JPH0254768A - Member with diamond film and its production - Google Patents

Abstract

PURPOSE:To obtain a member with diamond film excellent in adhesive strength between member and film by forming an intermediate layer containing metallic silicon compound on the surface of a metallic member and then bringing a gas prepared by exciting carbon-source gas into contact with the above member. CONSTITUTION:An intermediate layer containing metallic silicon compound, such as WSi2, is formed on the surface of a metallic member by a coating method. Then, a gas obtained by exciting a carbon source-containing gaseous raw material prepared by mixing CO, etc., with hydrogen gas is brought into contact with the above intermediate layer, by which a diamond film is formed. This member with diamond film has superior adhesive resistance between the member and the film and can be suitably used, e.g., for members requiring wear resistance and chemical resistance.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a member with a diamond film and a method for manufacturing the same, and more specifically, the present invention relates to a member with a diamond film and a method for producing the same, and more specifically, it has excellent abrasion resistance and chemical resistance, and is suitable for use in tools, etc. The present invention relates to a member with a diamond film that can be used for and a method of manufacturing the same.

[Prior Art and Problems to be Solved by the Invention] In recent years, with the progress of diamond synthesis technology, members with diamond films formed on the surface of metal members have been widely used. Since the attachment member has a high hardness on its surface, it is used in cutting tools, sharpeners A, etc.

By the way, in the past, the adhesion between a metal member and a diamond film could not be said to be good, and as a result, those diamond film-coated members had significantly poor wear resistance.

On the other hand, for the purpose of improving the adhesion between a metal member and a diamond film, for example, a technique of forming a diamond film containing silicon on the surface of the member (Japanese Patent Laid-Open No. 163273/1983) has been reported. However, in these diamond film coated members, the adhesion between the surface of the member and the diamond film was not yet sufficient.

In addition, there is a technology (in which metals or metal compounds are dotted on a metal member and used as a core material to form a diamond).
JP-A-63-166733) has been reported.

In this technique, metals or metal compounds are dotted on a metal member for the purpose of improving the speed of diamond film synthesis and the uniformity of the diamond film.

Therefore, it is difficult to say that the adhesion of the diamond film grown on the metal member-L in which no metal or metal compound is present has been improved.

Furthermore, this method is effective only when the metal or metal compound is dotted on the metal member-L, and when the metal or metal compound is present on the layer, it no longer functions as a core material and is non-conductive. This has the disadvantage of promoting the precipitation of diamond.

This invention was made in view of the above circumstances.

That is, an object of the present invention is to provide a member with a diamond film that has excellent adhesion between the surface of the metal member and the diamond film, and a method for manufacturing the same.

[Means for Solving the Problems] In order to solve the problems described above, the inventor has made extensive studies and has found that a specific intermediate layer is provided on the surface of a metal member, and a specific intermediate layer is formed on the surface of the metal member using a specific forming method. It was discovered that the diamond film-coated member provided with the obtained diamond film has excellent adhesion between the surface of the member and the diamond film, and therefore has excellent wear resistance. , manufactured blade U with almost no non-diamond precipitation:
This invention was achieved by discovering that.

That is, the invention according to claim 1 for solving the above problem is a diamond film-attached method, characterized in that a diamond film is formed on the surface of a metal member via an intermediate layer containing a metal silicon compound. It is a member.

The invention according to claim 2 forms an intermediate layer containing a metal silicon compound on the surface of a metal member, and then contacts a gas obtained by exciting a raw material gas containing a carbon source gas onto the intermediate layer. 2. The method of manufacturing a member with a diamond film according to claim 1, wherein the diamond film is formed by applying the diamond film.

Below, the diamond film coated member of the present invention and its manufacturing method will be sequentially explained.

Diamond film coated member In the invention set forth in claim 1, gold and the &1 member are used as a substrate on which a diamond film is formed.

An important point of the invention according to claim 1 is that the metal member has an intermediate layer (on the surface thereof) containing a metal silicon compound (
Hereinafter, it may simply be referred to as the middle class. ), it has a diamond film.

The metal member is not particularly limited, and includes, for example, iron,
cobalt, nickel, chromium, manganese, vanadium,
Examples include metals and alloys such as tungsten, thallium, molybdenum, and silicon, and ceramics such as tantalum silicon, molybdenum carbide, tungsten carbide, alumina, spinel, and silicon carbide.

