JP7240045B2 - AlCr oxidation-resistant wear-resistant coating and its coating - Google Patents

Description

The present invention provides an AlCr oxidation wear-resistant coating comprising an aluminum chromium oxynitride film laminated on at least part or all of the surface of a base material, and applying the AlCr oxidation wear-resistant coating to at least part or all of the surface of the base material. It relates to coated articles such as fully coated tools.

Cemented carbide and high-strength materials are used for cutting tools such as drills and end mills, mold tools such as punches, dies, and presses, and cutting tools used for processing metal and non-metal workpieces at production sites. Speed tool steel is used. In order to further increase the durability of the base material made of these materials, it is mostly used as a tool provided with a coated portion in which a coating is laminated on at least part or all of the surface of the base material.
Among the above coatings, non-oxide coatings such as titanium nitride (TiN), titanium aluminum nitride (TiAlN), chromium nitride (CrN), aluminum chromium nitride (AlCrN), and titanium carbonitride (TiCN) are dense and adhere well. Due to its good and stable performance, it is used for tools that perform various processing. Also, by adding various additive elements, performances such as wear resistance, impact resistance, adhesion resistance, lubricity, etc., have been imparted according to the purpose of processing and have been used.

In recent years, there has been a remarkable increase in the strength of materials, regardless of whether they are metals or non-metals. When machining difficult-to-cut materials, the cutting edge temperature of cutting tools can reach nearly 1000°C, and there are increasing cases where sufficient performance cannot be obtained with non-oxide coatings due to problems with heat resistance and oxidation resistance.

Various attempts have been made to coat an oxide film over the non-oxide film in order to supplement the performance of the non-oxide film described above. In particular, with respect to aluminum oxide, JP-A-2001-522725 (Patent Document 1) uses a γ-type aluminum oxide coating, and JP-A-07-216549 (Patent Document 2) uses an α-type aluminum oxide coating. Their effectiveness has been demonstrated.
However, α-type aluminum oxide has a corundum-type (hcp) crystal structure, and although it has high hardness and thermal stability, it has the drawback that crystal grains tend to coarsen and cracks tend to develop during cutting. In addition, γ-type aluminum oxide has a spinel-type (fcc) crystal structure and has fine crystal grains, but has the drawback of being lower in hardness and inferior in thermal stability than α-type.

It is necessary to compensate for the drawbacks of these α-type aluminum oxide and γ-type aluminum oxide. In Japanese Patent No. 4921984 (Patent Document 3), an attempt is made to reduce deterioration in wear resistance due to crack growth by arranging γ-type aluminum oxide in a multi-layered structure. However, γ-type aluminum oxide alone is an unstable oxide, and even a γ-type aluminum oxide multilayer structure is inevitably unstable.
In addition, in Japanese Patent No. 5074772 (Patent Document 4), a multi-layer structure of α-type aluminum oxide and γ-type aluminum oxide is used to suppress coarsening of crystal grains of α-type aluminum oxide, thereby improving wear resistance and chipping resistance. Attempts are being made to improve it. However, as described above, the γ-type aluminum oxide multilayer structure is an unstable oxide, and even a multilayer structure cannot avoid instability.

Furthermore, in Japanese Patent Application Publication No. 2019-522721 (Patent Document 5), a multilayer structure in which an oxynitride layer of aluminum oxynitride and a nitride layer of aluminum nitride are laminated in two stages, and alternating layers with a thickness of 0.1 μm to 1 μm are laminated many times. Attempts have been made to improve wear resistance by forming However, the multilayer structure is a multilayer structure in which an oxynitride layer and a nitride layer are alternately laminated, and the oxynitride layer and the nitride layer, which are different compound layers, are interfacially bonded to form a multilayer structure. Become. In other words, since the interfacial bonding is performed between oxynitride and nitride, which are different compounds, there is a drawback that the bonding strength is considerably weaker than the bonding strength between the same compounds. In other words, since it has a repeated multi-layered structure of oxynitride layers and nitride layers, there is a drawback that sufficient wear resistance and oxidation resistance cannot be obtained.
In addition, since the alternating layers are as thick as 0.1 μm to 1 μm, the thicknesses of the oxynitride layer and the nitride layer forming the alternating layers are also increased. Therefore, the bonding between the oxynitride layer and the nitride layer, which are adjacent foreign substances, is only at the contact surface, and the bonding force does not reach the inside of the thick layer, and the oxynitride layer and the nitride layer are bonded together. There is a weak point that the bonding force between layers is weaker. In addition, since the alternating layers of considerable thickness are laminated many times, there is a drawback that the adhesion as a whole is reduced by the number of times.
Thus, when different compound layers such as oxide and nitride, oxynitride and nitride, or oxynitride and oxide are stacked many times, there is a concern that the adhesion between the layers may decrease. , as a whole, sufficient wear resistance cannot be obtained. That is, as the number of uses increases, the layer will flake off and wear out.

Japanese Patent Publication No. 2001-522725 JP-A-07-216549 Patent No. 4921984 Patent No. 5074772 Japanese Patent Publication No. 2019-522721

SUMMARY OF THE INVENTION The present invention has been devised to overcome the drawbacks of the above-mentioned conventional examples. First, the present invention realizes an AlCr oxidation-resistant and wear-resistant coating composed of an aluminum chromium oxynitride coating in which oxidation-resistant aluminum oxide and wear-resistant chromium nitride are crystallized in a mixed crystal state. Chromium nitride reinforces the weak points of aluminum oxide, and aluminum oxide reinforces the weak points of chromium nitride. Therefore, as the aluminum oxide, either α-type or γ-type can be used depending on the application. However, it is preferable to use α-type aluminum oxide because α-type aluminum oxide alone has higher stability.
Secondly, this aluminum chromium oxynitride film (hereinafter referred to as oxynitride film) is a super multilayer in which a large number of nano-order thin aluminum chromium oxynitride unit layers (hereinafter referred to as oxynitride unit layers) are laminated. Configure with structure. Since the multiple oxynitride unit layers are aluminum chromium oxynitride unit layers with slightly different composition ratios, it has a super multilayer structure in which multiple oxynitride unit layers of the same kind of compound are laminated. Therefore, since adjacent unit layers are compound layers of the same kind, the bonding strength between the layers is much stronger than that between different compound layers. Further, when the unit layer thickness is reduced, the contact surfaces are connected by atomic force, and the atomic force acts even inside the unit layer. Therefore, adjacent unit layers are strongly bonded together by atomic force, realizing a super-multilayer structure in which extremely strong integral bonding is achieved. As a result, an AlCr oxidation-resistant and wear-resistant coating having higher oxidation resistance and wear resistance than those of the prior art can be realized.
Therefore, a cutting tool/die provided with the AlCr oxidation-resistant and wear-resistant coating is realized.
In addition, such coatings include not only coatings covering the entire surface of the base material, but also coatings that are partially uncoated or partially different in lamination form.

A first embodiment of the present invention is a coating composed of oxynitrides of aluminum and chromium that covers and protects at least a part or all of the surface of a substrate, and in the composition formula AlaCrbMcOdNe of the coating, the composition ratio a, b, c, d and e are atomic ratios, 0.2≤a≤0.45, 0.02≤b≤0.2, 0≤c≤0.2, 0.15≤d≤0.5, 0.1≤e≤0.4 and a+b+c +d + e = 1 is satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M is added or not added, and the composition ratio The coating is composed of an oxynitride super multilayer coating in which at least two or more types of oxynitride unit layers with different combinations of a, b, c, d, and e are laminated periodically or substantially periodically, and the coating is oxidation resistant. It is an AlCr oxidation-resistant and wear-resistant coating characterized by having high strength and wear resistance.

A second form of the present invention is the AlCr oxidation-resistant and wear-resistant coating in the first form, wherein the unit layer thickness of the oxynitride unit layer is 0.5 nm to 50 nm.

A third aspect of the present invention is the AlCr oxidation-resistant and wear-resistant coating according to the first or second aspect, wherein the crystal structure of the oxynitride unit layer is α-type aluminum oxide.

A fourth form of the present invention is the AlCr oxidation-resistant and wear-resistant coating according to any one of the first to third forms, wherein the oxynitride super-multilayer coating has a thickness of 0.2 μm to 10 μm.

A fifth form of the present invention is any one of the first to fourth forms, wherein an oxynitride gradient layer is provided between the base material and the oxynitride super multilayer coating, and the oxynitride gradient layer has a composition formula of AlaCrbMcOdNe and the composition ratios a, b, c, d, and e are atomic ratios, 0.2 ≤ a ≤ 0.45, 0.02 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.2, 0
≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4 and a + b + c + d + e = 1 are satisfied, M is an additive element of one or more types of Si, Hf, B and M, with or without addition,
The oxynitride gradient layer is characterized in that the composition ratios a, b, c, d, and e between the base material and the oxynitride super multilayer coating gradually change within the range of the composition ratio. In the case of the oxynitride gradient continuous film in which the composition ratios a, b, c, d, and e are graded while continuously changing, the composition ratios a, b, c, and d are used in the oxynitride gradient layer. The AlCr oxidation-resistant and wear-resistant coating is characterized by including at least the case of an oxynitride-graded multilayer coating in which two or more types of oxynitride-graded unit layers are laminated in which the combination of , e changes in a graded manner.

A sixth aspect of the present invention is any one of the first to fourth aspects, wherein an intermediate layer is provided between the substrate and the oxynitride super multilayer coating, and the intermediate layer is represented by the composition formula AlfCrgMhNi. Nitride film, composition ratio f, g, h, i is atomic ratio, 0.25≦f≦0.6, 0.1≦g≦0.37, 0≦h≦0.2, 0.15≦i≦0.57 and f+g+h Satisfying +i=1, M is an additive element of one or more of Si, Hf, and B, and AlCr oxidation wear resistance including the case where the additive element M is added and the case where it is not added It is a coating. In addition, depending on the compatibility with the selected base material, known coating techniques such as titanium nitride coating (TiN), titanium aluminum nitride coating (TiAlN), chromium nitride coating (CrN), etc. may be used as intermediate layers. .

According to a seventh aspect of the present invention, in the sixth aspect, the intermediate layer includes at least two types of nitrided unit layers having different combinations of the composition ratios f, g, h, and i periodically or substantially periodically. This is an AlCr oxidation-resistant and wear-resistant coating composed of laminated nitrided super multilayer coatings. In addition, depending on the affinity with the selected base material, titanium nitride coating (TiN), titanium aluminum nitride coating (TiAlN), chromium nitride coating (CrN), etc., which are known coating technologies, can be used as a nitride super multilayer coating as an intermediate layer. may be configured.

According to an eighth aspect of the present invention, in the sixth aspect, the intermediate layer is configured by laminating a first intermediate layer and a second intermediate layer, the first intermediate layer is configured by the nitride film, and the 2 The intermediate layer is an AlCr oxidation and wear resistant AlCr oxidation wear resistant coating composed of a nitrided super multilayer coating in which at least two types of nitrided unit layers having different combinations of the composition ratios f, g, h, and i are laminated periodically or substantially periodically. It is a sexual membrane. In addition, depending on the affinity with the selected base material, known coating techniques such as titanium nitride coating (TiN), titanium nitride aluminum coating (TiAlN), chromium nitride coating (CrN), etc. may be used for the first intermediate layer and the second intermediate layer. It may be configured as a layer.

A ninth form of the present invention is any one of the sixth to eighth forms, wherein a nitrided gradient layer is provided between the base material and the intermediate layer, the nitrided gradient layer has a composition formula AlfCrgMhNi, and has a composition The ratios f, g, h, and i are atomic ratios, satisfying 0.25≤f≤0.6, 0.1≤g≤0.37, 0≤h≤0.2, 0.15≤i≤0.57 and f+g+h+i=1. and M is an additive element of one or more of Si, Hf, and B, and the additive element M may or may not be added. It is an AlCr oxidation-resistant and wear-resistant coating in which the composition ratios f, g, h, and i between the intermediate layers change gradually within the range of the composition ratios. In addition, depending on the affinity with the selected base material, titanium nitride coating (TiN), titanium aluminum nitride coating (TiAlN), chromium nitride coating (CrN), etc., which are known coating technologies, may be used as a nitride gradient layer as an intermediate layer. You can

A tenth form of the present invention is the ninth form, wherein the nitrided graded layer is a nitrided graded continuous coating in which the composition ratios f, g, h, and i are graded while continuously changing, or The AlCr oxidation-resistant and wear-resistant coating is a nitrided-gradient multi-layer coating in which two or more types of nitrided-gradient unit layers with composition ratios f, g, h, and i varying in combination are laminated. In addition, depending on the compatibility with the selected base material, known coating technologies such as titanium nitride coating (TiN), titanium nitride aluminum coating (TiAlN), chromium nitride coating (CrN), etc. A multi-layer coating may be used as an intermediate layer.

