JPS62133068A - Diamond coated member - Google Patents

Abstract

PURPOSE:To produce a diamond coated member having excellent exfoliation resistance by interposing an adhesive strengthening layer consisting of group 4a, 5a, 6a metals, etc., of the periodic table and diamond as an intermediate layer between a base body and outside layer. CONSTITUTION:The intermediate layer consisting of one or multiple layers is interposed between the base body and the outside layer in the stage of forming the outside layer consisting of diamond and/or diamond-like carbon on the surface of the base body. The intermediate layer contiguous to the outside layer is formed of the adhesive strengthening layer consisting of at least one kind among the group 4a, 5a, 6a metals of the periodic table, or carbide and nitride of Si and the solid soln. thereof and diamond and/or diamond-like carbon. The adhesive strengthening layer is formed to 50Angstrom -5mu thickness and the outside layer is formed to 0.1-50mum thickness. The diamond coated member having the excellent adhesiveness of the base body and the outside layer is thus obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applicable to tool members such as cutting tools, wear-resistant tools, or grinding tools, and electronics such as heat sinks such as semiconductor lasers or diodes, and diaphragms for speakers. This invention relates to a diamond-coated member that can be applied to river members.

(Prior Art) Many methods have been proposed for synthesizing diamond from a gas phase, and diamond-coated members in which diamond coating layers are formed on the surfaces of various substrates using these methods have also been proposed.

When forming a diamond coating layer on the surface of a substrate, especially in the vapor phase synthesis method, carbon also precipitates at the same time as the coating layer is formed, and soft amorphous carbon or graphite tends to be mixed in the coating layer. . For this, for example, containing iron group metals such as cemented carbide and thermeft↓
(When a diamond coating layer is formed on the surface of the body, the carbon mixed in the coating layer reacts with the iron group metal of the substrate, diffuses into the substrate as a solid solution, and generates free carbon.
), (There is a problem that it reduces the strength of the body and the adhesion between the substrate and the coating layer.In addition, if iron group metal is present on the surface of the substrate, this iron group metal will be used as a supply material for the vapor phase synthesis method. act as a catalyst for the decomposition of hydrocarbon gases, or
There is a problem of reducing the quality of the coating layer due to absorption of the hydrogen gas supplied for the diamond synthesis process.

An attempt was made to solve these problems in the Japanese Patent Laid-open Publication No. 5
There is a publication No. 8-126972. This JP-A-58-12
No. 6972 discloses 4a, 5a, 6a on the surface of cemented carbide.
carbides and nitrides of group elements.

Borides, oxides and their compounds, mixtures and A
Sentence? o:+, A/N, B4 C, SiC.

Sir N4. This diamond-coated cemented carbide is formed by forming an inner layer selected from No. 5i07, and then forming an outer layer of diamond on the surface of the inner layer. This Japanese Patent Application Laid-Open No. 58-126972 eliminates the influence of iron group metals present on the surface of the cemented carbide by forming an inner layer between the cemented carbide and the outer layer. However, because an outer layer made of diamond is formed on the surface of the inner layer through covalent bonding and hardly reacts with other substances,
There is a problem in that the adhesion between the inner layer and the outer layer is poor, and the outer layer peels off with very low stress, making it impossible to put it into practical use.

Japanese Unexamined Patent Publication No. 59-93869 is an attempt to further solve these problems.

(Problems to be Solved by the Invention) JP-A No. 59-93869 discloses that 30% by volume of the coating
It is a structure in which the surface of a base material is coated with a hard film containing diamond, in which 95% by volume is diamond or a diamond-like phase, and the remainder is an iron group metal or an inorganic hard metal compound. The structure disclosed in JP-A-59-93869 has a coating layer made of diamond, which hardly reacts with other substances, mixed or dispersed with an iron group metal or an inorganic hard metal compound. Diamond grains P in the coating layer increase in the area that holds the grains.
It is thought that this improves the adhesion between the steel and the base material. However, the diamond coating layer containing iron group metals
As mentioned above, there is a problem in that amorphous carbon is mixed in the coating layer due to the influence of the iron group metal, reducing various properties such as strength and hardness of the coating layer. Also,! I
The coating layer with all hard metal compound diamond is a mixture of inorganic hard metal compound particles and diamond particles, and the adhesion between these particles is poor, or the inorganic hard metal compound particles and diamond are a mixture of inorganic hard metal compound particles and diamond particles. There is a problem in that the strength within the coating layer is low due to the formation of pores between the particles.

Book 9: Since lrA has solved the above-mentioned problems, specifically, it is easy to form an outer layer of 1 diamond between the 1 body and the outer layer of diamond, and it also has a high density with the outer layer. ! The object of the present invention is to provide a diamond-coated member having an interlayer interposed therebetween which has excellent ionic properties.

(Step-L to solve the problem) Diamond is generally used as a substrate because it has extremely poor wettability with other substances, has a small coefficient of thermal expansion, and has low diffusion of other atoms into diamond. It is very difficult to form a highly adhesive coating layer of diamond and/or diamond-like carbon on the surface of the diamond. Therefore, the groove of the present invention was developed by considering a substance that facilitates the formation of a coating layer made of diamond and/or diamond-like carbon, and a substance that increases the adhesion of a coating layer made of diamond and/or diamond-like carbon.
At least one metal of group 4a, 5a, 6a of the periodic table or St and periodic table 4a.

5a, 6a group metals or Si carbides, nitrides, and solid solutions of these phases.The surface of the substance is composed of at least one of diamond and/or diamond-like carbon. The present invention was completed based on the knowledge that the coating layer is easier to form and has excellent adhesion.

Specifically, the diamond-covered member of the present invention is a coated member in which an outer layer made of diamond and/or diamond-like carbon is formed on the surface of a base, and an intermediate layer composed of one layer or multiple layers between the base and the outer layer. The intermediate layer adjacent to the outer layer has a layer interposed therebetween, and the intermediate layer adjoins the outer layer.
At least one metal of group a, 6a or St, at least one metal of group 4a, 5a, or 6a of the periodic table or carbide, nitride of St, and mutual solid solution thereof, and diamond and/or diamond. It is characterized by being formed by an adhesion reinforcing layer made of carbon.

The substrate used here is not particularly limited as long as it can withstand the manufacturing conditions described below; for example, it can be made of various types of full-flexure 2 alloys, sintered high speed steel, Itli hard alloys, cermets, or ceramics. It can be used depending on the purpose.

The intermediate layer interposed between these substrates and the outer layer is characterized in that the intermediate layer adjacent to the outer layer is formed of an adhesion reinforcing layer, and is characterized by the fact that the intermediate layer adjacent to the outer layer is formed of an adhesion reinforcing layer, and the intermediate layer is formed by the material of the substrate used or the diamond-coated member of the present invention. Various configurations can be made depending on the purpose or shape.

For example, in the first configuration, the intermediate layer adjacent to the outer layer is made of at least one metal of groups 4a, 5a, or 6a of the periodic table or St, and is 4a of the periodic table.

It is formed by an adhesion reinforcing layer made of at least one of carbides, nitrides, and mutual solid solutions of metals of Groups 5a and 6a or Si, and diamond and/or diamond-like carbon. In this case, an adhesion reinforcing layer is interposed between the base and the outer layer. This adhesion reinforcing layer is made of at least one metal of group 4a, 5a or 6a of the periodic table or Si and a metal of group 4a, 5a or 6a of the periodic table.
carbides, nitrides and their mutual interaction [
Even a mixture consisting of at least one of the 1OiI solutions and diamond and/or diamond-like carbon has an excellent effect on the adhesion between the adhesion reinforcing layer and the outer layer and an effect on promoting the synthesis of the outer layer. In particular, diamond y! in the adhesion reinforcement layer! If it contains the ll structure,
These are preferable because their effects are even better and the strength of the adhesion reinforcing layer is increased. The intermediate layer having the first configuration can be applied to a substrate having excellent adhesion to the adhesion reinforcing layer, for example, a substrate made of various ceramics.