Among these, preferred are WC-Co alloy, WC-Tie-Co alloy, and wC-Tic-TaC-
It is a cemented carbide such as Cio alloy.

The intermediate layer is mainly composed of a metal silicon compound,
It can be formed by the coating method described below.

There are no particular restrictions on the silicon compound of the metal, but
Silicon compounds of metals of groups TV, Va, Vl, 6, and 2 of the periodic table can be suitably used.

Specific examples include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, hafnium, thallium, tungsten,
Examples include silicon compounds such as rhenium, osmium, iridium, and platinum.

Among these, silicon compounds of the same metal as the metal component of the member used are preferred. For example, if a metal tool is used as the member, silicon compounds of the metal conventionally used for tools, such as NiSi2 and NiSi2, are preferred. ,
Pd2Si, PtSi, MoSi2, CrSi
2. CoSi2. FeSi, MnSi, V2S
i, etc. can be mentioned.

Among these, WSi2, NiSi2,
They are Pd2Si, PtSi, and MoSi2.

By using a combination of a metal component of a member and a silicon compound having the same metal as the metal component, the adhesion between one member and the intermediate layer can be further improved.

The thickness of the intermediate layer is usually 0.01 to 10 gm, preferably 0.05 to 5 gm.

In addition, when the layer thickness is less than 0.0ip, m,
The adhesion between the member and the diamond film may deteriorate, and even if the thickness exceeds 10 tm, the corresponding effect may not be obtained.

The member of the present invention has a diamond film formed on the intermediate layer by a method described below.

The thickness of the diamond film is usually 0.1 to 2 Jtm.
and preferably 0.5 to 10 ILm.

Note that if the film thickness is less than 1.1 gm, the wear resistance of the member may decrease, and even if it exceeds 20 pm, the corresponding effect may not be obtained.

Such a member with a diamond film can be produced by the manufacturing method shown below.

Method for manufacturing a member with a diamond film The important point of this invention is that an intermediate layer containing a silicon compound of the metal is formed on the surface of the member, and then a raw material gas containing a carbon source gas is applied to the intermediate layer 1-. A diamond film is formed by bringing the excited gas into contact with the diamond film.

The method for forming the intermediate layer and the method for forming the diamond film will be explained below.

(2) Method for Forming Intermediate Layer The intermediate layer can be formed by bringing a gas obtained by exciting the raw material of the silicon compound of the metal into contact with the surface of the member.

Methods for coating the metal silicon compound layer on the surface of the member include conventionally used vacuum evaporation methods;
A sputtering method, a chemical vapor deposition method (CVD method), a coating method, etc. can be suitably employed.

Examples of the vacuum deposition method include a resistance heating method, a single bombardment method, and a high frequency induction heating method.

Examples of the sputtering method include a two-pole DC sputtering method, a high frequency sputtering method, and a reactive sputtering method.

As the CVD method, plasma CVD method, high frequency CV
D method, microwave CVD method, etc. can be mentioned.

During the coating, the surface temperature of the member is as follows:
Although it cannot be determined unconditionally depending on the coating method, it is usually from room temperature to t, ooo°C, preferably from room temperature to 90θ°C.

The reaction pressure is usually 10-'-10-tart, preferably 10-6 to 10-Qorr.

Although the precipitation rate cannot be unconditionally determined by appropriately setting it within the range of the reaction conditions, it is usually IOA/sec.

Under these conditions, a metal silicon compound layer is formed to have the thickness of the intermediate layer, and then J2 is formed.

A diamond film is formed by the method shown below.

(2) Method for forming a diamond film A diamond film can be formed by exciting a raw material gas containing a carbon source gas and bringing the gas into contact with the silicon compound layer 1- of the metal.

1i? 1. As the carbon source gas, gases such as various hydrocarbons, oxygen-containing compounds, nitrogen-containing compounds, etc. can be used.

Examples of hydrocarbon compounds include paraffinic hydrocarbons such as methane, ethane, propane, and butane; olefinic hydrocarbons such as ethylene, flopylene, and butylene; acetylenic hydrocarbons such as acetylene and arylene; and diolefinic hydrocarbons such as butadiene. Hydrogen; alicyclic R such as cyclopropane, cyclobutane, cyclopentane, cyclohexane
Hydrogen; examples include aromatic hydrocarbons such as cyclobutadiene, benzene, toluene, xylene, and naphthalene.

Examples of oxygen-containing compounds include ketones such as acetone, diethyl ketone, and benzophenone; alcohols such as methanol, ethanol, propatool, and butanol; methyl ether, ethyl ether, methyl ethyl ether, methyl propyl ether, phenol ether, dioxane, etc. Ethers: aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde; acetic acid.

Organic acids such as propionic acid and succinic acid; Acid esters such as methyl acetate and ethyl acetate; Dihydric alcohols such as ethylene glycol and diethylene glycol;
Examples include carbon dioxide.

Examples of the nitrogen-containing compound include amines such as trimethylamine and triethylamine.

In addition, as a carbon source, although not a single substance, Class 4 dangerous substances stipulated in the Fire Service Act: Type 1 petroleum such as gasoline, Type 2 petroleum such as kerosene, turpentine, ginger oil, and pine oil, and heavy oil. It is also possible to use tertiary petroleum oils such as tertiary petroleum oils, and tertiary petroleum petroleum oils such as gear oil and cylinder oil. It is also possible to use a mixture of the various carbon compounds mentioned above.

Among these carbon sources, paraffin hydrocarbons such as methane, ethane, and propane, which are gases or have high vapor pressure at room temperature, ketones such as acetone and benzophenone, alcohols such as methanol and ethanol, carbon oxide, and carbon dioxide. Oxygen-containing compounds such as gases are preferred.

Note that the raw material gas may contain hydrogen gas, water vapor, oxygen gas, etc. in addition to the carbon source gas.

By using a raw material gas that is a combination of these gases and a carbon source gas, a high quality diamond film can be formed at high speed.

The concentration of the hydrogen gas in the raw material gas is 0.1 to 99.9 mol% relative to the carbon source gas.

The concentration of the water vapor in the raw material gas is 0.05 to 10 mol% with respect to the raw material gas.

The concentration of the oxygen gas in the source gas is 0.01 to 10 mol% relative to the source gas.

An inert gas may be mixed in the raw material gas, and the inert gas can be used as a carrier gas for the carbon source gas.

Examples of this inert gas include nitrogen gas, helium gas, argon gas, neon gas, and xenon gas.

For the f-stage excitation of the carbon source gas, any method can be used from among the various methods conventionally used for diamond synthesis.

Specifically, for example, a method of plasma decomposition by applying direct current, a method of plasma decomposition by applying high frequency, a method of plasma decomposition by applying microwave, or a method of performing plasma decomposition in an ion chamber or an ion gun, Examples include various plasma decomposition methods such as an ion beam method in which ions are extracted using an electric field, and thermal decomposition methods in which thermal decomposition is performed by heating a hot filament. Among these, preferred are the various plasma decomposition methods described above.

Note that the plasma output when plasma decomposing the carbon source gas is usually 0.05 Kw or more.

If the plasma output is less than 0.05 Kw, sufficient plasma may not be generated.

In order to excite the source gas to the above), the reaction can usually proceed under the following conditions.

That is, since the temperature of the surface of the member varies depending on the excitation stage of the carbon source gas in the vapor phase synthesis method and the cooling of the member, it cannot be generally determined, but for example, when using the plasma decomposition method, 400-1,200°C is preferred.

The reaction pressure is usually 10-6 to t03 torrffi, preferably lo-5 to 800 torrffi.

If the reaction pressure is lower than 10-6 torr, no diamond particles may be precipitated. On the other hand, 103
Even if it is made higher than torr, a corresponding effect cannot be obtained.

The reaction time can be appropriately set according to the formation rate of the diamond film so that the thickness of the diamond film becomes the thickness described above.

The diamond-coated member thus obtained has excellent adhesion between the member and the diamond film, and can be suitably used for members requiring wear resistance and chemical resistance.

[Example] In order to explain this invention more specifically, examples are given below.

(Example 1) A cemented carbide cutting tip (JIS KIO3PGN422) was used as a member for forming a diamond film.