An eleventh form of the present invention is any one of the sixth to tenth forms, wherein an oxynitride gradient layer is provided between the intermediate layer and the oxynitride super multilayer coating, and the oxynitride gradient layer has a composition formula of AlaCrbMcOdNe and the composition ratios a, b, c, d, and e are atomic ratios, 0.2 ≤ a ≤ 0.45, 0.02 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.2, 0 ≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4 and satisfies a+b+c+d+e=1, M is an additive element of one or more of Si, Hf, and B, and the additive element M is added or not added wherein the composition ratios a, b, c, d, and e between the intermediate layer and the oxynitride super multilayer coating change gradually within the range of the composition ratios. AlCr oxidation resistant wear resistant coating.

A twelfth form of the present invention is the eleventh form, wherein the oxynitride gradient layer is a continuous oxynitride gradient coating in which the composition ratios a, b, c, d, and e are graded while continuously changing. Or an AlCr oxidation-resistant and wear-resistant coating, which is an oxynitride-graded multilayer coating in which two or more types of oxynitride-graded unit layers are laminated in which the combination of the composition ratios a, b, c, d, and e changes in a graded manner. be.

A thirteenth form of the present invention is a coating characterized in that the AlCr oxidation-resistant and wear-resistant coating according to any one of the first to twelfth forms is coated on at least part or all of the surface of the substrate. be.

A fourteenth form of the present invention is, in the thirteenth form, a coating in which the base material is a hard base material, and the coating is used as a high-hardness tool.

A fifteenth form of the present invention is the fourteenth form, wherein the hard base material is selected from WC cemented carbide, cermet, ceramics, high-speed tool steel, and die steel, and the high-hardness tool are cutting tips, drills, end mills, punches, dies, cold dies, hot dies or coatings used as cutting tools.

SUMMARY OF THE INVENTION According to a first aspect of the present invention, there is provided a coating composed of aluminum and chromium oxynitrides that covers and protects at least a portion or all of the surface of a substrate. This oxynitride of aluminum and chromium is a crystal in which aluminum oxide having oxidation resistance and chromium nitride having wear resistance are in a mixed crystal state. Since it is in a mixed crystal state, an AlCr oxidation-resistant and wear-resistant coating is formed. There is a mutual relationship that aluminum oxide reinforces the weaknesses of chromium nitride and chromium nitride reinforces the weaknesses of aluminum oxide. As the aluminum oxide, α-type, γ-type, or a mixed type of α-type and γ-type is selected according to its use.
In the composition formula AlaCrbMcOdNe of the coating, the composition ratios a, b, c, d, and e are atomic ratios, and 0.2 ≤ a ≤ 0.45, 0.02 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.2, 0.15 ≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4 and a + b + c + d + e = 1 are satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M is added and not added. It indicates that the composition ratio of c is 0≦c≦0.2 including “0”, including the case where it is not added. At this time, it is considered that the addition of the additive element M to the aluminum chromium oxynitride exerts the effect of suppressing the coarsening of the crystal grains. That is, as the crystal grains become finer, compressive stress is applied to the crystals, thereby improving wear resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.

The most important feature of the first form is the oxynitride super multilayer coating in which at least two or more types of oxynitride unit layers with different combinations of the composition ratios a, b, c, d, and e are laminated periodically or substantially periodically. It is to constitute the coating. Accordingly, the vertically adjacent unit layers are made of aluminum chromium oxynitride with different composition ratios, and thus are unit layers of the same kind of compound. Homogeneous compounds are bonded by atomic force at the contact surface between the unit layers, and since they are the same kind of compounds, the atomic force acts deeply into the unit layer. It is clear that this binding force is much stronger than that between heterogeneous compounds. In other words, adjacent unit layers are strongly bonded to each other by atomic force, and a super multilayer structure in which extremely strong integral bonding is achieved is realized. As a result, an AlCr oxidation-resistant and wear-resistant coating having higher oxidation resistance and wear resistance than those of the prior art can be realized.

Furthermore, in the first embodiment, by changing the ratio of aluminum and chromium in the target used in the film manufacturing apparatus, the combination of the composition ratios a, b, c, d, and e can be easily changed.
It is possible to easily form a super multilayer coating in which more than one type of oxynitride unit layers are stacked periodically or substantially periodically. As a result, it is characterized by improved oxidation resistance and wear resistance compared to conventional films.
Specifically, a super multilayer structure can be realized by simultaneous discharge using two or more kinds of alloy targets of aluminum and chromium. Regarding the combination of periodic lamination, if the oxynitride unit layers are A layer, B layer, C layer, and D layer, not only repeating such as A layer B layer A layer B layer, etc., but also A layer B layer C Repetition such as layer A layer B layer C layer . . . and repetition such as A layer B layer C layer D layer . Also, regarding the combination of almost periodic lamination, in the case of A layer B layer A layer A layer B layer . . .
Such cases are included. In the present invention, it is important to have a periodicity of 70% or more even if it is substantially periodic, in order to achieve the above effects of the present invention. With such an oxynitride super multilayer coating, it is possible to realize a coating having a higher degree of oxidation resistance and wear resistance than conventional ones.
In the combination of the composition ratios a, b, c, d, and e of the above coating, the composition ratios a, b, c, d, and e for realizing a more stable aluminum chromium oxynitride coating are 0.27 ≤ a ≤ 0.35, 0.07. It must be in the range of ≤b≤0.15, 0≤c≤0.2, 0.29≤d≤0.35, 0.23≤e≤0.35.

According to a second aspect of the present invention, in the first aspect, the AlCr oxidation-resistant and wear-resistant coating is preferable, wherein the unit layer thickness of the oxynitride unit layer is 0.5 nm to 50 nm. Since the unit layer thickness of the oxynitride unit layer is nano-order, the interfacial bonding force between the vertically adjacent oxynitride unit layers, which are of the same material, not only acts on the interface, but also the atomic force deep inside the unit layer. , and the structural stability of the AlCr oxynitride super multilayer coating is dramatically enhanced.

According to the third aspect of the present invention, in the first or second aspect, it is possible to realize an AlCr oxidation-resistant and wear-resistant coating in which the crystal structure of the oxynitride unit layer is α-type aluminum oxide. As described above, α-type aluminum oxide has a corundum-type (hcp) crystal structure and is characterized by high hardness and thermal stability. In this embodiment, since this α-type aluminum oxide is in a mixed crystal state with chromium nitride, both substances are in a bound state and do not separate. Therefore, since aluminum chromium oxynitride is formed while mutually reinforcing weak points, a stable AlCr oxidation-resistant and wear-resistant coating can be realized.

According to a fourth aspect of the present invention, in any one of the first to third aspects, an AlCr oxidation and wear resistant coating is realized, wherein the oxynitride super multilayer coating has a thickness of 0.2 μm to 10 μm. can be done. Since the film thickness of the oxynitride super multilayer coating applied to the substrate is 0.2 μm to 10 μm, it is possible to strongly exhibit oxidation resistance and wear resistance. Therefore, it is possible to realize a long-life AlCr oxidation-resistant and wear-resistant coating that can withstand multiple uses.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, an oxynitride gradient layer may be provided between the substrate and the oxynitride super multilayer coating, and the oxynitride gradient The composition formula and composition ratio conditions of the layers are almost the same as those of the oxynitride super multilayer coating. That is, the oxynitride graded layer has the composition formula AlaCrbMcOdNe, the composition ratios a, b, c, d, and e are atomic ratios, and 0.2≦a≦0.45, 0.02≦b≦0.2, 0≦c≦0.2, 0 ≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4 and a + b + c + d + e = 1 are satisfied, M is an additive element of one or more types of Si, Hf, B and M includes cases where it is added and cases where it is not added, and particularly regarding d, it is assumed to include the composition ratio range of 0 at% to 50 at% of the oxynitride multilayer coating (0≤d≤0.5). At this time, it is considered that the addition of the additive element M to the aluminum chromium oxynitride exerts the effect of suppressing the coarsening of the crystal grains. That is, as the crystal grains become finer, compressive stress is applied to the crystals, thereby improving wear resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.
In particular, the oxynitride graded layer is characterized in that the composition ratios a, b, c, d, and e between the base material and the oxynitride super multilayer coating gradually change within the range of the composition ratio. It is characterized by The graded oxynitride graded layer includes an oxynitride graded continuous coating in which the composition ratios a, b, c, d, and e are graded while continuously changing. It also includes an oxynitride graded multilayer coating in which two or more types of oxynitride graded unit layers are laminated in which the combination of the composition ratios a, b, c, d, and e changes in a graded manner.
In the absence of the oxynitride gradient layer, the oxynitride super multilayer coating is directly laminated on the surface of the substrate. At this time, the substrate surface and the bottom surface of the oxynitride super multilayer coating should be firmly bonded, but the chemical affinity of the bottom surface of the oxynitride super multilayer coating may be weak with respect to the substrate surface. In such a case, an oxynitride graded layer is sandwiched between them, and the composition ratio is adjusted so that the composition of the lower surface of the oxynitride graded layer is strongly bonded to the substrate surface, and the composition of the upper surface of the oxynitride graded layer is adjusted. The composition ratio can be adjusted so as to firmly bond with the lower surface of the oxynitride super multilayer coating. Then, if the composition between the lower surface and the upper surface of the oxynitride gradient layer is changed continuously or in multiple layers, AlCr oxidation-resistant AlCr oxidation-resistant films in which the base material, the oxynitride gradient layer, and the oxynitride super-multilayer coating are closely bonded in three layers can be obtained. It becomes possible to realize an abradable coating.

According to a sixth aspect of the present invention, in any one of the first to fourth aspects, an intermediate layer is provided between the substrate and the oxynitride super multilayer coating, and the intermediate layer has a composition ratio of f, g , h, and i.
The reason why the intermediate layer is provided in this embodiment is that the aluminum chromium oxynitride according to the present invention has relatively good adhesion to various substrates, but in order to further improve the adhesion, a is introduced with an aluminum chromium nitride coating as an intermediate layer. The reason for this is that the composition ratio of aluminum chromium nitride is not far from that of aluminum chromium oxynitride, and that chemical affinity improves the adhesion between layers, and that aluminum chromium oxynitride is produced in manufacturing equipment. The productivity is high because the same target as the film-forming target can be used.
From the viewpoint of adhesion between layers, the composition ratio of the intermediate layer is preferably within a range not far from the composition ratio of the oxynitride super multilayer coating. Therefore, in the composition formula AlfCrgMhNi of the nitride film forming the intermediate layer, the composition ratios f, g, h, and i are atomic ratios, and 0.25≦f≦0.6, 0.1≦g≦0.37, 0≦h≦0.2, 0.15 ≤ i ≤ 0.57 and f + g + h + i = 1 are satisfied, M is an additive element of one or more types of Si, Hf, B, and the additive element M is added Includes cases where it is not added. At this time, the additive element M is considered to have the effect of suppressing the coarsening of the crystal grains by being dissolved in the aluminum chromium nitride. Improves abrasion resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. - Titanium nitride aluminum film (TiAlN), chromium nitride film (CrN) or the like may be used as an intermediate layer. Furthermore, this nitride film may improve the adhesion between the substrate and the interface by changing the substrate bias during film formation and continuously changing the crystal structure.

According to a seventh aspect of the present invention, in the sixth aspect, the intermediate layer comprises at least two types of nitrided unit layers having different combinations of the composition ratios f, g, h, and i periodically or substantially periodically. It is possible to provide an AlCr oxidation-resistant and wear-resistant coating composed of nitrided super-multilayer coatings that are stacked in layers.
Nitride unit layers that are vertically adjacent to each other are aluminum chromium nitrides with different composition ratios, so they are unit layers of the same kind of compound. Compounds of the same kind are bonded by atomic force at the contact surfaces between the unit layers, and the atomic force acts even inside the unit layers, so that adjacent nitrided unit layers are strongly bonded by the atomic force. Therefore, an intermediate layer of a super-multilayer structure with extremely strong integral bonding can be realized.
In addition, by changing the ratio of aluminum and chromium in the target used in the apparatus for producing the coating of the present invention, it is possible to easily produce two or more nitriding unit layers with different combinations of composition ratios f, g, h, and i periodically. Alternatively, it is possible to form a super-multilayer coating layered in a substantially periodic manner.
Specifically, a super-multilayered structure can be realized by simultaneous discharge using two or more types of alloy targets of aluminum and chromium. Regarding the combination of periodic lamination, if the nitrided unit layers are E, F, G, and H layers, not only the E layer, F layer, E layer, F layer, etc., but also E layer, F layer, G layer. Repetition such as E layer F layer G layer . . . and repetition such as E layer F layer G layer H layer . In addition, the combination of approximately periodic lamination includes cases such as E layer F layer E layer E layer F layer . . . or E layer F layer G layer E layer F layer E layer . Even if it is substantially periodic, it is considered necessary to have a periodicity of 70% or more in order to exhibit the above effects of the present invention. Such a nitrided super-multilayer coating as an intermediate layer can realize a coating having a higher degree of oxidation resistance and wear resistance than conventional ones. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention.・A nitride super multi-layer coating may be formed with a titanium nitride aluminum coating (TiAlN), a chromium nitride coating (CrN), etc., and used as an intermediate layer. Furthermore, this nitride super-multilayer coating may improve the adhesion between the substrate and the interface by changing the substrate bias during film formation and continuously changing the crystal structure.

