JP5303732B2 - Coated tool - Google Patents
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- JP5303732B2 JP5303732B2 JP2008009958A JP2008009958A JP5303732B2 JP 5303732 B2 JP5303732 B2 JP 5303732B2 JP 2008009958 A JP2008009958 A JP 2008009958A JP 2008009958 A JP2008009958 A JP 2008009958A JP 5303732 B2 JP5303732 B2 JP 5303732B2
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Description
本願発明は、密着性に優れた酸化アルミニウム膜を被覆した被覆工具であり、切削工具等への適用に関する。 The present invention is a coated tool coated with an aluminum oxide film having excellent adhesion, and relates to application to a cutting tool or the like.
特許文献１〜４は、突起形状を有した結合膜を介して酸化アルミニウム膜を被覆する技術が開示されている。 Patent Documents 1 to 4 disclose techniques for coating an aluminum oxide film through a bonding film having a protruding shape.
本願発明は、酸化アルミニウム膜の密着性を高め、皮膜の耐剥離性に優れた被覆工具を提供することである。 The present invention is to provide a coated tool that improves the adhesion of an aluminum oxide film and is excellent in the peel resistance of the film.
本願発明は、基体表面に周期律表４ａ、５ａ、６ａ族金属から選択される元素の炭化物、窒化物、炭窒化物、酸化物、炭酸化物、窒酸化物及び炭窒酸化物のいずれか１種の単層皮膜又は２種以上の多層皮膜が形成され、該皮膜の上層に結合膜を介してα型酸化アルミニウム膜が形成されている被覆工具において、該結合膜と該α型酸化アルミニウム膜との界面における該結合膜の表面形状が樹状突起とこれに連なる枝状突起とからなる樹枝形状を有し、該枝状突起の長さ（ｎｍ）をＬＢとしたとき、５≦ＬＢ≦２００、であり、該枝状突起の格子縞と該α型酸化アルミニウム膜の格子縞との界面は透過電子顕微鏡の観察により連続した格子縞を有してエピタキシャル成長しており、該結合膜の該樹状突起はＴｉ（ＣＯ）又はＴｉ（ＣＮＯ）であり、該枝状突起は（ＴｉＡｌ）（ＣＮＯ）であることを特徴とする被覆工具である。上記の構成を採用することによって、酸化アルミニウム膜の密着性を高め、皮膜の耐剥離性に優れた被覆工具を提供することができる。 In the present invention, any one of carbides, nitrides, carbonitrides, oxides, carbonates, nitrides and carbonitrides of an element selected from the group 4a, 5a, and 6a metals of the periodic table is provided on the substrate surface. In a coated tool in which a single monolayer coating or two or more multi-layer coatings are formed, and an α-type aluminum oxide film is formed on the upper layer of the coating via a binding film, the binding film and the α-type aluminum oxide film When the surface shape of the binding film at the interface with the substrate has a dendritic shape composed of dendrites and branching projections connected to the dendrites, and the length (nm) of the branching projections is LB, 5 ≦ LB ≦ 200 is, the interface between the plaid plaid and the α-type aluminum oxide film of the branches like protrusions to have a continuous lattice fringes by observation of a transmission electron microscope has been epitaxially grown, dendritic projections of the coupling film Is Ti (CO) or Ti (CNO) , The branches like protrusions are coated tool, wherein der Rukoto (TiAl) (CNO). By adopting the above configuration, it is possible to provide a coated tool that improves the adhesion of the aluminum oxide film and is excellent in the peel resistance of the film.
本願発明により、酸化アルミニウム膜の密着性を高め、皮膜の耐剥離性に優れた被覆工具を提供することができた。 By this invention, the adhesiveness of the aluminum oxide film was improved and the coated tool excellent in the peeling resistance of a film | membrane could be provided.
