JP4398224B2 - Wear resistant parts - Google Patents

Description

  The present invention improves wear resistance, heat resistance and welding resistance, particularly at high temperatures, and is suitable for cutting tools, wear-resistant tools, machine parts, sliding parts, electrical and electronic parts, etc. It is related with the wear-resistant member used suitably.

In recent years, in order to improve the wear resistance, heat resistance and lubricity of cutting tools, TiCN, TiAlN, TiSiN, Al ₂ O are formed on a substrate by PVD method (physical vapor deposition method) or CVD method (chemical vapor deposition method). _{In general} , a compound layer composed of ₃ is formed as one layer or a plurality of layers, and the surface of the substrate is covered with these compound layers.

  For example, Patent Document 1 proposes a cutting tool having a coating configuration including a first layer of a titanium-aluminum alloy and an alumina layer that is directly attached to the first layer by physical vapor deposition.

  Further, in Patent Document 2, a layer in which Si is 10% or more and 60% or less, and b layer in which Al is more than 40% and 75% or less are each alternately coated with one or more layers, and Ti is mainly used. There has been proposed a hard coating tool in which a c layer made of nitride is formed directly on the surface of the base material, and the b layer is directly above the c layer. These hard coatings are particularly formed by physical vapor deposition.

  However, the heat resistance of the film made of TiN or TiCN formed by the conventional PVD method is not sufficient, and the film made of TiAlN or TiSiN having relatively high heat resistance is also used in a high temperature environment, high speed cutting and high speed. There is a problem that the heat resistance during sliding is not always sufficient.

On the other hand, since a coating made of Al ₂ O ₃ is excellent in heat resistance, it can be said that using an Al ₂ O ₃ coating is the best method for obtaining a coating having sufficient heat resistance and wear resistance. The Al ₂ O ₃ layer is usually often used as a multilayer of TiCN—Al ₂ O ₃ , but in order to form the Al ₂ O ₃ layer, the thermal CVD method is 1000 ° C. or higher, and the PVD method is also used. A substrate temperature of 500-800 ° C is required. When the substrate temperature is high, oxygen for forming the Al ₂ O ₃ layer may pass through the underlayer such as the TiCN layer and reach the substrate surface or the interface between the substrate and the coating. When the surface of the substrate or the interface between the substrate and the coating is oxidized by oxygen, a brittle oxide layer is formed and the adhesion between the substrate and the coating is reduced, so that sufficient wear resistance and heat resistance are obtained. The problem of not being able to occur.

As a method of forming an Al ₂ O ₃ layer at a lower temperature, Patent Document 3 discloses that an oxide film having the same corundum structure as the Al ₂ O ₃ layer is formed as an intermediate layer at a low temperature of 300 to 700 ° C. A method of forming an Al ₂ O ₃ layer having a corundum structure has been proposed. However, even if the film formation is performed at a low temperature, the oxidation of the substrate during film formation can be suppressed. Since the material reaches the base material and the base material is oxidized, the problem that sufficient wear resistance and heat resistance cannot be obtained due to a decrease in adhesion between the base material and the coating has not been solved.
JP-A-9-192906 JP 2000-326107 A JP 2002-53946 A

  The present invention solves the above-mentioned problems, improves the wear resistance particularly at high temperatures, and can be suitably used for cutting tools, wear-resistant tools, machine parts, sliding parts, electricity, electronic parts and the like. An object is to provide a wearable member.

The present invention relates to a single layer or multilayer Al ₂ O ₃ layer and a single layer or multilayer (Ti _x Si _1-x ) (C _y N _1-y ) layer (where 0 <x <1 and 0 ≦ y <1, the same shall apply hereinafter), and a substrate, and the (Ti _x Si _1-x ) (C _y N _1-y ) layer and the Al ₂ O ₃ layer The present invention relates to a wear-resistant member formed between materials.

In the present invention, the (Ti _x Si _1-x ) (C _y N _1-y ) layer formed between the substrate and the Al ₂ O ₃ layer has an amorphous structure or an amorphous phase. It is preferable to have a nanocomposite structure having a crystalline phase in the range of 1 to 50 nm. It is also preferable that the crystalline phase is composed of a columnar structure having a particle diameter in the range of 1 to 50 nm.

At least one of the (Ti _x Si _1-x ) (C _y N _1-y ) layers is in the range of x = 0.6 to 0.95 and y = 0 to 0.6. Is preferred.

The present invention also relates to a wear resistant member in which the formed Al ₂ O ₃ layer is crystalline. In particular, the Al ₂ O ₃ layer preferably has an α-Al ₂ O ₃ structure.