According to an eighth aspect of the present invention, in the sixth aspect, the intermediate layer is configured by laminating a first intermediate layer and a second intermediate layer, and the first intermediate layer is configured by the nitride film. , the second intermediate layer is an AlCr oxidation-resistant AlCr oxidation-resistant coating composed of a nitrided super multilayer coating in which at least two or more types of nitrided unit layers having different combinations of the composition ratios f, g, h, and i are laminated periodically or substantially periodically A wear resistant coating can be provided. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. The first intermediate layer and the second intermediate layer may be composed of a titanium aluminum nitride film (TiAlN), a chromium nitride film (CrN), or the like, and used as the intermediate layer.
As described above, in the sixth embodiment, the intermediate layer is composed of a nitride coating, and in the seventh embodiment, the intermediate layer is composed of a nitride super multilayer coating. In this eighth embodiment, the intermediate layer is divided into a first intermediate layer and a second intermediate layer, the first intermediate layer is composed of a nitride coating, and the second intermediate layer is composed of a nitride super multilayer coating. The nitride coating can also be a continuous coating of nitride. By adopting a two-stage lamination structure in this way, it is possible to widen the variety of intermediate layers so as to meet various conditions. Further, by changing the substrate bias at the time of film formation of each or either of the first intermediate layer and the second intermediate layer, and continuously changing the crystal structure, the adhesion between the substrate and the interface is improved. can be

According to the ninth aspect of the present invention, in any one of the sixth to eighth aspects, a nitrided gradient layer may be provided between the base material and the intermediate layer, and the composition formula of the nitrided gradient layer and The conditions for the composition ratio are the same as those for the nitride film of the intermediate layer. That is, the graded nitriding layer has the composition formula AlfCrgMhNi, the composition ratios f, g, h, and i are atomic ratios, and 0.25≦f≦0.6, 0.1≦g≦0.37, 0≦h≦0.2, 0.15≦i≦. 0.57 and f + g + h + i = 1 are satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M is added and not added. include. At this time, the additive element M is considered to have the effect of suppressing the coarsening of the crystal grains by being dissolved in the aluminum chromium nitride. It is thought that the abrasion resistance is improved. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.
In particular, the nitrided gradient layer is characterized in that the composition ratios f, g, h, and i between the base material and the intermediate layer change gradiently within the range of the composition ratios. The nitrided graded layer that changes in a gradient includes a nitrided graded continuous film in which the composition ratios f, g, h, and i are graded while continuously changing, and the composition ratios f, g, h, and i It includes at least a nitrided gradient multilayer coating in which two or more types of nitrided gradient unit layers whose combination changes in a gradient are laminated. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention.・A titanium nitride aluminum film (TiAlN), a chromium nitride film (CrN), etc. may be used as an intermediate layer to form a nitride gradient layer.
In the absence of the nitrided graded layer, the intermediate layer is laminated directly to the surface of the substrate. At this time, the surface of the base material and the lower surface of the intermediate layer should be strongly bonded, but the lower surface may have a weak chemical affinity with the surface of the base material. In such a case, a nitrided graded layer is sandwiched between them, and the composition ratio is adjusted so that the composition of the lower surface of the nitrided graded layer is strongly bonded to the substrate surface, and the composition of the upper surface of the nitrided graded layer is adjusted to that of the intermediate layer. The composition ratio is adjusted so as to firmly bond with the lower surface. By changing the composition between the lower surface and the upper surface of the nitrided gradient layer continuously or in multiple layers, an AlCr oxidation-resistant and wear-resistant coating in which the base material, the nitrided gradient layer, and the intermediate layer are closely bonded in three layers can be realized. can do.

According to the tenth form of the present invention, in the ninth form, the nitrided gradient layer is a nitrided gradient continuous coating in which the composition ratios f, g, h, i are graded while continuously changing, Alternatively, it is possible to provide an AlCr oxidation-resistant and wear-resistant coating which is a nitrided-graded multi-layer coating in which two or more types of nitrided-graded unit layers in which the combination of the composition ratios f, g, h, and i changes in a graded manner are laminated. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention.・A titanium nitride aluminum film (TiAlN), a chromium nitride film (CrN), etc. may be used as an intermediate layer to form a nitride gradient layer.
The nitride gradient continuous coating is a nitride coating deposited while the composition ratio is continuously graded, and does not have multi-layered properties. On the other hand, the graded nitrided multilayer coating is a nitrided coating in which nitrided graded unit layers are stacked in multiple layers, and the composition ratio within a single nitrided graded unit layer changes in a graded manner as it is stacked. .

According to the eleventh form of the present invention, in any one of the sixth to tenth forms, an oxynitride gradient layer is provided between the intermediate layer and the oxynitride super multilayer coating, and the oxynitride gradient layer has a composition It has the formula AlaCrbMcOdNe, the composition ratios a, b, c, d, e are atomic ratios, 0.2≤a≤0.45, 0.02≤b≤0.2, 0
≦c≦0.2, 0≦d≦0.5, 0.1≦e≦0.4 and a+b+c+d+e=1, and M is at least one additive element selected from Si, Hf, and B and the additive element M includes cases where it is added and cases where it is not added, and particularly regarding d, the composition ratio range of the oxynitride multilayer coating is from 0 at% to 50 at% (0 ≤ d
≤ 0.5). At this time, it is considered that the addition of the additive element M to the aluminum chromium oxynitride exerts the effect of suppressing the coarsening of the crystal grains. That is, as the crystal grains become finer, compressive stress is applied to the crystals, thereby improving wear resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element M.
is not limited by the addition of The feature of the oxynitride gradient layer is that between the intermediate layer and the oxynitride super multilayer coating, the composition ratios a, b, c, d, and e change gradiently within the range of the composition ratio. It is possible to provide a chemical wear-resistant coating.
The oxynitride graded layer that changes in a graded manner includes an oxynitride graded continuous film that grades while the composition ratios a, b, c, d, and e change continuously. It also includes an oxynitride graded multilayer coating in which two or more types of oxynitride graded unit layers whose combination of the composition ratios a, b, c, d, and e change in a graded manner are laminated. Other oxynitride graded layers are also included.
In the absence of the oxynitride graded layer, the oxynitride super multilayer coating is laminated directly on the surface of the intermediate layer. At this time, the surface of the intermediate layer and the lower surface of the oxynitride super multilayer coating should be firmly bonded, but the chemical affinity of the lower surface of the oxynitride super multilayer coating may be weak with respect to the surface of the intermediate layer. In such a case, an oxynitride graded layer is sandwiched between them, and the composition ratio is adjusted so that the composition of the lower surface of the oxynitride graded layer is strongly bonded to the intermediate layer surface, and the composition of the upper surface of the oxynitride graded layer is adjusted. The composition ratio can be adjusted so as to firmly bond with the lower surface of the oxynitride super multilayer coating. Then, if the composition between the lower surface and the upper surface of the oxynitride graded layer is varied continuously or in multiple layers, the intermediate layer, the oxynitride graded layer, and the oxynitride super-multilayer coating are closely bonded in three layers to form an AlCr oxidation resistant layer. It becomes possible to realize an abradable coating.

According to the twelfth form of the present invention, in the eleventh form, the oxynitride gradient layer is an oxynitride gradient continuous film in which the composition ratios a, b, c, d, and e are graded while continuously changing. or AlCr oxidation wear resistance, which is an oxynitride gradient multilayer coating in which two or more types of oxynitride gradient unit layers are laminated in which the combination of the composition ratios a, b, c, d, and e changes gradiently A coating can be provided.
The oxynitride continuous gradient coating is an oxynitride coating deposited while the composition ratio is continuously graded, and does not have multi-layered properties. On the other hand, the oxynitride graded multilayer coating is an oxynitride coating in which oxynitride graded unit layers are stacked in multiple layers. It is a nitride film.

According to the thirteenth mode of the present invention, there is provided a coating in which at least part or all of the surface of the substrate is coated with the AlCr oxidation-resistant and wear-resistant coating of any one of the first to twelfth modes.
At least part of the surface of the base material may be only one side, or part of one side or both sides of the planar base material, or may be only part of the outer surface of the block-shaped base material. The entire surface of the substrate means the entire surface. A coating refers to the whole thing consisting of a base material and a coating.

According to a fourteenth aspect of the present invention, in the thirteenth aspect, there can be provided a coating in which the base material is a hard base material, and the coating is used as a high-hardness tool.
The base material includes a soft base material, a hard base material, and an ultra-hard base material. Among them, the present embodiment includes a hard base material and an ultra-hard base material. Among these coatings obtained by forming coatings on hard substrates, the present embodiment is intended for coatings used as high-hardness tools.

A fifteenth form of the present invention is the fourteenth form, wherein the hard base material is selected from WC cemented carbide, cermet, ceramics, high-speed tool steel, and die steel, and the high-hardness tool can provide a coating for use as cutting tips, drills, end mills, punches, dies, cold dies, hot dies or cutting tools.
In this embodiment, the hard base material is limited to WC cemented carbide, cermet, ceramics, high-speed tool steel or die steel, and the high-hardness tools are cutting tips, drills, end mills, punches, dies, cold metal It is characterized by being limited to molds, hot dies or cutting tools.

FIG. 1 is a first embodiment of a coating 1 according to the present invention, which is a two-stage configuration diagram of a coating 1 in which a substrate 2 is coated with an AlCr oxidation-resistant and wear-resistant coating 10 composed of an oxynitride super multilayer coating 11. is. FIG. 2 shows a second embodiment of a coating 1 according to the present invention, in which a substrate 2 is coated with an AlCr oxidation-resistant and wear-resistant coating 10 comprising an oxynitride super multilayer coating 11 and an oxynitride gradient layer 12. 1 is a three-stage configuration diagram of FIG. FIG. 3 shows a third embodiment of the coating 1 according to the present invention. It is a three-stage block diagram. FIG. 4 shows a fourth embodiment of a coating 1 according to the present invention, in which a substrate 2 is coated with an AlCr oxidation-resistant and wear-resistant coating 10 comprising an oxynitride super multilayer coating 11, an intermediate layer 13, and a nitrided gradient layer 14. FIG. 2 is a four-stage configuration diagram of the coated article 1. FIG. FIG. 5 shows a fifth embodiment of a coating 1 according to the present invention, in which an AlCr oxidation-resistant and wear-resistant coating 10 comprising an oxynitride super multilayer coating 11, an oxynitride gradient layer 12, and an intermediate layer 13 is applied to a substrate 2. FIG. 4 is a four-stage diagram of a coated coating 1; FIG. 6 shows a sixth embodiment of a coating 1 according to the present invention, an AlCr oxidation wear resistant coating 10 comprising an oxynitride super multilayer coating 11, an oxynitride graded layer 12, an intermediate layer 13 and a nitride graded layer 14. is a five-stage configuration diagram of a coating 1 in which a base material 2 is coated with. FIG. 7 shows the cases (7A) and (7B) and (7C) where the lamination of two or more types of oxynitride unit layers constituting the oxynitride super multilayer coating 11 is periodic in the present invention. 1 is a configuration diagram of an oxynitride super multilayer coating 11. FIG. FIG. 8 shows the case where the intermediate layer 13 is the nitride film 13x in the present invention (8A), the case of the nitride super multilayer film 13y (8B), and the case of the laminated film of the nitride film 13x and the nitride super multilayer film 13y. 8C is a configuration diagram of the intermediate layer 13 showing (8C). FIG. 9A and 9B show the case where the oxynitride graded layer 12 is the oxynitride graded continuous film 12x and the oxynitride graded multilayer coating 12y (9B), and the nitride graded layer 14 is the nitridation graded continuous film 14x in the present invention. FIG. 9C is a configuration diagram of the graded layers 12 and 14 showing the case (9C) and the case (9D) of the nitrided graded multilayer coating 14y. FIG. 10 is a schematic diagram of a film forming apparatus for forming the AlCr oxidation-resistant and wear-resistant coating 10 according to the present invention on the substrate 2. As shown in FIG. FIG. 11 is a list of target composition ratios used in production experimental examples of the AlCr oxidation-resistant and wear-resistant coating 10 according to the present invention and a list of coating films formed in the experimental examples in Tables 1 and 2. FIG. FIG. 12 is a film composition ratio analysis diagram obtained by analyzing the film obtained in the production experimental example of the AlCr oxidation-resistant and wear-resistant film 10 according to the present invention with an X-ray photoelectron spectrometer. FIG. 13 is a binding energy diagram of aluminum in the film of the present invention obtained in a production experiment example of the present invention. FIG. 14 is a binding energy diagram of chromium in the film of the present invention obtained in a production experimental example of the present invention. FIG. 15 is an X-ray diffraction position diagram of aluminum oxide obtained by an X-ray diffraction apparatus for the coating of the present invention. FIG. 16 is a cross-sectional view obtained by high resolution analytical scanning electron microscopy of the coating of the present invention. FIG. 17 is a layer thickness relationship diagram per super multilayer calculated from the etching rate of the film of the present invention in X-ray photoelectron spectroscopic analysis. FIG. 18 is an illustration of cutting when a workpiece is cut with a cutting tip having the coating of the present invention. FIG. 19 is a photographic view of a cutting test using a cutting tip having the coating of the present invention and an explanatory view of crater wear. FIG. 20 is a cutting test evaluation diagram showing the correlation between the amount of crater wear and the cutting distance in the cutting test using cutting inserts having the coating of the present invention. FIG. 21 is a photograph of crater wear observed at a cutting distance of 277 m and a cutting distance of 492 m.

