KR970001005B1 - Wear resistant components coated with a diamond particle dispersed hard ceramic films and its synthesis methods - Google Patents

Abstract

Process for coating carbide, ceramic and diamond on a mother metal one after another is described. Thus, the process is composed of i)coating a carbide product on a surface of transition metal with a thickness of 0.5-200 microns, ii)grinding the surface of carbide coated mother metal with one of diamond powder, SiC powder, SiO2 powder, and Al2O3 powder to control a nucleus production density, iii)vapor depositing a diamond particle on the carbide coated mother metal with a thickness of 0.2-100 microns, iv)vapor depositing the hard ceramic on the diamond vapor-deposited layer.

Description

Wear-resistant products having a granular diamond-containing hard ceramic coating layer and a method of manufacturing the same

1 is a block diagram of a deposition apparatus for depositing a particulate diamond layer according to the present invention, (a) is a hot filament deposition apparatus, (b) is a high frequency plasma deposition apparatus, (c) is a microwave plasma deposition apparatus, (d) is a block diagram of a DC plasma deposition apparatus.

2 is a texture diagram of the soot surface of diamond deposited on the transition metal Fe.

3 is an example of a particulate diamond deposition film according to an embodiment of the present invention, (a) is a chemical vapor deposition treatment or a photograph of the surface of the diamond in the state of cutting the base material, (b) is an emery cloth (# 1000) (C) is a photograph of the diamond particles coated with a diamond coating after the substrate is polished with an emery cloth (# 1000) and polished with Al ₂ O ₃ powder.

4 is a configuration diagram of a physical vapor deposition apparatus for depositing a hard ceramic of the present invention, (a) sputtering apparatus by ion collision, (b) vacuum deposition and ion plating apparatus by resistance heating or electron beam heating Degree.

5 is a cross-sectional view of a wear resistant article having a particulate diamond-containing ceramic coating layer obtained in accordance with a preferred embodiment of the present invention.

* Explanation of symbols for main parts of the drawings

11,11b, 11c, 11d: Gas charging device 13,13b, 13c, 13d: Vacuum pump

14,14b, 14c, 14d, 44,44b: vacuum vessel 15: tungsten filament

16,16b, 16c, 16d, 48,48b, 50,50b, 50c, 50c, 50d: Base material

18: coil 19: high frequency power supply

20: magnetron 21: wave guide

22: coolant 23: anode

24: cathode 41,41b: vacuum exhaust port

42,42b: gas inlet 43: cathode voltage

45: target 46: glow discharge

47: evaporation source 49: charged metal

51: carbide generating layer 52: carbide generating layer

52 diamond deposited layer 53 ceramic layer

The present invention relates to a wear-resistant product having a diamond-containing hard ceramic coating layer and a method for manufacturing the same. Particularly, a diamond-containing hard material prepared by depositing a particulate diamond layer having excellent wear resistance on a base metal of a transition metal and coating the hard ceramic layer thereon A wear resistant product having a ceramic coating layer and a method of manufacturing the same.

Diamond is one of the best known materials, which has the highest hardness, electrical insulator, high thermal conductivity, and excellent chemical resistance and abrasion resistance. Therefore, it has unlimited possibilities for cutting tools and wear-resistant mechanical parts. The diamond layer forms a layer through nucleation and growth in a specific material. Carbide materials such as Si, Mo, Ti and the like form diamond thin films well, while transition metals such as Fe, Ni, and Co do not form diamond thin films well, and soot or graphite thin films are formed. On the other hand, even if a diamond thin film is formed, the adhesion between the base material and the diamond thin film is not good, and thus the thin film cannot be exhibited. Therefore, the improvement of the adhesion force is essential for application to mechanical parts, cutting tools, and molds.

The thin film of deposited diamond has similar characteristics to that of natural diamond, so its application can be very important. However, diamond thin films have not yet been put to practical use because they cannot be obtained to the extent that they can withstand the required parts due to the wear resistance of tools, molds, and mechanical parts in adhesion to the substrate.

Accordingly, an object of the present invention is to solve the above problems and wear-resistant products having a particulate diamond mode-containing hard gel-ceramic coating layer having excellent hardness and abrasion resistance of the granular diamond and excellent adhesion of the hard ceramic thin film to the base metal of the transition metal and It is to provide a method for producing the same.