本願発明の被覆工具は、結合膜とα型酸化アルミニウム膜との界面における結合膜の表面形状が樹状突起と、これに連なる枝状突起からなる樹枝形状を有していることを特徴とする被覆工具である。結合膜の表面形状が樹状突起と枝状突起とを併せ持つことによって、結合膜とα型酸化アルミニウム膜との界面における密着強度の改善に大きく寄与して皮膜の耐剥離性に優れた被覆工具を得ることができる。この理由は、結合膜における樹枝形状の突起がα型酸化アルミニウム膜へ食い込み、アンカー効果により密着性が格段に改善されるからである。樹状突起と、これに連なる枝状突起の複数の突起は、より好ましくは、先端形状が鋭角形状を有することであり、このような場合にα型酸化アルミニウム膜へ突起が鋭く食い込むことからアンカー効果が効果的に作用して密着強度は最大となる。また、本願発明における樹枝形状を有した結合膜において、樹状突起に連なる枝状突起のＬＢ値（ｎｍ）は、５≦ＬＢ≦２００、である。より好ましくは、枝状突起の先端形状が鋭角形状を有することであり、これによって結合膜とα型酸化アルミニウム膜との密着性が優れる。ＬＢ値が５ｎｍ以上であることにより、アンカー効果が有効に作用し、また、２００ｎｍ以下であることにより、α型酸化アルミニウム膜表面の凹凸を減少させることができ、皮膜の結晶粒径の粗大化を回避して優れた密着性を得ることができる。この理由は、α型酸化アルミニウム膜が枝状突起を起点として成長するためである。枝状突起のＬＢ値が２００ｎｍを超えて大きいと、α型酸化アルミニウム膜の表面凹凸が大きくなってしまう。
更に、本願発明における樹枝形状を有した結合膜において、樹状突起に連なる枝状突起の格子縞とα型酸化アルミニウム膜の格子縞との界面は、透過電子顕微鏡の観察により連続した格子縞を有してエピタキシャル成長しており、該結合膜の該樹状突起はＴｉ（ＣＯ）又はＴｉ（ＣＮＯ）であり、該枝状突起は（ＴｉＡｌ）（ＣＮＯ）である。両者の格子縞を連続させることにより、結合膜とα型酸化アルミニウム膜との密着性及び耐剥離性に優れる。
The coated tool of the present invention is characterized in that the surface shape of the bonding film at the interface between the bonding film and the α-type aluminum oxide film has a dendritic shape and a dendritic shape consisting of branching protrusions connected thereto. It is a coated tool. Coated tool with excellent peeling resistance of the coating because the surface shape of the binding film has both dendritic protrusions and branch-like protrusions, which greatly contributes to improving the adhesion strength at the interface between the binding film and the α-type aluminum oxide film. Can be obtained. The reason for this is that dendritic protrusions in the binding film bite into the α-type aluminum oxide film, and the adhesion is remarkably improved by the anchor effect. More preferably, the plurality of projections of the dendrite and the branch-like projections connected to the dendrite has an acute-angled tip shape. In such a case, the projections sharply bite into the α-type aluminum oxide film. The effect acts effectively and the adhesion strength is maximized. Further, in the coupling film having a dendritic shape in the present invention, the LB value (nm) of the branch-like projections connected to the dendrites is 5 ≦ LB ≦ 200. More preferably, the tip shape of the branch-like protrusion has an acute angle shape, and thereby the adhesion between the binding film and the α-type aluminum oxide film is excellent. When the LB value is 5 nm or more, the anchor effect works effectively, and when it is 200 nm or less, the unevenness of the surface of the α-type aluminum oxide film can be reduced, and the crystal grain size of the film becomes coarse. And excellent adhesion can be obtained. This is because the α-type aluminum oxide film grows starting from the branch-like projections. If the LB value of the branch protrusions exceeds 200 nm, the surface unevenness of the α-type aluminum oxide film becomes large.
Further, in the binding film having a dendritic shape in the present invention, the interface between the lattice fringes of the branch projections continuous with the dendrites and the lattice fringes of the α-type aluminum oxide film has a continuous lattice fringe by observation with a transmission electron microscope. and epitaxially growing, dendritic projections of the coupling film is Ti (CO) or Ti (CNO), the branches like projections Ru der (TiAl) (CNO). By making both the lattice stripes continuous, the adhesion between the bonding film and the α-type aluminum oxide film and the peel resistance are excellent.
本願発明の被覆工具の結合膜において、樹状突起はＴｉ（ＣＯ）又はＴｉ（ＣＮＯ）であり、また枝状突起は（ＴｉＡｌ）（ＣＮＯ）であることが必要である。上記の組成を有することによって樹状突起や枝状突起の先端部が針状や棒状の鋭角突起となる。また、本願発明における樹枝形状を有した結合膜の樹状突起のＬＡ値（μｍ）は、０．２≦ＬＡ≦１．５、であることが好ましい。ＬＡ値が０．２μｍ以上であることにより、樹状突起に連なる枝状突起を多数形成することに好都合となり、α型酸化アルミニウム膜との密着性向上に有効である。また、ＬＡ値が１．５μｍ以下であることにより、α型酸化アルミニウム膜の結晶粒子の粗大化を回避することに好適となり、高硬度、高密度で優れた皮膜を得ることができる。 In the bonding film of the coated tool of the present invention, the dendrite is required to be Ti (CO) or Ti (CNO), and the branch protrusion is required to be (TiAl) (CNO). That Do tip of dendrites or branched projections acicular or rod-like sharp projections by having the above composition. Further, the LA value (μm) of the dendrite of the binding membrane having a dendritic shape in the present invention is preferably 0.2 ≦ LA ≦ 1.5. When the LA value is 0.2 μm or more, it is convenient to form a large number of branch protrusions connected to the dendrite, and it is effective for improving the adhesion with the α-type aluminum oxide film. Further, when the LA value is 1.5 μm or less, it is suitable for avoiding the coarsening of the crystal grains of the α-type aluminum oxide film, and an excellent film with high hardness and high density can be obtained.
