JP2007111835A - Surface-coated carbide cutting tool having carbide coating layer of excellent chipping resistance in heavy cutting - Google Patents
Surface-coated carbide cutting tool having carbide coating layer of excellent chipping resistance in heavy cutting Download PDFInfo
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この発明は、硬質被覆層がすぐれた高温硬さ・耐熱性とともに、一段とすぐれた高温強度を備え、したがって、鋼や鋳鉄等を、高送り、高切り込みの重切削条件下で切削加工を行なった場合にも、硬質被覆層が重切削加工時に必要とされる高温強度を十分に備え、高温強度の不足から発生するチッピングを防止することによって、長期に亘ってすぐれた耐摩耗性を発揮する、炭化タングステン基超硬合金または炭窒化チタン基サーメットで構成された基体の表面に、化学蒸着により硬質被覆層を形成してなる表面被覆超硬切削工具（以下、被覆超硬工具という）に関するものである。 This invention has a hard coating layer with excellent high-temperature hardness and heat resistance, as well as excellent high-temperature strength. Therefore, steel, cast iron, etc. were cut under heavy feed conditions with high feed and high cutting depth. Even in this case, the hard coating layer is sufficiently equipped with the high temperature strength required at the time of heavy cutting, and exhibits excellent wear resistance over a long period of time by preventing chipping that occurs due to insufficient high temperature strength. It relates to a surface-coated carbide cutting tool (hereinafter referred to as a coated carbide tool) in which a hard coating layer is formed by chemical vapor deposition on the surface of a substrate composed of tungsten carbide-based cemented carbide or titanium carbonitride-based cermet. is there.
被覆超硬工具として、炭化タングステン（以下、ＷＣで示す）基超硬合金または炭窒化チタン（以下、ＴｉＣＮで示す）基サーメットからなる基体（以下、これらを総称して超硬基体と云う）の表面に、
（ａ）いずれも化学蒸着形成されたＴｉの炭化物（以下、ＴｉＣで示す）層、窒化物（以下、同じくＴｉＮで示す）層、炭窒化物（以下、ＴｉＣＮで示す）層、炭酸化物（以下、ＴｉＣＯで示す）層、および炭窒酸化物（以下、ＴｉＣＮＯで示す）層のうちの１層または２層以上からなり、かつ０．５〜１５μｍの全体平均層厚を有するＴｉ化合物層からなる下部層、
（ｂ）化学蒸着で形成された、０．５〜１３μｍの平均層厚を有し、ＡｌとＣｒの相互含有割合を示す組成式：（Ａｌ１−ＸＣｒＸ）（ただし、原子比で、Ｘは０．０５〜０．３５を示す）を満足するＡｌとＣｒの複合酸化物［以下、（Ａｌ，Ｃｒ）２Ｏ３で示す］層からなる上部層、
上記の下部層と上部層で構成された硬質被覆層を形成してなる、被覆超硬工具が知られている。
As a coated carbide tool, a substrate made of tungsten carbide (hereinafter referred to as WC) -based cemented carbide or titanium carbonitride (hereinafter referred to as TiCN) -based cermet (hereinafter collectively referred to as a cemented carbide substrate). On the surface,
(A) All of these are Ti carbide (hereinafter referred to as TiC) layer, nitride (hereinafter also referred to as TiN) layer, carbonitride (hereinafter referred to as TiCN) layer, carbon oxide (hereinafter referred to as TiC) formed by chemical vapor deposition. And a Ti compound layer having an overall average layer thickness of 0.5 to 15 μm. Lower layer,
(B) Composition formula formed by chemical vapor deposition and having an average layer thickness of 0.5 to 13 μm and showing a mutual content ratio of Al and Cr: (Al 1-X Cr X ) (however, in atomic ratio, X represents 0.05 to 0.35) and an upper layer composed of a composite oxide of Al and Cr [hereinafter referred to as (Al, Cr) 2 O 3 ] layer;
A coated cemented carbide tool formed by forming a hard coating layer composed of the above lower layer and upper layer is known.
また、上記の従来被覆超硬工具の硬質被覆層を構成する上部層である（Ａｌ，Ｃｒ）２Ｏ３層が、Ａｌによる高温硬さおよび耐熱性と、Ｃｒによる高温強度を具備することから、かかる被覆超硬工具を各種の鋼や鋳鉄などの通常の切削条件下での切削加工に用いた場合にすぐれた切削性能を発揮することも知られている。 In addition, the (Al, Cr) 2 O 3 layer, which is the upper layer constituting the hard coating layer of the conventional coated carbide tool, has high-temperature hardness and heat resistance due to Al, and high-temperature strength due to Cr. It is also known that such coated carbide tools exhibit excellent cutting performance when used for cutting under normal cutting conditions such as various steels and cast iron.
さらに、上記の従来被覆超硬工具が、例えば図１に概略縦断面図で示される通り、中央部にステンレス鋼製の反応ガス吹き出し管が立設され、前記反応ガス吹き出し管には、図２（ａ）に概略斜視図で、同（ｂ）に概略平面図で例示される黒鉛製の超硬基体支持パレットが串刺し積層嵌着され、かつこれらがステンレス鋼製のカバーを介してヒーターで加熱される構造を有する化学蒸着装置を用い、超硬基体を前記超硬基体支持パレットの底面に形成された多数の反応ガス通過穴位置に図示される通りに載置した状態で前記化学蒸着装置に装入し、ヒータで装置内を、例えば８５０〜１０５０℃の範囲内の所定の温度に加熱した後、まず、硬質被覆層の下部層として、例えば表３に示される形成条件でＴｉ化合物層を形成し、ついで、
（ａ）反応ガス組成：容量％で（以下、反応ガスの％は容量％を示す）、
ＡｌＣｌ３： １．４３〜２．０９ ％、
ＣｒＣｌ２： ０．１１〜０．７７ ％、
ＣＯ２： ５〜６ ％、
ＨＣｌ： ２〜３ ％、
Ｈ２：残り、
（ｂ）反応雰囲気温度： ９８０〜１０５０ ℃、
（ｃ）反応雰囲気圧力： １０〜２０ ｋＰａ、
の条件で、上記の（Ａｌ，Ｃｒ）２Ｏ３層からなる上部層を形成することにより製造されることも知られている。
Further, in the above conventional coated carbide tool, for example, as shown in a schematic longitudinal sectional view in FIG. 1, a reaction gas blowing pipe made of stainless steel is erected at the center portion. (A) is a schematic perspective view, and (b) is a schematic plan view illustrating a carbide substrate support pallet made of graphite that is skewered and laminated, and these are heated by a heater through a stainless steel cover. The chemical vapor deposition apparatus having the structure described above is used, and the cemented carbide substrate is placed on the chemical vapor deposition apparatus in a state where the carbide substrate is placed as illustrated in a plurality of reaction gas passage hole positions formed on the bottom surface of the carbide substrate support pallet. After charging and heating the inside of the apparatus with a heater to a predetermined temperature within a range of 850 to 1050 ° C., for example, a Ti compound layer is first formed as a lower layer of the hard coating layer under the formation conditions shown in Table 3, for example. Forming, then
(A) Reaction gas composition: in volume% (hereinafter,% of reaction gas indicates volume%)
AlCl 3 : 1.43 to 2.09%,
CrCl 2: 0.11~0.77%,
CO 2: 5~6%,
HCl: 2-3%,
H 2 : Remaining
(B) Reaction atmosphere temperature: 980-1050 ° C.,
(C) Reaction atmosphere pressure: 10 to 20 kPa,
It is also known that it is manufactured by forming an upper layer made of the above (Al, Cr) 2 O 3 layer under the above conditions.