In the present invention, the thickness of the entire wear-resistant coating is preferably set in the range of 0.5 to 15 μm. In addition, the film thickness of at least one of the Al ₂ O ₃ layers is within a range of 0.1 to 10 μm, and the film thickness of at least one of the (Ti _x Si _1-x ) (C _y N _1-y ) layers. Is preferably set in the range of 0.2 to 10 μm.

The present invention further relates to a wear-resistant member in which a single-layer or multi-layer adhesion layer is formed between a (Ti _x Si _1-x ) (C _y N _1-y ) layer and a substrate. The adhesion layer includes at least one of Ti and / or Al carbides, nitrides, carbonitrides, nitride oxides, or Ti, and the adhesion layer has a thickness of 0.1 to 10 μm. It is preferable to be formed as follows.

The present invention further relates to a wear-resistant member having a single-layer or multi-layer intermediate layer between a (Ti _x Si _1-x ) (C _y N _1-y ) layer and an Al ₂ O ₃ layer. The intermediate layer includes one or more of carbides, nitrides, oxides, carbonitrides, and nitrides of one or more elements selected from Ti, Cr, Si, and Al, and is a film of the entire intermediate layer The thickness is preferably in the range of 0.2 to 10 μm.

  The present invention further relates to a wear-resistant member having a single-layer or multi-layer surface layer formed on the outermost surface. The surface layer preferably contains at least one of Ti carbide, nitride, carbonitride, and nitride oxide, and the thickness of the entire surface layer is preferably in the range of 0.05 to 5 μm.

In the wear-resistant coating used in the present invention, the formation method of each layer is not limited, but at least an Al ₂ O ₃ layer, preferably a (Ti _x Si _1-x ) (C _y N _1-y ) layer and Al _2. A method in which the O ₃ layer, more preferably all the layers constituting the abrasion-resistant film, is formed by the PVD method is suitable.

The present invention further relates to an abrasion resistant member in which at least a part of a substrate is coated with an abrasion resistant coating. As the base material, high-speed steel, cemented carbide, cermet, cBN sintered body, diamond sintered body, TiC-Al ₂ O ₃ sintered body, Si ₃ N ₄ sintered body can be used. Speed steel is preferably used.

  The wear-resistant member of the present invention can be used for cutting tools, wear-resistant tools, machine parts, sliding parts, electricity, electronic parts, and the like, but can be suitably used particularly for cutting tools for cutting work. .

  The wear-resistant member of the present invention is particularly excellent in wear resistance at high temperatures, and can be suitably used for cutting tools, wear-resistant tools, machine parts, sliding parts, electricity, electronic parts, and the like.

The wear-resistant member in the present invention comprises a wear-resistant film made of cemented carbide, cermet, cBN sintered body, diamond sintered body, TiC-Al ₂ O ₃ sintered body, Si ₃ N ₄ sintered body, high speed. It is provided by coating a substrate such as steel.

FIG. 1 is a cross-sectional view showing an example of the configuration of the wear-resistant member according to the present invention. The wear-resistant member 12 of the present invention is obtained by forming an Al ₂ O ₃ layer 17 on the surface of a base material 13 with a (Ti _x Si _1-x ) (C _y N _1-y ) layer 15 interposed therebetween. It is characterized by being able to. FIG. 1 shows a particularly preferred embodiment of the present invention, in which an adhesion layer 14, (Ti _x Si ₁₋ ) is formed between a base material 13 and a (Ti _x Si _1−x ) (C _y N _1−y ) layer 15. _x ) A surface layer 18 is formed on the surface of the intermediate layer 16 and the Al ₂ O ₃ layer 17 between the (C _y N _1-y ) layer 15 and the Al ₂ O ₃ layer 17, respectively. Is configured. The wear-resistant coating film 11 thus obtained is formed on the surface of the base material 13 to obtain the wear-resistant member 12.

The wear-resistant member of the present invention comprises a single-layer or multilayer Al ₂ O ₃ layer, and a single-layer or multilayer (Ti _x Si _1-x formed between the Al ₂ O ₃ layer and the substrate. ) (C _y N _1-y ) layer.

The presence of a physically and chemically stable and hard Al ₂ O ₃ layer can greatly improve the overall heat resistance of the wear-resistant member, but it forms an Al ₂ O ₃ layer on the substrate. When the Al ₂ O ₃ layer is formed, oxygen atoms diffuse and permeate the Al ₂ O ₃ layer and diffuse to the base material, and a brittle oxide layer is formed on the base material surface. Adhesive strength with the adhesive film is reduced. In particular, the oxidation of the base material and the decrease in adhesion between the base material and the wear-resistant coating are remarkable in a high-temperature environment, and it is difficult to maintain sufficient wear resistance and heat resistance as a wear-resistant member. is there.

In the present invention, a (Ti _x Si _1-x ) (C _y N _1-y ) layer is interposed between the Al ₂ O ₃ layer and the substrate. TiSiCN is a single compound having excellent oxidation resistance, and is hardly oxidized even when oxygen is present at a high temperature. Therefore, when the Al ₂ O ₃ layer is formed and when the wear-resistant member is used, the (Ti _x Si _1-x ) (C _y N _1-y ) layer existing between the Al ₂ O ₃ layer and the substrate is used. The diffusion of oxygen atoms from the Al ₂ O ₃ layer to the substrate is suppressed.

As a mechanism for diffusing oxygen atoms in the coating, there are diffusion accompanied by oxidation of the coating within the crystal grains existing in the coating and diffusion that occurs independently of the oxidation of the coating at the grain boundary. By forming the (Ti _x Si _1-x ) (C _y N _1-y ) layer, it becomes difficult for oxygen atoms to diffuse inside the crystal grains, so that oxygen atoms from the Al ₂ O ₃ layer to the base material While diffusion can be _{suppressed, (Ti x Si 1-x} ) (C y N 1-y) by layer for suppressing the diffusion of oxygen atoms at the grain boundary _{unit, (Ti x Si 1-x} ) (C y N _1-y ) The effect of suppressing the diffusion of oxygen atoms in the layer can be further improved.

Examples of a method for suppressing the diffusion of oxygen atoms in the crystal grains of the (Ti _x Si _1-x ) ( _Cy N _1-y ) layer and in the grain boundaries include the quantity ratio of Ti and Si and the formation of the layers. There is a method of controlling the film quality of the (Ti _x Si _1-x ) (C _y N _1-y ) layer by adjusting the conditions. For example, it is preferable that the (Ti _x Si _1-x ) ( _Cy N _1-y ) layer has an amorphous structure, because the number of grain boundaries is small, so that diffusion of oxygen atoms in the crystal grains and at the grain boundaries is suppressed.

On the other hand, when the (Ti _x Si _1-x ) (C _y N _1-y ) layer has a crystalline phase, by controlling the film quality so that there is almost no continuous grain boundary, (Ti _x Si _{1- x} ) The diffusion of oxygen atoms in the ( _{CyN1 -y} ) layer can be effectively suppressed. Specifically, a nanocomposite containing an Si-N or Si-rich TiSiCN phase forming an amorphous parent phase and a TiN or Ti-rich TiSiN crystalline phase having a particle size of 1 to 50 nm therein A method of forming a structure can be employed. In this case, since the continuous grain boundary connected from the surface side of the formed layer to the substrate surface is hardly generated, diffusion of oxygen atoms by the grain boundary can be effectively prevented. If the grain size of the crystalline phase is 1 nm or more, the (Ti _x Si _1-x ) (C _y N _1-y ) layer exhibits good wear resistance and heat resistance due to the presence of microcrystals, and is 50 nm or less. If this is the case, it is difficult for the grain boundaries to be continuously generated, and diffusion of oxygen atoms can be prevented.

Furthermore, the (Ti _x Si _1-x ) (C _y N _1-y ) layer may have a fine columnar structure having a particle size in the range of 1 to 50 nm. In this case, the (Ti _x Si _1-x ) (C _y N _1-y ) layer has good mechanical properties and is excellent in the effect of preventing oxygen atom diffusion due to the presence of dense grain boundaries.

The crystalline / amorphous structure of the (Ti _x Si _1-x ) ( _Cy N _1-y ) layer, the grain size of the crystalline phase, the formation of columnar structures, etc. The film temperature, film forming pressure, substrate temperature, bias voltage, reaction gas, and the like can be controlled by selecting optimum conditions when forming the (Ti _x Si _1-x ) (C _y N _1-y ) layer.

In the (Ti _x Si _1-x ) (C _y N _1-y ) layer used in the present invention, desired physical properties and heat resistance can be ensured by controlling the composition and film forming conditions. Therefore, although the composition is adjusted in relation to the film formation conditions, at least one of the (Ti _x Si _1-x ) (C _y N _1-y ) layers has x = 0.6 to 0.95, and x It is preferable to contain Si so that it may become in the range of = 0.7-0.9. When x is 0.6 or more, the desired film hardness can be obtained by the presence of Ti and Si at an appropriate composition ratio, and the progress of oxidation under high temperature conditions can be prevented. When x is 0.95 or less, good heat resistance as a (Ti _x Si _1-x ) (C _y N _1-y ) layer can be obtained by containing a certain amount or more of Si.

In the composition formula (Ti _x Si _1-x ) (C _y N _1-y ), when y = 0 to 0.6, and further y = 0 to 0.3, N is a certain amount or more. By containing, the heat resistance of the (Ti _x Si _1-x ) (C _y N _1-y ) layer is secured, which is preferable.

In particular, in the composition formula _{(Ti x Si 1-x)} (C y N 1-y), x = 0.7~0.9, and when the composition falls within a range of y = 0 to 0.3 Can obtain a (Ti _x Si _1-x ) (C _y N _1-y ) layer having good wear resistance and heat resistance under a relatively wide range of film forming conditions.

In the single-layer or multi-layer (Ti _x Si _1-x ) (C _y N _1-y ) layer, the thickness of at least one layer may be in the range of 0.4 to 10 μm, and further 0.5 to 5 μm. preferable. If it is 0.4 μm or more, the effect of suppressing the diffusion of oxygen atoms is sufficiently obtained, while if it is 10 μm or less, adhesion with other layers can be ensured and peeling can be prevented.

A single layer or a multilayer Al ₂ O ₃ layer is formed on the wear resistant member of the present invention. The Al ₂ O ₃ layer is preferably crystalline in the cutting edge portion, machine part, and sliding part of a cutting tool that is subjected to a particularly high surface load and becomes a high temperature environment. In this case, the Al ₂ O ₃ layer has a crystal structure of α-Al ₂ O ₃ or γ-Al ₂ O ₃ , but the crystal structure of α-Al ₂ O ₃ is preferable because it is thermally stable. When the Al ₂ O ₃ layer is crystalline, the heat resistance and wear resistance of the wear-resistant member can be improved because the Al ₂ O ₃ layer is superior in terms of high-temperature stability and hardness as compared with the amorphous case.

In the single-layer or multi-layer Al ₂ O ₃ layer, the thickness of at least one layer is preferably set in the range of 0.1 to 10 μm, more preferably 0.2 to 5 μm. If the thickness is 0.1 μm or more, the Al ₂ O ₃ layer can sufficiently exhibit heat resistance, and if it is 10 μm or less, the adhesion to other layers and the wear resistance are excellent.

The crystal structure of the Al ₂ O ₃ layer can be controlled by adjusting the pressure during film formation, the substrate temperature, the sputtering power, and the oxygen flow rate to optimum conditions.

In the wear-resistant member of the present invention, a single-layer or multi-layer adhesion layer may be formed between the base material and the (Ti _x Si _1-x ) (C _y N _1-y ) layer. In particular, when the adhesion layer contains any one or more of Ti and / or Al carbide, nitride, carbonitride, nitride oxide, or Ti, the substrate and (Ti _x Si _1-x ) ( C _y N _1-y) can improve adhesion between the layers is preferable because peel resistance is improved. The thickness of the adhesion layer is preferably in the range of 0.1 to 10 μm, more preferably 0.2 to 5 μm in the entire adhesion layer. When the film thickness is 0.1 μm or more, a sufficient adhesion improvement effect is obtained, and when the film thickness is 10 μm or less, the wear resistance of the wear-resistant member as a whole is reduced and there is little risk of peeling.

In the present invention, a single-layer or multi-layer intermediate layer may be disposed between the (Ti _x Si _1-x ) (C _y N _1-y ) layer and the Al ₂ O ₃ layer. The intermediate layer strengthens the adhesion between the (Ti _x Si _1-x ) (C _y N _1-y ) layer and the Al ₂ O ₃ layer to prevent delamination at the interface between the two layers, When a layer with high wear resistance is selected, it has an effect of contributing to improvement of wear resistance of the wear resistant member as a whole.

  As the material for forming the intermediate layer, carbides, nitrides, carbonitrides, and the like of elements containing Ti as a main component are preferable. By using these, an improvement effect with high adhesion can be obtained. In particular, Ti carbides, nitrides, and carbonitrides containing Al, Cr, and Si are preferable because of their high hardness and excellent wear resistance improvement effect.

On the other hand, nitrides of elements mainly composed of Al and / or Si, and nitrides of various elements are also used for the (Ti _x Si _1-x ) (C _y N _1-y ) layer and the Al ₂ O ₃ layer. Good in terms of high adhesion. In particular, the element used as the nitride oxide can contain any of Ti, Cr, Al, and Si as a main component.

When oxides of various elements are used, the effect of improving the adhesion with the Al ₂ O ₃ layer is high, and the heat resistance can be improved. In this case, an oxide of an element mainly composed of Al and / or Si is particularly preferable.

These materials for forming the intermediate layer may be used alone, but by combining them appropriately to form a multilayer, the (Ti _x Si _1-x ) (C _y N _1-y ) layer and Al ₂ It is possible to further improve the adhesion with the O ₃ layer.

  The total thickness of the intermediate layer is preferably in the range of 0.001 to 10 μm, more preferably 0.1 to 5 μm. If it is 0.001 μm or more, the effect of improving adhesion is sufficiently obtained, and if it is 10 μm or less, it is possible to prevent a decrease in adhesion due to peeling in the intermediate layer.

In addition, a surface layer may be formed on the outermost surface of the wear-resistant coating of the present invention, for example, for the purpose of improving the surface lubricity. As the material that can be used for the surface layer, materials having high lubricity such as DLC (diamond-like carbon), MoS ₂ , and WC (tungsten carbide) are suitable. By forming a surface layer made of these materials, the initial sliding characteristics can be improved. Further, if a single-layer or multi-layer surface layer composed of at least one of Ti carbide, nitride, carbonitride, and nitride oxide is disposed, lubricity can be improved while maintaining wear resistance. it can.

  The film thickness of the surface layer is preferably in the range of 0.05 to 5 μm, more preferably 0.1 to 2 μm for the entire surface layer. If it is 0.05 μm or more, the outermost surface can be sufficiently covered, so that the effect of improving the lubricity can be exhibited. If it is 5 μm or less, peeling of the surface layer itself can be prevented.

The Al ₂ O ₃ layer of the present invention can be formed by either the CVD method (chemical vapor deposition method) or the PVD method (physical vapor deposition method), but when the CVD method is used, the substrate temperature is 1000 to 1100 ° C. It is necessary to hold to the extent. On the other hand, in the PVD method, the substrate temperature may be kept at a relatively low temperature of 500 to 800 ° C. Therefore, the PVD method that can be formed at a lower temperature is advantageous in that oxidation at the substrate surface or the interface between the substrate and the wear-resistant coating can be suppressed. Moreover, the Al ₂ O ₃ film formed by the PVD method has compressive residual stress in the film. Therefore, even if a crack is generated by applying an impact to a cutting tool, a machine part or the like, the crack is difficult to extend, and there is an advantage that the chipping resistance and chipping resistance are excellent.

In the present invention, only the Al ₂ O ₃ layer may be formed by the PVD method, but the (Ti _x Si _1-x ) (C _y N _1-y ) layer and the Al ₂ O ₃ layer, and further the wear resistance When all of the layers that make up the coating are formed by the PVD method, the effect of suppressing oxidation, chipping resistance and chipping resistance at the substrate surface or the interface between the substrate and the wear-resistant coating is even more pronounced It becomes.

Although the details of the PVD method applied to the present invention are not limited, an ion plating method, a sputtering method and the like can be suitably used. In particular, (Ti _x Si _1-x ) ( _Cy N _1-y ) layer and Al ₂ O ₃ layer are formed by cold cathode arc type ion plating method, unbalanced magnetron sputtering method, dual magnetron sputtering method, etc. In this case, a dense layer is formed by particles having higher energy, which is preferable.

  In addition, even when the adhesion layer, the intermediate layer, the TiN layer and the TiCN layer as the surface layer are formed by the MT-CVD method capable of forming a layer at a relatively low substrate temperature, It is possible to suppress oxidation at the interface with the wear-resistant coating and improve wear resistance and heat resistance.

As a typical structure of the wear-resistant member of the present invention, an adhesion layer, (Ti _x Si _1-x ) (C _y N _1-y ) layer, intermediate layer, Al ₂ O ₃ layer, surface on the substrate One in which the layers are laminated in this order is mentioned. Each layer may be a single layer or a plurality of layers, but another layer may be formed between the layers or in the case of a plurality of layers. Further, a method of repeatedly forming a (Ti _x Si _1-x ) (C _y N _1-y ) layer and an Al ₂ O ₃ layer on a base material or an adhesion layer formed on the base material a plurality of times. Thus, it is possible to obtain a wear-resistant member having better heat resistance while preventing the oxidation of the substrate surface or the interface between the substrate and the Al ₂ O ₃ layer to improve the wear resistance.

  The wear-resistant member of the present invention can have the above-described configuration, but the film thickness of the entire wear-resistant film is preferably in the range of 0.5 to 15 μm. If the film thickness is 0.5 μm or more, sufficient wear resistance can be obtained, and if it is 15 μm or less, peeling due to a decrease in adhesion between the substrate and the wear-resistant coating can be effectively prevented. Furthermore, in a cutting tool or a sliding part having a more severe environment, it is particularly preferable that the film thickness of the entire wear-resistant coating is in the range of 1 to 5 μm.

  Note that the film thickness of each layer formed in the present invention can be controlled by adjusting the deposition conditions when the CVD method or the PVD method is used. That is, the deposition conditions such as the pressure at the time of film formation by the discharge of the evaporation source and the discharge time may be selected according to the material composition and the desired film thickness.

  The layer thickness and film structure of the formed layer can be evaluated by SEM observation and TEM observation of the cross section. The crystal structure can be evaluated by an X-ray diffraction pattern obtained by a thin film method in which an X-ray incident angle is fixed at 1 ° and an electron beam diffraction pattern using a TEM apparatus.

<Example>
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

(Examples 1-12)
A cemented carbide cutting tip having a composition of JIS standard P30 and a shape of JIS-SNG432 is used as the substrate, and cold cathode arc type ion plating and unbalanced magnetron sputtering or dual magnetron sputtering is used on the substrate surface. A wear-resistant coating was formed using this method.

  FIG. 2 is a diagram for explaining a dual magnetron sputtering method preferably applied to the present invention. In the film forming apparatus, arc evaporation sources 21 and 22 and sputter evaporation sources 23 and 24 are arranged, and a base material holder 25 that rotates between these evaporation sources around a central point between the evaporation sources is attached to a base material. A cutting tip was mounted as 26.

The arc evaporation source 21 is made of a metal or ceramic material as a material for the adhesion layer, the arc evaporation source 22 is made of TiSi (titanium silicon) as a material for the (Ti _x Si _1-x ) (C _y N _1-y ) layer, sputter A metal material or ceramics material as an intermediate layer material was set in the source 23, and Al (aluminum) as an Al ₂ O ₃ layer material was set in the sputtering source 24, respectively.

The inside of the film forming apparatus was evacuated to a vacuum degree of 1 × 10 ⁻³ Pa or less, and Ar (argon) gas was introduced from the gas inlet 27. The degree of vacuum was maintained at 3 Pa, and the substrate was heated to 500 ° C. and held for 1 hour. A voltage of 1000 V was applied to the cutting tip, glow discharge was performed in Ar gas, the substrate surface was cleaned with Ar ions, and then Ar gas was exhausted.

  Next, after a predetermined reaction gas is introduced into the film forming apparatus and a predetermined substrate bias voltage is applied to the cutting tip, the arc evaporation source 21 is subjected to a vacuum arc discharge so that an evaporation source of a metal material or a ceramic material is used. An adhesion layer was formed on the cutting tip by ionization.

Subsequently, a predetermined reaction gas was introduced into the film forming apparatus, and the arc evaporation source 22 was discharged to form a (Ti _x Si _1-x ) (C _y N _1-y ) layer.

Next, Ar and a predetermined reaction gas were introduced into the film forming apparatus, and the sputtering source 23 was discharged to form an intermediate layer on the cutting tip. Similarly, Ar gas and O ₂ gas were introduced into the film forming apparatus to bring the base material to a predetermined film forming temperature, and then the sputtering source 24 was discharged to form an Al ₂ O ₃ layer. Finally, a predetermined reaction gas was introduced into the film forming apparatus, the arc evaporation source 21 was discharged again to form a surface layer, and a surface-coated cutting tip sample was obtained.

Incidentally, throughout the Examples and Comparative Examples of the present invention, as the reaction gas, carbide, nitride, N ₂ gas and CH ₄ gas for the formation of carbonitrides, N ₂ gas for the formation of carbonitrides, CH ₄ N ₂ gas and O ₂ gas were used for forming the gas, CO ₂ gas, and nitrogen oxide.

  The discharge conditions of the vapor deposition source, the pressure at the time of discharge, the substrate temperature, the introduction flow rate of the reaction gas, etc., adopted the most suitable conditions depending on the composition of the layer to be formed and the layer thickness. Table 1 shows film formation conditions for Example 1 as typical film formation conditions.

  Tables 1 to 3 show the composition, film thickness, and film structure of each layer formed. The composition of each layer was measured by XPS (X-ray photoelectron spectroscopy). The film thickness, texture structure, and crystalline phase particle size are evaluated by SEM observation and TEM observation of the cross section. And an electron beam diffraction pattern using a TEM apparatus.

Regarding the crystal structure of the (Ti _x Si _1-x ) (C _y N _1-y ) layer, the amorphous structure is “amo.”, The nanocomposite structure is “nc”, and the crystal structure has a columnar structure. For those having a crystalline phase and expressed as “columnar”, the grain size of the crystalline phase is shown.

Regarding the crystal structure of the Al ₂ O ₃ layer, the amorphous structure is “amo.”, The α-Al ₂ O ₃ structure is “α”, and the γ-Al ₂ O ₃ structure is “γ”. Indicated.

(Comparative Example 1)
A (Ti _x Si _1-x ) ( _Cy N _1-y ) layer was not formed, and a wear-resistant coating film was formed by a conventional thermal CVD method to obtain a surface-coated cutting tip sample. Table 4 shows the composition, film thickness, and film structure of each layer formed.

(Comparative Example 2)
An Al ₂ O ₃ layer was not formed, a TiAlN layer was formed by the conventional cold cathode arc type ion plating method, and a wear-resistant coating was coated on the cutting tip to obtain a surface-coated cutting tip sample. . Table 4 shows the composition, film thickness, and film structure of each layer formed.

(Comparative Example 3)
An abrasion-resistant film obtained by forming an Al ₂ O ₃ layer on a substrate and forming a (Ti _x Si _1-x ) ( _Cy N _1-y ) layer thereon is formed on a cutting tip. Covered. The adhesion layer and the (Ti _x Si _1-x ) (C _y N _1-y ) layer were formed by the cold cathode arc method, and the Al ₂ O ₃ layer was formed by the unbalanced sputtering method. Obtained. Table 4 shows the composition, film thickness, and film structure of each layer formed.

  With respect to the formed surface-coated cutting chip sample, SCM435 was used as a coating material, and a continuous cutting test and an intermittent cutting test were performed under the cutting conditions shown in Table 5 to measure the wear width of the cutting edge. The results are shown in Table 6.

  From the result of Table 6, in Examples 1-12 which concern on this invention, compared with Comparative Examples 1-3, the uneven | corrugated surface wear width is small about at least one of a continuous cutting test and an intermittent cutting test. As for ˜11, the uneven wear width is small in both the continuous cutting test and the intermittent cutting test. Therefore, it turns out that the abrasion-resistant member of this invention has favorable abrasion resistance and heat resistance.

(Examples 13 to 18)
As a commercially available cutting tip to be a base material, a cermet or cubic boron nitride sintered body is set, and three arc evaporation sources and three unbalanced magnetron sputtering sources of a film forming apparatus are used. A surface-coated cutting tip sample was obtained in the same manner as above. The intermediate layers 1 and 2 and the (Ti _x Si _1-x ) (C _y N _1-y ) layer use an arc evaporation source, and the adhesion layers 1 and 2 and the Al ₂ O ₃ layer use an unbalanced magnetron sputtering source. Each was formed using. Tables 7 and 8 show the composition, film thickness, and film structure of the formed layers.

(Comparative Example 4)
Surface-coated cutting tip samples were obtained in the same manner as in Comparative Example 1 except that the same substrates as in Examples 13 to 18 were used. Table 9 shows the composition, film thickness, and film structure of each layer formed.

(Comparative Example 5)
A surface-coated cutting tip sample was obtained in the same manner as in Comparative Example 2 except that the same substrate as in Examples 13 to 18 was used. Table 9 shows the composition, film thickness, and film structure of each layer formed.

(Comparative Example 6)
A surface-coated cutting tip sample was obtained in the same manner as in Comparative Example 3 except that the same substrate as in Examples 13 to 18 was used. Table 9 shows the composition, film thickness, and film structure of each layer formed.

  With respect to the formed surface-coated cutting tip sample, SCM435 was used as a coating material, and a continuous cutting test and a round bar cutting test with a groove were respectively performed under the cutting conditions shown in Table 10, and the wear width of the cut edge was measured. The results are shown in Table 11.

  From the results of Table 11, in Comparative Examples 4 to 6, the Nige surface wear width was large in both the continuous cutting test and the round bar cutting test having grooves, whereas in Examples 13 to 18 according to the present invention, continuous cutting was performed. At least one of the test and the round bar cutting test having a groove has a small uneven surface wear width. In particular, in Examples 16 to 18, the uneven surface wear width is small in both the continuous cutting test and the round bar cutting test having a groove. Therefore, it can be seen that the wear-resistant member of the present invention exhibits good wear resistance and fracture resistance.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

According to the present invention, on the surface of a substrate such as cemented carbide, cermet, cBN sintered body, diamond sintered body, TiC-Al ₂ O ₃ sintered body, Si ₃ N ₄ sintered body, a single layer or Excellent wear resistance and heat resistance by interposing multiple (Ti _x Si _1-x ) (C _y N _1-y ) layers and forming a single layer or multiple layers of Al ₂ O ₃ Thus, a wear-resistant member having peeling resistance and chipping resistance is obtained. When the wear-resistant member of the present invention is used as a cutting tool, a machine part, or the like, it is possible to maintain good wear resistance, heat resistance, and other characteristics over a long period of time.

It is sectional drawing which shows an example of a structure of the abrasion-resistant member which concerns on this invention. It is a figure explaining the dual magnetron sputtering method applied suitably for this invention.

Explanation of symbols

11 wear-resistant coating, 12 wear resistant member, 13 substrate, 14 adhesion _{layer, 15 (Ti x Si 1-} x) (C y N 1-y) layer, 16 an intermediate layer, 17 Al ₂ O ₃ layer, 18 Surface layer, 21, 22 Arc evaporation source, 23, 24 Sputter source, 25 Base material holder, 26 Base material, 27 Gas inlet.

Claims (16)

Single layer or multilayer Al ₂ O ₃ layer and single layer or multilayer (Ti _x Si _1-x ) (C _y N _1-y ) layer (where 0 <x <1 and 0 ≦ y < 1) and a base material, wherein the (Ti _x Si _1-x ) (C _y N _1-y ) layer is disposed between the Al ₂ O ₃ layer and the base material A wear-resistant member,
Wherein the Al ₂ O ₃ layer and the _{(Ti x Si 1-x)} (C y N 1-y) layer, Ri physical vapor deposition film der, and
The (Ti _x Si _1-x ) (C _y N _1-y ) layer is a wear-resistant member in which there is no continuous grain boundary connected from the surface side of the layer to the substrate surface side . 2. The (Ti _x Si _1-x ) (C _y N _1-y ) layer (where 0 <x <1 and 0 ≦ y <1) has at least one layer having an amorphous structure. A wear-resistant member as described in 1. At least _{one of the} (Ti _x Si _1-x ) (C _y N _1-y ) layers (where 0 <x <1 and 0 ≦ y <1) has a grain size in the amorphous phase. The wear-resistant member according to claim 1, comprising a nanocomposite structure having a crystalline phase in a range of 1 to 50 nm. At least _{one of the} (Ti _x Si _1-x ) (C _y N _1-y ) layers (where 0 <x <1 and 0 ≦ y <1) has a particle size in the range of 1 to 50 nm. The wear-resistant member according to claim 1, which has a columnar structure. In at least _{one of the} (Ti _x Si _1-x ) (C _y N _1-y ) layers (where 0 <x <1 and 0 ≦ y <1), x = 0.6 to 0.95 And the abrasion-resistant member of Claim 1 which exists in the range of y = 0-0.6. A crystalline the Al ₂ O ₃ layer having at least one layer α-Al ₂ O ₃ structure or γ-Al ₂ O ₃ structure of the the Al ₂ O ₃ layer, wear resistant member according to claim 1 . A single-layer or multi-layer adhesive layer is provided between the (Ti _x Si _1-x ) (C _y N _1-y ) layer (where 0 <x <1 and 0 ≦ y <1) and the substrate. The wear-resistant member according to claim 1.   At least one of the adhesion layers contains one or more of Ti and / or Al carbide, nitride, carbonitride, nitride oxide, or Ti, and the film thickness of the entire adhesion layer is 0.1. The wear-resistant member according to claim 7, which is in a range of −10 μm. A single layer or a multilayer between the (Ti _x Si _1-x ) (C _y N _1-y ) layer (where 0 <x <1 and 0 ≦ y <1) and the Al ₂ O ₃ layer The wear-resistant member according to claim 1, which has an intermediate layer.   At least one of the intermediate layers includes one or more of carbides, nitrides, oxides, carbonitrides, and nitrides of one or more elements selected from Ti, Cr, Si, and Al. The wear-resistant member according to claim 9, wherein the film thickness of the entire intermediate layer is in the range of 0.2 to 10 µm.   The wear-resistant member according to claim 1, which has a surface layer on the outermost surface.   At least one of the surface layers includes at least one of Ti carbide, nitride, carbonitride, and nitride oxide, and the film thickness of the entire surface layer is in the range of 0.05 to 5 μm. The wear-resistant member according to claim 11.   The wear-resistant member according to claim 1, wherein at least a part of the substrate is coated with the wear-resistant coating. Said substrate, a cemented carbide, cermet, cBN sintered, diamond sintered body, TiC-Al ₂ O ₃ sintered body is selected from Si ₃ N ₄ sintered body, resistance of Claim 1 Abrasive material.   The wear-resistant member according to claim 1, wherein the base material is high-speed steel.   The wear-resistant member according to claim 1, which is used for a cutting tool.

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