本願発明における樹状突起の長さＬＡ値と、枝状突起の長さＬＢ値は、次のように測定した。図１、２にＬＡ値を求める時の模式図を示す。図１、２の様に、樹状突起の成長基点Ｐ１から樹状突起の先端Ｐ２までを結んだ中心線を描き、この距離をＬＡ値とした。ここで樹状突起の成長基点Ｐ１は、樹状突起と下地の膜や基体とが接した点Ｐ３、Ｐ４を結んだ線の中間点とする。次に、図３にＬＢ値を求める時の模式図を示す。図３の様に、樹状突起と枝状突起との接点Ｐ５、Ｐ６を結んだ線の中間点である枝状突起の成長基点Ｐ７を求め、このＰ７と枝状突起の先端Ｐ８とを結んだ線を樹状突起の中心線と交わるまで延長させ、この交点Ｐ９を求めた。このＰ９と枝状突起先端Ｐ８との距離をＬＢ値とした。上記の測定方法により、各試料毎に任意に選んだ１０本の樹状突起を対象にしてＬＡ値（μｍ）を測定した。そして、０．２≦ＬＡ≦１．５の範囲内であるかどうかを確認した。また、ＬＡ値を測定した樹状突起を対象に、枝状突起のＬＢ値（ｎｍ）を測定した。そして、５≦ＬＢ≦２００の範囲内であるかどうかを確認した。 The dendrite length LA value and the branch-like length LB value in the present invention were measured as follows. 1 and 2 are schematic diagrams for obtaining the LA value. As shown in FIGS. 1 and 2, a center line connecting the dendrite growth base point P1 to the dendrite tip P2 was drawn, and this distance was defined as the LA value. Here, the growth base point P1 of the dendrite is an intermediate point of a line connecting the points P3 and P4 where the dendrite is in contact with the underlying film or substrate. Next, FIG. 3 shows a schematic diagram for obtaining the LB value. As shown in FIG. 3, the growth base point P7 of the branch projection, which is the midpoint of the line connecting the contact points P5 and P6 of the dendrite and the branch projection, is obtained, and this P7 is connected to the tip P8 of the branch projection. The ellipse was extended until it intersected the center line of the dendrite, and this intersection point P9 was obtained. The distance between this P9 and the branch projection tip P8 was taken as the LB value. The LA value (μm) was measured for 10 dendrites arbitrarily selected for each sample by the above measurement method. And it was confirmed whether it was in the range of 0.2 <= LA <= 1.5. Moreover, the LB value (nm) of the branch-like process was measured for the dendrite whose LA value was measured. And it was confirmed whether it was in the range of 5 <= LB <= 200.
本願発明の結合膜は、化学蒸着法（以下、ＣＶＤ法と記す。）により成膜することができる。結合膜の成膜条件を制御することにより、表面形状が樹状突起とこれに連なる枝状突起とからなる樹枝形状を得る。また、ＬＡ値、ＬＢ値を制御して、枝状突起の格子縞とα型酸化アルミニウム膜の格子縞との界面が透過電子顕微鏡の観察により連続した格子縞となるようにする。
先ず始めに、ＣＶＤ法においてキャリアーガスであるＨ２ガスと結合膜の原料ガスであるＴｉＣｌ４ガス、ＣＨ４ガス、Ｎ２ガスとＣＯガスを成膜容器内に流し、Ｔｉ（ＣＮＯ）の結合膜と針状、棒状の突起形状を有した樹状突起を形成する。針状、棒状の突起形状やＬＡ値は、ＣＨ４ガス、ＣＯガス流量、成膜温度や成膜圧力によって制御する。
次に、成膜ガスであるキャリアーガス以外の原料ガスを止め、成膜容器内圧力を高圧にし樹状突起表面に、枝状突起を形成するための起点を形成する。枝状突起の起点を形成するガスは、ＴｉＣｌ４ガス、Ｎ２ガス、ＣＯガスとＨ２キャリアーガスに、Ｃ量を多く含んだガスを使用する。Ｃ量を多く含んだガスとは、ＣＨ４ガスの代わりに、例えば組成はＣｘＨ（２ｘ＋２）のガス、但しｘ≧２、やＣＨ３ＣＨ２ＣＮを使用することができる。ＣＨ３ＣＨ２ＣＮガスはＣＨ４ガスと比べＣ量が多く、Ｔｉ（ＣＮＯ）の樹状突起表面に、枝状突起の起点を複数形成することができる。
次に、この起点から先端が鋭角形状の枝状突起を形成するために、ＡｌＣｌ３ガスを追加する。また、ＴｉＣｌ４ガス、ＣＨ３ＣＨ２ＣＮガスとＮ２ガスを徐々に少なくしてゆき、一方、ＣＯガスを徐々に多くしてゆくことで先端が鋭角形状となる枝状突起を形成することができる。この枝状突起の組成は（ＴｉＡｌ）（ＣＮＯ）である。そして、Ｔｉ（ＣＮＯ）の樹状突起と、これに連なる枝状突起の（ＴｉＡｌ）（ＣＮＯ）が成長する。また、ＬＢ値はガス流量、成膜温度や成膜時間によって制御することができる。その後、原料ガスにＣＯ２とＣＯガスの混合ガスを加え、（ＴｉＡｌ）（ＣＮＯ）の表面を強酸化状態にする。
次に、ＴｉＣｌ４ガス、ＣＨ３ＣＨ２ＣＮガスとＮ２ガスを止め、α型酸化アルミニウム膜を形成する。このとき、（ＴｉＡｌ）（ＣＮＯ）膜は強酸化状態であることから、α型酸化アルミニウム膜と格子縞が連続したエピタキシャル成長が可能となる。
The bonding film of the present invention can be formed by chemical vapor deposition (hereinafter referred to as CVD). By controlling the film forming conditions of the binding film, a dendritic shape whose surface shape is composed of dendrites and branching protrusions connected to the dendrites is obtained. Further, the LA value and the LB value are controlled so that the interface between the lattice stripes of the branch-like projections and the lattice stripes of the α-type aluminum oxide film becomes a continuous lattice stripe by observation with a transmission electron microscope.