また、一般に、上記の従来被覆超硬工具の硬質被覆層を構成するＴｉ化合物層や（Ａｌ，Ｃｒ）２Ｏ３層が粒状結晶組織を有し、さらに、前記Ｔｉ化合物層を構成するＴｉＣＮ層を、層自身の強度向上を目的として、通常の化学蒸着装置にて、反応ガスとしてＣＨ３ＣＮなどの有機炭窒化物を含む混合ガスを使用し、７００〜９５０℃の中温温度域で化学蒸着することにより形成して縦長成長結晶組織をもつようにすることも知られている。
近年の切削加工装置のＦＡ化はめざましく、一方で切削加工に対する省力化および省エネ化、さらに低コスト化の要求は強く、これに伴い、切削加工は、通常の切削条件に加えて、高い切削加工効率が得られるが、その反面、切刃部への機械的負荷が大きなものとなる高切り込みや高送りなどの重切削条件での切削加工が要求される傾向にあるが、上記の従来被覆超硬工具においては、各種の鋼や鋳鉄を通常条件下で切削加工した場合に特段の問題は生じないが、これを高送り、高切り込みの重切削条件下での切削加工に用いた場合には、特に硬質被覆層の上部層を構成する（Ａｌ，Ｃｒ）２Ｏ３層の高温強度不足が原因となって、切刃部にチッピング（微小割れ）が発生し易く、この結果比較的短時間で使用寿命に至るのが現状である。 In recent years, the use of FA for cutting devices has been remarkable. On the other hand, there are strong demands for labor saving, energy saving, and cost reduction for cutting processing. Accordingly, in addition to normal cutting conditions, cutting processing requires high cutting processing. Although efficiency can be obtained, on the other hand, there is a tendency to require cutting under heavy cutting conditions such as high cutting and high feed that increase the mechanical load on the cutting edge. In hard tools, there are no special problems when cutting various steels and cast irons under normal conditions, but when these are used for cutting under heavy feed conditions with high feed and high cutting depth. In particular, chipping (microcracking) is likely to occur in the cutting edge part due to insufficient high-temperature strength of the (Al, Cr) 2 O 3 layer constituting the upper layer of the hard coating layer, and as a result, a relatively short time At present, the service life is reached.
そこで、本発明者等は、上述のような観点から、特に各種の鋼や鋳鉄等の高送り、高切り込みの重切削加工でも、硬質被覆層がすぐれた耐チッピング性を発揮する被覆超硬工具を開発すべく、上記従来の被覆超硬工具を構成する硬質被覆層に着目し、研究を行った結果、
（１）下部層がＴｉ化合物層、上部層が（Ａｌ，Ｃｒ）２Ｏ３層からなる上記従来の硬質被覆層上に、例えば、
（ａ）反応ガス組成（容量％）：
ＺｒＣｌ４： ３．０ ％、
ＣＯ２： １０．５ ％、
ＨＣｌ： ３．５ ％、
Ｈ２ ： 残り、
（ｂ）反応雰囲気温度：１０００ ℃、
（ｃ）反応雰囲気圧力： ７ ｋＰａ、
の条件で化学蒸着を行い、ジルコニウム（Ｚｒ）酸化物（以下、ＺｒＯ２で示す）層を生成すると、従来の硬質被覆層上に、０．１〜０．８μｍの平均層厚の薄層からなる高温強度が非常に高いＺｒＯ２層が形成されること。
（２）上記（１）で蒸着形成した平均層厚０．１〜０．８μｍの薄層のＺｒＯ２層（以下、「薄層Ａ」という）の上に、さらに、従来の硬質被覆層の上部層を構成する層である（Ａｌ，Ｃｒ）２Ｏ３層を、
例えば、
（ａ）反応ガス組成（容量％）：
ＡｌＣｌ３： １．８ ％、
ＣｒＣｌ２： ０．５ ％、
ＣＯ２： ５．５ ％、
ＨＣｌ： ２．２ ％、
Ｈ２ ： 残り、
（ｂ）反応雰囲気温度： １０００ ℃、
（ｃ）反応雰囲気圧力： １０ ｋＰａ、
の条件で化学蒸着し、０．１〜０．６μｍの平均層厚を有する（Ａｌ，Ｃｒ）２Ｏ３層の薄層（以下、「薄層Ｂ」という）を形成し、さらに、この（Ａｌ，Ｃｒ）２Ｏ３層からなる薄層Ｂと、前記（１）の条件で蒸着形成したＺｒＯ２層からなる薄層Ａとを、交互に繰り返し積層して、その合計平均層厚が２〜１０μｍとなるように薄層Ａと薄層Ｂとの交互積層構造からなる交互多重積層を形成すると、該交互多重積層は、（Ａｌ，Ｃｒ）２Ｏ３層からなる薄層Ｂの有するすぐれた高温硬さ、耐熱性、高温強度に加えて、さらに、薄膜Ａの有する一段と高い高温強度をも具備するようになること、
（３）前記交互多重積層は、薄層Ｂの有するすぐれた高温硬さ、耐熱性、高温強度を損なうことなく、さらに、一段と高い高温強度をも備えることから、切削時に高熱発生を伴う条件下で、しかも、切刃部への機械的負荷が大きい重切削加工においても、前記交互多重積層の一段とすぐれた高温強度特性のため、硬質被覆層はすぐれた耐チッピング性を発揮するようになること。
以上（１）〜（３）に示される研究結果を得たのである。
In view of the above, the inventors of the present invention have a coated carbide tool that exhibits excellent chipping resistance with a hard coating layer, especially in high-feed, high-cut heavy cutting of various steels and cast irons. As a result of conducting research with a focus on the hard coating layer that constitutes the above conventional coated carbide tool,
(1) On the above conventional hard coating layer in which the lower layer is a Ti compound layer and the upper layer is an (Al, Cr) 2 O 3 layer, for example,
(A) Reaction gas composition (volume%):
ZrCl 4 : 3.0%,
CO 2 : 10.5%,
HCl: 3.5%,
H 2 : remaining,
(B) Reaction atmosphere temperature: 1000 ° C.
