WO2019084768A1 - Alliage dur présentant un revêtement de diamant et son procédé de préparation - Google Patents

Alliage dur présentant un revêtement de diamant et son procédé de préparation Download PDF

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Publication number
WO2019084768A1
WO2019084768A1 PCT/CN2017/108572 CN2017108572W WO2019084768A1 WO 2019084768 A1 WO2019084768 A1 WO 2019084768A1 CN 2017108572 W CN2017108572 W CN 2017108572W WO 2019084768 A1 WO2019084768 A1 WO 2019084768A1
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Prior art keywords
silicon nitride
diamond
cemented carbide
layer
carbide substrate
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PCT/CN2017/108572
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English (en)
Chinese (zh)
Inventor
唐永炳
黄磊
王陶
李星星
李振声
张文军
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B51/00—Tools for drilling machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D35/00—Tools for shearing machines or shearing devices; Holders or chucks for shearing tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D71/00—Filing or rasping tools; Securing arrangements therefor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material

Definitions

  • the invention belongs to the technical field of diamond coating preparation, and in particular relates to a cemented carbide with a diamond coating and a preparation method thereof.
  • Cemented carbide is widely used in tool materials due to its excellent properties such as high hardness, wear resistance and heat resistance.
  • diamond coatings are usually placed on the surface of cemented carbide.
  • the thermal expansion coefficients of diamond coatings and cemented carbide substrates differ greatly, resulting in better adhesion between the two. Poor, during the actual cutting process, the diamond coating is easily detached from the cemented carbide substrate, which reduces the service life of the cemented carbide tool.
  • the industry generally adopts a method of preparing an intermediate layer to alleviate thermal stress while preventing cobalt from diffusing to the surface in the matrix, thereby improving adhesion between the diamond coating and the cemented carbide substrate.
  • the thermal expansion coefficient of the cemented carbide after the preparation of the intermediate layer, the matrix, the intermediate layer and the diamond coating are still quite different.
  • the diamond coating has poor impact toughness and is prone to the film-based interface caused by thermal stress.
  • the adhesion is poor, and cracks are formed at the interface, which causes the diamond coating to fall off during the cutting process.
  • an embodiment of the present invention provides a cemented carbide having a diamond coating layer by sequentially providing a silicon nitride layer and a silicon nitride/diamond composite layer between the cemented carbide substrate and the diamond coating layer.
  • the thermal expansion coefficient of the surface of the cemented carbide substrate to the diamond coating is gradually reduced, thereby improving the adhesion between the diamond coating and the substrate, and solving the diamond coating and the hard alloy base in the prior art.
  • the problem that the diamond coating is easily peeled off due to poor adhesion between the bodies.
  • a first aspect of the present invention provides a cemented carbide having a diamond coating, comprising a cemented carbide substrate, and a silicon nitride layer, a silicon nitride/diamond composite layer sequentially disposed on the cemented carbide substrate. Layer and diamond coating.
  • the thickness of the silicon nitride layer is 1-8 ⁇ m
  • the thickness of the silicon nitride/diamond composite layer is 1-8 ⁇ m
  • the thickness of the diamond coating layer is 1-6 ⁇ m.
  • the mass ratio of silicon nitride to diamond is 1:1 to 4.
  • the diamond-coated cemented carbide provided by the first aspect of the present invention has a thermal expansion coefficient of each layer gradually decreased along the direction of the cemented carbide substrate-silicon nitride layer-silicon nitride/diamond composite layer-diamond coating layer, thereby improving
  • the bonding force between the diamond coating and the hard substrate can not only solve the problem that the thermal expansion coefficient between the diamond coating and the hard alloy is large, but also cause the crack to occur or the coating to fall off, and the diamond coating and the substrate can be ensured.
  • There is no hole defect in the three-dimensional space so that there is enough contact area between the diamond coating and the substrate to bite, which greatly improves the adhesion of the diamond coating on the cemented carbide substrate.
  • a second aspect of the present invention provides a method of preparing a cemented carbide having a diamond coating, comprising the steps of:
  • a diamond coating is deposited on the silicon nitride/diamond composite layer to obtain a cemented carbide.
  • the silicon nitride layer is prepared by hot wire chemical vapor deposition, and the deposition process is carried out
  • the gas includes ammonia, silane and hydrogen at a temperature of 800-1000 ° C, a pressure of 2000-2500 Pa, and a deposition time of 30-60 min.