First, H2 gas, which is a carrier gas, and TiCl4 gas, CH4 gas, N2 gas, and CO gas, which are raw material gases for the bonding film, are flowed into the film formation container in the CVD method, and the Ti (CNO) bonding film and the needle-like film A dendrite having a rod-like projection shape is formed. The needle-like and rod-like protrusion shapes and the LA value are controlled by CH4 gas, CO gas flow rate, film formation temperature and film formation pressure.
Next, the source gas other than the carrier gas, which is a film forming gas, is stopped, the pressure inside the film forming container is increased, and a starting point for forming the branch protrusions is formed on the surface of the dendrite protrusions. As the gas forming the starting point of the branch projections, a gas containing a large amount of C is used as TiCl4 gas, N2 gas, CO gas and H2 carrier gas. As the gas containing a large amount of C, for example, a gas having a composition of CxH (2x + 2), where x ≧ 2, or CH3CH2CN can be used instead of CH4 gas. The CH3CH2CN gas has a larger amount of C than the CH4 gas, and a plurality of branch protrusions can be formed on the surface of the dendrite of Ti (CNO).
Next, AlCl 3 gas is added in order to form a branch-like projection having an acute-angled tip from the starting point. In addition, branching protrusions having sharp edges can be formed by gradually reducing TiCl4 gas, CH3CH2CN gas, and N2 gas while gradually increasing CO gas. The composition of the branch protrusions is (TiAl) (CNO). Then, Ti (CNO) dendrite and branching (TiAl) (CNO) which is continuous to this grow. The LB value can be controlled by the gas flow rate, the film formation temperature, and the film formation time. Thereafter, a mixed gas of CO2 and CO gas is added to the raw material gas to bring the (TiAl) (CNO) surface into a strong oxidation state.
Next, the TiCl4 gas, CH3CH2CN gas and N2 gas are stopped to form an α-type aluminum oxide film. At this time, since the (TiAl) (CNO) film is in a strongly oxidized state, epitaxial growth in which the α-type aluminum oxide film and the lattice stripes are continuous is possible.
本願発明の被覆工具は、皮膜にＷ、Ｃｏ等の不可避の不純物を含んでいても良い。これはＣＶＤ法の場合では成膜温度が高いことから皮膜中に基体成分であるＷやＣｏを含有するためである。また、３％以下のＢ、Ｈｆ、Ｃｒ等を含有していても良く、これは皮膜の原料であるＺｒに微量のＨｆが含まれることや、更に、３％以下のＢ、Ｈｆ、Ｃｒの添加により、結晶粒径を制御することができるためである。またα型酸化アルミニウムは、必ずしも最外層である必要はない。この上層に、４ａ、５ａ、６ａ族元素の窒化物、炭窒化物、炭窒酸化物、酸化物を被覆することができる。 The coated tool of the present invention may contain inevitable impurities such as W and Co in the coating. This is because, in the case of the CVD method, since the film forming temperature is high, the base material contains W and Co in the film. Further, it may contain 3% or less of B, Hf, Cr, etc. This is because a small amount of Hf is contained in Zr which is a raw material of the film, and further, 3% or less of B, Hf, Cr. This is because the crystal grain size can be controlled by the addition. Further, the α-type aluminum oxide is not necessarily the outermost layer. This upper layer can be coated with nitrides, carbonitrides, carbonitrides and oxides of group 4a, 5a and 6a elements.
（実施例１）
質量％で、Ｃｏ：７％、Ｃｒ：０．６％、Ｚｒ：２．２％、Ｔａ：３．３％、Ｎｂ：０．２％、残ＷＣ及び不可避不純物からなる超硬合金製基体を、ＣＶＤ成膜装置内にセットした。基体は切削工具用インサート、工具形状はＣＮＭＧ１２０４０８を使用した。基体表面に１．５μｍ厚さのＴｉＮ膜を形成した。成膜条件は、Ｈ２キャリアーガス、ＴｉＣｌ４ガスとＮ２ガスとを用い、９２０℃、１２０Ｔｏｒｒであった。次に、７μｍ厚さのＴｉ（ＣＮ）膜を形成した。成膜条件は、Ｈ２キャリアーガス、ＴｉＣｌ４ガスとＣＨ３ＣＮガスとを原料ガスに用い、８５０℃、８０Ｔｏｒｒであった。次に、結合膜としてＴｉ（ＣＮＯ）膜を形成した。Ｔｉ（ＣＮＯ）膜の表面には針状、棒状の突起形状を有する樹状突起を形成した。成膜条件は、Ｈ２キャリヤーガス、ＴｉＣｌ４ガス、ＣＨ４ガス、Ｎ２ガスとＣＯガスを用い、１０００℃、８０Ｔｏｒｒであった。所定膜厚を形成した後、一旦、Ｈ２キャリアーガス以外の原料ガスを流すのをやめ、成膜装置内を１０００℃に保持したまま、圧力を５００Ｔｏｒｒにした。次に、ＴｉＣｌ４ガス、Ｎ２ガス、ＣＯガス、Ｈ２キャリアーガス、ＣＨ３ＣＨ２ＣＮガスを使用して、樹状突起表面に枝状突起を形成するための起点を形成した。続いてＡｌ金属小片を詰め３５０℃に保温した小筒中にＨ２ガスを流量３００ｍｌ／分とＨＣｌガス８０ｍｌ／分とを流すことにより発生させたＡｌＣｌ３ガスを追加して流した。また、ＴｉＣｌ４ガス、ＣＨ３ＣＨ２ＣＮガスとＮ２ガスを徐々に少なくし、一方、ＣＯガスを徐々に多くすることで（ＴｉＡｌ）（ＣＮＯ）の枝状突起を複数形成した。その後、原料ガスにＣＯ２とＣＯの混合ガスを追加し、（ＴｉＡｌ）（ＣＮＯ）を１０００℃と１００Ｔｏｒｒで形成するとともに、（ＴｉＡｌ）（ＣＮＯ）表面を強酸化状態にした。次に、ＣＯ２ガスを徐々に多くし、ＴｉＣｌ４ガス、ＣＨ３ＣＨ２ＣＮガスとＮ２ガスを止めた。その後、５μｍ厚さのα型酸化アルミニウム膜を形成した。成膜条件は、Ｈ２キャリアーガス、ＡｌＣｌ３ガス、ＣＯガス、ＣＯ２ガスとＨ２Ｓガスとを用い、１０００℃、５０Ｔｏｒｒであった。また、１μｍ厚さのＴｉ（ＣＮ）膜を形成した。成膜には、Ｈ２キャリアーガス、ＴｉＣｌ４ガス、ＣＨ４ガスとＮ２ガスを用いた。更に、１．５μｍ厚さのＴｉＮ膜形成し、本発明例１を作製した。成膜には、Ｈ２キャリアーガスとＴｉＣｌ４ガスとＮ２ガスを使用した。