(C) Reaction atmosphere pressure: 7 kPa,
When a zirconium (Zr) oxide (hereinafter referred to as ZrO 2 ) layer is formed under the conditions of chemical vapor deposition, a thin layer having an average layer thickness of 0.1 to 0.8 μm is formed on a conventional hard coating layer. A ZrO 2 layer having a very high high-temperature strength is formed.
(2) On the thin ZrO 2 layer (hereinafter referred to as “thin layer A”) having an average layer thickness of 0.1 to 0.8 μm formed by vapor deposition in (1) above, a conventional hard coating layer is further formed. (Al, Cr) 2 O 3 layer that is a layer constituting the upper layer,
For example,
(A) Reaction gas composition (volume%):
AlCl 3 : 1.8%,
CrCl 2 : 0.5%,
CO 2 : 5.5%,
HCl: 2.2%,
H 2 : remaining,
(B) Reaction atmosphere temperature: 1000 ° C.,
(C) Reaction atmosphere pressure: 10 kPa,
Chemical vapor deposition was performed to form a thin (Al, Cr) 2 O 3 layer (hereinafter referred to as “thin layer B”) having an average layer thickness of 0.1 to 0.6 μm. The thin layer B made of the Al, Cr) 2 O 3 layer and the thin layer A made of the ZrO 2 layer formed by vapor deposition under the condition (1) are alternately and repeatedly laminated, and the total average layer thickness is 2 When an alternate multilayer stack composed of an alternate multilayer structure of thin layers A and B is formed so as to have a thickness of 10 μm, the alternate multilayer stack is excellent in the thin layer B composed of (Al, Cr) 2 O 3 layers. In addition to the high temperature hardness, heat resistance, and high temperature strength, the thin film A also has a higher high temperature strength,
(3) The alternating multiple lamination does not impair the excellent high temperature hardness, heat resistance, and high temperature strength of the thin layer B, and further has a higher high temperature strength. Moreover, even in heavy cutting with a heavy mechanical load on the cutting edge, the hard coating layer will exhibit excellent chipping resistance due to the high-temperature strength characteristics that are superior to the above-mentioned alternate multi-layering. .
The research results shown in (1) to (3) above were obtained.
この発明は、上記の研究結果に基づいてなされたものであって、基体の表面に、硬質被覆層を形成してなる被覆超硬工具（表面被覆超硬切削工具）において、
（ａ）前記硬質被覆層は、基体の表面を被覆する下部層と、該下部層の表面を被覆する上部層からなり、
（ｂ）上記下部層は、Ｔｉの炭化物層、窒化物層、炭窒化物層、炭酸化物層、および炭窒酸化物層のうちの１層または２種以上で構成され、かつ０．５〜１５μｍの合計平均層厚を有するＴｉ化合物層からなり、
（ｃ）上記下部層の表面を被覆する上部層は、上部内周層と、該上部内周層を被覆する上部外周層とからなり、
（ｄ）上記上部内周層は、
組成式：（Ａｌ１−ＸＣｒＸ）２Ｏ３（ただし、原子比で、Ｘは０．０５〜０．３５を示す）を満足し、かつ、０．５〜１３μｍの平均層厚を有するＡｌとＣｒの複合酸化物（（Ａｌ，Ｃｒ）２Ｏ３）層からなり、
（ｅ）上記上部内周層を被覆する上部外周層は、０．１〜０．８μｍの平均層厚を有する薄層Ａと、０．１〜０．６μｍの平均層厚を有する薄層Ｂとを交互に積層して形成された、２〜１０μｍの合計平均層厚を有する交互多重積層からなり、
（ｆ）上記薄層Ａは、ジルコニウム（Ｚｒ）酸化物層（ＺｒＯ２層）からなり、
（ｇ）上記薄層Ｂは、
組成式：（Ａｌ１−ＸＣｒＸ）２Ｏ３（ただし、原子比で、Ｘは０．０５〜０．３５を示す）を満足するＡｌとＣｒの複合酸化物（（Ａｌ，Ｃｒ）２Ｏ３）層からなり、
前記硬質被覆層を、炭化タングステン基超硬合金または炭窒化チタン基サーメットで構成された基体の表面に化学蒸着により形成してなる、重切削加工で硬質被覆層がすぐれた耐チッピング性を発揮する被覆超硬工具（表面被覆超硬切削工具）に特徴を有するものである。
This invention was made based on the above research results, and in a coated carbide tool (surface coated carbide cutting tool) formed by forming a hard coating layer on the surface of a substrate,
(A) The hard coating layer comprises a lower layer covering the surface of the substrate and an upper layer covering the surface of the lower layer,
(B) The lower layer is composed of one or more of a Ti carbide layer, a nitride layer, a carbonitride layer, a carbonate layer, and a carbonitride layer, and 0.5 to Consisting of a Ti compound layer having a total average layer thickness of 15 μm,
(C) The upper layer covering the surface of the lower layer is composed of an upper inner peripheral layer and an upper outer peripheral layer covering the upper inner peripheral layer,
(D) The upper inner circumferential layer is
Composition formula: (Al 1-X Cr X ) 2 O 3 (wherein X is 0.05 to 0.35 in atomic ratio) and has an average layer thickness of 0.5 to 13 μm It consists of a complex oxide ((Al, Cr) 2 O 3 ) layer of Al and Cr,
(E) The upper outer peripheral layer covering the upper inner peripheral layer includes a thin layer A having an average layer thickness of 0.1 to 0.8 μm and a thin layer B having an average layer thickness of 0.1 to 0.6 μm. Formed by alternately laminating and having an alternating multiple lamination having a total average layer thickness of 2 to 10 μm,
(F) The thin layer A is composed of a zirconium (Zr) oxide layer (ZrO 2 layer),
(G) The thin layer B is
A composite oxide of (Al, Cr) 2 that satisfies the composition formula: (Al 1-X Cr X ) 2 O 3 (wherein X represents 0.05 to 0.35 in atomic ratio). O 3 ) layer,
The hard coating layer is formed by chemical vapor deposition on the surface of a substrate made of tungsten carbide base cemented carbide or titanium carbonitride base cermet, and the hard coating layer exhibits excellent chipping resistance by heavy cutting. It is characterized by a coated carbide tool (surface coated carbide cutting tool).
