JP2981012B2 - Manufacturing method of diamond coated tool - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing a diamond-coated tool. More specifically, the present invention relates to a long-life diamond-coated tool formed by forming a film-like diamond on a substrate surface with extremely good adhesiveness, which is suitably used, for example, for a cutting tool or a wear-resistant tool. .

[0002]

2. Description of the Related Art Conventionally, diamond is extremely hard and has high wear resistance. For industrial use, cutting tools made of non-ferrous and non-metal materials, wear-resistant tools requiring high wear resistance, Used for wear-resistant members.
Examples of the diamond material used for these diamond tools and wear-resistant members include natural or synthetic single-crystal diamond and sintered polycrystalline diamond. Furthermore, in recent years, the technique of synthesizing film diamond by vapor phase synthesis has remarkably developed, and by this vapor phase synthesis, film diamond is formed on the surface of a substrate, which is used for various diamond tools and wear-resistant members. Have been tried. As this gas phase synthesis method, for example, a chemical vapor deposition method (CVD) is used in which a raw material gas containing a carbon source is used, and this is plasma-decomposed, or a film-like diamond is deposited on the surface of the substrate by utilizing an uneven reaction. Method), a hot cathode PIG gun, a cold cathode PIG gun, an ionization deposition method of forming a film-like diamond on a substrate surface using a sputter gun, and the like. In particular, a method of depositing a film-like diamond on a substrate surface by a CVD method is as follows.
Recently, it has attracted attention because it does not require a high temperature, is easily operated continuously, and is industrially advantageous.
However, the film-like diamond formed on the surface of the substrate by such a vapor phase synthesis method has a disadvantage that the film-like diamond is easily peeled off from the substrate during use because of insufficient adhesion to the substrate. I have. Therefore, a film-like diamond is formed on the substrate surface by a gas phase synthesis method,
In order to use this as a diamond tool, it is necessary that the film diamond and the substrate are strongly adhered to each other, and development thereof has been strongly desired.

[0003]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention provides a method for efficiently producing a diamond-coated tool formed by forming a film-like diamond on a substrate surface with extremely good adhesion. It was made for the purpose of.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, have found that a carburized substrate surface has a high adhesion to film diamond. It has been found that the object can be achieved by providing a layer made of a silicon compound material described above and then forming a film-like diamond thereon, and based on this finding, the present invention has been completed.

That is, the present invention comprises the following items. (1) After carburizing the surface of the substrate, a layer made of SiC or Si ₃ N _{4 is} provided by a chemical vapor synthesis method, and then a film diamond is formed thereon by a gas phase synthesis method. Production method of diamond-coated tools. (2) After coating with a SiC or Si ₃ N ₄ layer, before coating with a second layer or film diamond by a vapor phase synthesis method, the coating surface of SiC or Si ₃ N ₄ is damaged. 2. The method for producing a diamond-coated tool according to claim 1, wherein the processing is performed. (3) After subjecting the surface of the substrate to a carburizing treatment, a coating lower layer made of a material having an adhesive property to SiC or Si ₃ N _{4 is} provided by a chemical vapor phase, and a Si lower layer is formed on the coating lower layer.
A method for producing a diamond-coated tool, comprising: providing a coating upper layer made of C or Si ₃ N ₄ by a chemical vapor synthesis method; and finally, forming a film-like diamond on the coating upper layer by a gas phase synthesis method. (4) The material having adhesiveness to SiC or Si ₃ N ₄ is W, Mo, Si, Ta, Nb, SiC, TiN, Ti
_4. The method for producing a diamond-coated tool according to claim 3, wherein the diamond-coated tool is at least one selected from C and Si ₃ N ₄ . (5) After the coating lower layer or the coating upper layer is provided, before the coating of the coating upper layer by the vapor phase synthesis method or the coating of the film diamond is performed, the surface of the coating lower layer and / or the coating upper layer is damaged. Item 3 or 4 characterized in that
The method for producing a diamond-coated tool according to the above item.

Hereinafter, the present invention will be described in detail. The material of the substrate used in the method of the present invention is not particularly limited, and those conventionally used for substrates in diamond-coated tools, for example, metals such as silicon, molybdenum, tantalum, tungsten, titanium, and alloys of these metals , Carbide, nitride, oxide, or TiC-N
i system, TiC-Co based, can be selected and used from among such cermet such as Al ₂ O ₃ -Fe system any, preferably cemented carbide substrate, especially tungsten carbide among these Used.

In the method of the present invention, the surface of a substrate made of these materials is first subjected to a carburizing treatment, and then a layer made of a material having an adhesive property to a film-like diamond is provided by a chemical vapor deposition method. is necessary. In the carburizing process, for example, a substrate is placed in a thermal CVD apparatus, and a mixed gas of a hydrocarbon gas such as methane and hydrogen is introduced into the substrate.
The treatment can be performed at a temperature of 900 to 1200 ° C. for 0.5 to 3 hours. When the adhesive material layer is provided on the surface of the substrate without performing the carburizing treatment, the effect of the present invention is not sufficiently exerted, and a diamond coated tool in which the film diamond is firmly adhered to the surface of the substrate can be obtained. Hateful.

[0008] The reason why the film-form diamond firmly adheres to the substrate by carburizing is not necessarily clear, but the following may be considered. That is, for example, W, Mo, Si, Ta, N
When a layer made of a metal such as b, TiN, or Si ₃ N ₄ or a nitride is provided as an intermediate layer by a chemical vapor synthesis method, these partially react with carbon fine particles deposited by carburizing to form a carbide. As a result, it is considered that the film diamond and the substrate are firmly adhered to each other through the adhesive layer. Further, when a layer made of a carbide such as SiC or TiC is provided as a bonding material layer by a chemical vapor synthesis method, when a film-like diamond is formed by a gas phase synthesis method, the SiC or TC is usually used.
The carbon in the iC is partially removed to become a metal of Si or Ti, but by carburizing, such unfavorable situation is prevented by the deposited carbon fine particles, and as a result, the adhesion between the film diamond and the substrate is prevented. It is thought that the decrease in sex is suppressed.

In a first aspect of the present invention, the intermediate layer is made of S
In this embodiment, iC or Si ₃ N ₄ is coated on the surface of a carburized substrate by a chemical vapor synthesis method, and a diamond film is coated on the coating layer by a chemical vapor synthesis method.
According to a second aspect of the present invention, in the first aspect, between the SiC or Si ₃ N ₄ layer as an intermediate layer in contact with the diamond film and the surface of the carburized substrate, a coating lower layer as a second intermediate coating layer Is provided. Then, in the second embodiment, SiC or Si ₃ N ₄ is coated on the coating lower layer as the coating upper layer in the same manner as in the first embodiment. The material used for the lower coating layer for coating the surface of the carburized substrate used in the second embodiment of the present invention needs to be a layer made of a material having adhesiveness to the material of the upper coating layer. For example, W, Mo, Si, Ta, Nb, TiN, T
A layer composed of at least one selected from iC, SiC and Si ₃ N ₄ is preferred.

The lower coating layer and the upper coating layer used in the present invention can be coated in the same manner. That is, when a layer composed of a metal layer such as W, Mo, Si, Ta, or Nb is provided as the intermediate coating layer, halides such as chlorides and fluorides of these metals are vaporized and chemically vaporized. A method of depositing a metal by a phase synthesis method or the like is used. Examples of the halide include WCl ₆ , WF ₆ ,
MoCl ₅ , MoF ₆ , SiCl ₄ , SiF ₄ , TaC
_{l 5, TaF 5, NbCl 5} , such as NbF _5, and the like.
When a layer made of a carbide such as SiC or TiC is provided, a method of vaporizing a halide or an organic halide such as Si or Ti and depositing the carbide by a chemical vapor synthesis method is used. As the halide,
For example, SiCl ₄ , SiF ₄ , TiCl ₄ , TiF _{4 and the} like can be mentioned, and as the organic halide, for example, SiCH ₃ Cl ₃ and TiCH ₃ Cl ₄ can be mentioned.

On the other hand, when a layer made of a nitride such as TiN or Si ₃ N ₄ is provided, a method of vaporizing a halide such as Ti or Si and depositing the nitride by a chemical vapor deposition method in a nitrogen atmosphere. Are used. Examples of the halide include SiCl ₄ , SiF ₄ , TiCl ₄ , Ti
Such as F _4, and the like. The thickness of the intermediate coating layer provided on the surface of the carburized substrate and the coating lower layer in this manner is usually selected in the range of 1 to 100 μm.

In the method of the present invention, the film-like diamond is formed on the surface of the substrate on which the intermediate coating layer of SiC or Si ₃ N ₄ is provided in any of the first and second embodiments by a gas phase synthesis method. If necessary, in order to increase the film-forming speed, the surface of the substrate provided with the intermediate coating layer is subjected to a friction treatment or a collision treatment with a high-hardness powder in advance to form a sharp surface flaw. The film-like diamond can be formed. SiC or Si ₃ N _{4 of the} present invention
By performing a scratching treatment on the coating upper layer made of, the density of generation of crystal nuclei of the diamond film in the diamond film coating by the vapor phase synthesis method can be increased, so that the production speed of the diamond film is increased and the production time can be shortened.

In the case where the upper layer of the coating of the present invention is coated on the lower layer of the coating by a chemical vapor synthesis method, if the surface of the lower layer of the coating is subjected to a surface damage treatment with fine diamond particles or the like, The contact area with the SiC or Si ₃ N ₄ layer is large, and the upper layer of the film is firmly fixed to the surface. The scratching treatment of the present invention is not particularly limited as long as it is a method of uniformly and finely scratching the surface, and can be appropriately performed. There is no particular limitation on the vapor phase synthesis method of the diamond film in the present invention, and a method conventionally used for forming a film diamond, for example, various chemical vapor deposition methods (CVD)
Method) or an arbitrary method can be selected from physical vapor deposition methods such as an ionization vapor deposition method, and the CVD method is preferable.

This CVD method includes, for example, (1) a thermal decomposition CVD method in which the raw material gas is activated by passing the raw material gas in the vicinity of a glowing filament; A high frequency plasma CVD method in which a high frequency is applied to an introduction portion of a source gas and plasma is formed by the high frequency to bring the source gas into an activated state. (3) Microwave plasma CVD using a microwave instead of the high frequency And (4) an ion beam CVD method for bringing a source gas into an activated state by an ion beam, and any of these methods can be used in the present invention.

As a source gas used in the CVD method, a mixed gas of a carbon source gas and hydrogen is used. There is no particular limitation on the carbon source gas.
Used in the formation of diamond by the method, for example, carbon monoxide or carbon dioxide, or alkanes, alkenes, alkynes, aromatic hydrocarbons, cycloparaffins, cycloolefins, oxygenated carbon compounds, One or a mixture of two or more selected from nitrogen-carbon compounds and the like is used. These source gases may contain an inert gas such as nitrogen, argon, neon, or xenon, if desired.

The thickness of the film-like diamond thus formed varies depending on the purpose of use, but it is usually 1 to 10
It is selected in the range of 00 μm. In the method of the present invention, as described above, a SiC or Si ₃ N ₄ layer is provided directly on the surface of the substrate which has been carburized in advance, and a diamond film is formed thereon, or the SiC or Si ₃ N ₄
After a layer made of an adhesive material is provided on the surface of the carburized substrate, the SiC or Si ₃ N ₄ layer is indirectly provided thereon as a coating upper layer, and a film diamond is formed on the coating upper layer. By forming the diamond coated tool, a diamond-coated tool on which a film-like diamond having high adhesiveness to the substrate is formed can be obtained.

The diamond-coated tool of the present invention obtained as described above has a film-like diamond formed on the surface of a substrate with good adhesiveness, is extremely hard, has high wear resistance, and can be used during use. Since the film-like diamond does not easily peel off from the substrate, it is suitably used for cutting tools and wear-resistant tools made of non-ferrous or non-metallic materials.

[0018]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 A cemented carbide TAT was used as a substrate, and a carburizing treatment was first performed as follows. That is, a cemented carbide TAT was inserted into the reaction vessel and carburized at a carburizing temperature of 1050 ° C., a flow rate of H ₂ gas of 100 cc / min, a flow rate of CH ₄ gas of 10 cc / min, and a reaction time of 1 hour. Next, after the reaction vessel was evacuated, the carburized substrate temperature was 900 ° C., WCl
₍₆₎ Tungsten was vapor-phase grown by CVD under the conditions of an evaporation temperature of 200 ° C., a WCl ₆ evaporation rate of 8 g / hr, an H ₂ gas flow rate of 90 cc / min, an Ar gas flow rate of 10 cc / min, and a reaction time of 40 min. After the reaction vessel was evacuated to the tungsten-coated substrate prepared by the above method, SiCH ₃ Cl ₃
10 g / hr was introduced into the reaction vessel together with 100 cc / min of H ₂ , and CV was performed under the conditions of a reaction temperature of 1200 ° C. and a reaction time of 2 hours.
By method D, SiC was deposited on the surface of the substrate. SiC
Film-like diamond was formed on the surface of the substrate having the layer by microwave plasma CVD to prepare a diamond-coated TAT. Diamond coating T treated like this
AT cutting speed 340m / min, feed 0.15mm / rev,
As a result of using for dry cutting of Al alloy containing 8% Si (AC4A) under the cutting condition of 0.15 mm depth, continuous cutting for 120 minutes is possible, the flank wear is 10 μm, and TAT made of cemented carbide is used. 1/20 of the flank wear.

Example 2 A TAT substrate made of cemented carbide was carburized in the same manner as in Example 1. Then, after evacuation of the reaction vessel, the temperature of the carburized substrate was 700 ° C., the evaporation temperature of MoCl _{5 was} 250 ° C.,
MoCl ₅ evaporation rate 10 g / hr, H ₂ flow rate 90 cc / min,
CVD with Ar flow rate of 10 cc / min and reaction time of 1 hr
Molybdenum was vapor-phase grown by the method. After the reaction vessel was evacuated to the molybdenum-coated substrate produced by the above method, SiCl ₄ was purged with H _{2 at} 100 cc / min and NH _{3 at} 600 cc / mi.
n was introduced into the reaction vessel together with n, and Si ₃ N ₄ was deposited by the CVD method under the conditions of a reaction temperature of 1100 ° C. and a reaction time of 1 hour,
An Si ₃ N ₄ layer was provided on the substrate surface. Further, a cutting test was carried out by forming a film-like diamond on the surface of the substrate in the same manner as in Example 1. As a result, the flank wear was 22 μm in continuous cutting for 100 minutes.

Example 3 A TAT substrate made of cemented carbide was carburized in the same manner as in Example 1. Next, after evacuation of the reaction vessel, SiCl ₄ was introduced into the reaction vessel together with 100 cc / min of H ₂ and 20 cc / min of CH _4, and the surface of the substrate was formed by CVD at a reaction temperature of 1250 ° C. and a reaction time of 1 hour. SiC was deposited. The surface of the substrate subjected to the above treatment was rubbed with a paste made of fine diamond powder, and the surface after the scratching treatment was further coated with diamond in the same manner as in Example 1. The time for coating was 8 hours. When a cutting test was performed using the obtained tool, the flank wear was 17 μm in continuous cutting for 120 minutes.

Example 4 A diamond-coated drill was produced in the same manner as in Example 1 except that a drill for a printed board made of cemented carbide was used as a substrate, and the coating lower layer and the coating upper layer were subjected to a scratching treatment. When a glass-epoxy resin substrate was drilled using this diamond-coated drill, it was possible to drill more than 150,000 holes, and the outer diameter of the drill was measured. Drilling of 10,000 holes was possible, and the life was 30 times longer than that of a conventional drill for printed board made of cemented carbide.

Comparative Example 1 A diamond-coated TAT was produced in the same manner as in Example 1 except that the carburizing treatment was not performed. When a cutting test was performed using this material,
In continuous cutting for 20 minutes, the flank wear is 150
μm.

Comparative Example 2 A diamond-coated TAT was produced in the same manner as in Example 1 except that the carburizing treatment and the tungsten coating treatment were not performed. When a cutting test was performed using this material, in continuous cutting for 120 minutes,
The flank wear was 250 μm.

[0025]

According to the present invention, after carburizing a substrate surface, a layer made of a SiC or Si ₃ N ₄ material having adhesiveness to the film diamond is provided, and then a film diamond is formed thereon. By forming a diamond-coated tool, it is possible to obtain a long-life diamond-coated tool in which the adhesion between the film-shaped diamond and the substrate is significantly improved. Further, under the SiC or Si ₃ N ₄ layer, SiC or Si ₃
A layer having adhesion to N ₄ , for example, W, Mo, S
i, Ta, Nb, SiC, TiN, TiC, and Si ₃ N ₄
The effect of the present invention can be increased by providing a layer made of and bonding the diamond film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C23C 14/16 C23C 14/16 16/02 16/02 16/22 16/22 16/26 16/26 C30B 29/04 C30B 29 / 04 Q (56) References JP-A-3-56675 (JP, A) JP-A-2-267284 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C23C 28/04

Claims (5)

(57) [Claims] 1. After subjecting a substrate surface to a carburizing treatment, SiC
Alternatively, a layer made of Si ₃ N _{4 is} provided by a chemical vapor synthesis method,
Next, a method of manufacturing a diamond-coated tool, wherein a film-like diamond is formed thereon by a vapor phase synthesis method. 2. A coated surface of SiC or Si ₃ N ₄ after coating with a layer of SiC or Si ₃ N ₄ before coating of a second layer or coating of film diamond with a vapor phase synthesis method thereon. 2. The method for producing a diamond-coated tool according to claim 1, wherein a scratching process is performed on the diamond-coated tool. 3. After subjecting the substrate surface to a carburizing treatment, the SiC
Alternatively, a coating lower layer made of a material having an adhesive property to Si ₃ N _{4 is} provided by a chemical vapor synthesis method, and a coating upper layer made of SiC and / or Si ₃ N _{4 is} further formed on the coating lower layer by a chemical vapor deposition method. A method for producing a diamond-coated tool, comprising: forming a film-form diamond on the upper coating layer by a vapor phase synthesis method. 4. A material having adhesiveness to SiC or Si ₃ N ₄ is W, Mo, Si, Ta, Nb, SiC, Ti.
At least one selected from N, TiC and Si ₃ N ₄
The method for producing a diamond-coated tool according to claim 3, which is a seed. 5. After the lower coating layer or the upper coating layer is provided, the surface of the lower coating layer and / or the upper coating layer is damaged before the coating of the upper coating layer or the coating of the diamond film is performed thereon. 4. The method according to claim 3, wherein
Or the method for producing a diamond-coated tool according to 4.