Example 1
A cemented carbide substrate comprising, in mass%, Co: 7%, Cr: 0.6%, Zr: 2.2%, Ta: 3.3%, Nb: 0.2%, residual WC and inevitable impurities. And set in a CVD film forming apparatus. The base was a cutting tool insert, and the tool shape was CNMG120408. A TiN film having a thickness of 1.5 μm was formed on the surface of the substrate. The film formation conditions were 920 ° C. and 120 Torr using H 2 carrier gas, TiCl 4 gas and N 2 gas. Next, a Ti (CN) film having a thickness of 7 μm was formed. The film forming conditions were 850 ° C. and 80 Torr using H 2 carrier gas, TiCl 4 gas and CH 3 CN gas as source gases. Next, a Ti (CNO) film was formed as a coupling film. Dendrites having needle-like and rod-like projection shapes were formed on the surface of the Ti (CNO) film. Film formation conditions were 1000 ° C. and 80 Torr using H 2 carrier gas, TiCl 4 gas, CH 4 gas, N 2 gas and CO gas. After forming the predetermined film thickness, the flow of the source gas other than the H2 carrier gas was once stopped, and the pressure was set to 500 Torr while the inside of the film forming apparatus was kept at 1000 ° C. Next, using TiCl4 gas, N2 gas, CO gas, H2 carrier gas, and CH3CH2CN gas, a starting point for forming branch protrusions on the dendrite surface was formed. Subsequently, AlCl 3 gas generated by flowing H 2 gas at a flow rate of 300 ml / min and HCl gas 80 ml / min in a small tube filled with Al metal pieces and kept at 350 ° C. was added and flowed. Further, TiCl4 gas, CH3CH2CN gas, and N2 gas were gradually reduced, while CO gas was gradually increased to form a plurality of (TiAl) (CNO) branch protrusions. Thereafter, a mixed gas of CO2 and CO was added to the source gas to form (TiAl) (CNO) at 1000 ° C. and 100 Torr, and the (TiAl) (CNO) surface was brought into a strongly oxidized state. Next, CO2 gas was gradually increased, and TiCl4 gas, CH3CH2CN gas, and N2 gas were stopped. Thereafter, an α-type aluminum oxide film having a thickness of 5 μm was formed. The film forming conditions were H 2 carrier gas, AlCl 3 gas, CO gas, CO 2 gas and H 2 S gas, and 1000 ° C. and 50 Torr. A 1 μm thick Ti (CN) film was formed. For film formation, H2 carrier gas, TiCl4 gas, CH4 gas and N2 gas were used. Further, a TiN film having a thickness of 1.5 μm was formed to produce Inventive Example 1. For film formation, H2 carrier gas, TiCl4 gas and N2 gas were used.
一方、結合膜が樹枝状形状であることの効果を明らかにするため比較例４を作製した。比較例４は、結合膜の形成において樹状突起の形成工程は施したが、枝状突起の形成工程は行わなかった。即ち、比較例４は、本発明例１と同様の成膜条件をもちいて結合膜の針状や棒状の突起形状のＴｉ（ＣＮＯ）を形成した後、（ＴｉＡｌ）（ＣＮＯ）を形成することなく、α型酸化アルミニウム膜、Ｔｉ（ＣＮ）膜、ＴｉＮ膜を形成した。 On the other hand, Comparative Example 4 was prepared in order to clarify the effect of the binding membrane having a dendritic shape. In Comparative Example 4, the dendrite formation step was performed in the formation of the binding film, but the branch projection formation step was not performed. That is, in Comparative Example 4, Ti (CNO) having a needle-like or rod- like projection shape of the binding film is formed using the same film formation conditions as in Invention Example 1, and then (TiAl) (CNO) is formed. Instead, an α-type aluminum oxide film, a Ti (CN) film, and a TiN film were formed.
