CN111411282A - Polycrystalline composite material - Google Patents
Polycrystalline composite material Download PDFInfo
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- CN111411282A CN111411282A CN202010286907.4A CN202010286907A CN111411282A CN 111411282 A CN111411282 A CN 111411282A CN 202010286907 A CN202010286907 A CN 202010286907A CN 111411282 A CN111411282 A CN 111411282A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/12—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/003—Cubic boron nitrides only
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of superhard materials, and particularly relates to a polycrystalline composite material. The polycrystalline composite material is prepared from a superhard material and a metal composite binding agent; the superhard material is cubic boron nitride; the metal composite bonding agent comprises metal and titanium-aluminum-chromium-nitrogen nano powder. In the polycrystalline composite material, the metal and the titanium-aluminum-chromium-nitrogen nano powder are used as a binding agent, and the titanium-aluminum-chromium-nitrogen nano powder can promote grain refinement of the metal and realize solid solution strengthening and precipitation strengthening, so that the wear resistance of the polycrystalline composite material is effectively improved.
Description
Technical Field
The invention belongs to the technical field of superhard materials, and particularly relates to a polycrystalline composite material.
Background
Polycrystalline diamond (PCD) and Polycrystalline Cubic Boron Nitride (PCBN) have excellent properties such as high hardness and wear resistance, high stability, and high temperature hardness, and thus are widely used in the technical fields of cutting tools, welding, and the like. Because diamond particles and cubic boron nitride particles have the defect of being difficult to sinter, most of PCD and PCBN are polycrystalline composite materials formed by sintering diamond, cubic boron nitride and a binding agent. The bonding agent commonly used in the prior art is a metal bonding agent, but the metal bonding agent is easy to soften or even melt at a higher temperature, so that the wear resistance of PCD and PCBN, especially the high-temperature wear resistance, is reduced, and the use of the PCD and PCBN is influenced.
Disclosure of Invention
The invention aims to provide a polycrystalline composite material which has better wear resistance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a polycrystalline composite material is prepared from a superhard material and a metal composite binder; the superhard material is cubic boron nitride; the metal composite bonding agent comprises metal and titanium-aluminum-chromium-nitrogen nano powder.
In the polycrystalline composite material, metal and titanium-aluminum-chromium-nitrogen nano powder are used as a binding agent, and the titanium-aluminum-chromium-nitrogen nano powder can promote the refinement of metal grains in the metal binding agent and realize solid solution strengthening and precipitation strengthening, so that the wear resistance of the polycrystalline composite material is effectively improved. When the fine grain metal is acted by external force, plastic deformation occurs, the fine grain metal can be dispersed in more grains, the plastic deformation is uniform, the stress concentration is less, and the small grain boundary area and the large grain boundary tortuosity of grains are not beneficial to crack propagation. Meanwhile, the titanium-aluminum-chromium-nitrogen nano powder has fine granularity, and CrN, AlN and other fine particles are separated out and dispersed in the material at a high temperature, so that the effect of dispersion strengthening is achieved.
Preferably, the atomic ratio of titanium, aluminum, chromium and nitrogen in the titanium-aluminum-chromium-nitrogen nano powder is 1: (0.2-0.5): (0.2-0.3): (0.9-1.2). The titanium aluminum chromium nitrogen nano powder has the structure that excessive aluminum and chromium elements are introduced into titanium nitride, so that the lattice of titanium nitride crystals is enlarged, and aluminum and chromium enter gaps of the titanium nitride crystals.
The size of the nano material (with the size of 1-100 nm) is close to the coherence length of electrons, the particle size is small, the specific surface area is large, and compared with a macroscopic material, the nano material has the characteristics of excellent surface effect, small size effect, quantum size effect, macroscopic quantum tunneling effect and the like. The titanium-aluminum-chromium-nitrogen composite material is formed by the titanium-aluminum-chromium-nitrogen composite material and the superhard material in the form of nano powder, and the performance of the polymeric composite material is effectively improved by utilizing the size effect of the titanium-aluminum-chromium-nitrogen composite material.
Preferably, the titanium-aluminum-chromium-nitrogen nano powder is synthesized by a direct current arc plasma method, and during synthesis, titanium-aluminum-chromium alloy is used as an anode target material, and argon, hydrogen and nitrogen are used as plasma working gases. The principle of the nano powder prepared by the direct current arc plasma method is that under a certain atmosphere and pressure, the cathode continuously performs arc discharge to generate high temperature, the molten anode target material is forced to evaporate, and a series of physical and chemical reaction processes are performed to generate a corresponding product. The method has the advantages that the prepared nano powder has uniform size and small particle size.
The particle size of the titanium-aluminum-chromium-nitrogen nano powder is optimized by adjusting specific process parameters of a direct current arc plasma method, and preferably, the current used when the titanium-chromium-aluminum-nitrogen nano powder is synthesized by the direct current arc plasma method is 90-120A. Preferably, the volume ratio of the argon to the hydrogen to the nitrogen is (10-15): (1-5): (8-12).
The performance of the polycrystalline composite material is optimized by adjusting the mass of the titanium-aluminum-chromium-nitrogen nano powder, preferably, the mass of the titanium-aluminum-chromium-nitrogen nano powder is 5-10% of the total mass of the superhard material and the metal in the metal composite binder.