つぎに、この発明の被覆超硬工具において、これを構成する硬質被覆層の構成を上記の通りに限定した理由を説明する。
（１）下部層（Ｔｉ化合物層）
Ｔｉ化合物層は、基本的には上部層の上部内周層を構成する（Ａｌ，Ｃｒ）２Ｏ３層の下部層として存在し、自身の具備するすぐれた高温強度によって硬質被覆層の高温強度向上に寄与するほか、基体と上記上部内周層（（Ａｌ，Ｃｒ）２Ｏ３層）のいずれにも強固に密着し、よって硬質被覆層の基体に対する密着性を向上させる作用を有するが、その合計平均層厚が０．５μｍ未満では、前記作用を十分に発揮させることができず、一方その合計平均層厚が１５μｍを越えると、切削時の発生熱によって偏摩耗の原因となる熱塑性変形を起し易くなることから、その合計平均層厚を０．５〜１５μｍと定めた。
（２）上部内周層（（Ａｌ，Ｃｒ）２Ｏ３層）
上記した通り上部内周層を構成する（Ａｌ，Ｃｒ）２Ｏ３層（従来硬質被覆層における上部層に相当）におけるＡｌ成分は高温硬さおよび耐熱性、同Ｃｒ成分は高温強度を向上させるが、ＡｌとＣｒ成分の相互含有割合を示す組成式：（Ａｌ１−ＸＣｒＸ）で、Ｘ値が原子比で（以下同じ）０．３５を越えると、相対的にＡｌの含有割合が低くなることから、層自体の高温硬さおよび耐熱性の低下は避けられず、これが摩耗促進の原因となり、一方、Ｘ値が０．０５未満になると、層自体の高温強度の低下は避けられず、この結果チッピングなどが発生し易くなることから、Ｘ値を０．０５〜０．３５と定めた。
Next, in the coated carbide tool of the present invention, the reason why the structure of the hard coating layer constituting the tool is limited as described above will be described.
(1) Lower layer (Ti compound layer)
The Ti compound layer basically exists as the lower layer of the (Al, Cr) 2 O 3 layer that constitutes the upper inner peripheral layer of the upper layer, and the high temperature strength of the hard coating layer by the excellent high temperature strength possessed by itself. In addition to contributing to the improvement, the substrate and the upper inner peripheral layer ((Al, Cr) 2 O 3 layer) are firmly adhered to each other, and thus have the effect of improving the adhesion of the hard coating layer to the substrate. If the total average layer thickness is less than 0.5 μm, the above-mentioned effect cannot be sufficiently exerted. On the other hand, if the total average layer thickness exceeds 15 μm, the thermoplastic deformation causing uneven wear due to heat generated during cutting. Therefore, the total average layer thickness was determined to be 0.5 to 15 μm.
(2) Upper inner peripheral layer ((Al, Cr) 2 O 3 layer)
As described above, the Al component in the (Al, Cr) 2 O 3 layer (corresponding to the upper layer in the conventional hard coating layer) constituting the upper inner peripheral layer improves the high temperature hardness and heat resistance, and the Cr component improves the high temperature strength. Is a composition formula showing the mutual content ratio of Al and Cr components: (Al 1-X Cr X ), and when the X value exceeds 0.35 in terms of atomic ratio (hereinafter the same), the Al content ratio is relatively The lowering of the high-temperature hardness and heat resistance of the layer itself is unavoidable because it becomes lower, which causes wear promotion. On the other hand, when the X value is less than 0.05, the lowering of the high-temperature strength of the layer itself is avoided. As a result, chipping and the like are likely to occur, so the X value was set to 0.05 to 0.35.
また、その平均層厚が０．５μｍ未満では、所望の耐摩耗性を長期に亘って確保することができず、一方その平均層厚が１３μｍを越えると、チッピングが発生し易くなることから、その平均層厚を０．５〜１３μｍと定めた。
（３）上部外周層（薄層Ａと薄層Ｂとからなる交互多重積層）
すでに述べたように、（Ａｌ，Ｃｒ）２Ｏ３層からなる上部内周層は、通常条件の切削加工においては十分な高温硬さ、耐熱性、高温強度を備えるものの、切削時の熱発生による高温条件下で切刃部への機械的負荷が大きい重切削加工にあっては、チッピング（微小割れ）の発生を抑える足る十分な高温強度を備えているわけではないことから、上部内周層上に、より一段と高い高温強度を有するＺｒＯ２層からなる薄層Ａと、（Ａｌ，Ｃｒ）２Ｏ３層からなる薄層Ｂとの交互多重積層を設けることにより、上部内周層の備える高温硬さと耐熱性とを特段低下させることなく、高温強度のより一層の向上を図った。つまり、薄層Ａと薄層Ｂの交互多重積層からなる上部外周層が、所定の高温硬さと耐熱性に加え、より一層の高温強度を備え、その結果として、所定の耐チッピング性を発揮するためには、薄層Ａは、少なくとも０．１μｍの厚さが必要とされ、これ未満の厚さでは重切削加工において必要とされる高温強度を具備することはできず、また、その厚みは０．８μｍ以下であれば、上部外周層の高温硬さおよび耐熱性を損なうことなく、十分な高温強度を保持することができるから、薄層Ａの平均層厚を０．１〜０．８μｍに定めた。また、薄層Ｂの平均層厚が０．１μｍ未満の場合には、上部外周層に最小限必要とされる高温硬さ、耐熱性を維持することができず、一方、薄層Ｂの平均層厚が０．６μｍを超えるような場合には、上部外周層の全体層厚に占める薄層Ｂの割合が多くなるため、薄層Ａを交互に積層し交互多重積層構造としたことによる高温強度の改善効果を期待できなくなることから、薄層Ｂの平均層厚を０．１〜０．６μｍに定めた。
Further, if the average layer thickness is less than 0.5 μm, the desired wear resistance cannot be ensured over a long period of time, while if the average layer thickness exceeds 13 μm, chipping tends to occur. The average layer thickness was set to 0.5 to 13 μm.