Embodiments of the AlCr oxidation-resistant and wear-resistant coating and coating thereof according to the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a first embodiment of a coating 1 according to the present invention, which is a two-stage configuration diagram of a coating 1 in which a substrate 2 is coated with an AlCr oxidation-resistant and wear-resistant coating 10 composed of an oxynitride super multilayer coating 11. is.
In FIG. 1A, the base material 2 is composed of a hard base material. It is formed in As an outer coating layer, an AlCr oxidation-resistant and wear-resistant coating 10 is formed, which is an oxynitride super-multilayer coating 11 in which oxynitrides of aluminum Al and chromium Cr, which are coatings of the present invention, are laminated in a super-multilayer shape. In other words, aluminum oxide and chromium nitride form a coating in a mixed crystal state, and the oxidation resistance of aluminum oxide and the wear resistance of chromium nitride are exhibited at the same time. is configured.
In the composition formula AlaCrbMcOdNe of the oxynitride super multilayer coating 11, the composition ratios a, b, c, d, and e are atomic ratios, and 0.2≤a≤0.45, 0.02≤b≤0.2, 0≤c≤0.2, 0.15≤d. ≤ 0.5, 0.1 ≤ e ≤ 0.4 and a + b + c + d + e = 1, M is an additive element of one or more of Si, Hf, and B, and the additive element M is Includes cases where it is added and cases where it is not. AlCrMON is added and AlCrON is not added. It is considered that the addition of the additive element M to aluminum chromium oxynitride exerts an effect of suppressing coarsening of crystal grains. That is, as the crystal grains become finer, compressive stress is applied to the crystals, thereby improving wear resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.
In particular, the super multilayer coating is at least two different combinations of the composition ratios a, b, c, d, and e.
It is a film in which more than one type of oxynitride unit layer (such as 11a in FIG. 7 to be described later) is stacked periodically or substantially periodically. This oxynitride super multilayer coating 11 has strong oxidation resistance and wear resistance, and in the present invention, a coating having these properties is called an AlCr oxidation-resistant and wear-resistant coating 10 .
In FIG. 1B, an AlCr oxidation-resistant and wear-resistant coating 10 is formed on the entire surface of the substrate 2 . 1C and 1D show the case where the AlCr oxidation-resistant and wear-resistant coating 10 is formed on a part of the surface of the substrate 2 . As described above, the present invention includes the case where the AlCr oxidation-resistant and wear-resistant coating 10 is formed on at least a part or the entire surface of the base material 2 at the right place.
The features of the substrate 2 and the oxynitride super-multilayer coating 11 described above, and the features of the AlCr oxidation-resistant and wear-resistant coating 10 in which at least the oxynitride super-multilayer coating 11 is arranged, are common throughout FIGS.

As will be described later with reference to FIG. 7, the unit layer thickness of the oxynitride unit layer is adjusted in the range of 0.5 nm to 50 nm. Each unit layer is made of the same kind of compound, and the thickness of the unit layer is nano-order. Therefore, the bonding force between the vertically adjacent unit layers extends between the surfaces and inside the layers, and the bonding force is extremely large. , a stable oxynitride super multilayer coating 11 having strong oxidation resistance and wear resistance is formed.
Further, as described above, in the coating of the present invention, aluminum oxide and chromium nitride constitute the coating in a mixed crystal state, so aluminum oxide and chromium nitride have a relationship of reinforcing each other's weak points. Therefore, α-type aluminum oxide or γ-type aluminum oxide can be used as aluminum oxide depending on the application. Among them, it is desirable to use α-type aluminum oxide, which has particularly high hardness and thermal stability.
Furthermore, the film thickness of the oxynitride super multilayer coating 11 according to the present invention is desirably adjusted within the range of 0.2 μm to 10 μm in order to ensure practicality as a high-hardness tool.

FIG. 2 shows a second embodiment of a coating 1 according to the present invention, in which a substrate 2 is coated with an AlCr oxidation-resistant and wear-resistant coating 10 comprising an oxynitride super multilayer coating 11 and an oxynitride gradient layer 12. 1 is a three-stage configuration diagram of FIG.
Since the substrate 2 and the oxynitride super multilayer coating 11 have been described with reference to FIG. 1, the oxynitride gradient layer 12 will be mainly described below. A feature of the second embodiment is that an oxynitride gradient layer 12 is provided between the base material 2 and the oxynitride super multilayer coating 11 . The oxynitride super multilayer coating 11 and the oxynitride gradient layer 12 as the outermost coating layer constitute the AlCr oxidation-resistant and wear-resistant coating 10 in a two-stage lamination state.
The composition formula and composition ratio conditions of the oxynitride gradient layer 12 are substantially the same as those of the oxynitride super multilayer coating 11 . That is, the oxynitride graded layer 12 has the composition formula AlaCrbMcOdNe, and the composition ratios a, b, c, d, e
is the atomic ratio, 0.2 ≤ a ≤ 0.45, 0.02 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.2, 0 ≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4
In addition, a+b+c+d+e=1 is satisfied, and particularly regarding d, the composition ratio range of 0at% to 50at% of the oxynitride multilayer coating (0≤d≤0.5) is included. M is one or more additive elements selected from Si, Hf, and B, and the additive element M may or may not be added. AlCrMON is added and AlCrON is not added. It is considered that the addition of the additive element M to aluminum chromium oxynitride exerts an effect of suppressing coarsening of crystal grains. That is, as the crystal grains become finer, compressive stress is applied to the crystals, thereby improving wear resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.
In particular, the oxynitride gradient layer 12 is characterized in that the composition ratios a, b, c, d, and e between the base material 2 and the oxynitride super multilayer coating 11 change gradually within the range of the composition ratio. characterized by As will be described later with reference to FIG.
, d, and e are continuously changed and the oxynitride gradient continuous film 12x is included. Also included is an oxynitride graded multilayer coating 12y in which two or more types of oxynitride graded unit layers (12a in FIG. 9, etc.) are laminated in which the combination of the composition ratios a, b, c, d, and e changes in a graded manner. .
In the absence of the oxynitride gradient layer 12 , the oxynitride super multilayer coating 11 is directly laminated on the surface of the substrate 2 . At this time, the upper surface of the substrate 2 and the lower surface of the oxynitride super multilayer coating 11 should be firmly bonded, but the chemical affinity of the lower surface of the oxynitride super multilayer coating 11 may be weaker than the substrate lower surface. In such a case, the oxynitride graded layer 12 is interposed therebetween, and the composition ratio is adjusted so that the composition of the lower surface of the oxynitride graded layer 12 and the upper surface of the substrate are firmly bonded, and the upper surface of the oxynitride graded layer 12 is adjusted. The composition ratio can be adjusted so that the composition of is strongly bonded to the lower surface of the oxynitride super multilayer coating 11 . By changing the composition between the bottom surface and the top surface of the oxynitride gradient layer 12 continuously or in multiple layers, the base material 2, the oxynitride gradient layer 12, and the oxynitride super-multilayer coating 11 are tightly bonded in three layers. It becomes possible to realize an AlCr oxidation-resistant and wear-resistant coating 10 .

FIG. 3 shows a third embodiment of the coating 1 according to the present invention. It is a three-stage block diagram.
A feature of the third embodiment is that an intermediate layer 13 is interposed between the substrate 2 and the oxynitride super multilayer coating 11 . Since the substrate 2 and the oxynitride super multilayer coating 11 have already been described with reference to FIG. 1, the intermediate layer 13 will be mainly described in detail.
The reason why the intermediate layer 13 is provided in the third embodiment is that the aluminum chromium oxynitride according to the present invention has relatively good adhesion to various substrates. An aluminum chromium nitride coating is introduced as an intermediate layer 13 between the super multilayer coatings 11 (ie aluminum chromium oxynitride). In other words, the composition ratio of aluminum chromium nitride is not far from that of aluminum chromium oxynitride, and due to its chemical affinity, the adhesion between layers is improved. The productivity is high because the same target can be used. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. , a titanium aluminum nitride film (TiAlN), a chromium nitride film (CrN), or the like may be used as the intermediate layer 13 .

The intermediate layer 13 has three modes. The first is a nitride coating, the second is a nitride super multilayer coating, and the third is a stack of nitride coating and nitride super multilayer coating. These are shown in FIG. 8, which will be described later.
From the viewpoint of adhesion between layers, the composition ratio of the first nitride coating is preferably in a range not far from the composition ratio of the oxynitride super multilayer coating 11 . Therefore, the composition formula of the nitride film is AlfCrgMhNi, and the composition ratios f, g, h, and i are atomic ratios, and 0.25 ≤ f ≤ 0.6, 0.1 ≤ g ≤ 0.37, 0 ≤ h ≤ 0.2, 0.15 ≤ i. ≤ 0.57 and f + g + h + i = 1 are satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M is added or not added Includes case. AlCrMN is added and AlCrN is not added. It is thought that the additive element M is dissolved in aluminum chromium nitride, and has the effect of suppressing the coarsening of crystal grains, that is, the grains become finer. expected to improve. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.
The second super multilayer nitride coating comprises a super multilayer nitride coating in which at least two types of nitride unit layers having different combinations of the composition ratios f, g, h, and i are laminated periodically or substantially periodically. . Nitride unit layers that are vertically adjacent to each other are aluminum chromium nitrides with different composition ratios, so they are unit layers of the same kind of compound. Homogeneous compounds are bonded by atomic force at the contact surfaces between the unit layers, and the atomic force acts even inside the unit layers, so that the adjacent nitrided unit layers are strongly bonded by the atomic force. Therefore, an intermediate layer 13 having a super-multilayered structure that is integrally bonded extremely strongly can be realized.
In the third multilayer coating, the intermediate layer 13 is divided into a first intermediate layer and a second intermediate layer, the first intermediate layer is composed of the nitride coating, and the second intermediate layer is composed of the nitride super multilayer coating. there is
In addition, in all of these first to third intermediate layers, depending on the compatibility with the selected substrate, known coating techniques such as titanium nitride coating (TiN), titanium aluminum nitride coating (TiAlN), and chromium nitride coating may be used. (CrN) or the like may be used as the intermediate layer 13, and the adhesion between the substrate and the interface may be improved by changing the substrate bias during film formation and continuously changing the crystal structure. good.

FIG. 4 shows a fourth embodiment of a coating 1 according to the present invention, in which a substrate 2 is coated with an AlCr oxidation-resistant and wear-resistant coating 10 comprising an oxynitride super multilayer coating 11, an intermediate layer 13, and a nitrided gradient layer 14. FIG. 2 is a four-stage configuration diagram of the coated article 1. FIG.
A feature of the fourth embodiment is that a nitride gradient layer 14 is interposed between the substrate 2 and the intermediate layer 13 . Since the base material 2, the oxynitride super multilayer coating 11 and the intermediate layer 13 have already been described with reference to FIG. 3, the nitriding gradient layer 14 will now be described in detail.
In the absence of the nitrided graded layer 14, the intermediate layer 13 is laminated directly on the upper surface of the substrate 2. FIG. At this time, the upper surface of the substrate 2 and the lower surface of the intermediate layer 13 should be strongly bonded, but the lower surface may have weak chemical affinity with the upper surface of the substrate. In such a case, the nitrided graded layer 14 is sandwiched between them, the composition ratio of the lower surface of the nitrided graded layer 14 is adjusted so as to be firmly bonded to the upper surface of the base material, and the composition of the upper surface of the nitrided graded layer 14 is adjusted to an intermediate composition. The composition ratio is adjusted so as to firmly bond with the lower surface of layer 13 . If the composition between the bottom surface and the top surface of the nitrided gradient layer 14 is varied continuously or in multiple layers, the substrate 2, the nitrided gradient layer 14, and the intermediate layer 13 can be tightly bonded in three layers.
The compositional formula and composition ratio of the nitrided graded layer 14 are the same as those of the nitride film of the intermediate layer 13 in order to achieve close bonding with the intermediate layer 13 . That is, the graded nitriding layer 14 has the composition formula AlfCrgMhNi, and the composition ratios f, g, h, and i are atomic ratios, 0.25≤f≤0.6, 0.1≤g≤0.37, 0≤h≤0.2, 0.15≤i. ≤ 0.57 and f + g + h + i = 1 are satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M is added or not added including. AlCrMN is added and AlCrN is not added. It is thought that the additive element M is dissolved in aluminum chromium nitride, and has the effect of suppressing the coarsening of crystal grains, that is, the grains become finer. expected to improve. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M.
In particular, a feature of the nitrided gradient layer 14 is that the composition ratios f, g, h, and i between the base material 2 and the intermediate layer 13 change gradiently within the range of the composition ratios. . In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. The nitrided gradient layer 14 may be formed by changing the composition of an aluminum film (TiAlN), a chromium nitride film (CrN), or the like in a gradient manner.

