JP3249277B2 - Wear resistant coating - 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 a metal, an alloy or a ceramic sintered body to obtain abrasion resistance, high hardness and peel resistance. , High-toughness, corrosion-resistant, decorative coatings suitable for decorative members, specifically cutting tools such as turning tools, milling tools, end mills, drills,
The present invention relates to a wear-resistant coating member suitable for a decorative component such as a wear-resistant tool or fishing gear represented by a slitter, a can-making tool, a metal mold, a clock member, a frame of glasses, a tie pin, and a broach.

[0002]

2. Description of the Related Art On a metal, alloy or sintered ceramic substrate, a single layer or a single layer of carbides, nitrides and mutual solid solutions of metals belonging to groups 4a, 5a and 6a of the periodic table is formed. Numerous coating members coated with multiple or more kinds of coatings have been proposed, and some of them have been put to practical use.

[0003] These coated members are intended to effectively utilize the excellent abrasion resistance of the coating and the excellent toughness of the substrate, but have poor adhesion between the substrate and the coating and have a multilayer structure. Then, there is a problem that the adhesion between the coatings is inferior, or the abrasion resistance of the coatings themselves is not satisfactory.

In order to solve these problems, there have been proposed a large number of coated members in which a solid compound composite compound film, particularly a composite compound film containing Ti, is coated on a substrate. And JP-A-55-58364.
JP, JP-A-62-56564, JP-A-62-56564
192576, JP-A-62-270764, JP-A-2-50948 and JP-A-4-29.
No. 7568.

[0005]

[0005] Japanese Patent Application Laid-Open No. 55-58364 discloses a cemented carbide member in which a Ti-containing composite compound film is coated on a base material of a metal, alloy or ceramic sintered body. (Hf, Ti) C, (Hf, T
i) A coated member coated with a composite compound film of N and (Hf, Ti) CN is described in JP-A-62-56.
Japanese Patent Application Publication No. 564 describes a coated member in which the surface of a base material is coated with a single compound layer of a carbide, nitride or carbonitride of Ti and Zr or a composite compound film composed of two or more layers. Japanese Patent Application Laid-Open No. 62-192576 discloses a carbide, nitride or carbonitride of titanium, chromium, vanadium or zirconium with an inner layer interposed on the surface of a substrate of a cemented carbide, cermet or ceramic sintered body. JP-A-62-270764 describes a coated member coated with a composite compound film. JP-A-62-270764 discloses a single layer of one of carbides, nitrides and carbonitrides of Ti, Zr and Hf on the surface of a substrate. It describes a coated member coated with a composite compound film composed of two or more multilayers.
No. 8 discloses that Ti and Cr carbides, nitrides,
It describes a coated member coated with a single compound layer of carbonitride or a composite compound film composed of two or more layers. The composite compound coatings described in these publications are:
It is composed of a stoichiometric composition or a composition close to the stoichiometric composition in which the atomic ratio of the metal element and the nonmetal element is 1: 1. Therefore, the resistance between the base material and the composite compound film and between the composite compound film and the other films is high. Due to poor peelability and poor abrasion resistance of the composite compound film itself, there is a problem that the service life becomes short when used under severe conditions such as a cutting tool.

[0006] Japanese Patent Application Laid-Open No. 2-50948 discloses that
(Ti, Zr, Hf) N _0.8 to _1.0
A coated member coated with the composite compound film of the above is described. The coating member described in the publication has an improved adhesion and abrasion resistance between the substrate and the coating as compared with the coating member described in the above-mentioned JP-A-55-58364. However, there is a problem that the durability is not sufficiently satisfied with the peeling resistance and the abrasion resistance, and the life is short when used as a cutting tool.

The present invention has solved the above-mentioned problems. Specifically, the present invention covers a substrate having a non-stoichiometric composition having optimal properties on its surface, and has a hardness, An object of the present invention is to provide a wear-resistant coated member having improved wear resistance, peel resistance, heat resistance, oxidation resistance, and fracture resistance.

[0008]

Means for Solving the Problems The inventors of the present invention have studied the improvement of the service life when a coated member in which a Ti compound is coated on the surface of a cemented carbide or cermet is used as a cutting tool. By adjusting the composition components of the film made of a compound, specifically, by forming a Ti-containing composite compound film having a non-stoichiometric composition containing an excessive amount of nonmetallic elements, a high compressive stress remains in the film, As a result, the fact that the hardness is high, the lubricity of the coating itself, the oxidation resistance is excellent, and the exfoliation resistance is excellent, the knowledge that the life can be remarkably improved when used as a cutting tool. As a result, the present invention has been completed.