(3) Upper outer peripheral layer (alternate multiple lamination consisting of thin layer A and thin layer B)
As described above, the upper inner peripheral layer made of (Al, Cr) 2 O 3 layer has sufficient high-temperature hardness, heat resistance, and high-temperature strength in cutting under normal conditions, but generates heat during cutting. In heavy cutting with a high mechanical load on the cutting edge under high temperature conditions, the upper inner circumference does not have sufficient high temperature strength to suppress chipping (microcracking). On the layer, by providing an alternating multiple stack of thin layers A composed of ZrO 2 layers having higher high-temperature strength and thin layers B composed of (Al, Cr) 2 O 3 layers, The high temperature strength was further improved without particularly reducing the high temperature hardness and heat resistance provided. In other words, the upper outer peripheral layer composed of the alternating multiple layers of the thin layer A and the thin layer B has a higher temperature strength in addition to a predetermined high temperature hardness and heat resistance, and as a result, exhibits a predetermined chipping resistance. For this purpose, the thin layer A is required to have a thickness of at least 0.1 μm, and a thickness less than this can not have the high temperature strength required in heavy cutting, and the thickness is If it is 0.8 μm or less, sufficient high-temperature strength can be maintained without impairing the high-temperature hardness and heat resistance of the upper outer peripheral layer, so the average layer thickness of the thin layer A is 0.1 to 0.8 μm. Determined. In addition, when the average layer thickness of the thin layer B is less than 0.1 μm, the minimum high temperature hardness and heat resistance required for the upper outer peripheral layer cannot be maintained, while the average of the thin layer B When the layer thickness exceeds 0.6 μm, the ratio of the thin layer B occupying the entire layer thickness of the upper outer peripheral layer increases. Since the strength improvement effect cannot be expected, the average layer thickness of the thin layer B is set to 0.1 to 0.6 μm.
そして、薄層Ａと薄層Ｂを、それぞれ前記所定平均層厚の薄層として交互に積層することにより、薄層Ａと薄層Ｂの交互多重積層からなる上部外周層は、すぐれた高温硬さと耐熱性、さらに、一段とすぐれた高温強度を具備したあたかも一つの層であるかのように機能する。ただ、上部外周層（交互多重積層）の合計平均層厚が２μｍ未満では、所定の高温硬さ、耐熱性、高温強度を硬質被覆層に長期に亘って付与できず、工具寿命短命の原因となり、一方その合計平均層厚が１０μｍを越えても、耐チッピング性の改善効果には、それほど大きな変化は生じないことから、その合計平均層厚を２〜１０μｍと定めた。 Then, by alternately laminating the thin layer A and the thin layer B as the thin layers having the predetermined average layer thickness, the upper outer peripheral layer composed of the alternating multiple lamination of the thin layer A and the thin layer B is excellent in high temperature hardness. It functions as if it were a single layer with excellent high temperature strength and heat resistance. However, if the total average layer thickness of the upper outer peripheral layer (alternate multiple layers) is less than 2 μm, the predetermined high temperature hardness, heat resistance, and high temperature strength cannot be imparted to the hard coating layer over a long period of time, resulting in a short tool life. On the other hand, even if the total average layer thickness exceeds 10 μm, the effect of improving the chipping resistance does not change so much, so the total average layer thickness was set to 2 to 10 μm.
この発明の被覆超硬工具は、硬質被覆層を、基体を覆う下部層、該下部層を覆う上部内周層、該上部内周層を覆う上部外周層で構成し、かつ、該上部外周層を薄層Ａ（ＺｒＯ２層）と薄層Ｂ（（Ａｌ，Ｃｒ）２Ｏ３層）との交互多重積層として構成することにより、硬質被覆層の下部層（Ｔｉ化合物層）および上部内周層（（Ａｌ，Ｃｒ）２Ｏ３層）の具備する高温硬さ、耐熱性、高温強度の諸特性を何ら損なうことなくこれを維持したままで、硬質被覆層がさらにすぐれた高温強度特性を具備することになるので、各種の鋼、鋳鉄等の通常条件の切削加工に用いることができるばかりか、特に、切刃部への機械的負荷が大きなものとなる鋼、鋳鉄等の高送り、高切り込み条件の重切削加工においても、下部層であるＴｉ化合物層の具備するすぐれた層間密着性および高温強度と相俟って、硬質被覆層がすぐれた耐チッピング性を示し、長期に亘ってすぐれた耐摩耗性を発揮するのである。 In the coated carbide tool of the present invention, the hard coating layer is composed of a lower layer covering the base, an upper inner peripheral layer covering the lower layer, an upper outer peripheral layer covering the upper inner peripheral layer, and the upper outer peripheral layer. Is formed as an alternating multiple lamination of thin layer A (ZrO 2 layer) and thin layer B ((Al, Cr) 2 O 3 layer), so that the lower layer (Ti compound layer) and upper inner circumference of the hard coating layer While maintaining the high temperature hardness, heat resistance, and high temperature strength characteristics of the layer ((Al, Cr) 2 O 3 layer) without any loss, the hard coating layer has superior high temperature strength characteristics. Because it will be equipped, not only can it be used for cutting under normal conditions such as various steels and cast iron, in particular, high feed of steel, cast iron, etc. that will increase the mechanical load on the cutting edge, Even in heavy cutting under high cutting conditions, the lower layer is equipped with a Ti compound layer Combined with excellent interlayer adhesion and high-temperature strength, the hard coating layer exhibits excellent chipping resistance and exhibits excellent wear resistance over a long period of time.
つぎに、この発明の被覆超硬工具を実施例により具体的に説明する。 Next, the coated carbide tool of the present invention will be specifically described with reference to examples.