本発明例１、比較例４の皮膜断面を日本電子製ＪＥＭ−２０１０Ｆ型の電界放射型透過電子顕微鏡（以下、ＴＥＭと記す。）により加速電圧２００ｋＶの条件で観察した。図４は本発明例１の皮膜構成の模式図を示している。基体１から表面側に向かって、ＴｉＮ膜２、Ｔｉ（ＣＮ）膜３、結合膜４、α型酸化アルミニウム膜５、Ｔｉ（ＣＮ）膜６、ＴｉＮ膜７である。図５は、図４における結合膜４の観察写真であり、倍率２００ｋ倍で観察したＴＥＭ像である。また図６は、図５における樹状突起８の先端拡大図であり、倍率１６００ｋ倍で観察したＴＥＭ像である。図５、図６より、結合膜４とα型酸化アルミニウム膜５との界面における結合膜の表面形状が樹状突起８と、これに連なる枝状突起９とからなる樹枝形状を有していることがわかった。図７、８、９は、夫々図６における分析スポット１、２、３の極微電子回折像である。図７より分析スポット１はα型酸化アルミニウムの結晶構造であり、図８、９より、分析スポット２、３は面心立方構造であることがわかった。図１０、図１１は、図６におけるスポット４、５を倍率４０００ｋ倍で観察したＴＥＭ像である。図１０、図１１より、枝状突起とα型酸化アルミニウム膜との界面は、透過電子顕微鏡の観察により連続した格子縞を有することがわかった。一方、図１２は、比較例４の結合膜４を倍率２００ｋ倍で観察したＴＥＭ像である。また図１３は、図１２における樹状突起８の先端拡大図であり、倍率１６００ｋ倍で観察したＴＥＭ像である。図１２、図１３より、比較例４の結合膜は針形状をした樹状突起はあるが、この樹状突起とこれに連なる枝状突起とからなる樹枝形状は観察されなかった。 The film cross sections of Invention Example 1 and Comparative Example 4 were observed under the condition of an acceleration voltage of 200 kV using a JEM-2010F type field emission transmission electron microscope (hereinafter referred to as TEM) manufactured by JEOL. FIG. 4 shows a schematic diagram of the film configuration of Example 1 of the present invention. From the substrate 1 toward the surface side, there are a TiN film 2, a Ti (CN) film 3, a bonding film 4, an α-type aluminum oxide film 5, a Ti (CN) film 6, and a TiN film 7. FIG. 5 is an observation photograph of the binding film 4 in FIG. 4, which is a TEM image observed at a magnification of 200 k. FIG. 6 is an enlarged view of the tip of the dendrite 8 in FIG. 5, which is a TEM image observed at a magnification of 1600 k. 5 and 6, the surface shape of the binding film at the interface between the binding film 4 and the α-type aluminum oxide film 5 has a dendritic shape including a dendrite 8 and a branch-like projection 9 connected to the dendrite 8. I understood it. 7, 8 and 9 are micro electron diffraction images of the analysis spots 1, 2 and 3 in FIG. 6, respectively. 7 that the analysis spot 1 has an α-type aluminum oxide crystal structure, and FIGS. 8 and 9 show that the analysis spots 2 and 3 have a face-centered cubic structure. 10 and 11 are TEM images obtained by observing spots 4 and 5 in FIG. 6 at a magnification of 4000 k. 10 and 11, it was found that the interface between the branch protrusions and the α-type aluminum oxide film has continuous lattice fringes by observation with a transmission electron microscope. On the other hand, FIG. 12 is a TEM image obtained by observing the binding film 4 of Comparative Example 4 at a magnification of 200 k. FIG. 13 is an enlarged view of the tip of the dendrite 8 in FIG. 12, which is a TEM image observed at a magnification of 1600 k. From FIG. 12 and FIG. 13, the binding film of Comparative Example 4 has a needle-like dendrite, but a dendrite shape consisting of this dendrite and a branch-like projection connected thereto was not observed.
本発明例１から３、比較例４のＬＡ値μｍ、ＬＢ値ｎｍの評価を行った。本発明例１は、測定対象にした１０本の樹状突起のＬＡ値μｍは全て、０．２≦ＬＡ≦１．５の範囲内であり、また、測定対象にした樹状突起に連なる複数の枝状突起のＬＢ値ｎｍは全て、５≦ＬＢ≦２００の範囲内であった。次に、ＬＡ値の影響効果を明らかにするため準備した本発明例２、３の評価を行った。本発明例２、３は、本発明例１と同じ基体と皮膜構成であり、本発明例２は、樹状突起となるＴｉ（ＣＮＯ）の成膜時間を本発明例１の０．２倍に、本発明例３は、成膜時間を３倍にした。その後、本発明例１と同様に枝状突起の形成工程を施し、次にα型酸化アルミニウム膜、Ｔｉ（ＣＮ）膜とＴｉＮ膜を成膜した。本発明例２のＬＡ値は、成膜時間を反映して、最大値のものでも０．１μｍ程度と短いものであり、本発明例３は、最小値のものでも１．６μｍ程度と長いものであった。本発明例２、３における枝状突起とα型酸化アルミニウム膜との界面も、透過電子顕微鏡の観察により連続した格子縞を有することを確認した。 Inventive Examples 1 to 3 and Comparative Example 4 were evaluated for the LA value μm and LB value nm. In Example 1 of the present invention, the LA values μm of 10 dendrites measured are all in the range of 0.2 ≦ LA ≦ 1.5, and a plurality of dendrites connected to the dendrites measured The LB values nm of the branch projections were all in the range of 5 ≦ LB ≦ 200. Next, the inventive examples 2 and 3 prepared for clarifying the effect of the LA value were evaluated. Inventive Examples 2 and 3 have the same substrate and coating structure as Inventive Example 1, and Inventive Example 2 has a film formation time of Ti (CNO) that becomes dendrites 0.2 times that of Inventive Example 1. Furthermore, in Invention Example 3, the film formation time was tripled. Thereafter, branching protrusions were formed in the same manner as in Invention Example 1, and then an α-type aluminum oxide film, a Ti (CN) film, and a TiN film were formed. The LA value of Example 2 of the present invention reflects the film formation time, and the maximum value is as short as about 0.1 μm, and Example 3 of the present invention is as long as about 1.6 μm even if the minimum value. there were. It was confirmed that the interface between the branch-like projections and the α-type aluminum oxide film in Invention Examples 2 and 3 also had continuous lattice fringes by observation with a transmission electron microscope.