The cutting tip was treated with Rangel E liquid (manufactured by Oka Seiko Co., Ltd.).
Washing was performed three times each using a 10-fold diluted solution (liquid temperature: 50° C.), then pure water, and then isopropyl alcohol.

The time for each cleaning was 60 seconds, and among the three cleanings, the second cleaning was performed in combination with ultrasonication.

After placing the two cutting chips cleaned in this way in a reaction chamber, the pressure in the reaction chamber was set to 1O-5 torr, the temperature of the cutting chip was set to 300°C, and the top of the cutting chip was coated using a vacuum evaporation method. Then, an intermediate layer of WSi2 was formed.

Note that the thickness of the obtained intermediate layer was 0.1 gm.

The silicon compound analysis on the surface of the cutting tip was performed by X-ray diffraction (hereinafter simply referred to as XRD).

Next, the cutting chip with the intermediate layer formed thereon was placed in a reaction chamber, the temperature of the cutting chip was 900°C, and the pressure in the reaction chamber was 50 to
Under the conditions of rr, the output of a microwave power source with a frequency of 2.45 GHz is set to 350 W, and a total of carbon monoxide gas and hydrogen gas are supplied as raw material gases into the reaction chamber. I set the time to 100 seconds■.

The concentration of the carbon oxide gas was 25 mol%.

The reaction was continued under these conditions for 1 hour to form the intermediate layer t.
A deposit of 2.5 μm was obtained.

When the obtained deposit was subjected to Raman spectroscopic analysis, a peak attributed to diamond was observed near 1333cs+-' in the Raman spectrum, confirming that it was a diamond film free of impurities.

Furthermore, the thicknesses of the intermediate layer and diamond film formed on the surface of the cutting tip were measured using a scanning electron WJ microscope.

Furthermore, a cutting test was conducted under the following conditions with respect to a cutting tip formed with a diamond film formed through an intermediate layer.

Wave cutting material: A vertical-8 weight t1% Si alloy Cutting speed: 800m/sec feed; Depth of cut: 0.1 mm 7cm; 0.25 mm Cutting time: 100 minutes, after testing for t, ooo minutes, it adhered to the cutting tip. The deposits on the material to be cut were removed with dilute hydrochloric acid, and the state of the cutting edge of the cutting tip was observed using a scanning electron microscope.

The above test results and observation results are shown in Table 1.

(Examples 2 to 8) Same as Example 1 except that the intermediate layer thickness, diamond synthesis conditions (carbon source gas composition, C degree and synthesis time) and diamond film thickness were as shown in Table 1. Then, an intermediate layer and a diamond film were formed.

Furthermore, a cutting test was conducted in the same manner as in Example 1 for the obtained cutting tip with diamond.

The results are shown in Table 1.

(Example 9) A cutting chip similar to that in Example 1 was cleaned in the same manner as in Example 1, and the pressure in the reaction chamber was set to 1°5 torr and the cutting chip was
The temperature of the plate was set at 400° C., and an intermediate layer of (:oSi2) having a thickness of 0.6 μm was formed by sputtering.

On this intermediate layer, the diamond synthesis conditions shown in Table 1 (
A diamond film with a thickness of 2.5 JLm was formed using carbon source gas and its concentration.

Note that the conditions for synthesizing the diamond film other than those described above were the same as in Example 1.

Further, a cutting test was conducted in the same manner as in Example 1 for the obtained cutting tip with a diamond film.

The results are shown in Table 1.

(Example 10) A cutting tip similar to that in Example 1 was cleaned in the same manner as in Example 1, the pressure in the reaction chamber was set to 101 torr, the temperature of the cutting tip was set to 400°C, and a one-layer OJ layer was formed by sputtering.
An intermediate layer of 4H1 and NiSi2 was formed.

This intermediate layer was coated with a film thickness of 3.5 mm under the diamond synthesis conditions (carbon source gas and its concentration) shown in Table 1. A diamond film of θ m was formed.

Note that the conditions for synthesizing the diamond film other than those described above were the same as in Example 1.

Further, a cutting test was conducted in the same manner as in Example 1 for the obtained cutting tip with a diamond film.

The results are shown in Table 1.

(Example 11) A cutting tip similar to that in Example 1 was cleaned in the same manner as in Example 1, the pressure in the reaction chamber was set to 1O-3 torr, the temperature of the cutting tip was set to 300°C, and by vacuum evaporation method, Layer thickness 0
．． 5 pm to form an intermediate layer of Pd2Si.

On this intermediate layer, the diamond synthesis conditions shown in Table 1 (
Carbon source gas and its concentration) and film thickness 3. A diamond film of OJLm was formed.

Note that the conditions for synthesizing the diamond film other than those described above were the same as in Example 1.

In addition, a cutting test was conducted in the same manner as in Example 1 on a cutting chip with a diamond film of 11 tons.

The results are shown in Table 1.

(Example 12) A cutting tip similar to that in Example 1 was cleaned in the same manner as in Example 1, the pressure in the reaction chamber was set to 1O-5 torr, the temperature of the cutting tip was set to 500°C, and a layer was formed by sputtering. Thickness 0
．． An intermediate layer of PtSi was formed.

On this intermediate layer, the diamond synthesis conditions shown in Table 1 (
A diamond film with a film thickness of 2.5 m was formed using carbon source gas and its concentration.

Note that the conditions for synthesizing the diamond film other than those described above were the same as in Example 1.

Further, a cutting test was conducted in the same manner as in Example 1 for the obtained cutting tip with a diamond film.

The results are shown in Table 1.

(Example 13) An intermediate layer was formed in the same manner as in Example 7.

Next, the cutting tip with the intermediate layer formed thereon was placed in a plasma generator, and the diamond synthesis was performed using an RF plasma method instead of the microwave plasma method of Example 7.

As a power source, a high frequency power source with a frequency of 4 MHz is used.
The output was set to 50 KW, and methane gas was flowed into the reaction chamber as a raw material gas at r: 0.5 exchange/min.
Hydrogen gas was set at a flow rate of 10 m/min, and Ar gas was set at a flow rate of 25 fL/min as a gear gas.

Note that the temperature of the cutting tip was set to 900° C. by water cooling, and the reaction pressure was set to 1 atmosphere.

In this way, a cutting tip with a diamond film is created,
A cutting test was conducted in the same manner as in Example 7.

The results are shown in Table 1.

(Example 14) An intermediate layer was formed in the same manner as in Example 7.

Next, the cutting chip with the intermediate layer formed thereon was installed in the reaction chamber, and the diamond synthesis method was replaced with the microwave plasma method of Example 7, and a direct current thermal plasma jet method with a discharge power of 20 KW was adopted.

The temperature of the cutting tip was set at 1,000° C., and the reaction pressure was set at 500 torr.

Next, methane gas was flowed into the reaction chamber as a raw material gas for 127 minutes, and hydrogen gas was flowed at a rate of 10 m/min.
Ar gas was used as a gear gas at a flow rate of 20 alternations/min.

In this way, Diamond II! A 2+1 cutting tip was prepared, and a J cutting test was conducted in the same manner as in Example 7.

The results are shown in Table 1.

(Comparative Example 1) A cutting tip with a diamond film was prepared in the same manner as in Example 1, except that the intermediate layer of WSi2 was not provided on the cutting tip, and a cutting test was conducted in the same manner as in Example 1. .

The results are shown in Table 1.

(Comparative Example 2) A J cutting tip with a diamond film was prepared in the same manner as in Example 13, except that the intermediate layer of WSi2 was not provided on the cutting tip, and a cutting test was conducted in the same manner as in Example 13. Ta.

The results are shown in Table 1.

[Advantageous Effects of the Invention 1] According to the present invention, diamond has excellent adhesion between the surface of a metal member and a diamond film, and thus has excellent wear resistance and can be suitably used for knives etc. that require a long service life. A membrane-coated member and a method for manufacturing the same can be provided.

Claims (2)

[Claims] (1) A member with a diamond film, characterized in that a diamond film is formed on the surface of a metal member via an intermediate layer containing a metal silicon compound. (2) A diamond film is formed by forming an intermediate layer containing a metal silicon compound on the surface of a metal member, and then bringing a gas obtained by exciting a raw material gas containing a carbon source gas onto the intermediate layer. 2. The method of manufacturing a member with a diamond film according to claim 1, further comprising: forming a diamond film-coated member.