原料粉末として、いずれも１〜３μｍの平均粒径を有するＷＣ粉末、ＴｉＣ粉末、ＴｉＮ粉末、ＴａＣ粉末、ＮｂＣ粉末、Ｃｒ３Ｃ２粉末、およびＣｏ粉末を用意し、これら原料粉末を、表１に示される配合組成に配合し、ボールミルで７２時間湿式混合し、乾燥した後、１００ＭＰａ の圧力で圧粉体にプレス成形し、この圧粉体を６Ｐａの真空中、温度：１４００℃に１時間保持の条件で焼結し、焼結後、切刃部分にＲ：０．０７のホーニング加工を施してＩＳＯ規格・ＣＮＭＧ１２０４０８のチップ形状をもったＷＣ基超硬合金製の超硬基体Ａ１〜Ａ１０を形成した。 As raw material powders, WC powder, TiC powder, TiN powder, TaC powder, NbC powder, Cr 3 C 2 powder, and Co powder, all having an average particle diameter of 1 to 3 μm, were prepared. And then wet-mixed with a ball mill for 72 hours, dried, and press-molded into a green compact at a pressure of 100 MPa. The green compact was vacuumed at 6 Pa at a temperature of 1400 ° C. for 1 hour. Sintered under the holding conditions, and after sintering, the cutting edge portion was subjected to honing of R: 0.07, and the carbide bases A1 to A10 made of WC-base cemented carbide having ISO standard CNMG120408 chip shape Formed.
また、原料粉末として、いずれも０．５〜２μｍの平均粒径を有するＴｉＣＮ（質量比で、ＴｉＣ／ＴｉＮ＝５０／５０）粉末、Ｍｏ２Ｃ粉末、ＺｒＣ粉末、ＮｂＣ粉末、ＴａＣ粉末、ＷＣ粉末、Ｃｏ粉末、およびＮｉ粉末を用意し、これら原料粉末を、表２に示される配合組成に配合し、ボールミルで２４時間湿式混合し、乾燥した後、１００ＭＰａの圧力で圧粉体にプレス成形し、この圧粉体を２ｋＰａの窒素雰囲気中、温度：１５００℃に１時間保持の条件で焼結し、焼結後、切刃部分にＲ：０．０７のホーニング加工を施してＩＳＯ規格・ＣＮＭＧ１２０４０８のチップ形状をもったＴｉＣＮ系サーメット製の超硬基体Ｂ１〜Ｂ６を形成した。 In addition, as raw material powders, TiCN (mass ratio, TiC / TiN = 50/50) powder, Mo 2 C powder, ZrC powder, NbC powder, TaC powder, WC, all having an average particle diameter of 0.5 to 2 μm. Prepare powder, Co powder, and Ni powder, mix these raw material powders into the composition shown in Table 2, wet mix for 24 hours with a ball mill, dry, and press-mold into green compact at 100 MPa pressure The green compact was sintered in a nitrogen atmosphere of 2 kPa at a temperature of 1500 ° C. for 1 hour. After sintering, the cutting edge portion was subjected to a honing process of R: 0.07 and ISO standard TiCN-based cermet carbide substrates B1 to B6 having a chip shape of CNMG120408 were formed.
上記の超硬基体Ａ１〜Ａ１０およびＢ１〜Ｂ６のそれぞれを、アセトン中で超音波洗浄し、乾燥した後、図１に示される化学蒸着装置内に、第２図に示される超硬基体支持パレットの位置決め穴に載置した状態で装入し、まず、表３（表３中のｌ−ＴｉＣＮは特開平６−８０１０号公報に記載される縦長成長結晶組織をもつＴｉＣＮ層の形成条件を示すものであり、これ以外は通常の粒状結晶組織の形成条件を示すものである）に示される通常の条件にて、表６に示される組み合わせおよび目標平均層厚のＴｉ化合物層を硬質被覆層の下部層として蒸着形成した。 Each of the above-mentioned carbide substrates A1 to A10 and B1 to B6 is ultrasonically cleaned in acetone and dried, and then placed in the chemical vapor deposition apparatus shown in FIG. 1 and the carbide substrate support pallet shown in FIG. First, Table 3 (l-TiCN in Table 3 indicates the conditions for forming a TiCN layer having a vertically grown crystal structure described in JP-A-6-8010). In the normal conditions shown in Table 6 above, the combinations shown in Table 6 and the Ti compound layer with the target average layer thickness are applied to the hard coating layer. Vapor deposition was formed as the lower layer.
つぎに、表４に示される条件で、かつ同じく表６に示される目標平均層厚の（Ａｌ，Ｃｒ）２Ｏ３層を硬質被覆層の上部内周層として蒸着形成した。 Next, an (Al, Cr) 2 O 3 layer having the target average layer thickness shown in Table 6 under the conditions shown in Table 4 was formed by vapor deposition as the upper inner peripheral layer of the hard coating layer.
その後、表５に示される条件で、かつ同じく表６に示される目標平均層厚のＺｒＯ２層を、硬質被覆層の上部外周層の薄層Ａとして蒸着形成し、ついで、表４に示される条件で、かつ同じく表６に示される目標平均層厚の（Ａｌ，Ｃｒ）２Ｏ３層を、硬質被覆層の上部外周層の薄層Ｂとして蒸着形成した。薄層Ａと薄層Ｂの蒸着形成は、上部外周層の目標合計平均層厚に達するまで、交互に繰り返し行い、本発明表面被覆超硬切削工具である本発明表面被覆超硬スローアウエイチップ（以下、本発明被覆超硬チップと云う）１〜１６をそれぞれ製造した。 Thereafter, a ZrO 2 layer having the target average layer thickness also shown in Table 6 under the conditions shown in Table 5 was deposited as a thin layer A of the upper outer peripheral layer of the hard coating layer, and then shown in Table 4 The (Al, Cr) 2 O 3 layer having the target average layer thickness shown in Table 6 under the same conditions was deposited as a thin layer B of the upper outer peripheral layer of the hard coating layer. The vapor deposition of the thin layer A and the thin layer B is alternately repeated until the target total average layer thickness of the upper outer peripheral layer is reached, and the surface-coated carbide throwaway tip of the present invention which is the surface-coated carbide cutting tool of the present invention ( Hereinafter, the coated carbide chips of the present invention were produced.