That is, the coating member of the present invention is formed by coating (Tia, M
b) (C _X , N _Y ) _R (where Ti is titanium, M is Zr,
Hf, V, Nb, Ta, Cr, Mo, W represent at least one element, C represents carbon, N represents nitrogen, and a and b represent respective atoms of metal elements Ti and M X and Y represent the respective atomic ratios of the non-metallic elements C and N, and R is the atomic ratio of the non-metallic element summing C and N to the metal element summing Ti and M. Where a + b = 1, 1>a> 0, X +
Y = 1, 1 ≧ X ≧ 0, 1.8 ≧ R ≧ 1.01. ) Is coated with a non-stoichiometric titanium-containing composite compound film represented by the formula:

The base material of the coating member of the present invention is, for example, a metal of Group 4a, 5a or 6a of the periodic table,
u, Al, Fe, Ni, Co metals, stainless steel, high-speed steel, heat-resistant alloys, Ti alloys, Al alloys, Cu alloys or cermets, sintered alloys represented by cemented carbides, Al ₂
O ₃ based ceramic sintered body, Si ₃ N ₄ based ceramic sintered body, Sialon based ceramic sintered body, ZrO ₂ based ceramic sintered body, SiC based ceramic sintered body, Al
An N-based ceramic sintered body can be used.

Coated on these substrates (Tia, M
b) The titanium-containing composite compound film represented by the formula of (C _X , N _Y ) _R is specifically, for example, (Ti, Zr) C _R ,
_{(Ti, Hf) C R,} (Ti, Ta) C R, (Ti, N
b) C _R , (Ti, V) C _R , (Ti, Cr) C _R , (T
i, Mo) C _R , (Ti, W) C _R , (Ti, Zr)
N _R , (Ti, Hf) N _R , (Ti, Ta) N _R , (T
i, Nb) N _R , (Ti, V) N _R , (Ti, Cr)
N _R , (Ti, Mo) N _R , (Ti, W) N _R , (Ti,
Zr) (C, N) _R , (Ti, Hf) (C, N) _R , (T
i, Ta) (C, N) _R , (Ti, Nb) (C, N) _R ,
(Ti, V) (C, N) _R , (Ti, Cr) (C,
N) _R , (Ti, Mo) (C, N) _R , (Ti, W)
(C, N) _R , (Ti, Zr, Hf) C _R , (Ti, T
a, Hf) C _R , (Ti, W, Hf) C _R , (Ti, W,
Ta) C _R , (Ti, Cr, Zr) C _R , (Ti, Zr,
Hf) N _R , (Ti, Ta, Hf) N _R , (Ti, W, Z
r) N _R , (Ti, Cr, Zr) N _R , (Ti, Zr, H
f) (C, N) _R , (Ti, Ta, Hf) (C, N) _R ,
(Ti, W, Zr) (C, N) _R , (Ti, Cr, Z
r) (C, N) _R.

When _{R in} the titanium-containing composite compound coating represented by the formula of (Tia, Mb) (C _X , N _Y ) R is less than 1.01 or R is more than 1.8, R is determined to be 1.01 to 1.8 because the decrease in hardness and abrasion resistance becomes remarkable. In order to maintain high hardness and excellent abrasion resistance, R is preferably 1 to 1. 0.05 to 1.7 is preferred.

Further, since the titanium-containing composite compound coating is made of carbide, nitride or carbonitride, 1 ≧ X ≧
0, 1 ≧ Y ≧ 0, and X + Y = 1.

When a in the formula of the titanium-containing composite compound coating becomes zero, b becomes relatively one, and as a result, the thermal shock resistance and the impact resistance are significantly reduced.
a> 0, and preferably 1>a> 0.5 in order to particularly enhance the thermal shock resistance and the impact resistance.

The thickness of the titanium-containing composite compound film varies depending on the composition, use, shape and the like of the film to be coated on the base material. For example, the composition of the film consists only of the titanium-containing composite compound film. In the case where the impact on the coating is weak, it is preferable to increase the thickness of the titanium-containing composite compound coating, and conversely, the configuration of the coating is composed of the titanium-containing composite compound coating and another film quality In the case of a combination with a coating or an application in which the impact on the coating is strong, it is preferable to selectively use the titanium-containing composite compound coating in the direction of decreasing the film thickness. The film thickness of the composite compound coating is 1 to 15 μm in the former case, and 0.5 in the latter case.
If it is not used as the former or the latter, it is preferably 1 to 10 μm, particularly preferably 1 to 10 μm.
５5 μm.