As for the nitrided graded layer 14, which will be described later with reference to FIG. 9, there are two types of embodiments. First, the nitrided graded layer 14 is a nitrided graded continuous film 14x in which the composition ratios f, g, h, and i are graded while continuously changing. Second, the nitrided gradient layer 14 is a nitrided gradient multi-layer film 14y in which two or more types of nitrided gradient unit layers (14a, etc.) whose combination of the composition ratios f, g, h, and i change gradiently are laminated. . The nitride gradient continuous film 14x is a nitride film deposited while the composition ratio is continuously graded, and does not have multi-layered properties. On the other hand, the graded nitrided multi-layer coating 14y is a nitrided coating in which the graded nitrided unit layers are stacked in multiple layers, and the composition ratio within a single graded nitrided unit layer changes in a graded manner as it is stacked. be. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. 14x and 14y may be composed of an aluminum coating (TiAlN), a chromium nitride coating (CrN), or the like.

FIG. 5 shows a fifth embodiment of a coating 1 according to the present invention, in which an AlCr oxidation-resistant and wear-resistant coating 10 comprising an oxynitride super multilayer coating 11, an oxynitride gradient layer 12, and an intermediate layer 13 is applied to a substrate 2. FIG. 4 is a four-stage diagram of a coated coating 1;
The three-stage configuration of the oxynitride super multilayer coating 11, the intermediate layer 13, and the base material 2 has already been described with reference to FIG. A feature of the fifth embodiment is that the oxynitride gradient layer 12 explained in FIG.
As described above, the composition of the oxynitride graded layer 12 is substantially the same as the composition of the oxynitride super multilayer coating 11 . That is, the oxynitride graded layer 12 has a composition formula of AlaCrbMcOdNe, and composition ratios a, b, c, d, and e are atomic ratios, and 0.2≦a≦0.45, 0.02≦b≦0.2, and 0≦c≦0.2. , 0 ≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4 and a+b+c+d+e=1 are satisfied, especially regarding d, from 0 at% to 50 at% of the composition ratio range of the oxynitride multilayer coating ( 0≤d≤0.5). M is an additive element of one or more of Si, Hf, and B, and the additive element M may or may not be added. AlCrMON is added and AlCrON is not added. It is considered that the addition of the additive element M to aluminum chromium oxynitride exerts an effect of suppressing coarsening of crystal grains. That is, as the crystal grains become finer, compressive stress is applied to the crystals, thereby improving wear resistance. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M. In particular, the oxynitride graded layer 12 is characterized in that the composition ratios a, b, c, d, and e are graded within the composition ratio range between the intermediate layer 13 and the oxynitride super multilayer coating 11. is to change to
If the oxynitride graded layer 12 is absent, the oxynitride super multilayer coating 11 is directly laminated on the upper surface of the intermediate layer 13 . At this time, the upper surface of the intermediate layer 13 and the lower surface of the oxynitride super multilayer coating 11 should be firmly bonded, but the chemical affinity of the lower surface of the oxynitride super multilayer coating 11 may be weak with respect to the upper surface of the intermediate layer. In such a case, the oxynitride graded layer 12 is interposed therebetween, and the composition ratio is adjusted so that the composition of the lower surface of the oxynitride graded layer 12 is firmly combined with the upper surface of the intermediate layer. The composition ratio can be adjusted so that the composition of is strongly bonded to the lower surface of the oxynitride super multilayer coating 11 . By changing the composition between the bottom surface and the top surface of the oxynitride gradient layer 12 continuously or in multiple layers, the intermediate layer 13, the oxynitride gradient layer 12, and the oxynitride super-multilayer coating 11 are tightly coupled in three layers. It becomes possible to realize an AlCr oxidation-resistant and wear-resistant coating 10 . In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. Intermediate layer 1 with aluminum coating (TiAlN), chromium nitride coating (CrN), etc.
3 may be configured.

As will be described later with reference to FIG. 9, there are two modes for the configuration of the oxynitride graded layer 12 . The first is the oxynitride gradient continuous film 12x in which the composition ratios a, b, c, d, and e are graded while continuously changing. The second is a graded oxynitride multilayer film 12y in which two or more types of oxynitride graded unit layers are laminated in which the combination of the composition ratios a, b, c, d, and e changes in a graded manner.
The continuous gradient oxynitride film 12x is an oxynitride film deposited while the composition ratio is continuously changed in gradient, and does not have multi-layered properties. On the other hand, the oxynitride graded multilayer coating 12y is an oxynitride coating in which oxynitride graded unit layers are stacked in multiple layers, and the composition ratio in a single oxynitride graded unit layer changes in a graded manner as it is stacked. It is an oxynitride film.

FIG. 6 shows a sixth embodiment of a coating 1 according to the present invention, an AlCr oxidation wear resistant coating 10 comprising an oxynitride super multilayer coating 11, an oxynitride graded layer 12, an intermediate layer 13 and a nitride graded layer 14. is a five-stage configuration diagram of a coating 1 in which a base material 2 is coated with.
As already described in detail with reference to FIG. 4, which is the fourth embodiment of the present invention, there is already a coating 1 having a four-stage configuration consisting of an oxynitride super multilayer coating 11, an intermediate layer 13, a nitrided gradient layer 14, and a substrate 2. do. The sixth embodiment can be realized only by inserting the oxynitride gradient layer 12 between the oxynitride super multilayer coating 11 and the intermediate layer 13 in the coating 1 having the four-stage structure.
Although the oxynitride gradient layer 12 has been described with reference to FIG. 5, it will be described again as the sixth embodiment. First, the composition of the oxynitride graded layer 12 is the same as the composition of the oxynitride super multilayer coating 11 . That is, the oxynitride graded layer 12 has a composition formula of AlaCrbMcOdNe, and composition ratios a, b, c, d, and e are atomic ratios, and 0.2≦a≦0.45, 0.02≦b≦0.2, and 0≦c≦0.2. , 0 ≤ d ≤ 0.5, 0.1 ≤ e ≤ 0.4 and a+b+c+d+e=1. ≤ d ≤ 0.5). M is an additive element of one or more of Si, Hf, and B, and the additive element M may or may not be added. AlCrMON is added and AlCrON is not added. It is thought that the additive element M is dissolved in aluminum chromium nitride, and has the effect of suppressing the coarsening of crystal grains, that is, the grains become finer. expected to improve. However, this is a secondary effect, and in the present invention, the above-mentioned mixed crystals of aluminum oxide and chromium nitride exhibit oxidation wear resistance, and as described above, the additive element It is not limited by the addition of M. In particular, the oxynitride graded layer 12 is characterized in that the composition ratios a, b, c, d, and e are graded within the composition ratio range between the intermediate layer 13 and the oxynitride super multilayer coating 11. is to change to In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. The intermediate layer 13 may be composed of an aluminum coating (TiAlN), a chromium nitride coating (CrN), or the like.

As will be described later with reference to FIG. 9, there are two modes for the configuration of the oxynitride graded layer 12 . The first is the oxynitride gradient continuous film 12x in which the composition ratios a, b, c, d, and e are graded while continuously changing. The second is a graded oxynitride multi-layer coating 12y in which two or more types of graded oxynitride unit layers (12a, etc.) whose combination of the composition ratios a, b, c, d, and e change in a graded manner are laminated.
The continuous gradient oxynitride film 12x is an oxynitride film deposited while the composition ratio is continuously changed in gradient, and does not have multi-layered properties. On the other hand, the oxynitride graded multilayer coating 12y is an oxynitride coating in which oxynitride graded unit layers are stacked in multiple layers, and the composition ratio in a single oxynitride graded unit layer changes in a graded manner as it is stacked. It is an oxynitride film.

FIG. 7 shows the cases (7A) and (7B) and (7C) where the lamination of two or more types of oxynitride unit layers constituting the oxynitride super multilayer coating 11 is periodic in the present invention. 1 is a configuration diagram of an oxynitride super multilayer coating 11. FIG.
FIG. 7A shows a case where two types of oxynitride unit layers forming the oxynitride super multilayer coating 11 are stacked periodically. In the figure, two kinds of oxynitride unit layers 11a and 11b are completely and periodically laminated as 11a, 11b, 11a, 11b, . . . 11a, 11b. Periodization can be similarly performed with three or four types of oxynitride unit layers.
FIG. 7B shows a case where three types of oxynitride unit layers forming the oxynitride super multilayer coating 11 are stacked in a substantially periodic manner. In the figure, three kinds of oxynitride unit layers 11a, 11b, 11c are laminated like 11a, 11b, 11a, 11b, 11c, 11a, 11b, . imperfect periodicity. Therefore, a substantially periodic stacking is shown.
FIG. 7C shows a case where the lamination of three types of oxynitride unit layers constituting the oxynitride super multilayer coating 11 is substantially periodic. In the drawing, three types of oxynitride unit layers 11a, 11b, 11c are laminated in the manner of 11a, 11b, 11c, 11a, 11b, 11a, 11b, 11c, . The layer 11c is missing and the periodicity is imperfect. Therefore, a substantially periodic stacking is shown.
In the present invention, even if the oxynitride unit layers are laminated substantially periodically, the technical effects of the present invention can be obtained as long as the periodicity is 70% or more.

FIG. 8 shows the case where the intermediate layer 13 is the nitride film 13x in the present invention (8A), the case of the nitride super multilayer film 13y (8B), and the case of the laminated film of the nitride film 13x and the nitride super multilayer film 13y. 8C is a configuration diagram of the intermediate layer 13 showing (8C). FIG.
In FIG. 8A, the entire intermediate layer 13 is composed of the nitride film 13x and does not have multilayer properties.
In FIG. 8B, the entire intermediate layer 13 is composed of the nitride super multilayer coating 13y. As the nitrided super multi-layer coating 13y, there are cases where the stacking of nitrided unit layers is periodic and cases where the nitrided unit layer is substantially periodic with a periodicity of 70% or more. In particular, FIG. (8B) shows the case where the lamination of two types of nitriding unit layers is periodic. In the figure, and are completely cyclically stacked. Three or more types of nitriding unit layers can be similarly periodicized.
Moreover, although not shown, there is also a substantially periodic case. For example, the nitride unit layer may be partially irregular such as 13a, 13b, 13c, 13a, 13b, . . . 13a, 13b. However, if there is a periodicity of 70% or more as a whole, the technical effects of the present invention can be obtained.
In FIG. 8C, the intermediate layer 13 is divided into a first intermediate layer and a second intermediate layer, the first intermediate layer is composed of the nitride film 13x of FIG. The nitride super multi-layer coating 13y of FIG. 8B is formed periodically or substantially periodically. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. 13x and 13y may be composed of an aluminum coating (TiAlN), a chromium nitride coating (CrN), or the like.

9A and 9B show the case where the oxynitride graded layer 12 is the oxynitride graded continuous film 12x and the oxynitride graded multilayer coating 12y (9B), and the nitride graded layer 14 is the nitridation graded continuous film 14x in the present invention. FIG. 9C is a configuration diagram of the graded layers 12 and 14 showing the case (9C) and the case (9D) of the nitrided graded multilayer coating 14y.
FIG. 9A shows the case where the oxynitride graded layer 12 is an oxynitride graded continuous film 12x that does not have multilayer properties. As an oxynitride, the composition ratio changes while continuously sloping from the bottom surface to the top surface.
FIG. 9B shows the case where the oxynitride graded layer 12 is an oxynitride graded multilayer film 12y having multiple layers. The oxynitride graded multilayer coating 12y has oxynitride graded unit layers 12a, 12b, . . . 12n stacked from the bottom to the top. The composition ratio inside a single oxynitride graded unit layer is the same, and the composition ratio gradually changes in a graded manner from the bottom surface to the top surface of each oxynitride graded unit layer.
FIG. 9C shows the case where the nitrided graded layer 14 is a nitrided graded continuous film 14x without multi-layers. As a nitride, the composition ratio changes while continuously sloping from the bottom surface to the top surface.
FIG. 9D shows the case where the nitrided graded layer 14 is a nitrided graded multilayer film 14y having multiple layers. The nitrided graded multilayer film 14y has nitrided graded unit layers 14a, 14b, . . . The composition ratio inside a single nitrided graded unit layer is the same, and the composition ratio gradually changes in a graded manner for each nitrided graded unit layer from the lower surface to the upper surface.