また、比較の目的で、これら超硬基体Ａ１〜Ａ１０およびＢ１〜Ｂ６を、アセトン中で超音波洗浄し、乾燥した後、同じくそれぞれ図１，２に示される通常の化学蒸着装置に装入し、表７に示されるＴｉ化合物層を硬質被覆層の下部層として蒸着形成した（なお、表７に示される従来被覆超硬工具１〜１６の下部層（Ｔｉ化合物層）は、本発明被覆超硬工具１〜１６のそれぞれと同じにしてあるので、下部層の具体的な形成条件、目標平均層厚は、表３、表６に示されているとおりである）。 For comparison purposes, these carbide substrates A1 to A10 and B1 to B6 were ultrasonically cleaned in acetone and dried, and then charged into the normal chemical vapor deposition apparatus shown in FIGS. The Ti compound layer shown in Table 7 was vapor-deposited as the lower layer of the hard coating layer (Note that the lower layer (Ti compound layer) of the conventional coated carbide tools 1 to 16 shown in Table 7 was coated with the present invention. Since it is the same as each of the hard tools 1-16, the specific formation conditions of the lower layer and the target average layer thickness are as shown in Tables 3 and 6.
次に、表４に示される条件で、かつ同じく表７に示される目標平均層厚の（Ａｌ，Ｃｒ）２Ｏ３層を硬質被覆層の上部層として下部層（Ｔｉ化合物層）の表面に蒸着形成し、従来表面被覆超硬切削工具としての従来表面被覆超硬スローアウエイチップ（以下、従来被覆超硬チップと云う）１〜１６をそれぞれ製造した。 Next, the (Al, Cr) 2 O 3 layer having the target average layer thickness shown in Table 7 under the conditions shown in Table 4 is used as the upper layer of the hard coating layer on the surface of the lower layer (Ti compound layer). The conventional surface-coated carbide throwaway tips (hereinafter referred to as conventional coated carbide tips) 1 to 16 as conventional surface-coated carbide cutting tools were produced by vapor deposition.
つぎに、上記の各種の被覆超硬チップを、いずれも工具鋼製バイトの先端部に固定治具にてネジ止めした状態で、本発明被覆超硬チップ１〜１６および従来被覆超硬チップ１〜１６について、
被削材：ＪＩＳ・Ｓ４５Ｃの丸棒、
切削速度： ３００ ｍ／ｍｉｎ．、
切り込み： ６．５ ｍｍ、
送り： ０．４ ｍｍ／ｒｅｖ．、
切削時間： ５ 分、
の条件（切削条件Ａという）での炭素鋼の乾式連続高切り込み切削加工試験（通常の切り込み量は２．０ｍｍ）、
被削材：ＪＩＳ・ＳＣＭ４４０の長さ方向等間隔４本縦溝入り丸棒、
切削速度： ２５０ ｍ／ｍｉｎ．、
切り込み： ６．５ ｍｍ、
送り： ０．３５ ｍｍ／ｒｅｖ．、
切削時間： ５ 分、
の条件（切削条件Ｂという）での合金鋼の乾式断続高切り込み切削加工試験（通常の切り込み量は１．５ｍｍ）、
被削材：ＪＩＳ・ＦＣ２５０の丸棒、
切削速度： ４５０ ｍ／ｍｉｎ．、
切り込み： ２．５ ｍｍ、
送り： ０．７ ｍｍ／ｒｅｖ．、
切削時間： ５ 分、
の条件（切削条件Ｃという）での鋳鉄の乾式連続高送り切削加工試験（通常の送りは０．３ｍｍ／ｒｅｖ．）を行い、いずれの切削加工試験でも切刃の逃げ面摩耗幅を測定した。この測定結果を表８に示した。
Next, the coated carbide chips 1 to 16 of the present invention and the conventional coated carbide chip 1 in the state in which each of the various coated carbide chips is screwed to the tip of the tool steel tool with a fixing jig. About ~ 16
Work material: JIS / S45C round bar,
Cutting speed: 300 m / min. ,
Incision: 6.5 mm,
Feed: 0.4 mm / rev. ,
Cutting time: 5 minutes,
Dry continuous high-cut cutting test of carbon steel under the above conditions (referred to as cutting condition A) (normal cutting amount is 2.0 mm),
Work material: JIS · SCM440 lengthwise equidistant 4 vertical grooved round bar,
Cutting speed: 250 m / min. ,
Incision: 6.5 mm,
Feed: 0.35 mm / rev. ,
Cutting time: 5 minutes,
Dry interrupted high cut cutting test of alloy steel under the conditions (cutting condition B) (normal cutting depth is 1.5 mm),
Work material: JIS / FC250 round bar,
Cutting speed: 450 m / min. ,
Cutting depth: 2.5 mm,
Feed: 0.7 mm / rev. ,
Cutting time: 5 minutes,
The dry continuous high-feed cutting test (normal feed is 0.3 mm / rev.) Of cast iron under the above conditions (referred to as cutting condition C), and the flank wear width of the cutting edge was measured in any cutting test. . The measurement results are shown in Table 8.
この結果得られた本発明被覆超硬チップ１〜１６および従来被覆超硬チップ１〜１６の硬質被覆層を構成する各層について、その組成を、オージェ分光分析装置を用いて測定したところ、いずれのＴｉ化合物層、（Ａｌ，Ｃｒ）２Ｏ３層も目標組成と実質的に同じ組成を示し、各層の層厚も目標平均層厚と実質的に同じ値を示した。さらに、本発明被覆超硬チップ１〜１６の硬質被覆層の上部外周層の薄層Ａを構成するＺｒＯ２層についても、目標平均層厚と実質的に同じ値を示すＺｒＯ２層が形成されていることが確認された。 About each layer which comprises the hard coating layer of this invention coated carbide | carbonized_material chip | tip 1-16 obtained as a result of this and the conventional coated carbide | carbonized_material chip | tip 1-16, when the composition was measured using the Auger spectroscopic analyzer, The Ti compound layer and the (Al, Cr) 2 O 3 layer also showed substantially the same composition as the target composition, and the layer thickness of each layer also showed substantially the same value as the target average layer thickness. Further, the ZrO 2 layer constituting the thin layer A of the upper outer peripheral layer of the hard coating layer of the coated carbide chips 1 to 16 of the present invention is also formed with a ZrO 2 layer showing substantially the same value as the target average layer thickness. It was confirmed that
表８に示される結果から、硬質被覆層の上部層が、上部内周層（（Ａｌ，Ｃｒ）２Ｏ３層）と、薄層Ａ（ＺｒＯ２層）及び薄層Ｂ（（Ａｌ，Ｃｒ）２Ｏ３層）の交互多重積層からなる上部外周層とで構成されている本発明被覆超硬チップ１〜１６は、いずれも鋼、鋳鉄などの切削加工を、切刃部への機械的負荷が大きなものとなる高切り込みや高送りなどの重切削条件で行なった場合にも、硬質被覆層がすぐれた耐チッピング性を発揮し、すぐれた耐摩耗性を長期に亘って発揮するのに対して、硬質被覆層の上部層が、（Ａｌ，Ｃｒ）２Ｏ３層のみからなる従来被覆超硬チップ１〜１６においては、特に前記上部層の高温強度の不足が原因となり、チッピングが発生し易く、比較的短時間で使用寿命に至ることが明らかである。 From the results shown in Table 8, the upper layer of the hard coating layer is the upper inner peripheral layer ((Al, Cr) 2 O 3 layer), thin layer A (ZrO 2 layer) and thin layer B ((Al, Cr ) The coated carbide chips 1 to 16 of the present invention, which are composed of upper outer peripheral layers composed of alternating multiple layers of 2 O 3 layers), are all mechanically processed to the cutting edge part by cutting steel, cast iron and the like. Even when heavy cutting conditions such as high cutting and high feed with heavy loads are applied, the hard coating layer exhibits excellent chipping resistance and long-term wear resistance. On the other hand, in the conventional coated carbide chips 1 to 16 in which the upper layer of the hard coating layer is composed of only the (Al, Cr) 2 O 3 layer, chipping occurs due to the lack of high-temperature strength of the upper layer. It is clear that it reaches the service life in a relatively short time.