In order to achieve the above object, the present invention provides a base metal of a transition metal, a carbide generation layer coated on the surface of the base material, a diamond layer deposited on the surface of the carbide generation layer in a particulate form, and deposited on the particulate diamond deposition layer. A wear resistant product having a particulate diamond-containing hard ceramic coating layer, which is characterized by being composed of a hard ceramic layer, is provided.

The present invention also provides a particulate diamond-containing hard ceramic coating layer comprising a base material that is easy to generate carbide, a diamond layer deposited on the surface of the base material in a particulate form, and a hard ceramic layer deposited on the particulate diamond deposition layer. To provide a wear resistant product.

The present invention further comprises the steps of coating a carbide generating material on the surface of the base metal of the transition metal, pretreating the carbide generating layer to control the nucleation density of the surface, depositing a particulate diamond coating layer on the carbide generating layer, It provides a method for producing a wear-resistant product having a diamond-containing hard ceramic coating layer comprising the step of depositing a hard ceramic layer on the diamond deposition layer.

According to another feature of the invention, the present invention comprises the steps of pretreatment to control the nucleation density of the surface of the carbide generating material, depositing a particulate diamond coating layer on the carbide product, and a hard ceramic layer on the particulate diamond deposition layer It provides a method for producing a wear-resistant product having a diamond-containing hard ceramic coating layer, characterized in that comprising the step of depositing.

Hereinafter, the configuration and operation of the present invention will be described with reference to the accompanying drawings.

The process of manufacturing a particulate diamond layer is as follows.

In general, there are metals (Si, Mo, Ti) that coat high-quality diamonds when coating diamond films or particles, while transition metals such as Fe, Ni, Co, and the like do not coat high-quality diamonds.

Therefore, in the present invention, for example, metals coated with high-quality diamond layers such as WC-Co (carbide) SiC, Si ₃ N _4, and Al ₂ O ₃ are coated with particulate diamond only by surface treatment, and in the case of transition metals, A diamond such as Si, Mo, Ti, etc. is coated to a thickness of 0.5 ~ 200㎛ to coat the particulate diamond.

First, in the case of transition metals, metals that produce carbides such as Si, Mo, and Ti are first coated. The coated substrate is treated with one or any of diamond powder, SiC powder, SiO ₂ powder, Al ₂ O ₃ powder and Cr ₂ O ₃ powder to maintain the density of nucleation at an appropriate level. The powder grinds the surface of the base material while it is put together with the base material as a powder to lift the base material; Mixing the powder with acetone, alcohol, water and the like and performing ultrasonic vibration treatment; It is done by rubbing the base material by making the powder into a paste state.

Subsequently, the surface-treated base material is exposed to a hydrogen plasma state for a predetermined time (0.5 to 30 minutes) in order to adjust the density of diamond particles, or undergoes a vacuum heat treatment process in a vacuum heat treatment ranging from 200 ° C. to 1400 ° C.

Subsequently, a matrix of 0.2-100 μm thick and 0.2-100 μm granular diamond layer is formed by chemical vapor deposition such as thermal filament chemical vapor deposition (CVD), RF plasma CVD, microwave plasma CVD, or direct current (DC) plasma CVD. Deposit on the surface. In this case, the thickness of the diamond particles can be adjusted according to the type of pretreatment and the coating time.

In chemical vapor deposition to deposit the above-described first granular diamond thin film of claim 1 also (a) a vacuum to the vacuum container 14 by a hot-filament chemical vapor deposition apparatus shown in the vacuum pump 13 is 10 ^-3 to 10 ^-1 Torr After drawing up to (Torr), the pressure in the vacuum vessel 14 was charged by 1 torr while charging H ₂ and CH ₄ gas (the CH ₄ gas concentration was changed in the range of 0.1% to 10%) through the gas charging device 11. Thermal filament chemical vapor deposition may be used to deposit a particulate diamond layer on the base material 16 by decomposition of hydrocarbons while the tungsten filament 15 is heated from 1500 ° C. to 2500 ° C. while maintaining up to 100 cor at.

In addition, the vacuum vessel 14b is extracted with a vacuum pump 13b to 10 ^-3 to 10 ^-1 Torr by the RF plasma CVD apparatus shown in FIG. 1 (b), and then a mixture of H ₂ and CH ₄ RF plasma which can deposit a particulate diamond thin film on the base material 16b by charging and filling the gas in the vacuum vessel 13b from 10 ^-2 to 200 Torr by the coil 18 connected to the high frequency power supply 11b. CVD methods may also be used.