<Manufacturing method>
The product of the present invention is not subject to any restrictions in the film forming method. However, as a method for forming the film of the present invention, the film formation by the physical vapor deposition method is desirable. The physical vapor deposition method is a method that can form a dense and crystalline film, and the temperature during film formation is about 600 ° C or less, so deterioration of the base material such as iron-based annealing and tempering is suppressed. Therefore, it can be applied to a relatively wide range of materials. As other advantages, aluminum-chromium alloy targets for forming the aluminum chromium oxynitride according to the present invention are generally available and are readily available. It is mentioned that the additive element can be easily contained in the aluminum chromium oxynitride film.

Physical vapor deposition includes a sputtering method, an arc ion plating method, and the like. Since the arc ion plating method has a higher ionization rate than the sputtering method, the film formation speed is high and the productivity is also high. On the other hand, the sputtering method has the advantage of obtaining a smooth surface and improving the accuracy of the finished surface of the processed product, but the deposition rate is slow and the productivity is inferior. Either method can be used in the product of the present invention.
When the product of the present invention is formed by the arc ion plating method or other film forming methods, known specific conditions can be used without particular limitation.

Particularly in the present invention, in order to form an aluminum chromium oxynitride film capable of exhibiting oxidation resistance and wear resistance, it is preferable to form the film by the arc ion plating method among the physical vapor deposition methods. Therefore, the film is characterized by being formed by the arc ion plating method or the filtered arc ion plating method.
In the arc ion plating method (that is, the AIP method), in a vacuum atmosphere, a vacuum arc discharge is generated between a target (film forming material) that is a cathode (cathode) and an anode (anode), and the target This is a thin-film coating method in which a film is formed by evaporating and ionizing materials from the surface and depositing ions on the surface of a workpiece (object to be coated) to which a negative bias voltage is applied.
The filtered arc ion plating method (that is, the FAIP method) is a method in which droplets are removed from the vacuum arc plasma generated by the AIP method, and film formation is performed using the cleaned plasma. Generally, it is called Filtered Arc Deposition (FAD) or Filtered Arc Ion Plating (FAIP).

Examples of coating films according to the present invention and a film forming apparatus will be described in detail below.
<Coating structure: base material + intermediate layer + oxynitride super multilayer coating in Fig. 3>
The coating produced as an example of the product of the present invention is the coating of FIG. 3 described above, that is, the substrate 2+intermediate layer 13+oxynitride super multilayer coating 11 (outer layer coating layer).
Of course, the nitrided graded layer 14 may be provided below the intermediate layer 13 as shown in FIG. 4, and the oxynitride graded layer 12 may be provided above the intermediate layer 13 as shown in FIG. The nitrided graded layer 14 may be provided on the lower side of the intermediate layer 13 and the oxynitride graded layer 12 may be provided on the upper side as shown in FIG. In addition, the intermediate layer 13 is not necessarily required, and may be the substrate 2 + the oxynitride super multilayer coating 11 as shown in FIG. Of course it's good.
In the examples described later, the substrate 2 + intermediate layer 13 + oxynitride super multilayer coating 11 (outer coating layer) is used for comparison with the existing coating of the applicant of the present invention.

<Deposition equipment: Arc ion plating equipment>
FIG. 10 is a schematic diagram of a film forming apparatus for forming the AlCr oxidation-resistant and wear-resistant coating 10 according to the present invention on the substrate 2. As shown in FIG.
A known arc ion plating apparatus 20 is used as a film forming apparatus for forming the film of the present invention. An evacuation system 22 is connected to the vacuum chamber 21 . A rotary pump RP for rough evacuation, a turbo-molecular pump TMP for high evacuation, and a cryopump CP are connected to the evacuation system 22 . It can be evacuated to a film-forming ultimate vacuum (approximately 5.0×10 ^-3 Pa) or less and maintained.
The vacuum chamber 21 includes a heater 23 for heating, a filament discharge system 24 for bombardment treatment (cleaning of the substrate surface) before film formation, and an arc discharge power source 25a to extract ions from the aluminum chromium target by applying voltage. A cathode system 25 AD connected to 25d is provided. Each of the cathode systems 25 A to D can be provided with three targets in the vertical direction.
A rotating base mechanism 26 for mounting and rotating the base material 2 is mounted. In the rotation base mechanism 26, six shafts 26c rotating in the direction of arrow c are set on a large table 26a rotating in the direction of arrow a. A rotating small disk 26b is mounted on each shaft 26c, and a sprocket can be mounted on the small disk 26b to rotate in the direction of arrow b. Further, a bias power supply 26d is connected to the rotating base mechanism 26 so that a negative bias voltage can be applied. Further, a gas introduction system 27 for introducing reaction gases (nitrogen, oxygen, argon) is arranged inside the vacuum chamber 21 . The gas introduction system 27 includes a gas pipe, a gas stop valve, and a gas cylinder, and is also connected to a gas introduction port. Therefore, the amount of nitrogen and the amount of oxygen in the film can be adjusted by introducing the gas species according to need while adjusting the flow rate.

Heating at 450° C. was performed for 120 minutes using the heater 23 for heating, also serving as a degassing process that is a pre-stage of film formation. Next, as a bombardment process, argon gas was introduced so that the pressure inside the chamber was 2.6 Pa. Thereafter, a negative voltage of 40 V was applied to the filament discharge system 24 and a negative voltage of 400 to 500 V was applied to the rotating base mechanism 26 to generate plasma and clean the substrate surface.

FIG. 11 is a list of target composition ratios used in production experimental examples of the AlCr oxidation-resistant and wear-resistant coating 10 according to the present invention and a list of coating films formed in the experimental examples in Tables 1 and 2. FIG.
Table 1 shows aluminum chromium alloy targets having five different composition ratios used for forming the aluminum chromium oxynitride film of the present invention. By combining two types of targets having different composition ratios among these targets, a coating having a structure of substrate 2+intermediate layer 13+oxynitride super multilayer coating 11 (outer coating layer) as shown in FIG. 3 was formed. For the substrate 2, a square cutting tip of 12 mm×12 mm×5 mm made of SKH51 material (high-speed tool steel), which is widely used, was used.

<Film Formation of Intermediate Layer 13: Nitride Super Multilayer Coating 13y>
After cleaning the surface of the base material by bombardment, a film was formed on the base material 2 using a combination of targets shown in Table 1. First, nitrogen was introduced as a reaction gas so that the pressure inside the chamber was 5.0 Pa, and a negative voltage of 150 V was applied to the cathode system A to D to which the targets were attached, and a negative voltage of 50 V was applied to the rotating base mechanism 26 . As a result, ions are drawn out by arc discharge to deposit an aluminum chromium nitride multilayer film (that is, a nitride super multilayer film 13y) as the intermediate layer 13 on the substrate 2 .
<Deposition of Oxynitride Super Multilayer Coating 11>
After that, a mixed gas of nitrogen and oxygen was introduced as a reaction gas so that the pressure inside the chamber was 3.9 Pa, and a voltage of 150 V was applied to the cathode system A to D to which the targets were attached, and a voltage of 75 V was applied to the rotating base mechanism 26 . As a result, an aluminum chromium oxynitride super multilayer film (that is, a super multilayer oxynitride film 11) is deposited on the intermediate layer 13 as an outer film layer. At this time, the substrate rotating mechanism 26 is used to rotate the substrate, that is, the large table 26a and the small disk 26b, and the two types of targets are simultaneously arc-discharged, thereby forming a sloped layer, which is a feature of the product of the present invention. A super multilayer film can be formed. At this time, by adjusting the number of revolutions of the substrate rotation mechanism 26, it is possible to adjust the thickness of each layer of the super multilayer film. In this film formation, the number of rotations of the large table 26a and the small disc 26b, that is, the number of rotations of the substrate, was set to 2 rpm under all conditions.

In this manner, films of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 2 of FIG. 11 were formed. In Examples 1 to 5, the AlCr oxynitride layer is an AlCr oxynitride super multilayer, that is, the oxynitride super multilayer coating 11 of the present invention. In Comparative Example 1, the AlCr oxynitride layer is a single AlCr oxynitride layer, and in Comparative Example 2, the AlCr oxynitride layer is a single AlCrSi oxynitride layer, both of which are different from the present invention. Comparative Example 3 has only the intermediate layer 13 without the AlCr oxynitride layer, which is produced for comparative study, that is, the aluminum chromium nitride super multilayer coating (that is, the nitride super multilayer coating 13y). These Examples 1 to 5 and Comparative Examples 1 to 3 were formed by the above-described manufacturing method, and were formed under the same conditions except for using targets with different composition ratios. It is a thing.

12, 13, and 14 below show the aluminum chromium oxynitride film, which is the product of the present invention, analyzed with a high-performance X-ray photoelectron spectrometer (PHI5000Versa P manufactured by ULVAC-Phi).
robe) shows an example of compositional analysis data.
<Aluminum chromium oxynitride film>
FIG. 12 is a film composition ratio analysis diagram obtained by analyzing the film obtained in the production experimental example of the AlCr oxidation-resistant and wear-resistant film 10 according to the present invention with an X-ray photoelectron spectrometer. The vertical axis is the composition ratio (atomic ratio) and the horizontal axis is the etching time.
X-ray photoelectron spectroscopy is a technique that measures the kinetic energy of photoelectrons emitted from the sample surface by irradiating the sample surface with X-rays, and can obtain elemental information in a region of several nanometers from the sample surface. Therefore, it was determined that it is suitable for analyzing the super multilayer structure of the order of several nanometers to several tens of nanometers in the present invention. In this method, it is also possible to determine the chemical bonding state by observing the change in binding energy caused by the electronic bonding state around the atom to be analyzed.

The dots, dashed lines, dashed-dotted lines, and solid lines in Fig. 12-A correspond to the elements Al, Cr, O, and N, and the super-multilayer coating is formed while etching from the coating surface. A structural analysis was performed. As the graph progresses to the right, it shows the elemental composition ratio inside the super multilayer coating. Focusing on points 1 to 6 of the peaks and valleys formed by each line on the graph, each element in the range of Al: 25 to 33 at%, Cr: 7 to 17 at%, O: 19 to 45 at%, N: 15 to 35 at% the ratio is changing. That is, the vertical dotted lines drawn on the graph correspond to the 1st, 2nd, 3rd layers, etc. of the super multilayer coating, and each point of the ridges and valleys formed by each line is It shows one layer of super multi-layer coating. The composition ratio of each layer of the super multilayer structure is shown as a table in FIG. From this measurement data and cross-sectional observation by FE-SEM, which will be described later, it was identified that the product of the present invention is a super multilayer coating having a super multilayer structure. At the same time, as shown in the above table, it was possible to specify the composition ratio of each element for each layer of the super multilayer coating.
FIG. 12-B is an analysis of the film composition ratio of the product of the present invention formed by a combination of targets with the maximum Al ratio (Example 4, a combination of Al:Cr=9:1 and Al:Cr=8:2). It is a diagram. The structure of the graph is the same as that of FIG. 12-A. Focusing on points 1 to 4 of the ridges and valleys formed by each line on the graph, Al: 37 to 43 at%, Cr: 2 to 5 at%, O: 24 ∼42at%, N: 14~28at%, the ratio of each element is changed. Focusing on the ratio of Al and Cr in the target used for film formation, although there is a measurement error of about 5% due to measurement with a high-performance X-ray photoelectron spectrometer, the ratio is the ratio of Al and Cr in the film composition. It can be seen that it shows the same degree as Together with the results of FIG. 12-A, the range of element composition ratios that can constitute the AlCr oxidation-resistant and wear-resistant coating of the present invention is Al: 20 to 45 at%.
, Cr: 2 to 20 at%, O: 15 to 50 at%, and N: 10 to 40 at%.

FIG. 13 is an aluminum binding energy diagram in the film of the present invention obtained in a production experimental example of the present invention.
FIG. 13 shows the binding energy state of aluminum in the product of the present invention. The binding energy at the peak position shown in FIG. 13 is 119 (eV). According to a known database, aluminum shows 118.2 (eV) and aluminum oxide shows 119 (eV), so it can be seen that aluminum oxide is formed in the product of the present invention.

FIG. 14 is a chromium binding energy diagram in the film of the present invention obtained in a production experiment example of the present invention.
In FIG. 14, the binding energy at the peak position is around 575 (eV). On the other hand, according to a known database, chromium shows around 574 (eV), and chromium oxide and chromium nitride show around 575 (eV). As mentioned above, since aluminum oxide is formed, oxygen is believed to preferentially bond with aluminum, and chromium is believed to preferentially form chromium nitride. From these facts, it can be seen that a mixed crystal of aluminum oxide and chromium nitride is formed in the product of the present invention. Since the coating is in a mixed crystal state of aluminum oxide and chromium nitride, coarsening of crystal grains, which is a drawback of α-type aluminum oxide, is suppressed, contributing to the improvement of oxidation resistance and wear resistance. Conceivable.