[0016] The coating member of the present invention can be directly applied to the surface of a substrate.
It is also preferable that the above-mentioned titanium-containing composite compound film is coated. Further, one of Ti carbides, nitrides, and carbonitrides is provided between the substrate and the titanium-containing composite compound film.
It is also preferable to interpose an inner layer consisting of a single kind of layer or two or more kinds of layers. Further, the surface of the base material is directly coated with a titanium-containing composite compound film, and the surface of the titanium-containing composite compound film is coated with Ti carbide, nitride, etc. , An oxide, a nitride of Al and a mutual solid solution thereof, it is also preferable that one or a plurality of outer layers are coated, and the inner layer and the titanium-containing composite compound are coated on the base material. It is also preferable to form a coating in which a coating and an outer layer are sequentially coated.

The outer layer at this time is, specifically, TiC,
TiN, Ti (C, N), Al ₂ O ₃ , AlN, Al
(O, N) (Ti, Al) N, (Ti, Al) (C,
N), (Ti, Al) C, (Ti, Al) (N, O),
(Ti, Al) (C, O) (Ti, Al) (C, N,
O). The outer layer and the inner layer each have a thickness of 0.1 to 5 μm, preferably 0.5 to 5 μm.
3 μm, the composition of which is composed of a stoichiometric composition or a non-stoichiometric composition in which the amount of nonmetallic elements relative to metal elements is small or large.

Further, as another coating constitution of the coating member of the present invention, as a coating in which the inner layer and the titanium-containing composite compound coating are made into one cycle, when this is repeated two or more cycles, or when the titanium-containing composite compound In the case of a film in which a compound film and an outer layer constitute one cycle, when this is repeated and repeated two or more times, and in the case of a film in which an inner layer, a titanium-containing composite compound film and an outer layer constitute one cycle, this is repeated two or more cycles. Repeated lamination is also preferable from the viewpoint of improving the strength of the coating.

The total coating thickness of the coating member of the present invention described in detail above can be variously selected depending on the application and the shape.
The thickness is preferably 0 μm or less, and particularly in applications where a large impact is applied, such as a cutting tool, the total coating thickness is preferably 5 μm or less.

The coating in the coated member of the present invention is preferably composed of as fine grains as possible. In particular, the titanium-containing composite compound coating has a half-value width of X-ray diffraction lines which is a standard for refining the particle size. Has a Cu-Kα ray (11
1) and / or (200) crystal plane having a half width of 0.6
It is preferable to consist of the above.

The coating member of the present invention can be produced by using various conventional or commercially available substrates and applying a conventional CVD method or PVD method. Specifically, it is important to adjust the gas pressure in the CVD method or the PVD method. Further, when the coated member of the present invention is manufactured by a PVD method such as an ion plating method or a sputtering method, it is a film having a large R, and a large compressive stress is easily left in the film, so that the fracture resistance is remarkably excellent. This is preferable.

[0022]

In the coated member of the present invention, the atomic ratio of the non-metallic element to the metallic element in the coated titanium-containing composite compound coating on the substrate acts to increase the hardness of the coating and, as a result, indirectly reduces wear resistance. In the case of a titanium-containing composite compound film produced by a PVD method,
The action of leaving a large compressive stress in the coating occurs, which has the indirect effect of increasing the strength and wear resistance of the coating.

[0023]

Example 1 A commercially available cemented carbide (JIS standard, P30 equivalent grade, S) was placed in a reaction vessel of an ion plating apparatus.
After installing the base material (DKN42ZTN shape), a heating step, an Ar etching step, and a coating step were performed to obtain inventive products 1 to 5 and comparative products 1 and 2. Among them, the present invention products 1 to 5 are 1 × in an electron heating type reaction vessel in which a base material is installed.
After evacuation at 10 ^-5 Torr, Ar gas was introduced and
× 10 ⁻³ Torr and the products of the present invention 1, 2, 4, 5
Is electronically heated at an output of 10 kW for 60 minutes, and the product 3 of the present invention is electronically heated at an output of 12 kW for 60 minutes.
380 ° C., and the substrate temperature of the product 4 of the present invention was 390 ° C.
C., a heating step of maintaining the substrate temperature of the product 5 of the present invention at 395 ° C., and applying a DC voltage of 300 V in Ar gas at a pressure of 1 × 10 ⁻³ Torr to generate a glow discharge, thereby causing the substrate surface to be exposed. It was produced by an Ar etching process by Ar ion bombardment for 30 minutes and a coating process under the respective coating conditions shown in Table 1 (using nitrogen gas purity of 5N).