  • the silicon nitride/diamond composite layer is prepared by hot wire chemical vapor deposition, wherein the gas introduced includes ammonia gas, silane, methane and hydrogen gas, the temperature is 800-1000 ° C, and the pressure is 2000- 2500Pa, deposition time is 1-2h; the diamond coating is prepared by hot wire chemical vapor deposition, wherein the gas introduced includes methane and hydrogen, the temperature is 800-1000 ° C, and the pressure is 2000-2500 Pa. The deposition time is 1-2h.
  • the specific operation of the etching treatment is: placing the cleaned hard alloy substrate in an alkali solution first Ultrasonic cleaning for 2-6 minutes, then ultrasonic cleaning in acid solution for 10-50s.
  • the alkali solution is a mixed solution of potassium ferricyanide, potassium hydroxide and water
  • the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide
  • the cemented carbide substrate having a silicon nitride layer on the surface is first placed in the phytic crystal solution for 20-50 min, and then blown dry with nitrogen, the crystallization solution is detonation. Nanodiamond suspension.
  • the detonation nanodiamond suspension comprises detonation nanodiamond with a particle diameter of 10-20 nm and a mass fraction of 0.005%, and includes a dispersant and deionized water.
  • the preparation method of the diamond-coated cemented carbide provided by the second aspect of the invention has the advantages of simple preparation process, stable process, suitable for industrial production, good adhesion between the prepared product coating and the substrate, and high practicability.
  • Example 1 is a schematic structural view of a cemented carbide having a diamond coating prepared in Example 1 of the present invention
  • Example 2 is a topographical view of a Rockwell indentation backscatter of a sample of Example 1 of the present invention.
  • the embodiment of the invention provides a cemented carbide with a diamond coating, including a cemented carbide substrate, and sequentially disposed on the cemented carbide A silicon nitride layer, a silicon nitride/diamond composite layer, and a diamond coating on the substrate.
  • the cemented carbide with diamond coating provided by the embodiment of the invention has a thermal expansion coefficient of 4.5 ⁇ 10 -6 -6.0 ⁇ 10 -6 /K, and a thermal expansion coefficient of silicon nitride of 2.8 ⁇ 10 -6 - 3.2 ⁇ 10 -6 /K, the thermal expansion coefficient of diamond is 1.0 ⁇ 10 -6 -2.0 ⁇ 10 -6 /K, and the thermal expansion coefficient of silicon nitride/diamond composite layer is the thermal expansion coefficient of silicon nitride and the thermal expansion coefficient of diamond. between.
  • the thermal expansion coefficient is gradually reduced, and the thermal expansion coefficients between adjacent layers are small, so the thermal stress generated between the layers is small, so that the diamond coating and the hard coating can be avoided.
  • the alloy has a large difference in thermal expansion coefficient, which causes the diamond coating to crack or fall off, and improves the bonding force between the diamond coating and the substrate.
  • the silicon nitride layer can block the outward diffusion of cobalt in the cemented carbide and increase the nucleation density during diamond growth.
  • the thickness of the silicon nitride layer is 1-8 ⁇ m. Further, the thickness of the silicon nitride layer may be 2-6 ⁇ m, 3-5 ⁇ m, 4-7 ⁇ m.
  • the thickness of the silicon nitride/diamond composite layer is 1-8 ⁇ m. Further, the thickness of the silicon nitride/diamond composite layer may be 2-6 ⁇ m, 3-5 ⁇ m, 4-7 ⁇ m.
  • the diamond coating has a thickness of 1-6 ⁇ m.
  • the thickness of the silicon nitride/diamond composite layer may be 2-5 ⁇ m, 3-4 ⁇ m.
  • the thickness of each layer can be determined by the time of deposition and/or the flow rate of the reactive gas introduced. Adjustment, as the deposition time increases, the flow rate of the reaction gas increases, and the thickness of the obtained film layer increases. According to the mechanical simulation of finite element, the thickness of each layer will affect the concentrated distribution of stress. The above thickness range can be selected to concentrate the stress on the silicon nitride and silicon nitride/diamond composite layer, and the effective transfer stress is concentrated in the diamond. .
  • the mass ratio of silicon nitride to diamond in the silicon nitride/diamond composite layer is 1:1 to 4, for example, 3:7, 2:5, 1:3. , 1:2, 1:4, etc.
  • Such a content design can make the silicon nitride/diamond composite layer more similar in composition and properties to the surface diamond coating, and the thermal expansion coefficient between the two is closer, so that the stress existing between the layers is mainly Concentrated between the silicon nitride layer and the silicon nitride/diamond composite layer, the stress is mainly concentrated between the diamond coating and the silicon nitride/diamond composite layer, resulting in thermal stress generated by the diamond coating during use.