In the second configuration, the intermediate layer is composed of an adhesion reinforcing layer adjacent to the outer layer and an adhesion auxiliary layer adjacent to the adhesion reinforcing layer, and this adhesion reinforcing layer is in accordance with periodic table 4a.

Carbide or nitride of group 5a or 6a metals or Si.

It consists of at least one of borides and mutual solid solutions thereof. In this case, an adhesion reinforcing layer and an adhesion auxiliary layer are interposed between the base and the outer layer, the adhesion auxiliary layer is adjacent to the base, and the adhesion reinforcement layer is adjacent to the outer layer. Substrates with excellent properties, such as SiC
ceramics, Si3N4 ceramics, Ti
When applied to substrates such as C-based ceramics, cemented carbide, cermets, or various tool steels or non-ferrous metal materials,
The excellent properties of the outer layer can be demonstrated. In particular, when the adhesion reinforcing layer and the adhesion auxiliary layer contain the same element, for example, the adhesion reinforcing layer contains Ti, and the adhesion auxiliary layer contains TiC, TiN.

It is further preferable to include T f CN or TiB2 from the viewpoint of adhesion.

Other configurations of the intermediate layer may include various configurations, such as a case where the intermediate layer is composed of an adhesion reinforcing layer and a metal layer, or a case where the intermediate layer is composed of a metal layer of an adhesion reinforcing layer and an adhesion auxiliary layer. In this case, for example, Fe, Ni, Co, Cu, etc.
, Tf.

A metal layer such as Ta may be formed, and an adhesion reinforcing layer or an adhesion auxiliary layer may be formed on the surface of this metal layer.

The thickness of these intermediate layers is preferably 508 to log m, in which the mediating effect of promoting the synthesis of the outer layer and adhesion between the outer layer and the substrate is circulation, and does not cause a decrease in strength, and in particular,
The thickness of the adhesion reinforcing layer is preferably 50 Å to 5 μm.

The outer layer formed on the surface of these intermediate layers is made of diamond and/or diamond-like carbon, and its thickness varies depending on the use and shape of the diamond-coated member. For a member having a sharp cutting edge, the thickness is preferably 0.Lm to 5Lm, and for a wear-resistant tool or an electronics member, the thickness may be 0.11Lm to 50Ii,m depending on the application and shape.

The diamond-coated member of the present invention can be manufactured by the following method. First, after polishing and cleaning the surfaces of various substrates as necessary, if it is necessary to form an adhesion auxiliary layer, it is formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD), and then When forming an adhesion reinforcing layer, film-like diamond and/or diamond-like carbon can be formed, for example, by thermal filament CVD method, microwave plasma CVD method, high frequency plasma CVD method, or ion beam by magnetic field separation. Simultaneously with the synthesis of diamond and/or diamond-like carbon by a vapor deposition method or the like, at least one metal of the periodic table 4a, 5a, Ba group metal or Si and the periodic table 4a,
5a.

4a of the periodic table after at least one of carbides, nitrides, borides and mutual solid solutions of these metals of group 6a or St are formed.

Formation of at least one metal of groups 5a, 6a or St with at least one of carbides, nitrides, borides and mutual solid solutions of metals of groups 4a, 5a, 6a of the periodic table or St Canceled.

For example, the outer layer is formed by stopping the supply of a gas such as a hydride or halide containing an element in Groups 4a, 5a, or 6a of the periodic table or Si and continuing only the synthesis of diamond and/or diamond-like carbon. be done.

If, for example, it is necessary to form a metal layer on the surface of the substrate in order to further enhance the adhesion between the substrate and the intermediate layer due to the material or shape of the substrate, plating, vapor deposition, or PVD methods may be used. This can be done by

(Function) In the coated member of the present invention, the adhesion reinforcing layer as an intermediate layer promotes synthesis of the outer layer, and after the formation of the outer layer, the adhesion between the intermediate layer and the outer layer can be significantly improved. Also,
If the adhesion between the substrate and the adhesion reinforcing layer is poor due to the material or shape of the substrate, the adhesion between the substrate and the adhesion reinforcing layer can be strengthened by interposing an intermediate layer such as an adhesion auxiliary layer or a metal layer between the substrate and the adhesion reinforcing layer. It can improve the adhesion with the layer.