In addition, the initial vacuum was extracted from the vacuum vessel 14c by the microwave plasma CVD apparatus of FIG. 1 (c) to 10 ^-3 to 10 ^-1 Torr by the vacuum pump 13c, and then the mixed gas of CH ₄ and H _{2 was} When supplying microwaves through the wave guide 17 to the magnetron 20 while maintaining 1 to 500 torr while flowing a plasma is generated around the base material 16c and hydrocarbon gas decomposes to form the particulate material in the base material 16c. Microwave plasma CVD can also be used to allow diamond thin films to be deposited.

In addition, the vacuum pump 13d attached to the vacuum vessel 14d by the DC plasma CVD apparatus of FIG. 1 (d) is initially used to make a vacuum from 10 ^-3 to 10 ^-1 Torr, and the CH is supplied through the gas supply 11d. _When charging ₄ and H ₂ mixed gas and supplying power to the cathode 24 on the base material 16d having the coating layer of carbide generating material, plasma is generated, and diamonds are deposited on the light poles generated around the base material 16d. It can be used to deposit the granular diamond. At this time, since the base material 16d is increased in temperature due to a positive liquor, a DC plasma CVD method for flowing a coolant 23 is used for the specimen 16d, which is an anode. And the like can be used. In FIG. 1, reference numeral 12 denotes an electric furnace, 23 denotes a sheep, 25 denotes a plunger 26, a DC power supply, 27 denotes a shutter, and 5454 and 54b denote a sample stage. Particle diamond deposition by the diamond deposition treatment using the apparatus is determined by the pretreatment conditions of the base material before diamond deposition, rather than depending on the deposition conditions and methods.

FIG. 2 is a texture diagram of the surface of a soot deposited on a transition metal Fe under diamond coating conditions, and FIG. 3 is an example of a particulate diamond deposition film according to an embodiment of the present invention. A photograph of the surface of a particulate diamond, (b) is a photograph of the diamond coating treatment by the CVD method while the base material is polished with an emery cloth (# 1000), (c) is a polishing of the base material with an emery cloth (# 1000) And a photograph of diamond particles coated with Al ₂ O ₃ powder and then coated.

After forming the particulate diamond deposited on the base material as described above, as shown in FIG. 4, a hard ceramic layer is deposited on the diamond deposited layer having poor adhesion by physical physical devices to form a support layer to hold the particulate diamond.

In the physical vapor deposition method, a sputtering method is shown in FIG. 4 (a). The vacuum chamber 44 is evacuated from the initial vacuum degree of 10 ^-7 to 10 ^-4 torr through the vacuum exhaust port 41, and then the gas inlet 42 is discharged. Through Ar gas and the reaction gas such as N ₂ , C ₂ H ₂ , O ₂ , CH ₄ and charged from 10 ^-4 to 9 × 10 ^-1 Torr to apply a negative voltage (43), the target 45 The hard ceramic layer is formed by sputtering metal (Me) ions such as Ti, Ni Fe, Co, Cr, Mo, Al, Cu, Zr, Hf, Si, Ge, Ga Deposited on the particulate diamond layer.

In this case, for example, when the reaction gas is N ₂ , NH ₃ , these nitrides (MexNy, where x, y: 0 ~ 4): when charging a hydrocarbon gas such as CH ₄ C ₂ H ₂ as the reaction gas These carbides (MexNy, where x, y: 0-4): When charged with oxygen as a reaction gas, a hard ceramic layer of oxide (MexO, where x, y: 0-4) is respectively placed on the particulate diamond layer. Can be deposited.

In addition, as shown in FIG. 4 (b), the metal 48 loaded in the evaporation source 47 capable of heating the metal is heated and evaporated by resistance heating or electron beam heating, and as shown in FIG. As in the case of sputtering by ion collision as described above, vacuum deposition and ion plating by resistance heating or electron beam heating to deposit metals, nitrides, carbides, oxides, etc. according to the type of gas flowing through the gas inlet 42 are performed. This can be used.

In addition, it can be used for the purpose of holding a particulate diamond layer by coating a hard ceramic layer of the metal, nitride, carbide, oxide, etc. by arc ion plating.