The comparative products 1 and 2 were prepared by evacuating the inside of the resistance heating type reaction vessel having the base material to 1 × 10 ⁻⁵ Torr,
r gas was introduced, and for comparative products 1 and 2, 4 × 10 ^-4
１1 × 10 ^-4 Torr pressure, output 20 kW, heated at 500 ° C. for 60 minutes, pressure 8 × 10 ⁻² Torr
In this Ar gas, a DC voltage of 600 V was applied, and the substrate surface was subjected to Ar ion bombardment treatment for 10 minutes, and the substrate was produced by a coating process under the respective coating conditions shown in Table 1.

The coating thickness of each of the thus-obtained products 1 to 5 of the present invention and comparative products 1 and 2 was about 3.5 μm when examined with a scanning electron microscope.
The results were analyzed by a line diffraction apparatus and a glow discharge emission spectrometer, and are shown in Table 2. The hardness from the surface of each film, the residual stress of the film by X-ray diffraction using Cu-Kα ray, and the half width at the (111) crystal plane of the film were also shown in Table 2.

Next, products 1 to 5 of the present invention and comparative products 1 to 2
Work material: S48C (HB = 224 to 24)
2), tool shape: SDKN42ZTN, cutting speed: 13
0m / min, depth of cut: 1mm, feed: 0.2mm / r
ev, cutting was performed for 100 minutes under the cutting conditions by wet turning, and the respective flank wear amounts at that time were measured.
It was also described in.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

Example 2 Using the same apparatus and substrate used in Example 1, the same steps were performed to obtain products 6 to 11 of the present invention and comparative products 3 to 6. Of these, products 6 and 11 of the present invention were treated under the same heating conditions and Ar etching conditions as those of products 1 and 2 of the present invention, and then coated under the coating conditions shown in Table 3 (A single layer, a second layer, and a third layer in this order). The product 7 of the present invention was the same as the product 7 except that the bombarding time during the Ar etching step was set to 20 minutes.
After being treated under the same heating conditions and Ar etching conditions as those of the products 6 and 11 of the present invention, a coating process under the coating conditions shown in Table 3 was performed. The product 8 of the present invention has an output of 8.5 kw during the heating step, a heating time of 70 minutes, a substrate temperature of 380 ° C., and an Ar
The heating conditions were the same as those of the products 6 and 11 of the present invention except that the bombarding time during the etching step was 25 minutes.
After processing under the etching conditions described in Table 3, the coating process was performed under the coating conditions shown in Table 3 to produce the substrate. The product 9 of the present invention was treated under the same heating conditions and Ar etching conditions as those of the products 6 and 11 of the present invention except that the output during the heating step was 8.5 kw and the heating temperature was 350 ° C., and shown in Table 3. It was produced by applying a coating process under coating conditions. The product 10 of the present invention has a heating time of 65 minutes during the heating step and a heating temperature of 410 ° C.
After processing under the same heating conditions and Ar etching conditions as those of the products 6 and 11 of the present invention, a coating process under the coating conditions shown in Table 3 was performed.

The comparative products 3, 4, and 6 were prepared by treating them under the same heating conditions and Ar etching conditions as those of the comparative products 1 and 2 of Example 1, and then performing a coating process under the coating conditions shown in Table 4. did. Comparative product 5 was treated under the same heating conditions and Ar etching conditions as those of Comparative products 1 and 2, except that the output during the heating step was 18 kw and the heating temperature was 450 ° C., and then the coating was performed under the coating conditions shown in Table 3. It was produced by performing the steps.

The inventive products 6 to 11 thus obtained and the comparative product 3
As a result of examining each of the coating films Nos. To 6 by the method described in Example 1, the film thickness of the first layer was approximately 1 μm, and the film thickness of the second layer was approximately 2 μm.
m, the thickness of the third layer was about 0.3 μm. Table 5 shows the composition of the coating, the hardness of the coating, and the residual stress of the coating. Further, cutting tests were performed using the products 6 to 11 of the present invention and the comparative products 3 to 6 under the cutting conditions by wet turning in Example 1, and the results are also shown in Table 5.

Next, using a spiral drill having a diameter of 8 mm which is a covering member of the product 8 of the present invention and the comparative product 3, a work material:
SCM440 (HB = 230-250), cutting speed: 6
0m / min, feed: 0.2mm / rev, machining depth:
As a result of drilling 15m under the condition of 30mm,
The average flank wear of the product 8 of the present invention was 0.15 mm, while the flank wear of the comparative product 3 was 0.2 mm.