From the results of the above X-ray photoelectron spectroscopic analysis, the composition ratio of the aluminum chromium oxynitride of the present invention is the composition formula AlaCrbMcOdNe (a, b, c, d, e are atomic ratios 0.2 ≤ a ≤ 0.45, 0.02 ≤ b ≤ 0.2, 0≤c≤0.2, 0.15≤d≤0.5, 0.1≤e≤0.4 and a+b+c+d+e=1). Further, as can be seen from the table of FIG. 12, more preferably, a, b, c, d, and e are 0.27≦a≦0.35, 0.07≦b≦0.15, 0≦c≦0.2, 0.29≦d≦0.35, 0.23≦ It is desirable to be in the range of e≦0.35. That is, these composition ranges are also features of the present invention. M is one or more additive elements selected from Si, Hf, and B.

FIG. 15 is an X-ray diffraction position diagram of aluminum oxide obtained by an X-ray diffraction apparatus for the coating of the present invention.
In FIG. 15, the product of the present invention is shown in an X-ray diffractometer (D2 manufactured by Bruker AXS).
PHASER) analysis results are shown. X-ray diffraction is a diffraction phenomenon that occurs as a result of irradiating a material with X-rays and scattering and interfering with the electrons surrounding the atoms. Therefore, by analyzing this diffraction phenomenon, it is possible to specify the constituent elements of the material and analyze the crystal structure. In FIG. 15, the X-axis is the diffraction angle 2θ, and the Y-axis is the diffraction intensity. From a known database, it is known that α-type aluminum oxide has a crystal plane (113) peak at a position near 2θ=43.35° and a crystal plane (116) peak at a position near 2θ=57.5°. In FIG. 15-A, the aluminum oxide film of the product of the present invention shows 2θ=43.5°, indicating that it has the crystal structure of α-type aluminum oxide. Figure 15-B is Al
FIG. 10 is an X-ray diffraction position diagram in Example 4 in which a film was formed using a combination of targets that maximize the ratio of . From this result, there are peaks not only at the position (43.5°) near 2θ = 43.35° but also at the position ((58.3°) near 2θ = 57.5°). It can be seen that the crystal structure ratio of aluminum oxide of type 2 also increased, and the crystal structure of α type was strongly expressed.The results of the cutting test described later show that the cutting performance of Examples 3 and 4, in which the amount of Al was increased, was improved. By increasing the amount of Al, the crystal structure of α-type aluminum oxide is strongly expressed, and at the same time, the mixed crystal state of aluminum oxide and chromium nitride compensates for the drawbacks of α-type aluminum oxide and realizes stable performance. If the aluminum ratio is increased further, the crystal structure of α-type aluminum oxide can be strongly expressed, but due to the decrease in the ratio of chromium nitride accompanying the increase in the ratio of α-type aluminum oxide in the film, α It is thought that the drawbacks of the type aluminum oxide (the crystal grains tend to coarsen and cracks tend to develop during cutting) are also strongly expressed.For this reason, the composition ratio of aluminum chromium oxynitride is the composition formula AlaCrbMcOdNe (a, b, c where a, b, c, d, and e are 0.2≤a≤0.45, 0.02≤b≤0.2, 0≤c≤0.2, 0.15≤d≤0.5, 0.1≤e≤0.4 and a It is desirable to be in the range of +b + c + d + e = 1, and in order to develop more stable performance, 0.27 ≤ a ≤ 0.35, 0.07 ≤ b ≤ 0.15, 0 ≤ c ≤ 0.2, 0.29 ≤ d ≤ 0.35, 0.23≤e
It is preferably in the range ≦0.35.

FIG. 16 is a cross-sectional view obtained by high resolution analytical scanning electron microscopy of the coating of the present invention.
<Aluminum chromium oxynitride super multilayer coating>
FIG. 16 shows a cross-section of a cut specimen coated with the super multilayer oxynitride coating 11 of the present invention and observed with a high-resolution analytical scanning electron microscope (JSM-7001F, manufactured by JEOL Ltd.). From the observation results, it can be confirmed that a super multilayer structure is formed. Also, it can be seen that the thickness of one layer is about several nm to 10 nm. Compressive stress is introduced into the coating by constructing such a super multilayer coating, and wear resistance is improved.
On the other hand, it is well known that the introduction of excessive compressive stress causes a chipping phenomenon in which the film cracks. However, as shown in FIG. 12, the element ratio of each layer is continuously graded and changed, and it is considered to play a role of a kind of graded layer. It is believed that this contributes to the introduction of an appropriate compressive stress that is different from that of a normal multilayer film, thereby improving wear resistance and suppressing chipping. In the present invention, it is possible to independently change the composition ratio of each element of aluminum, chromium, oxygen, and nitrogen with respect to such a graded layer in which the composition ratio changes continuously. For example, a plurality of targets with different composition ratios of the aluminum-chromium target used for discharge may be placed and discharged simultaneously, and the amount of change in aluminum and chromium may be controlled by controlling the voltage applied to the targets. However, the amount of change can be controlled by changing the flow rate and pressure of oxygen and nitrogen introduced into the chamber.
As can be seen from FIG. 16, the thickness of each layer of the super multilayer film is preferably about 0.5 nm to 50 nm. If it deviates from this range, adequate compressive stress may not be introduced and wear resistance may not be obtained. In addition, the thickness of each layer may be the same as long as it is within the above range, or may be different. Further, from the above observation results, it is more preferable that the thickness of each layer is about 5 nm to 20 nm.

FIG. 17 is a diagram of the thickness per super multilayer calculated from the etching rate of the film of the present invention in X-ray photoelectron spectroscopy.
The right figure of FIG. 17 is an FE-SEM image, and it can be seen that an oxide film and a film surface are formed on the WC substrate. FE-SEM is a field-emission scanning electron microscope, and it is a microscope that observes minute substances using secondary electrons emitted when the target sample is irradiated with an electron beam. used for observation of Analysis of this FE-SEM image indicates that the thickness of the oxide film is about 278 nm.
The XPS measurement is performed while etching the film at 1 minute intervals until W is detected in the cemented carbide substrate. Here, XPS measures the kinetic energy distribution of photoelectrons emitted by X-ray irradiation, and obtains knowledge about the types, abundances, and chemical bonding states of elements present on the sample surface (depth of several nanometers). method. Since W started to be detected at about 85 min, it is assumed that it reached the substrate at 85 min. Therefore, dividing the film thickness of 278 nm by the etching time of 85 min gives an etching rate of 3 nm/min. From the left diagram of FIG. 17, it took about 4 minutes to etch one layer, so it was found that the film thickness per super multilayer layer was about 12 nm from 4 min.times.3 nm/min.
Therefore, the layer thickness of one supermultilayer layer is approximately 10 nm from FIG. 16, and approximately 12 nm from FIG.

<Intermediate Layer: Aluminum Chromium Nitride Super Multilayer Coating>
The aluminum chromium oxynitride super multilayer coating (super multilayer oxynitride coating 11), which is the product of the present invention, shows good performance without any decrease in adhesion even when directly formed on the substrate 2. Therefore, the intermediate layer 13 is not necessarily required. However, when the aluminum chromium oxynitride layer is a relatively thick single layer, the adhesion to the substrate (non-oxidized layer) may not be good. Therefore, in order to further stabilize the performance of the product of the present invention, an aluminum chromium nitride super multi-layer coating is interposed between the substrate 2 and the aluminum chromium oxynitride super multi-layer coating (super multi-layer coating 11) of the present invention. Introduced as layer 13 .
The reason for selecting the aluminum chromium nitride as the intermediate layer 13 is that the aluminum chromium nitride itself has been used as a known coating so far, and the product of the present applicant exhibits stable performance in adhesion to the base material 2, etc. In addition, the composition ratio is not far from aluminum chromium oxynitride and there is chemical affinity, so the adhesion between layers will be improved. The productivity is high because the same target can be used.
Also, this intermediate layer 13 can have a sloped base bias to control the internal stress of the film and increase wear resistance. Furthermore, from the viewpoint of chemical affinity, the above composition ratios a, b, c, d are provided between the intermediate layer 13 and the oxynitride super multilayer coating 11 (outer coating layer) in order to further improve the adhesion rate.
, e is continuously changed by introducing an aluminum chromium oxynitride gradient layer (oxynitride gradient layer 12), or by continuously changing the composition ratio f, g, h, i between the base material 2 and the intermediate layer 13. It is also possible to introduce an aluminum chromium nitride graded layer (nitride graded layer 14) with a graded It is also possible for each graded layer 12, 14 to have a super-multilayer structure. Including these gradient layers 12 and 14 can also be defined as an intermediate layer in a broad sense. That is, either or both of intermediate layer 13--oxynitride graded layer 12--oxynitride super multilayer coating 11 and substrate 2--nitride graded layer 14--intermediate layer 13 can be included.

As for the graded layer whose composition ratio changes continuously, it is possible to change each element of aluminum, chromium, oxygen, and nitrogen independently. For example, a plurality of targets in which the composition ratio of the aluminum-chromium target used for discharge is changed may be installed and discharged simultaneously, and the amount of change in aluminum and chromium may be controlled by controlling the voltage applied to the target. However, the amount of change may be controlled by changing the flow rate and pressure of oxygen and nitrogen introduced into the chamber.
Regarding the composition ratio of the intermediate layer 13, it is preferable that the composition ratio of the intermediate layer 13 is within a range not far from the aluminum chromium oxynitride from the viewpoint of the adhesion between the layers as described above. Therefore, in the composition formula AlfCrgMhNi of the intermediate layer 13, the composition ratios f, g, h, and i are atomic ratios, and It is desirable that f+g+h+i=1. M is
At least one additive element selected from Si, Hf, and B. In addition, an intermediate layer is provided in order to fully exhibit the performance of the aluminum chromium oxynitride of the present invention. The intermediate layer 13 may be composed of an aluminum coating (TiAlN), a chromium nitride coating (CrN), or the like.

FIG. 18 is an illustration of cutting when a workpiece is cut with a cutting tip having the coating of the present invention.
With the workpiece 40 rotated in the direction of arrow r, it is advanced in the cutting direction 33 by the cutting distance f while pressing against the rake face 31, which is the cutting surface of the cutting tip 30, at the cutting depth t. At this time, the flank 32 of the cutting tip 30 is set to be separated from the outer peripheral surface of the workpiece 40 at a certain angle.
Therefore, the rake face 31, which is the cutting surface of the cutting tip 30, tends to wear due to multiple cutting operations. As will be described later, this wear of the rake face 31 is called crater wear. Wear resistance in the present invention means resistance to crater wear.

FIG. 19 is a photographic view of a cutting test using a cutting tip having the coating of the present invention and an explanatory view of crater wear.
<Details of cutting test>
The cutting conditions are as follows. Work material: SCM440H (refined to HRC25), cutting speed: 30 m/min, feed rate: 0.15 mm/rev, depth of cut (radial direction): 1 mm.
A cutting test was performed using an NC lathe (XC-100 manufactured by Takamatsu Kikai Kogyo Co., Ltd.) under the above conditions.
In this cutting test, the cutting speed is slowed to 30m/min and the depth of cut is set to 1mm, which is a heavy cutting condition. As an evaluation method for this cutting test, it is common to observe the wear mode called crater wear that occurs on the rake face of the cutting tip. FIG. 19 shows the outline of the cutting test and crater wear.
The photo shows where the cutting tip is attached and how the rake face of the cutting tip is pressed against it to grind. The figure shows that the flat cutting tip rake face is dented due to wear, and the cutting tip rake face is dented to cause crater wear.