The thickness of the hard ceramic layer 53 may be thinner than the height of the particulate diamond layer as shown in FIG. 5 (a), or may be substantially the same as shown in FIG. 5 (b), As shown in FIG. 5C, the particulate diamond layer may be buried in the hard ceramic layer 53. On the other hand, as shown in Fig. 5 (d), the process of coating the granular diamond layer 52d on the Gati base material 50d and depositing the hard ceramic layer 53d is repeated from one to 100 times to make the particulate diamond hard. It may be dispersed in the ceramic layer to improve durability of the deposition layer.

Meanwhile, as another example, as shown in FIG. 5 (e), the base metal can be easily formed into a carbide such as WC-Co (carbide carbide), SiC, Si ₃ N _4, and AlO ₃ , instead of the transition metal. Wear products can be obtained.

As described above, the present invention may improve the performance and durability of components such as mechanical and electronic parts, cutting tools, and molds by applying a combination of excellent hardness, wear resistance, and the like and excellent adhesion of the hard ceramic layer. .

Claims (24)

A base metal of a transition metal, a carbide generation layer coated on the surface of the base material, a diamond layer that is particulately deposited on the surface of the carbide generation layer, and a hard ceramic layer deposited on the deposition layer on the particulate diamond deposition layer. A wear resistant product having a particulate, diamond-containing hard ceramic coating layer. The wear-resistant product having a particulate diamond-containing hard ceramic coating layer according to claim 1, wherein the transition metal is any one of Fe, Ni, and Co. The wear resistant article having a particulate diamond-containing hard ceramic coating layer according to claim 1, wherein the carbide generating layer is any one of Si, Mo, and Ti. The wear-resistant product having a particulate diamond-containing hard ceramic coating layer according to claim 1, wherein the carbide generating layer has a thickness of 0.5 to 200 µm. The wear-resistant product having a particulate diamond-containing hard ceramic coating layer according to claim 1, wherein the particulate diamond deposition layer has a thickness and a size of 0.2 to 100 µm. The method of claim 1, wherein the hard ceramic layer is any one of Ti, Ni Fe, Co, Cr, Mo, Al, Cu, Zr, Hf, Si, Ge, Ga, nitride of the metal, of the metal A wear resistant product having a granular diamond-containing hard cerium coating layer, characterized in that the carbide or any one of the oxide of the metal. Abrasion-resistant product having a particulate diamond-containing hard ceramic coating layer comprising an easy-to-carbide base material, a diamond layer deposited on the surface of the base material in a particulate form, and a hard ceramic layer deposited on the particulate diamond deposition layer. . 8. The wear resistant article having a particulate diamond-containing hard ceramic coating layer according to claim 7, wherein the carbide generating layer is any one of WC-Co, SiC, Si ₃ N ₄ and Al ₂ O ₃ . Coating a carbide generating material on the surface of the base metal of the transition metal, pretreating the carbide generating layer to control the nucleation density of the surface, depositing a particulate diamond coating layer on the carbide generating layer, and depositing the diamond. A method for producing a wear-resistant product having a particulate diamond-containing hard ceramic coating layer, characterized by depositing a hard ceramic layer on the layer. The method of claim 9, wherein the surface pretreatment is treated with any one or any one of diamond powder, SiC powder, SiO ₂ powder, Al ₂ O ₃ powder, and Cr ₂ O ₃ powder, and then put it together with the base material as another powder. The powder will grind the substrate surface while Mixing the powder with acetone, alcohol, water and the like and performing ultrasonic vibration treatment; A method of producing a wear-resistant product having a particulate diamond-containing hard ceramic coating layer, characterized in that the powder is made into a full state and rubbed the base material. 10. The method of claim 9, wherein the deposition of the diamond layer is performed by chemical vapor deposition. 