによるものである。
本発明例１、６から１１は、皮膜Ａの場合を示す。何れの組成においても、従来例、比較例に対して耐摩耗性に優れる結果となった。これらの結果より耐摩耗性の観点から、硬質皮膜内のＮｂとＣｒ含有量としてはＮｂ含有量よりもＣｒ含有量が多いほうが好ましく、Ａｌ含有量としては、０．５５を超え、０．８０未満がより好ましい結果であった。
本発明例２から５は、皮膜Ｂの場合を示す。Ｓｉを添加することにより更に耐摩耗性を改善することができた。皮膜Ｂは、Ｎｂに対してＣｒ含有量が多いことが好ましく、ＡｌとＳｉとの総含有量は、０．８０未満が耐摩耗性の観点から好ましい結果である。ＡｌとＳｉとの総含有量は、０．７０が最も優れた耐摩耗性を示した。
本発明例１２から１６は、皮膜Ａと皮膜Ｃの積層構造とした場合を示す。（ＴｉＳｉ）Ｎ系皮膜との積層構造とすることにより更に優れた耐摩耗性を示すことが確認された。本発明例１２、１３から、皮膜Ａの膜厚比の小さいほうが、より優れた耐摩耗性を示した。しかし、ドリルやスクエアエンドミルにおいては逆に皮膜Ａの膜厚比を大きくした方が耐摩耗性に優れる結果が得られている。このときの最適な膜厚比は、８０％のときに最も優れた耐摩耗性を示した。積層数、積層厚さとしては、すべての試料に関し膜厚を３μｍ前後に固定していることから、積層数を増加させることにより更に耐摩耗性を改善できた。積層する厚さは薄い方が好ましい結果となった。
以上のように本発明の硬質皮膜は従来例に比べ、極めて優れた耐摩耗性を示し、同一摩耗条件下において耐摩耗性に優れていることから、更に切削能率を向上させて加工することができた。従来例２１、従来例２２は高硬度を示すものの、基材との密着強度に乏しく、剥離進行型の摩耗形態を示した。
From Table 1 , the evaluation results of the wear resistance of the cutting tool, the results of the present invention example were superior to the conventional example and the comparative example in terms of wear resistance. In Examples 1 to 3 of the present invention, peeling was remarkably suppressed even in the wear resistance evaluation, and the cutting life could be dramatically improved as compared with Conventional Examples 21 and 22. By adding Nb, the decrease in Young's modulus can be suppressed, and the adhesion strength is greatly improved.
Invention Examples 1 and 6 to 11 show the case of film A. In any composition, the result was excellent in wear resistance compared to the conventional example and the comparative example. From these results, from the viewpoint of wear resistance, it is preferable that the Nb and Cr contents in the hard coating have a larger Cr content than the Nb content, and the Al content exceeds 0.55 and is 0.80. Less than was a more preferable result.
Invention Examples 2 to 5 show the case of the coating B. The wear resistance could be further improved by adding Si. The film B preferably has a large Cr content relative to Nb, and the total content of Al and Si is preferably less than 0.80 from the viewpoint of wear resistance. The total content of Al and Si was 0.70, which showed the most excellent wear resistance.
Invention Examples 12 to 16 show the case where a laminated structure of film A and film C is used. It was confirmed that a more excellent wear resistance was exhibited by adopting a laminated structure with the (TiSi) N-based film. From Examples 12 and 13 of the present invention, the smaller the film thickness ratio of the coating A , the better the wear resistance. However, in the case of a drill or a square end mill, conversely, increasing the film thickness ratio of the coating A has resulted in excellent wear resistance. The optimum film thickness ratio at this time showed the most excellent wear resistance at 80%. As the number of laminated layers and the laminated thickness, since the film thickness was fixed to about 3 μm for all the samples, the wear resistance could be further improved by increasing the number of laminated layers. The thinner the thickness, the better.
As described above, the hard coating of the present invention exhibits extremely superior wear resistance compared to conventional examples, and is excellent in wear resistance under the same wear conditions, so that it can be processed with further improved cutting efficiency. did it. Although Conventional Example 21 and Conventional Example 22 showed high hardness, they had poor adhesion strength with the base material, and showed a delamination progressive wear mode.