FIG. 20 is a cutting test evaluation chart between the amount of crater wear and the cutting distance regarding the cutting test with the cutting insert having the coating of the present invention.
The results of a cutting test performed under the above conditions using cutting inserts having coatings produced in Examples 1 to 5 and Comparative Examples 1 to 3 shown in FIG. 11 are shown. In the figure, No. 1 is Comparative Example 1, No. 2 is Comparative Example 2, and No. 8 is Comparative Example 3. No. 3 is Example 1, No. 4 is Example 2, No. 5 is Example 3, No. 6 is Example 4, and No. 7 is Example 5.
For the known aluminum chromium nitride coating, Comparative Example 3 of No. 8, the cutting distance was 492 m.
90mm of crater wear occurs at Further, in Comparative Example 1 of No. 1 and Comparative Example 2 of No. 2, crater wear of 35 to 45 mm occurred. However, in Examples 1 to 4 of Nos. 3 to 6, which are products of the present invention, the crater wear is suppressed to 25 mm or less. In particular, in Examples 3 and 4 of No. 5 and No. 6, it is clear that no crater wear occurred at all. Furthermore, No.
In Example 5 of 7, the oxynitride super multi-layer coating layer 11, which is the product of the present invention, is formed in an extremely thin film state of 0.2 μm. However, with respect to the overall film thickness, the ratio of the film thickness of the intermediate layer 13 was increased so as to be equivalent to those of Examples 1 to 4, and consideration was given so that the difference in life due to the film thickness does not occur. Even in the case of Example 5, the crater wear was 15 μm at a distance of 277 m, and the crater wear was 46 μm at a distance of 492 m. It can be seen that the crater wear is suppressed more than the aluminum chromium coating. From these experimental facts, it can be seen that the product of the present invention exhibits a dramatic effect on wear resistance.
First, it can be seen that the formation of the aluminum chromium oxynitride layer, which is the outer coating layer, dramatically improves the oxidation resistance/wear resistance.
Secondly, when comparing No.1-2 single-layer aluminum chromium oxynitride coatings with No.3-6 super multi-layer aluminum chromium oxynitride coatings, there is a significant difference in the amount of crater wear at a cutting distance of 492m. It can be confirmed that the abrasion resistance is remarkably improved by making it super multilayered.
Thirdly, No. 5 and 6 did not show any crater wear at a cutting distance of 492 m, showing a marked improvement in performance compared to No. 7. The amount of aluminum increased from No. 3 to No. 6, and it was confirmed that the performance was improved by increasing the ratio of α-type aluminum oxide in the coating.
In addition, although square cutting inserts were used in this embodiment, diamond-shaped or other shapes, cutting tools with chip breakers, cutting tools with polished surfaces, and die tools other than cutting tools are also available. etc. can also obtain the same effect as the present embodiment. Although SKH51 was used as the base material, effects similar to those of this embodiment can be obtained by using hard base materials such as WC cemented carbide, cermet, ceramics, high-speed tool steel, and die steel.

FIG. 21 is an observation diagram of crater wear at a cutting distance of 277 m and a cutting distance of 492 m. The effect of having the AlCr oxynitride super multilayer coating of the present invention as the outer coating layer can be confirmed only by observing the crater wear.
Crater wear appears at any cutting distance in No. 8, which has only an intermediate layer. In Nos. 1 and 2, which are AlCr oxynitride single-layer coatings as outer coating layers, crater wear is extremely small at a cutting distance of 277 m, but crater wear appears large at a cutting distance of 492 m.
In Nos. 3 and 4 of Examples 1 and 2, crater wear appears slightly at a cutting distance of 492 m. However, in Nos. 5 and 6 of Examples 3 and 4, no crater wear appeared at both cutting distances of 277 m and 492 m. It is considered that the difference in effect among the examples depends on the composition ratio of Al and Cr. It was confirmed that when the composition ratio of Al increases, the crystal structure of α-type aluminum oxide is strongly expressed, and by forming a mixed crystal with chromium nitride, the defects of α-type aluminum oxide are compensated for, and the performance is improved.
However, it was found that having an oxynitride AlCr super multi-layer coating as the outer coating layer has a remarkable effect compared with the conventional coating.

The present invention is not limited to the above embodiments, but includes various modifications, design changes, other embodiments, etc. within the technical scope of the present invention without departing from the technical idea of the present invention. Not even. That is, the scope of the present invention is not limited to the above description, but clearly includes all technical matters within the scope indicated by the claims.

The AlCr oxidation-resistant wear-resistant coating and its coating according to the present invention are used for cutting tools such as drills and end mills, mold tools such as punches, dies, presses, etc., which are used for machining workpieces made of metals and non-metals. It is used as a tool such as a knife. That is, when the AlCr oxidation-resistant and wear-resistant coating according to the present invention is formed on the surface of a substrate made of WC cemented carbide, cermet, ceramics, high-speed tool steel, die steel, etc., the coating can be used for various cutting tools and There is an advantage that it can be widely used as a tool such as a mold tool.

1 Coating 2 Substrate 10 AlCr oxidation-resistant and wear-resistant coating 11 Oxynitride super multilayer coating 11a Oxynitride unit layer 11b Oxynitride unit layer 11c Oxynitride unit layer 12 Oxynitride gradient layer 12a Oxynitride gradient unit layer 12b Oxynitride gradient Unit layer 12m Oxynitride graded unit layer 12n Oxynitride graded unit layer 12x Oxynitride graded continuous coating 12y Oxynitride graded multilayer coating 13 Intermediate layer 13a Nitride unit layer 13b Nitride unit layer 13x Nitride coating 13y Nitride super multilayer coating 14 Nitride graded layer 14a nitrided graded unit layer 14b nitrided graded unit layer 14c nitrided graded unit layer 14d nitrided graded unit layer 14m nitrided graded unit layer 14n nitrided graded unit layer 14x nitrided graded continuous coating 14y nitrided graded multilayer coating 20 arc ion plating apparatus 21 vacuum chamber 22 Evacuation system 23 Heater 24 Filament discharge system 25 Cathode system 25a Arc discharge power source a
25b Arc discharge power supply b
25c Arc discharge power supply c
25d Arc discharge power supply d
26 Rotating base mechanism 26a Large table 26b Small disc 26c Shaft 26d Base bias power source 27 Gas introduction system 30 Cutting tip 31 Rake face 32 Flank face 33 Cutting direction 40 Work piece RP Rotary pump for rough exhaust TMP Turbo for high exhaust Molecular pump CP Cryopump f Cutting distance t Cutting depth

Claims (14)

A coating composed of oxynitrides of aluminum and chromium that covers and protects at least part or all of the surface of a substrate, and in the composition formula AlaCrbMcOdNe of the coating, the composition ratios a, b, and c
, d and e are atomic ratios, 0.2≤a≤0.45, 0.02≤b≤0.2, 0≤c≤0.2, 0.15≤d≤0.5, 0.1≤e≤0.4 and a+b+c+d+e= 1 is satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M includes cases where it is added and cases where it is not added, and the composition ratios a, b, and c The coating is composed of an oxynitride super multilayer coating in which at least two or more types of oxynitride unit layers with different combinations of , d, and e are laminated periodically or substantially periodically, and the coating comprises aluminum oxide having oxidation resistance. Since the wear-resistant chromium nitride is in a mixed crystal state, the coating has oxidation resistance and wear resistance,
An intermediate layer is provided between the base material and the oxynitride super multilayer coating, the intermediate layer is a nitride coating represented by the composition formula AlfCrgMhNi, the composition ratios f, g, h, and i are atomic ratios, 0.25≤f≤0.6, 0.1
≤ g ≤ 0.37, 0 ≤ h ≤ 0.2, 0.15 ≤ i ≤ 0.57 and f + g + h + i = 1, and M is at least one additive element selected from Si, Hf, and B. An AlCr oxidation-resistant and wear-resistant coating characterized in that the additive element M may or may not be added. 2. The intermediate layer according to claim 1 , wherein the intermediate layer is composed of a nitride super multilayer coating in which at least two or more types of nitride unit layers having different combinations of the composition ratios f, g, h, and i are stacked periodically or substantially periodically. AlCr oxidation resistant wear resistant coating. The intermediate layer is configured by laminating a first intermediate layer and a second intermediate layer, the first intermediate layer is configured by the nitride film, and the second intermediate layer has the composition ratio f, g, h, i 2. The AlCr oxidation-resistant and wear-resistant coating according to claim 1 , comprising a nitrided super multilayer coating in which at least two or more types of nitrided unit layers having different combinations of are laminated periodically or substantially periodically. A nitrided gradient layer is provided between the base material and the intermediate layer, and the nitrided gradient layer has a composition formula of AlαCrβMγNδ , where the composition ratios α, β, γ, and δ are atomic ratios, and 0.25≦ α ≦0.6, 0.1 ≤ β ≤ 0.37, 0 ≤ γ ≤ 0.2, 0.15 ≤ δ ≤ 0.57 and α + β + γ + δ = 1 , M is an additive element of one or more of Si, Hf, B, and the additive element M is The characteristics of the nitrided gradient layer, including the case where it is added and the case where it is not added, are that the composition ratios α, β, γ, and δ between the base material and the intermediate layer are graded within the range of the composition ratios. The AlCr oxidation-resistant and wear-resistant coating according to any one of claims 1 to 3 , which changes to The nitrided graded layer is a nitrided graded continuous coating in which the composition ratios α, β, γ, and δ are graded while continuously changing, or the composition ratios α, β, γ, and 5. The AlCr oxidation-resistant and wear-resistant coating according to claim 4 , which is a nitrided-graded multi-layered coating in which two or more types of nitrided-graded unit layers are laminated. providing an oxynitride graded layer between the intermediate layer and the oxynitride super multilayer coating, the oxynitride graded layer having a composition formula AlvCrwMxOyNz, wherein the composition ratios v, w, x, y, and z are atomic ratios; 0.2≤v≤0.45
, 0.02 ≤ w ≤ 0.2, 0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.5, 0.1 ≤ z ≤ 0.4 and v + w + x + y + z = 1 , and M is at least one additive element selected from Si, Hf, and B and the additive element M
The feature of the oxynitride gradient layer is that between the intermediate layer and the oxynitride super multilayer coating, the composition ratios v, w, x, y, and z are the composition The AlCr oxidation-resistant and wear-resistant coating according to any one of claims 1 to 3 , wherein the ratio varies in a gradient manner. The oxynitride graded layer is an oxynitride graded continuous coating in which the composition ratios v, w, x, y, z are graded while continuously changing, or the composition ratios v, w, x, y, z 7. The AlCr oxidation-resistant and wear-resistant coating according to claim 6 , which is an oxynitride-graded multilayer coating in which two or more types of oxynitride-graded unit layers in which the combination of is changed in a graded manner. A nitrided gradient layer is provided between the base material and the intermediate layer, and the nitrided gradient layer has a composition formula of AlαCrβMγNδ , where the composition ratios α, β, γ, and δ are atomic ratios, and 0.25≦ α ≦0.6, 0.1. ≤ β ≤ 0.37, 0 ≤ γ ≤ 0.2, 0.15 ≤ δ ≤ 0.57 and α + β + γ + δ = 1 , M is an additive element of one or more of Si, Hf, B, and the additive element M is The characteristics of the nitrided gradient layer, including the case where it is added and the case where it is not added, are that the composition ratios α, β, γ, and δ between the base material and the intermediate layer are graded within the range of the composition ratios. is to change to
providing an oxynitride gradient layer between the intermediate layer and the oxynitride super multilayer coating, the oxynitride gradient layer having a composition formula AlvCrwMxOyNz, wherein the composition ratios v, w, x, y, and z are atomic ratios; 0.2≤v≤0.45
, 0.02 ≤ w ≤ 0.2, 0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.5, 0.1 ≤ z ≤ 0.4 and v + w + x + y + z = 1
is satisfied, M is an additive element of one or more of Si, Hf, and B, and the additive element M may or may not be added, and the oxynitride gradient layer is characterized by: 4. The composition according to any one of claims 1 to 3 , wherein the composition ratios v, w, x, y, and z between the intermediate layer and the oxynitride super multilayer coating gradually change within the range of the composition ratio. AlCr oxidation and wear resistant coating as described. The nitrided graded layer is a nitrided graded continuous coating in which the composition ratios α, β, γ, and δ are graded while continuously changing, or the composition ratios α, β, γ, and A nitrided gradient multilayer coating in which two or more different types of nitrided gradient unit layers are laminated,
The oxynitride graded layer is an oxynitride graded continuous coating in which the composition ratios v, w, x, y, z are graded while continuously changing, or the composition ratios v, w, x, y, z 9. The AlCr oxidation-resistant and wear-resistant coating according to claim 8 , which is an oxynitride-graded multilayer coating in which two or more kinds of oxynitride-graded unit layers whose combination is changed in a graded manner are laminated. The AlCr oxidation-resistant and wear-resistant coating according to any one of claims 1 to 3 , wherein the unit layer thickness of said oxynitride unit layer is 0.5 nm to 50 nm. The AlCr oxidation-resistant and wear-resistant coating according to any one of claims 1 to 3, wherein the crystal structure of the oxynitride unit layer has α-type aluminum oxide. The AlCr oxidation-resistant and wear-resistant coating according to any one of claims 1 to 3 , wherein the oxynitride super multilayer coating has a thickness of 0.2 µm to 10 µm. A coating comprising the AlCr oxidation-resistant and wear-resistant coating according to any one of claims 1 to 3 coated on at least part or all of the surface of the substrate. The substrate is a coating made of a hard substrate, the coating is used as a high-hardness tool, and the hard substrate is any one of WC cemented carbide, cermet, ceramics, high-speed tool steel, and die steel. 14. The coated article according to claim 13 , wherein said high hardness tool is a cutting tip, drill, end mill, punch, die, cold die, hot die or cutting tool.

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