(Example) Example 1 A specimen made of a cemented carbide equivalent to KIO classified as 15O (After grinding, washing and drying the body, it was placed in a microwave plasma CVD reaction vessel, and 870% TLC1s 5mm0 Text%CH4-87Ma0 exchange%H2 atmosphere, pressure 20To
r r , the surface of the substrate was coated with a T i C layer at a temperature of 1000°C and a holding time of 30 minutes 4 Then, after evacuating the inside of the reaction vessel, 5 mO/m1nT i C14-2m
1J/m1ncHa -300mfl/m1nH2 atmosphere, external heating 900℃, filament temperature 2000℃
, a coating layer was formed for a holding time of 35 minutes, and then 2J/z
inc Ha -300J/win) (2) In an atmosphere, external heating was performed at 900°C, filament temperature was 2000°C, and a holding time was 145 minutes, and a coating layer was further formed to obtain product 1 of the present invention.

For comparison, the cemented carbide substrate was placed in the reaction vessel, and 8vo% TiC A4-5 and 0% CHa-87
MaOi%H2 atmosphere, pressure 20 Torr, temperature 100
After coating the body surface with a T2C layer at 0°C for 30 minutes, the inside of the reaction vessel was heated at 2 mQ/m1nc Ha.
-300mlJ/m1nH2 atmosphere, external heating 9
00℃, filament temperature 2000℃, holding time 145
Comparative amount 1 was obtained by forming a coating layer in minutes.

Scanning electron wJ
When examined using a microscope, Raman spectroscopy, and electron beam microanalyzer, it was found that product 1 of the present invention has an outer layer of diamond with a thickness of 2 gm, and an intermediate layer of diamond with a thickness of 0.5 gm, Ti, and titanium carbide. It consists of an adhesion reinforcing layer mainly having a mold structure and an adhesion auxiliary layer of TiC with a thickness of 0.5 μm, and the comparative amount l is a diamond layer with a thickness of 1.6 μm as the outer layer and a layer with a thickness of 0.5 μm as the intermediate layer. The TiC layer was 5 gm thick.

As a result of comparing the peeling resistance of the coating layer by conducting a scratch test with a diamond indenter on this invention product 1 and comparative quantity 1,
Comparative amount 1 caused peeling of the coating layer at a load of 1.7 kg, while product 1 of the present invention did not cause peeling of the coating layer up to a load of 5.2 kg.

Example 2 A 1.3×10
3TorrN2-1.5XlO-4TorrC2H2
After evaporating Ti using a hollow cathode electron beam with a bias voltage of 20V (7) applied to the substrate in an atmosphere, 511Q/m1nT i Cl fl-5+nlJ/
winCHs -500mlJ/m1nH2, pressure 40
Using microwave plasma CVD method with Torr, output 350W, temperature 920℃, holding time 15 minutes, Y
Form a layer, then 5. Q/m1ncHn -500
Inventive product 2 was obtained by further forming a coating layer using a microwave plasma CVD method using yjJ/rainH2, a pressure of 40 Torr, an output of 350 W, a temperature of 920° C., and a holding time of 180 minutes.

For comparison, in the manufacturing process of the above-mentioned product of the present invention, 5mQ/
m1nT i Cla −5mO/m1nc Hs −
Comparative amount 2 was obtained by omitting only the formation of the coating layer, which was performed in a 500 mQ/m1 nH2 atmosphere.

The respective coating layers of Inventive Product 2 and Comparative Amount 2 were examined in the same manner as in Example 1, and it was found that Inventive Product 2 had an outer layer of diamond with a thickness of 2 gm, and an intermediate layer of diamond, Ti, and titanium carbide. It consists of an adhesion reinforcing layer with a thickness of 1 μm mainly having a diamond-shaped structure and an adhesion auxiliary layer made of T t CN with a thickness of 2.0 gm. Comparative amount 2 has an outer layer with a thickness of 1.5 μm.
Thick diamond layer, middle layer 2gm thick T1C
This invention product 2 and comparative amount 2 were made of work material A-18% Si, which was N layer.
j/] Cutting speed 25011/sin, feed speed 0.1
! As a result of a turning test conducted under the conditions of 1 ml rev, depth of cut fio, and 5 mm, it was found that with comparative amount 2, peeling of the Ya layer occurred in the early stage of cutting, whereas with product 2 of the present invention, there was almost no wear even after 30 minutes of cutting. It never happened.