Claims (2)
この硬質皮膜は、（Ａｌ１−ｘ−ｙＮｂｘＣｒｙ）の窒化物からなるＡｌ必須硬質皮膜（但し、ｘ及びｙは夫々原子比率を示し、０．０４＜ｘ＜０．４０、０．０６＜ｙ＜０．４０及び０．１０＜ｘ＋ｙ＜０．５０を満足する。）と、（ＳｉｕＴｉ１−ｕ）の窒化物からなるＳｉ必須硬質皮膜（但し、ｕは原子比率を示し、０．０４＜ｕ＜０．８０を満足する。）とを積層した構造を有し、
Ａｌ必須硬質皮膜の膜厚とＳｉ必須硬質皮膜の膜厚との総膜厚を１００％としたとき、Ａｌ必須硬質皮膜の膜厚比が１０％以上９９％未満であることを特徴とする硬質皮膜。 A hard film covering the surface of the substrate,
This hard film is an Al essential hard film made of a nitride of (Al 1-xy Nb x Cr y ), where x and y each indicate an atomic ratio, and 0.04 <x <0.40, 0 .06 <y <0.40 and 0.10 <x + y <0.50) and a Si essential hard coating made of a nitride of (Si u Ti 1-u ) (where u is the atomic ratio) And satisfying 0.04 <u <0.80.),
Hardness characterized in that the film thickness ratio of the Al essential hard coating is 10% or more and less than 99% when the total film thickness of the Al essential hard coating and the Si essential hard coating is 100%. Film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005309223A JP4578382B2 (en) | 2005-10-25 | 2005-10-25 | Hard coating and hard coating tool |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005309223A JP4578382B2 (en) | 2005-10-25 | 2005-10-25 | Hard coating and hard coating tool |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007119795A JP2007119795A (en) | 2007-05-17 |
| JP4578382B2 true JP4578382B2 (en) | 2010-11-10 |
Family
ID=38143943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005309223A Active JP4578382B2 (en) | 2005-10-25 | 2005-10-25 | Hard coating and hard coating tool |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4578382B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009016938A1 (en) * | 2007-08-02 | 2009-02-05 | Kabushiki Kaisha Kobe Seiko Sho | Hard coating film, material covered with hard coating film, mold for cold plastic forming, and method for forming hard coating film |
| JP4774080B2 (en) | 2007-08-02 | 2011-09-14 | 株式会社神戸製鋼所 | Hard coating material and cold plastic working mold |
| JP5234931B2 (en) * | 2008-06-23 | 2013-07-10 | 株式会社神戸製鋼所 | Hard coating member and molding tool |
| RU2528930C2 (en) * | 2008-07-09 | 2014-09-20 | Эрликон Трейдинг Аг, Трюббах | Coating system, coated component and method for production thereof |
| JP5424103B2 (en) * | 2008-09-24 | 2014-02-26 | 日立金属株式会社 | Covering mold for plastic working |
| CN102224273B (en) * | 2008-11-04 | 2014-09-24 | 欧瑞康贸易股份公司(特吕巴赫) | Wear protection layer and method for the manufacture thereof |
| DE112009005368B4 (en) | 2009-11-12 | 2023-12-28 | Osg Corp. | HARD COATE AND HARD COATED TOOL |
| JP5459618B2 (en) * | 2010-04-20 | 2014-04-02 | 三菱マテリアル株式会社 | Surface coated cutting tool |
| JP5975214B2 (en) * | 2012-10-09 | 2016-08-23 | 三菱マテリアル株式会社 | Surface coated cutting tool |
| JP5975338B2 (en) * | 2012-10-16 | 2016-08-23 | 三菱マテリアル株式会社 | Surface coated cutting tool |
| JP5975339B2 (en) * | 2012-10-16 | 2016-08-23 | 三菱マテリアル株式会社 | Surface coated cutting tool |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008505771A (en) * | 2004-07-15 | 2008-02-28 | オー・ツェー・エリコン・バルザース・アクチェンゲゼルシャフト | High oxidation resistant hard coat for cutting tools |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006524748A (en) * | 2003-04-28 | 2006-11-02 | ユナキス・バルツェルス・アクチェンゲゼルシャフト | Workpiece having hard material layer containing AlCr and manufacturing method |
-
2005
- 2005-10-25 JP JP2005309223A patent/JP4578382B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008505771A (en) * | 2004-07-15 | 2008-02-28 | オー・ツェー・エリコン・バルザース・アクチェンゲゼルシャフト | High oxidation resistant hard coat for cutting tools |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007119795A (en) | 2007-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4578382B2 (en) | Hard coating and hard coating tool | |
| CN1470350B (en) | Coating tool | |
| JP4966580B2 (en) | Coated tool | |
| JP2005344148A (en) | Wear-resistant film, and surface-coated cutting tool using the same | |
| JP4824989B2 (en) | Hard coating | |
| JP3963354B2 (en) | Coated cutting tool | |
| JP4405835B2 (en) | Surface coated cutting tool | |
| JP2006307323A (en) | Hard film coated member | |
| JP2008013852A (en) | Hard film, and hard film-coated tool | |
| CN110603342A (en) | Metal cutting tool with multi-layer coating | |
| JP2005305576A (en) | Coated-cutting tool | |
| JP2002018606A (en) | Coated cutting tool | |
| JPWO2020075356A1 (en) | Cutting tools and their manufacturing methods | |
| JP2007084899A (en) | Coating member, and method for coating coating member | |
| JP4393650B2 (en) | Wear-resistant coated tool | |
| JP4721281B2 (en) | Oxidation resistant film and member coated with the film | |
| JP2008284642A (en) | Coated cutting tool | |
| JP2007119810A (en) | Coated member | |
| JP2005262389A (en) | Surface-coated cutting tool for processing titanium alloy | |
| JP4353949B2 (en) | Covering member | |
| JP2005271106A (en) | Coated cutting tool | |
| JP2004176085A (en) | Hard film | |
| Braun et al. | Oxidation behaviour of TiAlYN/CrN and CrAlYN/CrN nanoscale multilayer coatings with Al2O3 topcoat deposited on γ-TiAl alloys | |
| JP2004136430A (en) | Coated tool | |
| JP4575009B2 (en) | Coated cutting tool |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090126 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090129 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090319 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090818 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091016 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100318 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100615 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100625 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100824 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100824 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130903 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4578382 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |