JP3249278B2 - Tool cover - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-stoichiometric ceramic film coated on a base material of an alloy or a ceramic sintered body to obtain abrasion resistance, high hardness, exfoliation resistance and high toughness. More specifically, the present invention relates to a coating body suitable as a structural tool member having corrosion resistance and decorativeness, for example, a cutting tool represented by a turning tool, a milling tool, an end mill, a drill, a slitter, a can-making tool, and a mold. The present invention relates to a wear-resistant tool or tool covering suitable for a decorative tool member such as a fishing gear, a watch member, a frame of glasses, a tie pin, and a broach.

[0002]

2. Description of the Related Art A coating in which a titanium compound coating comprising a single layer or a multilayer of two or more of Ti carbides, nitrides, and carbonitrides is coated on a base material of an alloy or a ceramic sintered body. Many bodies have been proposed, some of which are in practical use.

[0003] In a conventional body coated with a titanium compound coating typified by JP-A-51-144314, the titanium compound coating itself has a ratio of a nonmetallic element to Ti, which is a metal element, of 0.8 to 1. The stoichiometric composition or a composition close to the stoichiometric composition consisting of 0 is used to effectively utilize the excellent wear resistance of the coating itself and the excellent toughness of the base material itself. Depending on the material of the material, the adhesion between the base material and the coating is poor, the adhesion between the coatings is poor when multi-layered, and the coating itself has only tensile stress or weak compressive stress remaining in the coating. There is a problem that the properties of the coating itself are inferior, such as brittleness.

Japanese Patent Laid-Open Publication No. H2-222454 discloses an attempt to solve these problems.

[0005]

Among coatings in which a titanium compound film is coated on a substrate, Japanese Patent Application Laid-Open No. 22454/1990 discloses that titanium carbide, titanium nitride, carbon The coating thickness of the coating body coated with a single-layer coating of one kind of titanium nitride is 0.1 to 1.5 μm on average.
It describes that ion implantation was performed in the state described above, and the ion-implanted component was infiltrated to the surface of the substrate through the coating, thereby improving the adhesion between the coating and the substrate and the hardness of the coating itself.

[0006] The coating described in the publication has excellent effects as compared with the conventional coating, but the equipment for ion implantation is very expensive, and the setting of ion implantation conditions, In other words, it is not easy to implant ions and control the amount of ions implanted,
There is a problem that it is difficult to commercialize as an industrial product.

[0007] The present invention has solved the above-mentioned problems, and more specifically, a titanium compound film comprising a non-stoichiometric composition of titanium carbide, titanium nitride, and titanium carbonitride is coated on a substrate. In addition, it is an object of the present invention to provide a tool covering with improved hardness, wear resistance, peel resistance, heat resistance and fracture resistance.

[0008]

Means for Solving the Problems The inventors of the present invention have been studying to improve the life of a coated body in which a titanium compound coating is coated on the surface of a cemented carbide or cermet. Specifically, when a non-stoichiometric film is formed by increasing the amount of nitrogen and / or carbon, which is a non-metallic element, with respect to Ti, which is a metal element constituting the film, the compressive stress remaining in the film is high, With the knowledge that it becomes a high hardness film and also has excellent adhesion to the substrate,
The present invention has been completed.

[0009] That is, the coating for a tool of the present invention is obtained by forming Ti (C _x ,
N _Y ) _R (where Ti is titanium, C is carbon, N is nitrogen, X and Y represent the respective atomic ratios of non-metallic elements carbon and nitrogen, and R is relative to titanium as a metal element. X + Y = 1, 1 ≧ X ≧ 0, 1.5 ≧ R ≧
1.01) and a titanium compound coating comprising a single layer or a multilayer of two or more of titanium carbide, titanium nitride, and titanium carbonitride having a non-stoichiometric composition represented by the following formula: It is characterized by the following.

The base material in the coating of the present invention is, for example, a stainless steel, a high-speed steel, a heat-resistant alloy, a Ti alloy, an Al alloy, a Cu alloy or a sintered alloy represented by cermet or cemented carbide. , Al ₂ O ₃ based ceramic sintered body,
Examples include a Si ₃ N ₄ based ceramic sintered body, a sialon based ceramic sintered body, a ZrO ₂ based ceramic sintered body, a SiC based ceramic sintered body, and an AlN based ceramic sintered body.

The Ti (C _x ,
The titanium compound film represented by (N _Y ) _R is, specifically,
TiC _R titanium carbide, TiN _R titanium nitride, Ti
(C, N) One kind of monolayer or two of titanium carbonitride of _R
It consists of multiple layers of different types. This Ti (C _X , N _Y )
_R in the titanium compound film represented by R is 1.01
When the value is less than 1, the decrease in the residual compressive stress, the decrease in hardness and the decrease in wear resistance of the coating are remarkable. Is defined as 1.01 to 1.5, and R is preferably 1.03 to maintain high hardness and excellent wear resistance.
It is preferable that the weight ratio is from 1.45 to 1.45.

The thickness of the titanium compound film varies depending on the structure, application, shape, etc. of the film to be coated on the substrate. For example, when the structure of the film is composed only of the titanium compound film, or the impact on the film is weak. In the case of such an application, the direction in which the thickness of the titanium compound film is increased is preferable, and conversely, when the structure of the film is a combination of the titanium compound film and a film having another film quality, or exerts an influence on the film. In the case of applications where the impact is strong, it is preferable to use the titanium compound coating in the direction of decreasing the thickness,
Specifically, it is a titanium compound film having a thickness of 0.5 to 15 μm, preferably a titanium compound film having a thickness of 1 to 10 μm, and particularly preferably a titanium compound film having a thickness of 1 to 5 μm.

It is also preferable that the titanium compound film has the same composition over the entire surface of the substrate, or that the film has a substantially uniform film thickness. Alternatively, it is also preferable to change the composition and thickness of the coating depending on the surface of the base material. Specifically, for example, when used as a cutting tool, the rake face is a TiN _R coating, and the flank face is Use a TiC _R film, or make the rake face a thin film thickness, make the flank face a thick film thickness, or make the rake face film surface have a large N content, and the N content gradually decreases toward the inside of the film. Ti (CN) _R coating, the flank coating surface has a high C content, and the C content gradually decreases toward the inside of the coating.
In the case of a film of i (CN) _R , a film configuration in which these are combined can be given.

It is preferable that the coating of the present invention has a coating structure in which the above-mentioned titanium compound coating is directly applied to the surface of the substrate. Ti, Zr, H between compound film
It is also preferable that a metal thin film of one of f, V, Nb, Ta, Cr, and Mo be interposed, or that a film structure in which an outer layer of another film quality is coated on the surface of a titanium compound film be used. It is. Specifically, a titanium compound film is coated on a base material, and the surface of the titanium compound film contains aluminum oxide, a composite nitride containing Ti and Al, a composite nitrocarbide containing Ti and Al, and contains Ti and Al. Complex nitrogen oxides, complex carbonitrides containing Ti and Al, diamond,
It is preferable that the outer layer composed of one kind of single layer or two or more kinds of diamond-like carbon is further improved in abrasion resistance. This outer layer is preferably coated to a thickness of 0.1 to 5 μm from the viewpoint of the adhesion between the outer layer and the titanium compound coating and the wear resistance of the coating.

The coating in the coating of the present invention is preferably composed of fine grains as much as possible. In particular, the titanium compound coating has a half width of X-ray diffraction lines which is a standard for refining the particle size. (111) and / or
Alternatively, the half width of the (200) crystal plane is preferably 0.6 or more.

The coating of the present invention can be prepared by using various conventional or commercially available substrates and applying a conventional CVD method or PVD method. Specifically, the gas type, gas pressure, and excitation method in the CVD method, the gas type, gas pressure, the material of the target, and the excitation method in the PVD method are important. Further, when the coating of the present invention is produced by an ion plating method or a PVD method such as a sputtering method, a large compressive stress is likely to remain in the coating, which is preferable because the fracture resistance is remarkably excellent.

[0017]

According to the coating of the present invention, the atomic ratio of the non-metallic element to the Ti element in the titanium compound coating coated on the substrate acts to increase the hardness of the coating, and as a result, indirectly increases the wear resistance. In particular, in the case of a titanium compound film produced by the PVD method, an effect of causing a large compressive stress to remain in the film occurs, and as a result, an indirect effect of increasing the strength and abrasion resistance of the film becomes stronger.

[0018]

Example 1 Commercially available cemented carbide (JIS standard, SNGN1
20408 shape, P30 equivalent material) as a base material, this base material is placed in a container of a sputtering apparatus, and the inside of the container is 5 × 10
After evacuating to a vacuum of ^-6 Torr, Ar gas was flowed into the container to make the pressure 2 × 10 ⁻³ Torr. Next, while heating and holding the substrate at 500 ° C., the 5 × 10 × 1 mm-shaped carbon plate was irradiated with an ion beam in a state where the number of carbon plates shown in Table 1 was respectively set on the target plate shown in Table 1. Inventive products 1-4 and comparative products 1-3 shown in Table 1
I got (However, the products 1 to 4 of the present invention used a magnetron type sputtering device, and the comparative products 1 to 3 used a DC bipolar sputtering device).
The coating composition, film thickness and hardness of each of the coatings Nos. 1 to 3 were examined, and the results are shown in Table 1. The coating composition was measured and converted by a glow discharge optical emission spectrometer (GDS), and the film thickness was determined with a metallographic microscope and a scanning electron microscope.

Next, products 1-4 of the present invention and comparative products 1-3
Work material: S48C (250 mm diameter)
Round bar), cutting speed: 200 m / min, feed: 0.3
mm / rev, depth of cut: 1.5 mm, cutting oil: water-soluble,
Evaluation: A wet cutting test was performed under the condition that the flank wear was 0.3 mm or the life was at the time when chipping or peeling occurred. The results are also shown in Table 1.

[0020]

[Table 1]

[0021]

Example 2 A commercially available Ti (CN) -based cermet (JIS standard, S
After the base material (DKN42ZTN shape) was installed, a heating step, an Ar etching step and a coating step were performed to obtain inventive products 5 to 8 and comparative products 4 and 5. Among these, the present invention products 5 to 8 are 1 × in the electron heating type reaction vessel in which the base material is installed.
After evacuation to 10 ⁻⁵ Torr vacuum, Ar gas was introduced, the pressure was set to 2 × 10 ⁻³ Torr, electronic heating was performed at an output of 10 kW for 60 minutes, and a heating step of maintaining the substrate temperature at 450 ° C. A glow discharge is generated by applying a DC voltage of 300 V in an Ar gas of × 10 ⁻³ Torr, and the substrate surface is subjected to Ar ion bombardment treatment for 30 minutes.
And the coating process under the coating conditions shown in Table 2 (each container pressure was kept at 3 × 10 ⁻³ Torr, and nitrogen gas purity was 5N).

The comparative products 4 and 5 were evacuated to 1 × 10 ⁻⁵ Torr vacuum in the resistance heating type reaction vessel on which the base material was placed, and then introduced with Ar gas, and 4 × 10 ⁻⁴ to 1 × 10 ^{−. 4}
Torr pressure, output 20 kw, heating for 60 minutes, 4
A heating step of maintaining the temperature at 50 ° C. and a pressure of 8 × 10 ⁻² Torr
The substrate was manufactured by applying an Ar ion bombardment process to the substrate surface for 30 minutes by applying a DC voltage of 600 V in Ar gas of r, and a coating process under the coating conditions shown in Table 2.

The coating composition, film thickness, coating hardness, residual stress of the titanium compound coating, and half width of the titanium compound coating of the coatings of the products 5 to 8 of the present invention and the comparative products 4 and 5 thus obtained were obtained. 3 is shown. The coating composition, film thickness, and hardness were determined in Example 1.
The residual stress was determined by the X-ray diffraction method, and the half width was determined by C-
(11) of the titanium compound film at the Kα ray of the u target
1) It was obtained in terms of aspect.

Next, the inventive products 5 to 8 and the comparative products 4, 5
Work material: S48C: SCM440
(HB250-300), cutting speed: 161m / mi
n, feed: 0.2 mm / tooth, depth of cut: 2.0 mm, cutting conditions: 90 min.
The average flank wear at that time was determined and is shown in Table 3.
In addition, the wear mode after the cutting test of the present invention products 5 to 8 was normal wear, whereas the wear mode after the cutting test of the comparative products 4 and 5 was a little peeled.

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

Embodiment 3 Commercially available high-speed steel, Ti alloy, silicon nitride-based ceramics, aluminum oxide-based (Al ₂ O ₃ —Ti
C) Using each of the ceramic base materials, a coating was produced by treating in substantially the same manner as the product 1 of the present invention in Example 1.
These were designated as invention products 9, 10, 11, and 12, respectively.

As a comparison, the same substrates as used in the products 9 to 12 of the present invention were treated in substantially the same manner as the comparative product 1 in Example 1 to produce coatings.
8, 9.

The products 9 to 12 of the present invention thus obtained and the comparative product 6
The composition ingredients and coating hardness of ~ 9 of the coating was examined by the method performed in Example 1, the product of the present invention 9-12, high hardness of the product 1 of the present invention substantially similar to 3600 ± 50 (H _V) while was coated, comparative product 6-9 was comparative product 1 and substantially similar in film hardness 2700 ± 50 _{(H V).}

[0030]

The coating of the present invention has a hardness of about 3.4 to 37.5% higher than that of a conventional coating having a coating close to the stoichiometric composition, and has a residual compressive stress of the coating. Is about 1
5.5-40% higher, wear resistance in cutting test is 40
% Or more, and also has an effect of being excellent in peeling resistance. In particular, in the case of the coating of the present invention in which the titanium compound coating having a non-stoichiometric composition is coated on the outermost surface layer, compared with the conventional coating, There is a remarkable effect that the hardness of the coating is about 23 to 37.5% higher and the life in the cutting test is improved by 2 to 6 times.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C23C 14/00-14/58 C23C 16/00-16/56 B23B 27/14 C04B 35/42-35 / 51 C01B 21/076

Claims (4)

(57) [Claims] 1. Ti (C _x , N _y ) _R (where Ti is titanium, C is carbon, N is nitrogen, and X and Y are non-metallic elements) Represents the atomic ratio of carbon and nitrogen, and R represents the atomic ratio of the nonmetallic element obtained by adding carbon and nitrogen to titanium as the metal element, and X + Y = 1 and 1 ≧ X
≧ 0, 1.5 ≧ R ≧ 1.01) of a single layer or two or more layers of titanium carbide, titanium nitride, titanium carbonitride having a non-stoichiometric composition. A coating for tools, which is coated with a titanium compound coating. 2. The titanium compound film represented by Ti (C _X , N _Y ) _R is formed by removing C from the surface of the titanium compound film.
The tool coating according to claim 1, wherein a half-value width of the (111) and / or (200) crystal plane is 0.6 or more when subjected to X-ray diffraction by u-Kα radiation. 3. Ti (C _X , N _Y ) _R (where Ti is titanium, C is carbon, N is nitrogen, and X and Y are non-metallic elements) Represents the atomic ratio of carbon and nitrogen, and R represents the atomic ratio of a nonmetallic element obtained by adding carbon and nitrogen to titanium as a metal element, and X + Y = 1 and 1 ≧ X
≧ 0, 1.5 ≧ R ≧ 1.01) of a single layer or two or more layers of titanium carbide, titanium nitride, titanium carbonitride having a non-stoichiometric composition. Aluminum oxide, a composite nitride containing Ti and Al, a composite nitrocarbide containing Ti and Al, a composite oxynitride containing Ti and Al, A coating for a tool, wherein the coating is coated with one kind of single layer or two or more kinds of outer layers among composite carbonitrides containing Al, diamond and diamond-like carbon. 4. The titanium compound film represented by Ti (C _X , N _Y ) _R is formed by removing C from the surface of the titanium compound film.
The tool coating according to claim 3, wherein a half-value width of the (111) and / or (200) crystal plane is 0.6 or more when subjected to X-ray diffraction by u-Kα ray.