Example 3 After polishing, cleaning, and drying a substrate made of ceramics having a composition of Si:;
z N4-5voi% CH4-400tou% H2, pressure 30 Torr, temperature 900°C.

After forming a coating layer on the surface of the substrate for a holding time of 30 minutes,
The supply of 5iC1a into the reaction vessel was stopped, and the 5iC1a was changed to 0%.
CH4-400 ma 0% H2 atmosphere, retention time 200
Inventive product 3 was obtained by forming a coating layer under the same conditions as above.

For comparison, the same substrate as above was placed in the same reaction vessel as above, 570% CH4-400vo41%H7, pressure 30 Torr, temperature 900°C.

Comparative amount 3 was obtained by forming a coating layer with a holding time of 200 minutes.

Inventive product 3 and comparative amount 3 were investigated in the same manner as in Example 1, and it was found that inventive product 3 had a diamond layer with a thickness of 3 gm as the outer layer, and a diamond layer with an intermediate layer of diamond, Si, and silicon carbide. It consisted of an adhesion reinforcing layer with a thickness of 1.0 gm and the mold structure was t, and comparative amount 3 consisted of a diamond layer with a thickness of 2.3 gm.

This invention product 3 and comparative amount 3 were used as work material A4u-8%Si alloy! /J cutting speed 400 m/win, ! As a result of conducting a turning test under the conditions of , rJ depth of 11 m, feed rate of 0, and 15 arm/rema, the coating layer peeled off for comparison amount 3 after 30 minutes of cutting, whereas for product 1 of the present invention, the coating layer peeled off after 60 minutes of cutting. After that, no 'Agl occurred in the coating layer, and the wear was normal and the amount of wear was very small.

(Effects of the Invention) From the above results, the diamond-coated member of the present invention has extremely excellent adhesion between the outer layer made of diamond and/or diamond-like carbon and the substrate, and has an adhesion that is more than three times that of the conventional diamond-coated member. It has excellent peeling resistance and a correspondingly long service life. For this,
As cutting tools that are subject to severe loads, for example, it can be applied not only to turning tools, but also to rotating tools such as milling tools, drills, end mills, and micron drills. It can also be applied to wear-resistant J-type tools, including slitters for Jino machines. Furthermore, it is an industrially useful material that can be applied to heat sinks and other electronic components by taking advantage of the high electrical insulation and high thermal conductivity that diamond itself possesses.

Claims (3)

[Claims] (1) In a coating member that forms an outer layer made of diamond and/or diamond-like carbon on the surface of a base,
An intermediate layer composed of one layer or multiple layers is interposed between the base body and the outer layer, and the intermediate layer adjacent to the outer layer is made of at least one metal selected from Groups 4a, 5a, and 6a of the Periodic Table of Metals or Si. and at least one of carbides, nitrides, and mutual solid solutions of metals of groups 4a, 5a, and 6a of the periodic table, and diamond and/or diamond-like carbon. A diamond-coated member characterized by: (2) The intermediate layer is composed of the adhesion reinforcing layer adjacent to the outer layer and the adhesion auxiliary layer adjacent to the adhesion reinforcing layer, and the adhesion auxiliary layer is made of a metal of group 4a, 5a or 6a of the periodic table or S
The diamond-coated member according to claim 1, characterized in that the diamond-coated member is made of at least one of carbides, nitrides, borides, and mutual solid solutions thereof. (3) The diamond-coated member according to claim 1 or 2, wherein the adhesion reinforcing layer has a thickness of 50 Å to 5 μm. (3) The diamond-coated member according to claim 1 or 2, wherein the outer layer has a thickness of 0.1 μm to 50 μm.