JP2001152209A - High adhesion surface coated sintered member and its producing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem that, as for surface coated cemented carbide obtained by coating the surface of a base material of cemented carbide with a hard film by a chemical vapor deposition method in surface coated sinetred members obtained by coating the surface of a base material consisting of cemented carbide, cermet or a ceramics sintered body with a hard film, there is a case that the components in the base material such as Co and W are diffused and incorporated into the hard film, and in this case, the adhesion between the base material and the hard film is improved, but, when only the components in the base material are diffused and incorporated into the hard film, the adhesion and strength are not satisfied and insufficient. SOLUTION: In this high adhesion surface coated sintered member, cemented carbide, cermet or a ceramics sintered body is used as a base material, the surface of the base material is coated with a hard film of one kind of single layer composed of a hard substance having high hardness or a mixture containing the hard substance or composed of lamination of one or two or more layers, the surface part of the base material in the vicinity of the boundary between the base material and the hard film is incorporated with dissimilar elements different from the elements composing the inside of the base material, and also, all the layers or a part of the layers in the hard film is incorporated with the dissimilar elements.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for forming a surface of a base material comprising a cemented carbide, a cermet or a ceramic sintered body,
TECHNICAL FIELD The present invention relates to a high-adhesion surface-coated sintered member coated with a high-hardness hard film and a method for producing the same, and in particular, to a high-adhesion surface-coated sintered member characterized by the surface portion of a base material and the configuration in the hard film. And a method of manufacturing the same.

[0002]

2. Description of the Related Art TiC, TiCN, T is coated on the surface of a base material made of a cemented carbide, a cermet or a ceramic sintered body.
Hard films such as iN and Al ₂ O ₃ are formed by chemical vapor deposition (hereinafter referred to as “C
VD method), physical vapor deposition method (hereinafter referred to as “PVD method”), or a surface-coated sintered member coated by plasma CVD or the like, the strength and toughness of the base material, the wear resistance of the hard film, and the decoration It is widely used as a cutting tool, an abrasion-resistant tool, a mechanical part, a corrosion-resistant part, and a decorative part because of having both the corrosion resistance and the corrosion resistance. However, especially when used as a cutting tool, a wear-resistant tool, or a machine part, the adhesion between the base material and the hard film is poor, and the hard film itself is brittle. There is a problem that wear is rapidly caused by damage and the life is shortened.

On the other hand, generally, the base material of a surface-coated sintered member is
It is formed into a shape according to the application by grinding or the like, and is composed of a mechanically worked surface by this grinding or the like and a sintered surface that has not been ground. In particular, a typical case where the base material is made of a cemented carbide is a typical example. On the mechanically processed surface, machining dust containing Co is relatively uniformly adhered to the surface, but a process-affected layer is formed near the surface. (Specifically, cracks in the hard phase particles, interfacial defects between the hard phase particles or between the hard phase particles and the binder phase, work-affected layers typified by transformation of the binder phase, etc.) remain. There is a problem that the deteriorated layer becomes a defect, causing peeling of the hard film and causing minute damage. In addition, although there is no work-affected layer on the sintered surface, there is a problem of causing peeling of the hard film and micro-damage, including the fact that the surface is rough and the binder phase does not exist on the hard phase particles. is there.

[0004] With respect to the problem of the base material and the hard film in such a surface-coated sintered member, Japanese Patent Application Laid-Open No. Hei 5-237707 discloses a typical one proposed to solve mainly the structure of the hard film. JP-A-5-263252, JP-A-7-243023, JP-A-7-31
4207, JP-A-8-118105, JP-A-8-118108, JP-A-8-187605, JP-A-8-187606, JP-A-8-18
7607, JP-A-9-262705, and Japanese Patent No. 2861832.

On the other hand, with respect to the problem of the base material and the hard film in such a surface-coated sintered member, Japanese Patent Application Laid-Open No. 5-123903 has been proposed as a typical solution which is mainly proposed to solve the surface of the base material. JP-A-6-108253
And JP-A-7-97603.

[0006]

Among the prior art documents which disclose the adhesion between the base material and the hard film, Japanese Patent Application Laid-Open Nos. 5-237707, 7-243023 and 7-314207 disclose the prior art documents. JP, JP-A 8-118
No. 105, JP-A-8-118108, JP-A-8-187605, JP-A-8-187606, JP-A-8-187607, JP-A-9-262
No. 705 and Japanese Patent No. 2861832,
A surface-coated cemented carbide in which a hard film is coated on a base material surface of a WC-based cemented carbide is disclosed, and W, C forming a base material in a hard film in these surface-coated cemented carbides is disclosed.
It is disclosed that o and the like are diffused.

In the surface-coated cemented carbide disclosed in these publications, the adhesion between the base material and the hard film is improved by W, Co and the like diffused in the hard film. However, these surface-coated cemented carbides have the properties of hard film, composition of hard film, temperature for coating hard film, type of gas,
There is a problem that the adjustment of the coating conditions typified by the atmosphere such as the partial pressure of the gas is not enough to improve the adhesion, and the diffusion element is limited. And the wettability is not optimal, and the strength and adhesion of the hard film are not satisfactory.

Japanese Patent Application Laid-Open No. Hei 5-263252 discloses that, contrary to the above-mentioned publication, it is possible to prevent the diffusion of W and the like which constitute the base metal cemented carbide at the time of coating the hard film and the absorption of C. It is disclosed that the wear resistance and fracture resistance as a cutting tool are simultaneously improved. The surface-coated cemented carbide disclosed in the publication is intended to prevent C diffusion from the base material by increasing the amount of C and N in TiCN constituting the hard film. Co-WC-based composite carbide which is fragile on the surface of the base material at the interface with
Phase), and conversely, a diffusion layer with high adhesion due to diffusion of Co and W becomes difficult to form,
There is a problem that the strength and adhesion of the hard film are not satisfied.

On the other hand, among prior art documents mainly focusing on the surface condition of the base material, Japanese Patent Application Laid-Open No. 6-108253 discloses that the base material surface of a cemented carbide is, for example, brush-polished so that the average surface roughness Ra is zero. There is disclosed a surface-coated cemented carbide in which a hard film is coated on a surface having a polishing flaw of .15 to 0.4 μm and formed in a random direction. The surface-coated cemented carbide disclosed in the publication is characterized in that Co adheres to the hard particles on the surface of the base material somewhat uniformly due to the attachment of the grinding dust generated by brush polishing, and thus the hard film has Although the adhesion is enhanced, there is a problem that the adhesion of Co is small and the adhesion is insufficiently improved due to the process-affected layer.

[0010] Among the prior art documents focusing on the surface condition of the base material, Japanese Patent Application Laid-Open No. 5-123903 discloses that after the surface is ground, it is refired in a high-pressure inert gas atmosphere at a liquid phase appearance temperature or higher. A method of manufacturing a surface-coated cemented carbide in which a cemented cemented carbide is used as a base material and a hard film is coated on the surface of the base material by a CVD method is disclosed. A diamond coating ceramic in which the edge of the alloy tip is subjected to an arc honing process of R = 0.03 mm and then re-sintered in an atmosphere of 1% N ₂ -99% Ar to form a nitrogen-containing uneven layer on the surface. A base material and a method for manufacturing the same are disclosed.

[0011] In the re-sintered surface of the base material disclosed in these two publications, although the adhesion is slightly improved because the affected layer is completely removed, the surface is hardened on the hard particles by grinding. Since the adhered Co disappears by re-sintering, a diffusion layer is not formed, and there is a problem that the adhesion is insufficiently improved. Further, there is a problem that unevenness increases on the re-sintered surface and the surface becomes rough, so that the work material easily adheres to the surface, causing film peeling and a decrease in finished surface accuracy.

The present invention has solved the above-mentioned problems. Specifically, the present invention has greatly improved and improved the adhesion between the base material and the hard film, and at the same time, has improved the strength of the hard film itself. By greatly improving and increasing the resistance of the hard film from the base material and the micro-damage and micro-peeling resistance in the hard film, the life and durability are significantly improved, and It is an object of the present invention to provide a high-adhesion surface-coated sintered member in which variations in life and durability are extremely small and stable quality control is achieved, and a method for producing the same.

[0013]

SUMMARY OF THE INVENTION The present inventors have been studying a method for greatly improving the adhesion between a base material and a film of a surface-coated cemented carbide for many years. When the specific component element is diffused and contained in both the hard film and the cemented carbide base material near the interface with the hard alloy base material, the adhesion is enhanced by the effect of promoting the diffusion of the specific component element or improving the interface strength. Significant improvement, specific component elements are iron group metals, chromium, molybdenum, manganese, copper,
That at least one selected from silicon is optimal,
In order to diffuse the specific component element into the cemented carbide base material and the hard film, the metal, alloy or compound of the specific component element is dispersed or coated on the surface of the cemented carbide base material before coating the hard film. The present invention has been completed based on the finding that it is sufficient.

The high-adhesion surface-coated sintered member of the present invention is made of a hard metal, a cermet or a ceramic sintered body as a base material, and a hard material having a high hardness or a mixture containing the hard material on the surface of the base material. A hard film composed of one kind of a single layer or a laminate of two or more layers, and the inside of the base material is formed on a surface portion of the base material near an interface between the base material and the hard film. Different elements from the elements that are present,
In addition, all or some of the layers of the hard film contain the different element.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The base material of the high-adhesion surface-coated sintered member of the present invention is a sintered member produced by powder metallurgy represented by a conventional cemented carbide, cermet, ceramic sintered body and the like. There is no particular limitation, and specifically, a cubic crystal mainly composed of a hard phase mainly composed of tungsten carbide or tungsten carbide and one or more carbides or carbonitrides of elements of groups 4a, 5a and 6a of the periodic table. Cemented carbide, titanium carbide, titanium carbonitride, titanium and a group 4a, 5a, 6a of the periodic table containing, as a hard phase with at least one of the base compounds, a binder phase mainly composed of cobalt and / or nickel The hard phase mainly composed of at least one of carbides, carbonitrides, carbonates, nitrides and carbonitrides with one or more of the elements, mainly cobalt and / or nickel Cermet containing binder phase, oxide ceramics containing aluminum oxide or zirconium oxide as a main component, non-oxide ceramics containing silicon nitride, sialon or silicon carbide as a main component, diamond produced by ultra-high temperature and pressure And high-pressure ceramic sintered bodies represented by cubic boron nitride-containing sintered bodies.

[0016] Of these base materials, when the base material is a cemented carbide base material containing a hard phase and a binder phase, when the hard phase is made of only tungsten carbide, tantalum carbide is added to tungsten carbide. In the case of a hard phase, a hard phase composed of tungsten carbide and a cubic compound can be given as a typical example. A typical example of the binder phase, which is another main component, is made of Co, Ni or Co-Ni solid solution. Specific cemented carbide base materials include WC-Co-based cemented carbide, WC
-(Ni-Cr) -based cemented carbide, WC-TaC-Co-based cemented carbide, WC- (W, Ti, Ta) C-Co-based cemented carbide, WC- (W, Ti, Ta) C- ( Co, Ni, C
r) cemented carbide, WC- (W, Ti, Ta, Nb)
(C, N) -Co-based cemented carbide may be used. In the case of the base material of the cemented carbide, it is preferable that the content of the binder phase is 3 to 30% by volume.

Hard films coated on the surfaces of these base materials have conventionally been formed by CVD, PVD and plasma CVD.
The film quality is, for example, a film made of a hard material mixed with at least one of ceramics, diamond, hard carbon, cubic boron nitride, and hard boron nitride. It is.

The hard film will be described in detail. The structure of the hard film is a single layer of one kind of the above-mentioned hard substance, a single layer of a mixture of two or more kinds, or a layer of two or more kinds of these. There may be mentioned a case where the film thickness is 0.5 to 20 μm formed by lamination. Further, when the configuration of the hard film is described in detail from another direction, when the hard film is a layer of granular crystals,
Typical examples include a case where the surface of the base material is composed of a columnar crystal layer perpendicular to the surface of the base material and a case where the layer is composed of a mixture of a layer of a granular crystal and a layer of a columnar crystal. It is preferable that the film quality and configuration of the hard film be selected depending on the use, shape, material of the base material and the like.

The film quality and film structure of the hard film, particularly the ceramic film, are specifically, TiC, TiCN, TN produced by CVD, PVD or plasma CVD.
iN, TiCO, TiNO, TiCNO, (Ti, Z
r) N, (Ti, Al) N, (Ti, Al) NO, (T
i, Al) NC, (Ti, Al) C, (Ti, Al) C
One of O, (Ti, Al) CNO, CrN, and Al ₂ O ₃
It can be selected as a single-layer film in which two or more of these are mixed, or a laminated film in which these are stacked in two or more layers.

Among these hard films, a typical structure of the laminated film is such that a TiC layer / TiN layer / TiCN layer /
Stack of 4 layers of TiN layer, TiN layer / TiC layer / Al
Stack composed of three layers of ₂ O ₃ layers, TiN layer / TiCN layer / Ti
Lamination of 5 layers of C layer / Al ₂ O ₃ layer / TiN layer, TiN
Layer / (Ti, Al) N layer / TiN layer
Stack composed of two layers, TiN layer / Si ₃ N ₄ layer, CrN layer / V
A laminated film typified by a laminate of two N layers can be given.

Among these hard films, the hard film adjacent to the base material or the hard film near the interface with the base material is a single layer of titanium nitride, titanium carbide, titanium carbonitride, or It is preferable to form a titanium compound film having two or more kinds of layers because different elements are easily diffused into the hard film and the adhesion is further improved. Particularly, an oxide film represented by aluminum oxide, a diamond film, hard carbon In the case of a hard film having a laminated structure including a film, a cubic boron nitride film, a hard boron nitride film, and the like, a titanium compound film, a SiC film, a hard film adjacent to the base material or a hard film near the interface with the base material. It is also preferable that the Si ₃ N ₄ film is coated as one type of single layer or as a laminate of two or more types.

When these hard films have an amorphous structure and / or a crystalline structure in terms of crystal structure, they have a non-stoichiometric composition and / or a stoichiometric composition in terms of composition. In this case, the crystal shape may be a granular crystal, a plate-like crystal and / or a columnar crystal. Of these, when the hard film is formed of a columnar crystal layer grown vertically long in the direction perpendicular to the surface of the base material, or in the case of a hard film including the columnar crystal layer, the outer periphery of the columnar crystal has wettability. Contains excellent dissimilar elements, enhances the adhesion between columnar crystals, and can significantly improve the strength of the hard film itself, specifically, the crushing strength from each direction such as longitudinal, lateral, and oblique directions. This is particularly preferable.

The different elements in the high-adhesion surface-coated sintered member of the present invention are preferably selected mainly based on the material and composition of the base material and the quality and composition of the hard film.
It is preferable that the material is mainly composed of a substance having excellent wettability and adhesion to the hard film, particularly a substance having excellent wettability and adhesion to both the base material and the hard film.

The different element may be contained in the hard film or in the surface of the base material,
When it is contained in the hard film, it may be contained on the entire surface or a part of the hard film. The content of the different elements contained in the hard film becomes maximum at the interface between the base material and the hard film or at the interface of the hard film on the base material side, and the slope gradually decreases from these interfaces toward the surface of the hard film. This is preferable because the composition component is excellent in adhesion between the base material and the hard film, and excellent in strength and wear resistance of the hard film. Also, when contained in the surface of the base material,
In some cases, they are uniformly dispersed or non-uniformly dispersed, and especially when they gradually decrease from the surface of the base material to the inside, the strength of the base material and the base material and hard film This is preferable because it has excellent adhesion to the substrate.

Specifically, in the analysis of a microscopic portion in an arbitrary cross section substantially perpendicular to the surface of the high-adhesion surface-coated sintered member, the dissimilar element is at least 0.5 μm from the interface between the hard film and the base material. When the hard film and the base material contain at least 0.5 atomic% or more of a different element,
This is preferable because the improvement in strength and adhesion is remarkable. Further, when the base material is made of a cemented carbide or cermet base material and the binder phase component in the base material contains a different element, the different element in the surface of the base material within 0.5 μm from the interface is removed. A particularly preferred embodiment is one in which the content is higher than the content in the base material 100 μm from the interface by 0.5 atom% or more. And when it is made of a cemented carbide or cermet base material, the base material surface at the interface between the base material and the hard film has no hard phase particles of 0.2 μm or less, and is within the hard phase particles. In other words, in the case where there is no crack, in other words, it is preferable that the work-affected layer accompanying the mechanical working is removed from the surface of the base material, because the adhesion is further improved. Further, it is preferable that the element forming the base material be contained in the hard film because the effect of improving the strength and the adhesion becomes more remarkable.

The different element is preferably selected depending on the material of the base material and the film quality of the hard film. The base material of a cemented carbide or cermet, titanium nitride, titanium carbide, titanium carbonitride, titanium oxynitride, Titanium, titanium carbonitride,
Hard including titanium-containing compound film consisting of one kind of single layer or two or more kinds of nitride, carbide, carbonitride, nitride oxide, carbonate and carbonitride containing titanium and aluminum In the case of a combination with a film, the different element is N
i, Fe, Cr, Mo, Mn, Cu, Si, Mg, B,
This is preferable when it is made of at least one of Nb, Ta, Al, and Zr, since it is appropriately diffused into both the base material and the hard film, and the effect of improving strength and adhesion becomes remarkable. In the case of a combination of the above-mentioned base material of the ceramic sintered body and the above-mentioned hard film containing the titanium-containing compound film, the different elements are Al, Ni, Fe, C
The case of at least one of o, Cr, Mn, Si, Mg, and B is also preferable.

In addition to the structure of the hard film coated on the surface of the base material described above, the entire film structure including the hard film coated on the surface of the base material can be variously configured.
As a typical form thereof, specifically, by combining the material of the base material and the film quality of the hard film, it is also possible to interpose an underlayer between the base material and the hard film, and to improve the adhesion. It is a good thing. In this case, it is preferable that a typical underlayer be a layer mainly composed of a different element having an average thickness of 0.5 μm or less, since the adhesion is further improved. In particular, in the case of one or more kinds of hard films such as an oxide film typified by aluminum oxide, a diamond film, a hard carbon film, a cubic boron nitride film, and a hard boron nitride film, the underlayer effectively acts. Which is preferable.

[0028] The method for producing a high-adhesion surface-coated sintered member of the present invention uses a cemented carbide, a cermet or a ceramic sintered body as a base material, and at least a part of the surface of the base material includes an iron group metal, chromium, A first step of uniformly covering at least one kind of hetero element forming layer selected from molybdenum, manganese, copper, silicon, magnesium, boron and their alloys and compounds containing them; The base material having the layer formed thereon is subjected to physical vapor deposition, chemical vapor deposition, or plasma chemical vapor deposition on at least the surface of the heterogeneous element forming layer to form a group 4a, 5a, or 6a element of the periodic table, aluminum, silicon carbide, Ceramics, diamond, hard carbon, which consist of nitrides, oxides, and their mutual solid solutions,
A second coating of a hard film comprising a single layer selected from cubic boron nitride and hard boron nitride, or a stacked layer of two or more layers;
This is a method that is manufactured through steps.

The first step in the manufacturing method of the present invention is, specifically, an electroplating method, an electroless plating method, a vacuum deposition method, a PVD method, a CVD method, for forming a metal, an alloy or a compound for forming a different element. Blasting using a chemical coating method such as a plasma coating method, a plasma CVD method, a colloid coating method, and a solution coating method, or a shot material containing a different element forming component as a main component or a mixture of the shot material, a polishing material, and an abrasive material. processing,
A mechanical coating method such as a shot treatment is used. In particular,
It is preferable that a metal or an alloy, which is a component forming a dissimilar element, be coated by an electroplating method or an electroless plating method, because it can be uniformly coated at low cost. Here, the heterogeneous element-forming component is the above-mentioned heterogeneous element itself, for example, iron group metal, chromium, molybdenum, manganese, copper,
Silicon, magnesium, boron, and precursors thereof, and are made of at least one selected from substances that can become different elements after the second step.

The base material in the production method of the present invention is:
It is preferable that at least a part of the surface of the base material is a sintered surface, a polishing lap surface, an electropolished surface, or a chemically etched surface, since the work-affected layer is removed and the adhesion is excellent. In particular, it is preferable that the surface of the base material be an electrolytically treated surface or a chemically etched surface, since removal and smoothing of the work-affected layer are promoted and adhesion is further improved.

[0031]

According to the high-adhesion surface-coated sintered member of the present invention, an iron-group metal and a base metal are contained in the hard film near the interface between the hard film and the base material.
Containing at least one kind of different element among chromium, molybdenum, manganese, copper, silicon, magnesium, and boron;
Alternatively, by containing both the different elements and the constituent elements of the base material, the strength of the hard film itself and the function of enhancing the adhesion between the hard film particles, the strength of the base material surface, and the adhesion of the hard film and the base material are improved. It is a function of improving the performance. Further, the method for producing a high-adhesion surface-coated sintered member of the present invention includes:
The first step of uniformly coating the metal, alloy, or compound of iron group metal, chromium, molybdenum, manganese, copper, or silicon on the surface of the base material before coating the hard film, and the second step after that, the hard film near the interface is formed. And promotes diffusion and inclusion in both the base material and the base material.

[0032]

[Test 1] 86.0WC-1.5TiC-0.5T
Using a composition of iN-4.0TaC-8.0Co (% by weight), using a throwaway chip material with a breaker of CNMG120408 shape according to ISO standard, the boss surface of this chip material is ground with a 270 # diamond grindstone. Then, the blade edge portion was honed to a radius of 0.04 mm with a nylon brush containing silicon carbide abrasive grains of 320 # to obtain a base material for a coated sintered member. Next, after performing a surface treatment under the method and conditions shown in Table 1 and performing ultrasonic cleaning in acetone, a 1.0 μm-thick granular crystal TiN layer was formed from the base material side using a CVD coating apparatus. 8.0
Coating a laminated hard film consisting of a 11.0 μm total thickness consisting of a columnar crystal TiCN layer of μm, a granular crystal Al ₂ O ₃ layer of 1.5 μm thickness, and a granular crystal TiN layer of 0.5 μm thickness Then, surface-coated sintered members of inventive products 1 to 8 and comparative products 1 to 5 were obtained.

[0033]

[Table 1]

With respect to each chip of the surface-coated sintered member thus obtained, each of the chips was cut in the vicinity of one corner, and then cut into 0.1 mm.
The sample was lapped and polished with a 5 μm diamond paste to prepare a field emission type scanning electron microscope measurement sample. A line analysis from the hard film surface to the inside of the base material using an X-ray microanalyzer was performed on the cutting edge (brushed surface) of each sample, and the hard film inside each of the hard film and the base material was about 0.3 μm from the interface. Point analysis was performed for the inside and the base metal. The types and contents of the different elements (elements excluding the film and base metal components) detected by the line analysis and the base metal component elements contained in the hard film were measured by 10 point analysis, and the results were obtained. Are shown in Table 2. Also, the vicinity of the interface between the hard film and the base material was observed, and the thickness of the layer existing at the interface, cracks in the hard phase particles, 0.2 μm
Table 3 shows the measurement results of the following hard phase fine particles. In the line analysis of the products 1 to 8 of the present invention, the distribution state of the different elements gradually decreases from the interface side toward the hard film surface in the hard film, and gradually decreases from the interface side toward the inside of the base material at the base material surface. Tendency was confirmed.

[0035]

[Table 2]

[0036]

[Table 3]

The thus obtained inventive products 1 to 8 and comparative products 1 to
As a cutting test (1), using five coated throw-away tips of the surface-coated sintered member of No. 5 as the cutting material (S45C), four grooves were formed, and the cutting speed was 150 m / mi.
n, depth of cut: 2.0 mm, feed: 0.30 mm / re
v, an outer peripheral intermittent turning test was performed under wet conditions. As a result of this cutting test (1), the number of impacts due to
Table 4 shows the ratio of the number of chips that had a chipped edge before reaching 10,000 times and the number of chips that had reached 10,000 times where film peeling (chipping) occurred and the number of normal chips.

Next, as a cutting test (2), the product of the present invention 1
Workpiece: S48C disk (150φ × 30m) using one coated throw-away tip of Comparative Products 1 to 5 and Comparative Products 1 to 5
m), cutting speed: 50 to 180 m / min, cutting depth:
An intermittent turning test of the plate surface was performed under the conditions of 2.0 mm, feed: 0.30 mm / rev, and wet type. As a result of this cutting test (2), the average width of the flank wear on the flank and the maximum width of the crater wear on the rake face, which is the damage of the cutting edge after cutting the plate face 50 times, were measured. 4

[0039]

[Table 4]

[0040]

[Test 2] As a base material of a surface-coated cemented carbide, 88.
An SNGN120 having a composition of 0WC-2.0TaC-9.5Co-0.5Cr (% by weight) as indicated by the ISO standard.
Using a 408-shaped throw-away tip material, the upper and lower surfaces and the outer peripheral surface are ground with a 270 # diamond grindstone,
-25 ° × 0.1 with 400 # diamond grindstone on the cutting edge
After the honing process of 0 mm, each of the present invention products 9 to 12 for the throw-away chip base material was subjected to the same surface treatment conditions as the base materials for the present invention products 1, 3, 5, 7 described in Table 1 of the execution test 1, respectively. The base materials for the throw-away chips for the comparative products 6 to 8 were treated under the same surface treatment conditions as the base materials for the comparative products 1, 2, and 4.

After ultrasonic cleaning them in acetone,
Using a CVD coating apparatus, a granular TiN layer having a layer thickness of 0.5 μm, a columnar TiCN layer having a layer thickness of 3.5 μm, a granular Al ₂ O ₃ layer having a layer thickness of 0.5 μm,
The present invention 9 was coated with a laminated hard film having a total film thickness of 5.0 μm comprising a granular TiN layer having a layer thickness of 0.5 μm.
To 12 and Comparative Examples 6 to 8 were obtained. With respect to the corner rake surfaces of the throw-away chip base materials of the surface-coated sintered members of the present invention products 9 to 12 and comparative products 6 to 8 thus obtained, the same analysis as in the execution test 1 was performed. The results are shown in Table 6. The distribution of the different elements in the line analysis of the products 9 to 12 of the present invention gradually decreased from the interface side to the hard film surface in the hard film, and gradually decreased from the interface side to the inside of the base material at the base material surface. The tendency was confirmed.

[0042]

[Table 5]

[0043]

[Table 6]

Next, using the coated throw-away tips of the products 9 to 12 of the present invention and the comparative products 6 to 8, a work material: SCM440 (machined surface shape: 50 W × 200 L),
Cutting speed: 135 m / min, depth of cut: 2.0 mm, feed: 0.36 mm / blade, and dry conditions. 40p
At the time of ass processing, the tool tip was observed and the number of thermal cracks generated on the rake face, the area of film peeling at the crater, the average amount of wear on the flank, and the micro chipping of the cutting edge were evaluated. Are shown in Table 7.

[0045]

[Table 7]

[0046]

[Test 3] Commercially available 90.0WC-9.2C
Using a solid drill (6 mm) made of cemented carbide made of fine WC with a composition of o-0.8Cr (wt%), the base material for the products 5 and 7 of the present invention described in Table 1 of Test 1 was applied to the surface of the drill. Surface treatment was carried out under the same conditions as
It was used as a base material. The same drill that was not subjected to surface treatment (under the same conditions as Comparative Product 1 in Table 1 in Test 1) was used as a base material for Comparative Product 9. After ultrasonic cleaning of these base materials in acetone, a hard coating of a columnar crystal TiCN layer having a layer thickness of 2.0 μm was coated using a CVD coating apparatus. 9 were obtained.

As a result of analyzing the outer peripheral cutting edge portion of these surface-coated sintered member drills in the same manner as in the test 1, the Ni content of the product 13 of the present invention was 11 to 2 in the hard film.
0 at%, 5 to 9 at% in the surface of the base material, and 3 to 10 at% in the hard film and 2 in the surface of the base material.
６6 at% (0.8 at% inside 100 μm from interface)
Met. In addition, the Mn content of the product 14 of the present invention is:
The content in the hard film was 2 to 5 at%, and the content in the base material was 0.5 to 2 at%. In Comparative Product 9, these diffusion elements were not detected.

Using the surface-coated sintered member drills of the inventive products 13 and 14 and the comparative product 9, a work material: pre-hardened steel (HRC = 40), a cutting speed: 30 m / min, a cutting depth: 10 mm, and a table A grooving test was conducted under the conditions of feed: 64 mm, feed per blade: 0.02 mm / tooth, wet type, and when the cutting length was 50 m, the flank wear width of the cutting edge was measured. As a result, the product 13 of the present invention was 0.05 mm and the product 14 of the present invention was 0.06 mm, whereas the comparative product 9 was 0.13 mm.

[0049]

[Test 4] Approximately 10φmm × 60mm commercially available
Using a cemented carbide material for wear-resistant tools (V30 equivalent composition indicated in the classification of cemented carbide in JIS standard)
The entire surface was rough- and ground-grinded with 140 # and 800 # diamond grindstones to produce punches for punching, and the surface was treated under the same conditions as the base material for the product 3 of the present invention described in Table 1 of Example 1. This was treated as a base material for the product 15 of the present invention. As a comparison, the same punch not subjected to only this surface treatment was used as the base material for the comparative product 10.

After ultrasonic cleaning of these base materials in acetone, a granular TiN layer having a layer thickness of 0.5 μm and a granular TiC layer having a layer thickness of 3.5 μm were formed from the base material side using a CVD coating apparatus. The laminated hard films each having a total thickness of 4.0 μm were coated to obtain surface-coated sintered member punches of product 15 of the present invention and comparative product 10.

Using the product 15 of the present invention and the comparative product 10, a zinc steel plate having a thickness of 0.6 mm was punched out.
The number of shots until a defective product was generated due to burrs was measured. As a result, the product 15 of the present invention had about 1.1 million shots, while the comparative product 10 had about 430,000 shots.

[0052]

[Test 5] 30TiC-20TiN-20WC-5
The cermet consisting of TaC-5Mo ₂ composition component of C-7Ni-8Co over 5ZrC (wt%) as a base material, a Mn a different element, by PVD method which is conventionally used (Ti, Al) N a hard film A surface-coated sintered member treated almost the same as the inventive product 5 of Example 1 was obtained except for the above, which was designated as inventive product 16. Further, 50Ti (C, N) over 30 (Ti, Ta, W) C over 5Mo ₂ C-7Ni-8C
o (wt%) composition cermet as a base material, Al-
Except for using Mn as a different element and using a conventionally used (Ti, Al) N by a PVD method as a hard film, a surface-coated sintered member treated almost the same as the product 5 of the present invention in Example 1 was obtained. Thus, the product 17 of the present invention was obtained. For comparison, among the products 16 and 17 of the present invention, surface-coated sintered members produced by removing only different elements were designated as comparative products 11 and 12, respectively. Inventive products 16 and 17 thus obtained and Comparative product 1
Compared with Nos. 1 and 12, the products of the present invention 16 and 1
7 is the product 5 of the present invention in the execution test 1 and the comparative products 11 and 12
Has substantially the same configuration and effect as the comparative product 1 of the execution test 1.

[0053]

[Test 6] 70Al ₂ O ₃ -30Ti as base material
(C, N) aluminum oxide based ceramic sintered body having a composition consisting of components (weight%) of, 95Si ₃ N ₄ over 1AlN-
1.5MgO-1.5Y ₂ O ₃ -1HfO ₂ constituents of the composition (wt%) in comprising silicon nitride ceramic sintered body, 50
CuBN-35TiN-6Al ₂ O ₃ -9AlN is used, each of which is composed of a cubic boron nitride-based ceramics sintered body composed of a composition component (% by weight). The base material of the silicon-based ceramics sintered body was made of a different element of Mn, and the base material of the cubic boron nitride-based ceramics sintered body was made of a different element of Ni. The products 18, 19 and 20 of the present invention were obtained, respectively. For comparison, products of the present invention 18 to 20 prepared by removing only different elements were designated as comparative products 13 to 15, respectively. When the inventive products 18 to 20 thus obtained and the comparative products 13 to 15 were compared, the inventive products 18 to 20 were the inventive products 5 of the execution test 1, and the comparative products 13 to 15 were the comparative products of the execution test 1. It was confirmed that the structure and the effect were almost the same as those of Example 1.

[0054]

The high-adhesion surface-coated sintered member of the present invention is
Compared with the conventional surface-coated sintered member coated by the CVD method, PVD method or plasma CVD method, the hard film is diffused and contained in the hard film and the surface of the base material by the different elements. The strength between the base material and the base material surface is remarkably improved, and the adhesion between the base material and the hard film is significantly improved. Product with extremely reduced peeling, improved peeling resistance of the hard film from the base material surface, and as a result, remarkably improved long life and durability, and quality stable product with very little variation Is obtained.

Further, the method for producing a high-adhesion surface-coated sintered member of the present invention can easily form a substance for forming a different element which is optimal for the material of the base material and the film quality of the hard film. Easy diffusion of substances. This is an excellent production method that can be contained and does not require a significant process improvement.

As described above, the surface-hardened cemented carbide and the coated surface-hardened cemented carbide of the present invention require cutting tools represented by, for example, turning tools, milling tools, drills, and end mills, in particular, impact resistance. Cutting tools such as dies and punches, cutting tools such as slitters, cutting blades, etc., as well as corrosion-resistant tools such as nozzles and coating tools. It can exert excellent effects as a tool for civil engineering construction represented by cutting tools, excavating tools, burrowing tools, crushing tools used in mines, roads, civil engineering and the like.

[Procedure amendment]

[Submission date] August 11, 2000 (2008.1.
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

[0046]

[Test 3] Commercially available 90.0WC-9.2C
Using a solid end mill (6 mm) made of a cemented carbide made of fine-grain WC with a composition of o-0.8Cr (wt%), the base material for the products 5 and 7 of the present invention described in Table 1 of Test 1 was formed on the surface of the end mill. Surface treatment under the same conditions as in Example 1
A base material for 3, 14 was used. The same end mill that had not been subjected to surface treatment (under the same conditions as Comparative Product 1 in Table 1 in Example 1) was used as a base material for Comparative Product 9. After ultrasonic cleaning of these base materials in acetone, a columnar crystal TiCN having a layer thickness of 2.0 μm was formed using a CVD coating apparatus.
The hard films of the layers were covered to obtain end mills of the present invention products 13 and 14 and the comparative product 9 as surface-coated sintered members.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

As a result of analyzing the outer peripheral cutting edge portions of these surface-coated sintered member end mills in the same manner as in the test 1, the Ni content of the product 13 of the present invention was found to be 1 in the hard film.
1 to 20 at%, 5 to 9 at% in the surface of the base material,
The Cr content is 3 to 10 at% in the hard film, 2 to 6 at% in the surface of the base material (0.8 a in 100 μm from the interface.
t%). The Mn content of the product 14 of the present invention is 2 to 5 at% in the hard film, and 0.5 to 2 a in the base material.
The diffusion element was not detected in Comparative Product 9.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

Using these surface-coated sintered member end mills of the products 13 and 14 of the present invention and the comparative product 9, a work material: pre-hardened steel (HRC = 40) and a cutting speed: 30 m / mi
n, depth of cut: 10 mm, table feed: 64 mm, feed per blade: 0.02 mm / blade, a grooving test was performed under wet conditions, and the flank wear width of the cutting blade was measured when the cutting length was 50 m. As a result, the product 13 of the present invention was 0.05 mm and the product 14 of the present invention was 0.06 mm, whereas the comparative product 9 was 0.13 mm.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C22C 29/08 C22C 29/08 C23C 14/06 C23C 14/06 A 16/30 16/30 28/04 28 / 04 F-term (reference) 3C046 FF03 FF04 FF05 FF11 FF17 FF19 FF22 FF25 4K018 AD06 FA22 FA23 FA24 KA15 KA16 KA18 KA19 4K029 BA00 BA21 BA58 4K030 BA35 BA38 BA43 BB12 CA03 CA05 DA03 LA22 LA02 BA04 BA04 A04 BA04 ABA CA14 CA15 CA18 CA53

Claims (17)

[Claims] A hard metal, a cermet or a ceramic sintered body is used as a base material, and a single layer or two or more layers of a hard material having high hardness or a mixture containing the hard material is formed on the surface of the base material. A hard film formed of a laminate is coated, and a surface element of the base material near an interface between the base material and the hard film contains a different element different from an element constituting the inside of the base material. A high-adhesion surface-coated sintered member, wherein all or some of the layers of the hard film contain the different element. 2. The base material is made of a cemented carbide containing a binder phase containing cobalt as a main component and a hard phase containing tungsten carbide as a main component, and the hard film is made of 4a, 5a, or 4a of the periodic table.
2. The high adhesion surface coating according to claim 1, comprising a single layer or a laminate of two or more layers selected from group 6a elements, aluminum, silicon carbides, nitrides, oxides, and mutual solid solutions thereof. Sintered members. 3. The hard film according to claim 1, wherein the hard film near the interface with the base material or the hard film adjacent to the base material is titanium nitride,
3. The high-adhesion surface-coated sintered member according to claim 1 or 2, wherein the member is a titanium compound film formed of one kind of a single layer or two or more kinds of a carbide or a carbonitride. 4. The high-adhesion surface-coated sintered member according to claim 1, wherein the hard film also contains constituent elements of the base material. 5. The high-adhesion surface according to claim 1, wherein the hard film includes a columnar crystal layer grown vertically long in a direction perpendicular to the surface of the base material. Coated sintered member. 6. The high adhesion according to claim 1, wherein the content of the different element contained in the base material gradually decreases from the surface of the base material toward the inside. Surface-coated sintered member. 7. The hard film according to claim 1, wherein the content of said different element in said hard film is maximum at an interface between said base material and said hard film, and gradually decreases from said interface toward a surface of said hard film. 1
The high-adhesion surface-coated sintered member according to any one of Items 1 to 6. 8. The high adhesion surface coating according to claim 1, wherein said different element contains at least one of iron group elements, chromium, molybdenum, manganese, copper and silicon. Sintered members. 9. The high-adhesion surface-coated sintered member according to claim 1, wherein the hard film contains an element constituting the base material. 10. The method according to claim 1, wherein an underlayer containing said different element is formed at an average thickness of 0.5 μm or less at an interface between said base material and said hard film. Adhesive surface-coated sintered member. 11. The hard phase on the surface of the base material at the interface between the base material and the hard film has a particle size of 0.2 μm or more, and the hard phase has no cracks in the grains. The high-adhesion surface-coated sintered member according to any one of 2 to 10. 12. The high adhesion surface-coated sintered member is used as a cutting tool or a plastic working tool.
2. The high-adhesion surface-coated sintered member according to any one of 1. 13. The high-adhesion surface-coated sintered member according to claim 12, wherein the cutting tool is a throw-away tip, a drill, or an end mill. 14. The high-adhesion surface-coated sintered member according to claim 12, wherein the plastic working tool is a punch or a die. 15. A cemented carbide, cermet or ceramic sintered body is used as a base material, and at least a part of the surface of the base material is made of iron group metal, chromium, molybdenum, manganese, copper, silicon, and their alloys. A first step of uniformly covering at least one type of heterogeneous element forming layer selected from compounds containing these elements, and a step of physical vapor deposition, chemical vapor deposition, At least 4 of the periodic table is applied to at least the surface of the dissimilar element forming layer by plasma enhanced chemical vapor deposition.
a hard layer comprising a single layer or a laminate of two or more layers selected from the group consisting of a, 5a, and 6a elements, aluminum, silicon carbides, nitrides, oxides, and mutual solid solutions thereof; A method for producing a high-adhesion surface-coated sintered member produced through two steps. 16. The first step includes a blasting method, a shot processing method using a shot material mainly composed of an iron group metal or a mixture of the shot material, an abrasive material and an abrasive material.
And electroplating, electroless plating, vacuum deposition,
The method for producing a highly adhered surface-coated sintered member according to claim 15, wherein the member is at least one of a physical vapor deposition method, a chemical vapor deposition method, a colloid coating method, and a solution coating method. 17. The base material according to claim 15, wherein at least a portion of the surface of the base material is at least one of a sintered surface, a polishing lap surface, an electropolished surface, and a chemically etched surface. The method for producing a high-adhesion surface-coated sintered member according to the above.