上述のように、この発明の被覆超硬工具は、通常の条件での切削加工は勿論のこと、特に鋼、鋳鉄などを、高切り込みや高送りなどの重切削条件で切削加工を行なった場合にも、すぐれた耐チッピング性を発揮し、長期に亘ってすぐれた耐摩耗性を示すものであるから、切削装置のＦＡ化、並びに切削加工の省力化および省エネ化、さらに低コスト化に十分満足に対応できるものである。 As described above, the coated carbide tool of the present invention is not only for cutting under normal conditions, but particularly when steel, cast iron, etc. are cut under heavy cutting conditions such as high cutting and high feed. In addition, since it exhibits excellent chipping resistance and excellent wear resistance over a long period of time, it is sufficient for FA of cutting equipment, labor saving and energy saving of cutting, and cost reduction It can respond to satisfaction.
Claims (1)
（ａ）前記硬質被覆層は、基体の表面を被覆する下部層と、該下部層の表面を被覆する上部層からなり、
（ｂ）上記下部層は、Ｔｉの炭化物層、窒化物層、炭窒化物層、炭酸化物層、および炭窒酸化物層のうちの１層または２種以上で構成され、かつ０．５〜１５μｍの合計平均層厚を有するＴｉ化合物層からなり、
（ｃ）上記下部層の表面を被覆する上部層は、上部内周層と、該上部内周層を被覆する上部外周層とからなり、
（ｄ）上記上部内周層は、
組成式：（Ａｌ１−ＸＣｒＸ）２Ｏ３（ただし、原子比で、Ｘは０．０５〜０．３５を示す）を満足し、かつ、０．５〜１３μｍの平均層厚を有するＡｌとＣｒの複合酸化物層からなり、
（ｅ）上記上部内周層を被覆する上部外周層は、０．１〜０．８μｍの平均層厚を有する薄層Ａと、０．１〜０．６μｍの平均層厚を有する薄層Ｂとを交互に積層して形成された、２〜１０μｍの合計平均層厚を有する交互多重積層からなり、
（ｆ）上記薄層Ａは、ジルコニウム（Ｚｒ）酸化物層からなり、
（ｇ）上記薄層Ｂは、
組成式：（Ａｌ１−ＸＣｒＸ）２Ｏ３（ただし、原子比で、Ｘは０．０５〜０．３５を示す）を満足するＡｌとＣｒの複合酸化物層からなり、
前記硬質被覆層を、炭化タングステン基超硬合金または炭窒化チタン基サーメットで構成された基体の表面に化学蒸着により形成してなる、重切削加工で硬質被覆層がすぐれた耐チッピング性を発揮する表面被覆超硬切削工具。
In a surface-coated cemented carbide cutting tool in which a hard coating layer is formed on the surface of a substrate composed of a tungsten carbide-based cemented carbide alloy or a titanium carbonitride-based cermet,
(A) The hard coating layer comprises a lower layer covering the surface of the substrate and an upper layer covering the surface of the lower layer,
(B) The lower layer is composed of one or more of a Ti carbide layer, a nitride layer, a carbonitride layer, a carbonate layer, and a carbonitride layer, and 0.5 to Consisting of a Ti compound layer having a total average layer thickness of 15 μm,
(C) The upper layer covering the surface of the lower layer is composed of an upper inner peripheral layer and an upper outer peripheral layer covering the upper inner peripheral layer,
(D) The upper inner circumferential layer is
Composition formula: (Al 1-X Cr X ) 2 O 3 (wherein X is 0.05 to 0.35 in atomic ratio) and has an average layer thickness of 0.5 to 13 μm It consists of a complex oxide layer of Al and Cr,
(E) The upper outer peripheral layer covering the upper inner peripheral layer includes a thin layer A having an average layer thickness of 0.1 to 0.8 μm and a thin layer B having an average layer thickness of 0.1 to 0.6 μm. Formed by alternately laminating and having an alternating multiple lamination having a total average layer thickness of 2 to 10 μm,
(F) The thin layer A is composed of a zirconium (Zr) oxide layer,
(G) The thin layer B is
It consists of a composite oxide layer of Al and Cr that satisfies the composition formula: (Al 1-X Cr X ) 2 O 3 (where X is 0.05 to 0.35 in atomic ratio),
The hard coating layer is formed by chemical vapor deposition on the surface of a substrate made of tungsten carbide base cemented carbide or titanium carbonitride base cermet, and the hard coating layer exhibits excellent chipping resistance by heavy cutting. Surface coated carbide cutting tool.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011521796A (en) * | 2008-05-31 | 2011-07-28 | バルター アクチェンゲゼルシャフト | Tool with metal oxide coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011521796A (en) * | 2008-05-31 | 2011-07-28 | バルター アクチェンゲゼルシャフト | Tool with metal oxide coating |
| EP2281072B1 (en) * | 2008-05-31 | 2015-12-16 | Walter AG | Tool having a metal oxide coating |
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