12. The method of claim 11, wherein the chemical vapor deposition method is any one of thermal filament chemical vapor deposition, high frequency plasma chemical vapor deposition, microwave chemical vapor deposition, direct current filament chemical vapor deposition and plasma jet chemical vapor deposition method having a particulate diamond-containing hard ceramic coating layer. Method of making wear products. The method of claim 12, wherein the hot filament chemical vapor deposition method draws a vacuum vessel from 10 ^-3 to 10 ^-1 Torr of a vacuum pump, and then charges the pressure in the vacuum vessel while charging H ₂ and CH ₄ gas through a gas injector. Having a particulate diamond-containing hard ceramic coating layer comprising depositing a particulate diamond layer on a base material by decomposition of hydrocarbons while the tungsten filament is heated from 1500 ° C to 2500 ° C while maintaining from 1 to 100 torr. Method of making a wear resistant product. The method of claim 12, wherein the high-frequency plasma chemical vapor deposition method draws a vacuum vessel to a vacuum pump to 10 ^-3 ~ 10 ^-1 Torr, charges a mixture of H ₂ and CH ₄ gas and the pressure in the vacuum vessel at 10 ^-2 A method for producing a wear-resistant product having a particulate diamond-containing hard ceramic coating layer, comprising depositing a particulate diamond layer on a base material by filling a gas up to 200 Torr with a coil connected to a high frequency power supply. The method of claim 12, wherein the microwave plasma arc deposition method maintains the initial vacuum in a vacuum vessel to 10 ^-3 to 10 ^-1 Torr by a vacuum pump, and then maintains 1 to 500 Torr while flowing a mixture of CH ₄ and H _2. When the microwave is supplied to the magnetron through the wave guide, a plasma is generated around the base material, and the hydrocarbon gas is decomposed to deposit the particulate diamond on the base material. Manufacturing method. The method of claim 12, wherein the direct current plasma chemical vapor deposition is a vacuum pump attached to a vacuum vessel initially pumped to 10 ^-3 to 10 ^-1 Torr, charged with CH ₄ and H ₂ mixed gas through a gas supply device Wear-resistant having a particulate diamond-containing hard ceramic coating layer, characterized in that the plasma is generated by supplying power to the cathode installed on the base material, thereby depositing a particulate diamond layer on the base material by a positive liquor generated around the base material. Manufacturing method of the product. 10. The method of claim 9, wherein the deposition process of the hard ceramic layer is performed by physical vapor deposition. 18. The wear resistant product having a particulate diamond-containing hard ceramic coating layer according to claim 17, wherein the hard physical vapor deposition is any one of sputtering by collision, vacuum deposition by resistance heating or electron beam heating, and ion plating. Manufacturing method. 19. The method of claim 18, wherein the sputtering by the ion bombardment exhausts the initial vacuum degree to 10 ^-7 to 10 ^-4 Torr through the vacuum vent through the vacuum vent and then Ar gas and N ₂ , C ₂ H ₂ , O through the gas inlet ₂ , CH ₄ and the like, charged with 10 ^-4 to 9 × 10 ^-1 Torr to apply a negative voltage, generate a glow discharge at the target, and sputter the ceramic to deposit a ceramic thin film on the diamond layer. A method for producing a wear-resistant product having a particulate cyanide-containing hard ceramic coating layer. 19. The method of claim 18, wherein vacuum deposition and ion plating by resistance heating or electron beam heating are performed by evaporating a metal loaded in an evaporation source capable of heating the metal by resistance heating or electron beam heating, and reacting the gas through a gas suction port. A method for producing a wear resistant product having a particulate diamond-containing hard ceramic coating layer, comprising depositing a particulate diamond-containing hard ceramic coating layer, characterized by depositing the ceramic layer on the diamond layer. . The method of claim 9, wherein the coating material of the ceramic is a metal evaporated or sputtered one or a combination of Ti, Ni Fe, Co, Cr, Mo, Al, Cu, Zr, Hf, Si, Ge, and Ga. In the case of a hydrocarbon such as CH ₄ , C ₂ H ₂ , the reaction gas is one of the carbide of the metal, the oxide of the metal in the case of O ₂ , and the nitride of the metal in the case of N ₂ and NH _3. A method for producing a wear resistant product having a particulate diamond-containing hard ceramic coating layer. 10. The method of claim 9, wherein the thickness of the ceramic layer is thinner than the height of the diamond particles, the same thickness, or the diamond particle-containing hard ceramic coating layer, characterized in that the diamond particles to the ceramic layer. Method of making wear products. The wear-resistant product having a particulate diamond-containing hard ceramic coating layer according to claim 9, wherein the diamond layer is deposited on the base material and the ceracic thin film is deposited on the diamond deposition layer 1 to 100 times. Manufacturing method. Pretreating the carbide generating material to control the nucleation density of the surface, depositing a particulate diamond coating layer on the carbide product, and depositing a hard ceramic layer on the particulate diamond deposition layer. A method of producing a wear-resistant product having a particulate diamond-containing hard ceramic coating layer.