  • the superposition makes the diamond coating crack and fall off due to excessive stress, thus improving the impact toughness and adhesion of the diamond coating.
  • the cemented carbide substrate may be a cutter, a mold, a mechanical component or the like.
  • the cemented carbide substrate comprises a tungsten-cobalt-based cemented carbide substrate or a tungsten-titanium-based cemented carbide substrate.
  • the mass content of the cobalt element in the cemented carbide is generally from 6 wt.% to 10 wt.%.
  • an embodiment of the invention provides a method for preparing a cemented carbide with a diamond coating, comprising the following steps:
  • the silicon nitride layer is prepared by hot wire chemical vapor deposition, wherein the gas introduced includes ammonia gas, silane and hydrogen gas, the temperature is 800-1000 ° C, the pressure is 2000-2500 Pa, and the deposition time is 30-60min.
  • the gas introduced includes ammonia gas, silane and hydrogen gas
  • the temperature is 800-1000 ° C
  • the pressure is 2000-2500 Pa
  • the deposition time is 30-60min.
  • the specific operation of preparing the silicon nitride layer by hot wire chemical vapor deposition is: raising the temperature from room temperature to 800-1000 ° C at a temperature increase rate of 20-50 ° C / min, and maintaining the 15- 30 min; then introducing a gas, the introduced gas includes ammonia gas, silane and hydrogen; wherein the flow rate of the controlled ammonia gas is 80-150 mL/min, the total flow rate of the silane and the hydrogen gas is 70-140 mL/min, and the flow rate of the silane It is 10-40 mL/min, the rest is the flow rate of hydrogen, the pressure is 2000-2500 Pa, and the deposition time is 30-60 min, and a silicon nitride layer is obtained.
  • the flow rate of the ammonia gas is controlled to be 120 mL/min, the total flow rate of silane and hydrogen is 100 mL/min, the flow rate of the silane is 20 mL/min, and the balance is the flow rate of hydrogen.
  • Silicon nitride layers of different thicknesses can be obtained by controlling the flow rate of the reaction gas and the deposition time.
  • the silicon nitride/diamond composite layer is prepared by hot wire chemical vapor deposition, wherein the gas introduced includes ammonia gas, silane, methane and hydrogen gas, the temperature is 800-1000 ° C, and the pressure is 2000- 2500Pa, deposition time is 1-2h; the diamond coating is prepared by hot wire chemical vapor deposition, wherein the gas introduced includes methane and hydrogen, the temperature is 800-1000 ° C, and the pressure is 2000-2500 Pa. The deposition time is 1-2h.
  • the specific operation of sequentially preparing the silicon nitride/diamond composite layer and the diamond coating by hot wire chemical vapor deposition is as follows: increasing from room temperature to a temperature increase rate of 20-50 ° C/min 800-1000 ° C, and heat for 15-30 min; then pass the gas, the gas introduced includes ammonia, silane, methane and hydrogen; wherein the flow rate of ammonia control is 120 mL / min, total of silane, methane and hydrogen The flow rate is 100 mL/min.
  • the flow rate of methane may be 5-10 mL/min
  • the flow rate of silane may be 5-10 mL/min
  • the flow rate of hydrogen may be 80-90 mL/min
  • the pressure is 2000-2500 Pa, deposition time.
  • a silicon nitride/diamond composite layer is obtained; then ammonia and silane are turned off to make ammonia and silane
  • the flow rate is 0, and the flow rate of methane is controlled at 8-32 mL/min, the flow rate of hydrogen gas is controlled at 800 mL/min, the pressure is 2000-2500 Pa, and the deposition time is 1-2 h, and a diamond coating is obtained.
  • the specific operation of the etching treatment is: placing the cleaned hard alloy substrate in an alkali solution first Ultrasonic cleaning for 2-6 minutes, then ultrasonic cleaning in acid solution for 10-50s.
  • the invention performs corrosion treatment before the step of depositing a silicon nitride layer on the surface of the cemented carbide substrate, can remove a certain amount of cobalt on the surface of the cemented carbide, increase the surface roughness of the substrate, and improve the bonding force between the silicon nitride layer and the cemented carbide substrate.
  • the alkali solution is a mixed solution of potassium ferricyanide, potassium hydroxide and water
  • the acid solution is a mixed solution of sulfuric acid and hydrogen peroxide.
  • the alkali solution is a mixed solution of 2-10 g of potassium ferricyanide, 2-10 g of potassium hydroxide and 20-80 mL of water.
  • the alkali solution is a mixed solution of 5 g of potassium ferricyanide, 5 g of potassium hydroxide and 50 mL of water
  • the acid solution is a mixed solution of 10 mL of 98% sulfuric acid and 100 mL of hydrogen peroxide.
  • the diamond crystallization is performed by: placing a cemented carbide substrate having a silicon nitride layer on the surface in the crystallization solution for 20-50 min, and then drying it with nitrogen.
  • the solution is a detonation nanodiamond suspension.
  • the phytolithographic operation increases the nucleation density of the diamond coating and prevents heterogeneous nucleation of the diamond coating.
  • the crystallization operation in the embodiment of the present invention makes the nucleation density of the diamond reach 1 ⁇ 10 11 /cm 2 , which is 10 times of the highest nucleation density reported in the related research, so that there is no three-dimensional space between the diamond coating and the substrate. Hole defects, there is also enough contact area for the bite to improve the adhesion between the diamond coating and the substrate.
  • the detonation nanodiamond suspension comprises detonation nanodiamond having a particle size of 10-20 nm and a mass fraction of 0.005%, and includes a dispersant and deionized water.
  • the detonation nanodiamond is an emerging nanodiamond material prepared by a detonation product method, which not only has the comprehensive mechanical and physical properties of diamond low density, high hardness, high anti-wear, high anti-corrosion and high temperature resistance, but also has Small size effects of nanomaterials, large specific surface area effects, quantum size effects, quantum tunneling, etc.
  • the detonation nanodiamond can greatly increase the nucleation density of the diamond.
  • the dispersing agent is lysine, and its concentration in the diamond suspension may be 5 x 10 -6 mol/L.
  • the lysine can uniformly disperse the detonation nanodiamond, and according to the combined action of the etching treatment and the phytolith treatment, the detonation nanodiamond can be more easily adsorbed on the surface of the silicon nitride layer.
  • the whole matrix can be positively or negatively charged, and by adjusting the concentration of lysine, the nanodiamond particles in the phytic crystal solution can be positively or negatively charged as a whole.
  • the detonation nanodiamond is more easily adsorbed on the surface of the substrate with opposite charges, and a higher density of diamond nucleation is obtained, and the compactness of the film is improved.
  • the nucleation density of the diamond coating is increased by the process of crystallization after the silicon nitride layer is long, and the interface defects caused by the heterogeneous nucleation of the diamond coating and the nucleation density are not high.
  • a cleaning operation is also included.
  • the specific operation of the cleaning is as follows: firstly, ultrasonically cleaning with deionized water for 2-3 times, each time for 5-10 minutes, and then ultrasonically cleaning 2-3 times with alcohol for 5-10 minutes, and then drying with nitrogen.
  • a method for preparing a cemented carbide with a diamond coating comprising the steps of:
  • the commercially available YG6 (WC-6wt.%Co) cemented carbide sheet is used as the substrate, and the cleaning is pretreated: the substrate is firstly ultrasonically cleaned in deionized water for 2 times, each time for 5 minutes, and then Will go The ion-washed substrate was ultrasonically washed in an alcohol solution for 5 minutes and dried with nitrogen;
  • the cleaned carbide substrate is placed in an etching solution for corrosion treatment: firstly, the cleaned carbide substrate is ultrasonically cleaned in an alkali solution for 5 minutes, and then ultrasonically cleaned in an acid solution for 30 seconds, wherein the alkali solution a mixed solution comprising 5 g of potassium ferricyanide, 5 g of potassium hydroxide and 50 mL of water, the acid solution comprising a mixed solution of 10 mL of sulfuric acid and 100 mL of hydrogen peroxide;
  • a layer of silicon nitride is deposited on the surface of the substrate by hot-wire chemical vapor deposition.
  • the specific process parameters are as follows: from 20 ° C / min to 800 ° C from room temperature, and kept for 15 min, then flow It is 120 mL/min of ammonia gas, a flow rate of 20 mL/min of silane, a flow rate of 80 mL/min of hydrogen, a total flow rate of the silane and the hydrogen gas is 100 mL/min, a deposition process pressure of 2000 Pa, and a deposition time of 30 min;
  • a silicon nitride/diamond composite layer and a diamond coating are sequentially deposited on the surface of the silicon nitride layer after crystallization by hot wire chemical vapor deposition.
  • the specific process parameters are: rising from room temperature to 800 ° C at a temperature increase rate of 20 ° C / min, and holding for 15 min, then introducing a flow rate of 120 mL / min of ammonia, 5 mL / min of silane, 10 mL / min of methane, 85 mL/min of hydrogen, the total flow rate of the methane, the silane and the hydrogen is 100 mL/min, the deposition process pressure is 2000 Pa, and the deposition is performed for 1 h to obtain a silicon nitride/diamond composite layer; then the ammonia gas and the silane are closed. Adjust the flow rate of methane to 16mL/min, adjust the flow rate of hydrogen to 800mL/min, the pressure is 2000Pa, and deposit for 1h to
  • FIG. 1 is a schematic structural view of a cemented carbide having a diamond coating prepared according to an embodiment of the present invention, wherein 10 is a cemented carbide substrate, 20 is a silicon nitride layer, 30 is a silicon nitride/diamond composite layer, and 40 is a diamond coating.
  • 10 is a cemented carbide substrate
  • 20 is a silicon nitride layer
  • 30 is a silicon nitride/diamond composite layer
  • 40 is a diamond coating.
  • the loaded load is 80N
  • the loading time is 5s. It can be seen from the figure that the coating on the edge of the indentation remains intact and there is no shedding. Cracks are generated at the edge of the indentation, but the number of cracks is small, the crack length is short, and the crack distribution is relatively uniform. Therefore, it is known that the adhesion of the diamond coating to the cemented carbide substrate is very good and can reach the highest level of industrial production, and the adhesion rating is HF1 (HF1 is the best and HF6 is the worst).
  • Embodiment 1 differs from Embodiment 1 only in that the deposition time when depositing the silicon nitride layer is 1 h.
  • This embodiment differs from Embodiment 1 only in that the gas flow rate used in depositing the silicon nitride/diamond composite layer is methane 5 mL/min, silane 5 mL/min, and hydrogen gas 90 mL/min.
  • This embodiment differs from Embodiment 1 only in that the gas flow rate used in depositing the silicon nitride/diamond composite layer is 10 mL/min of methane, 10 mL/min of silane, and 80 mL/min of hydrogen.
  • This embodiment differs from Example 1 only in that, when the diamond coating is deposited, the ammonia gas flow rate is set to 32 mL/min after the ammonia gas and the silane are turned off.
  • This embodiment differs from Example 1 only in that, when the diamond coating is deposited, after the ammonia gas and the silane are turned off, the methane flow rate is set to 8 mL/min, and the deposition time is 2 h.

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Abstract

L'invention concerne un alliage dur présentant un revêtement de diamant et son procédé de préparation. L'alliage dur comprend une matrice d'alliage dur (10), une couche de nitrure de silicium (20), une couche composite de nitrure de silicium/diamant (30) et le revêtement de diamant (40) étant disposés séquentiellement sur la matrice d'alliage dur. Les étapes du procédé de préparation de l'alliage dur comprennent : après le lavage de la matrice d'alliage dur (10), le dépôt de la couche de nitrure de silicium (20) sur la surface de la matrice d'alliage dur ; l'implantation de germes cristallins de diamant sur la couche de nitrure de silicium, puis le dépôt en vue de préparer la couche composite de nitrure de silicium/diamant (30) sur la couche de nitrure de silicium ; et le dépôt en vue de préparer le revêtement de diamant (40) sur la couche composite de nitrure de silicium/diamant, de façon à obtenir l'alliage dur présentant le revêtement de diamant.
PCT/CN2017/108572 2017-10-31 2017-10-31 Alliage dur présentant un revêtement de diamant et son procédé de préparation Ceased WO2019084768A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102248187A (zh) * 2011-06-02 2011-11-23 深圳市金洲精工科技股份有限公司 金刚石涂层硬质合金刀具及其制备方法
EP2495080A1 (fr) * 2011-03-01 2012-09-05 GFD Gesellschaft für Diamantprodukte mbH Outil de coupe doté d'une lame en diamant cristallin fin
JP2014069258A (ja) * 2012-09-28 2014-04-21 Nachi Fujikoshi Corp 硬質皮膜被覆切削工具
CN105506574A (zh) * 2015-12-24 2016-04-20 富耐克超硬材料股份有限公司 纳米金刚石涂层的制备方法及纳米金刚石刀片

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2495080A1 (fr) * 2011-03-01 2012-09-05 GFD Gesellschaft für Diamantprodukte mbH Outil de coupe doté d'une lame en diamant cristallin fin
CN102248187A (zh) * 2011-06-02 2011-11-23 深圳市金洲精工科技股份有限公司 金刚石涂层硬质合金刀具及其制备方法
JP2014069258A (ja) * 2012-09-28 2014-04-21 Nachi Fujikoshi Corp 硬質皮膜被覆切削工具
CN105506574A (zh) * 2015-12-24 2016-04-20 富耐克超硬材料股份有限公司 纳米金刚石涂层的制备方法及纳米金刚石刀片

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