実施例２
本発明例１から３、比較例４を次の切削試験条件で評価した。切削加工は直径１６０ｍｍ、長さ６００ｍｍの丸棒材を連続加工し、工具刃先の酸化アルミニウム膜が剥離した時を工具寿命と判定した。刃先は倍率１００倍の光学顕微鏡で観察した。
試験条件
被削材：ＦＣＤ８００
加工方法：長手方向連続切削
工具形状：ＣＮＭＧ１２０４０８
切削速度：１５０ｍ／分
送り量：０．４０ｍｍ／回転
切込み量：３．０ｍｍ
切削液：湿式加工
Example 2
Invention Examples 1 to 3 and Comparative Example 4 were evaluated under the following cutting test conditions. In the cutting process, a round bar having a diameter of 160 mm and a length of 600 mm was continuously processed, and when the aluminum oxide film on the tool edge was peeled off, the tool life was determined. The cutting edge was observed with an optical microscope having a magnification of 100 times.
Test conditions Work material: FCD800
Machining method: Longitudinal continuous cutting Tool shape: CNMG120408
Cutting speed: 150 m / min Feed amount: 0.40 mm / rotation Cutting depth: 3.0 mm
Cutting fluid: wet machining
本発明例１から３は、夫々工具寿命が１６分、１２分、８分であった。これに対し、比較例４は４分であったことから、本発明例は比較例に対して工具寿命が２倍以上長く優れていた。これは、本発明例のＬＢ値が５≦ＬＢ≦２００を満たし、結合膜の表面形状が樹状突起と、これに連なる枝状突起とからなる樹枝形状を有していることから、酸化アルミニウム膜への突起が強く食い込み、アンカー効果が最大となって皮膜の密着性が優れていたためである。また枝状突起とα型酸化アルミニウム膜との界面は、連続した格子縞を有していることから、エピタキシャル成長により結晶サイズでも格子間の密着性が最大となっているためである。上記によって、切削時に酸化アルミニウム膜の密着性が高くなり、結晶粒の脱落も無く優れた工具寿命が得られた。
本発明例１から３を比較すると、ＬＡ値が０．２≦ＬＡ≦１を満たす本発明例１は、本発明例２と比較して、工具寿命が１．５倍以上長く優れていた。これは、本発明例１の樹枝形状、特にＬＡ値が十分な大きさを持ち、酸化アルミニウム膜へのアンカー効果が高く、密着性が優れていたためである。また、本発明例１は本発明例３と比較して、工具寿命が２倍以上長く優れていた。これは、本発明例１の酸化アルミニウム膜の結晶粒が粗大化することなく、結晶粒の脱落も無かったためである。比較例４は、４分間連続切削した時に酸化アルミニウム膜が剥離し工具寿命に至った。これは、比較例４の結合膜は針状や棒状の突起であったものの樹枝形状を有していないため、酸化アルミニウムの密着性が劣ったためである。
Inventive Examples 1 to 3 had tool lifes of 16 minutes, 12 minutes, and 8 minutes, respectively. On the other hand, since the comparative example 4 was 4 minutes, the example of this invention was excellent in the tool life 2 times or more with respect to the comparative example. This is because the LB value of the example of the present invention satisfies 5 ≦ LB ≦ 200, and the surface shape of the binding film has a dendritic shape composed of a dendritic protrusion and a branching protrusion connected to the dendritic protrusion. projections to the membrane bite strong anchoring effect is due to excellent adhesion of the film becomes the maximum. This is because the interface between the branch-like projections and the α-type aluminum oxide film has continuous lattice stripes, so that the adhesion between the lattices is maximized even in the crystal size by epitaxial growth. By the above, the adhesiveness of the aluminum oxide film became high at the time of cutting, and an excellent tool life was obtained without crystal grains falling off.
When Invention Examples 1 to 3 were compared, Invention Example 1 satisfying the LA value of 0.2 ≦ LA ≦ 1 was superior to Invention Example 2 in that the tool life was 1.5 times longer. This is because the dendritic shape of Example 1 of the present invention, in particular, the LA value was sufficiently large, the anchor effect to the aluminum oxide film was high, and the adhesion was excellent. In addition, the inventive example 1 was superior to the inventive example 3 in that the tool life was more than twice as long. This is because the crystal grains of the aluminum oxide film of Invention Example 1 did not become coarse and the crystal grains did not fall off. In Comparative Example 4, the aluminum oxide film peeled off when cutting continuously for 4 minutes, and the tool life was reached. This is because the bonding film of Comparative Example 4 was a needle-like or rod-like protrusion but did not have a dendritic shape, and therefore the adhesion of aluminum oxide was inferior.
１：基体
２：ＴｉＮ膜
３：Ｔｉ（ＣＮ）膜
４：結合膜
５：α型酸化アルミニウム膜
６：Ｔｉ（ＣＮ）膜
７：ＴｉＮ膜
８：樹状突起
９：枝状突起
Ｐ１：樹状突起の成長基点
Ｐ２：樹状突起の先端
Ｐ３：樹状突起と下地膜との接点
Ｐ４：樹状突起と下地膜との接点
Ｐ５：樹状突起と枝状突起との接点
Ｐ６：樹状突起と枝状突起との接点
Ｐ７：枝状突起の成長基点
Ｐ８：枝状突起の先端
Ｐ９：Ｐ７とＰ８とを結んだ線と樹状突起中心線との交点
1: Substrate 2: TiN film 3: Ti (CN) film 4: Bonding film 5: α-type aluminum oxide film 6: Ti (CN) film 7: TiN film 8: Dendritic protrusion 9: Branched protrusion P1: Dendritic Growth point of protrusion P2: Tip of dendrite P3: Contact point between dendrite and base film P4: Contact point between dendrite and base film P5: Contact point between dendrite and branch P6: Dendrite P7: Branch projection growth base point P8: Branch projection tip P9: Intersection of the line connecting P7 and P8 and the dendrite center line
Claims (2)
該結合膜と該α型酸化アルミニウム膜との界面における該結合膜の表面形状が樹状突起とこれに連なる枝状突起とからなる樹枝形状を有し、該枝状突起の長さ（ｎｍ）をＬＢとしたとき、５≦ＬＢ≦２００、であり、該枝状突起の格子縞と該α型酸化アルミニウム膜の格子縞との界面は透過電子顕微鏡の観察により連続した格子縞を有してエピタキシャル成長しており、
該結合膜の該樹状突起はＴｉ（ＣＯ）又はＴｉ（ＣＮＯ）であり、該枝状突起は（ＴｉＡｌ）（ＣＮＯ）であることを特徴とする被覆工具。 Single layer of any one of carbides, nitrides, carbonitrides, oxides, carbonates, nitrides and carbonitrides of the elements selected from the metals in the periodic table 4a, 5a, and 6a on the substrate surface In a coated tool in which a film or two or more kinds of multilayer films are formed, and an α-type aluminum oxide film is formed on the upper layer of the film via a bonding film,
The surface shape of the binding film at the interface between the binding film and the α-type aluminum oxide film has a dendritic shape composed of dendrites and branching protrusions connected thereto, and the length (nm) of the branching protrusions. the when the LB, 5 ≦ LB ≦ 200, an interface between the plaid plaid and the α-type aluminum oxide film of the branches like protrusions and closed to epitaxially grow a continuous lattice fringes by observation of a transmission electron microscope And
Coated tools dendritic projections of the coupling film is Ti (CO) or Ti (CNO), the branches like projections, characterized in (TiAl) (CNO) der Rukoto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008009958A JP5303732B2 (en) | 2008-01-21 | 2008-01-21 | Coated tool |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008009958A JP5303732B2 (en) | 2008-01-21 | 2008-01-21 | Coated tool |
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| JP2009166216A JP2009166216A (en) | 2009-07-30 |
| JP5303732B2 true JP5303732B2 (en) | 2013-10-02 |
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| JP2008009958A Active JP5303732B2 (en) | 2008-01-21 | 2008-01-21 | Coated tool |
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| US11534835B2 (en) | 2018-01-29 | 2022-12-27 | Kyocera Corporation | Coated tool and cutting tool including same |
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| JP3901477B2 (en) * | 2001-08-21 | 2007-04-04 | 日立ツール株式会社 | Aluminum oxide coated tool |
| JP3818961B2 (en) * | 2002-12-17 | 2006-09-06 | 日立ツール株式会社 | Aluminum oxide coated tools |
| JP4713137B2 (en) * | 2004-11-29 | 2011-06-29 | 京セラ株式会社 | Surface covering member and cutting tool |
| JP4711714B2 (en) * | 2005-03-30 | 2011-06-29 | 京セラ株式会社 | Surface coated cutting tool |
| WO2007122859A1 (en) * | 2006-03-28 | 2007-11-01 | Kyocera Corporation | Cutting tool, method for producing same and cutting method |
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| US11517966B2 (en) | 2018-01-29 | 2022-12-06 | Kyocera Corporation | Coated tool, and cutting tool comprising same |
| US11534835B2 (en) | 2018-01-29 | 2022-12-27 | Kyocera Corporation | Coated tool and cutting tool including same |
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| US11911829B2 (en) | 2018-11-29 | 2024-02-27 | Kyocera Corporation | Coated tool and cutting tool including same |
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