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

Embodiment 3 Of the product 8 of the present invention in the second embodiment, the coating on the flank is substantially the same as the product 8 of the present invention except that only the second layer thickness is 1 μm.
The product 12 of the present invention having the film configuration of the present invention and the film configuration of the flank of the comparative product 3 of the second embodiment.
Other than m, the film configuration of the comparative product 3 substantially corresponds to that of the comparative product 7. The work material: SCM (HB = 240 to 260, 6) With hole), Cutting speed: 150m / min, Feed: 0.25m
m / blade, depth of cut: 2 mm, tool shape: SDKN42ZT
N, as a result of performing dry milling, the product 12 of the present invention
Maximum relief wear at machining length 4m is 0.05mm
In contrast, the comparative product 7 had a maximum flank wear amount of 0.1 mm when the processing length was 4 m, and the coating film was slightly peeled off.

[0037]

Example 4 Commercially available high speed steel, Ti alloy, nitrogen containing titanium carbide (TiC-TiN) based cermet, a silicon group nitride ceramics, aluminum oxide-based (Al ₂ O ₃ -Ti
C) Using each of the ceramic base materials, treatment was performed in substantially the same manner as that of the product 2 of the present invention in Example 1 to produce a covering member, and each of them was coated with the products 13, 14, 15, 16 and 17 of the present invention.
And

As a comparison, the same base material used in the products 13 to 17 of the present invention was treated in substantially the same manner as the comparative product 1 in Example 1 to produce a covering member.
9, 10, 11, and 12.

The composition and hardness of the coatings of the inventive products 13 to 17 thus obtained and the comparative products 8 to 12 were examined by the method performed in Example 1. whereas the a high hardness coating goods 2 substantially the same at 2810 ± 50 (H _V), comparative 8-12 met comparative 1 with substantially the same as a coating hardness 2400 ± 50 (H _V) Was.

[0040]

The coated member of the present invention has a hardness of about 7 to 32% higher and a residual compressive stress of the coated film of about 21 to 21% as compared with a conventional coated member having a coating having a similar stoichiometric composition. ~
192% higher, wear resistance in cutting test about 10-6
It has a remarkable effect of improving the coating film by 9%, having excellent peeling resistance, and having a long life.

──────────────────────────────────────────────────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 (5)

(57) [Claims] An abrasion resistance characterized in that a non-stoichiometric titanium-containing composite compound film represented by the following formula (A) is coated on a base material of a metal, alloy or ceramic sintered body. Coating member. (Tia, Mb) (C _X , N _Y ) _R ‥‥‥ (A) [where, in the formula (A), Ti is titanium, and M is Zr, Hf,
V, Nb, Ta, Cr, Mo, W represents at least one element, C represents carbon, N represents nitrogen, a and b
Represents the atomic ratio of each of the metal elements Ti and M, X and Y represent the atomic ratios of the non-metal elements C and N, and R represents the total metal element of Ti and M Represents the atomic ratio of the non-metallic element sum of C and N, where a + b = 1, 1>a> 0, X + Y =
1, 1 ≧ X ≧ 0, 1.8 ≧ R ≧ 1.01. ] 2. The titanium-containing composite compound film represented by the above formula (A) has a relation of 1> a ≧ 0.5, 1.7 ≧ R ≧ 1.0.
5. The wear-resistant covering member according to claim 1, wherein said member has a relationship of 5. 3. A non-stoichiometric titanium-containing composite compound film represented by the following formula (A) is coated on a base material of a metal, alloy or ceramic sintered body. An abrasion-resistant coating characterized in that an inner layer comprising one kind of a single layer or two or more kinds of Ti carbides, nitrides and carbonitrides is coated between the coating and the composite compound coating. Element. (Tia, Mb) (C _X , N _Y ) _R ‥‥‥ (A) [where, in the formula (A), Ti is titanium, and M is Zr, Hf,
V, Nb, Ta, Cr, Mo, W represents at least one element, C represents carbon, N represents nitrogen, a and b
Represents the atomic ratio of each of the metal elements Ti and M, X and Y represent the atomic ratios of the non-metal elements C and N, and R represents the total metal element of Ti and M Represents the atomic ratio of the non-metallic element sum of C and N, where a + b = 1, 1>a> 0, X + Y = 1,
1 ≧ X ≧ 0 and 1.8 ≧ R ≧ 1.01. ] 4. The titanium-containing composite compound film represented by the above formula (A) has a relation of 1> a ≧ 0.5, 1.7 ≧ R ≧ 1.0.
4. A wear-resistant covering member according to claim 3, wherein said member has a relationship of 5. 5. A single layer of one of Ti carbides, nitrides, Al oxides, nitrides, and mutual solid solutions thereof on the surface of the titanium-containing composite compound film represented by the formula (A). 5. The wear-resistant covering member according to claim 3, wherein two or more kinds of outer layers are coated.