Preferably, the mass ratio of the superhard material to the metal in the metal composite bonding agent is (7-9): (3-1). Preferably, the superhard material used has a median particle size of 50 μm and the metal has a median particle size of 0.5 μm.
The metal used in the metal composite binder is a metal binder commonly used in the prior art, and preferably, the metal is at least two of titanium, aluminum, cobalt, chromium and niobium.
The polycrystalline composite material can be prepared into a required form according to actual conditions, such as a polycrystalline composite sheet formed by compounding the polycrystalline composite material with a hard alloy matrix. Preferably, the polycrystalline composite material is a stirring head for friction stir welding and a polycrystalline cubic boron nitride composite sheet.
The polycrystalline composite material is prepared from a superhard material and a metal composite binding agent, and specifically comprises the following components in percentage by weight: the super-hard material, the metal bond and the titanium-aluminum-chromium-nitrogen nano powder are mixed, pressed, molded and sintered to prepare the titanium-aluminum-chromium-nitrogen nano powder. Wherein the pressing molding is cold pressing molding, and the pressure is 450-500 MPa. The pressure during sintering is 4.5-7 GPa, and the temperature is 1300-1800 ℃.
Drawings
FIG. 1 is a front view of a friction stir welding tool according to example 1 of the present invention;
FIG. 2 is a plan view of a friction stir welding tool according to example 1 of the present invention;
reference numerals: 1-stirring pin and 2-stirring head.
Detailed Description
The present invention will be described with reference to examples.
Example 1
The polycrystalline composite material of the present embodiment is a stir head for friction stir welding, and the structure of the stir head is the same as that of a stir head in the prior art, specifically as shown in fig. 1 and fig. 2. The preparation method comprises the following steps:
uniformly mixing cubic boron nitride with a median particle size of 50 mu m and metal (the metal is a mixture of titanium, aluminum, cobalt and chromium) with a median particle size of 0.5 mu m according to the mass percentage of 85% and 15% respectively to obtain a mixture; then adding titanium-aluminum-chromium-nitrogen nano powder (the mass of the titanium-aluminum-chromium-nitrogen nano powder is 5% of the mass of the mixture) into the mixture, uniformly mixing, and then carrying out cold press molding under the pressure of 450-500 MPa to obtain a cylindrical blank; and (3) placing the blank into a cylindrical cavity of the pyrophyllite block, and sintering for 20min at 4.5GPa and 1350 ℃ to obtain the polycrystalline cubic boron nitride blank. And then machining the polycrystalline cubic boron nitride blank to the required diameter size through centerless grinding, and machining the required size of the end part of the stirring head by adopting a laser machining center to obtain the stirring head for friction stir welding.
The titanium-aluminum-chromium-nitrogen nano powder is prepared by the following method:
(1) calculating the mass of corresponding metal required for reaching the ratio of 1:1:1 according to the relative atomic mass of three transition metal elements of titanium, chromium and aluminum, weighing three metal blocks as smelting precursors, placing the three metal blocks in a vacuum reaction furnace (electric arc furnace), taking a tungsten needle as a cathode, closing a reaction cavity, then opening a water cooling system, carrying out vacuum treatment on the reaction cavity through a vacuum system, and pumping to 5 × 10-3After Pa, filling 40kPa of argon (the argon is used for arc starting and the stability of subsequent arc light), then switching on a power supply to adjust the current to be 100A, stopping arc after the metal is fully smelted, cooling, and taking out the smelted TiAlCr alloy after the temperature reaches the room temperature;
(2) synthesizing titanium-aluminum-chromium-nitrogen nano powder by using a direct current arc plasma method, namely taking a tungsten needle as a cathode, placing a TiAlCr alloy target material in the step (1) on an anode tray, adjusting the distance between the cathode tungsten needle and the alloy target material, then closing a cavity, performing vacuum treatment, simultaneously opening a water cooling system, waiting for a mechanical pump to 1-5 Pa, cleaning a required gas pipeline, removing other gas impurities, continuously vacuumizing until the vacuum degree is 5 × 10-3Pa, closing the vacuum system; introducing mixed gas of argon, hydrogen and nitrogen, wherein the argon is 15kPa, the hydrogen is 3kPa, and the nitrogen is 10 kPa; the arc control power supply is switched on, the current is adjusted to 90A, the arc is started, the arc temperature can reach about 3000K, nitrogen and hydrogen plasmas in a molecular state are dissociated into atoms at the high temperature, and the atoms generated by dissociation are more reactive than the molecular state and become active atoms. The amount of the metal dissolved in the molten metal is far larger than the amount of the metal dissolved in the molecular state, and the atoms to be dissolved move through the convection action of the molten metal, and once the metal is in contact with the non-arc gas phase, the metal becomes an atomic solubility over-saturated state and overflows on the metal surfaceWhen the Ti, Al, Cr and N are combined into molecules, heat is released, the molten metal is forced to evaporate, and in the process, the Ti, Al, Cr and N are subjected to physical and chemical reactions, and are bonded and combined to form a TiAlCrN compound which is deposited on the wall of the cavity. Passivating for 12h, and collecting the powder to obtain the titanium-aluminum-chromium-nitrogen nano powder (wherein the atomic ratio of titanium, aluminum, chromium and nitrogen is 1 (0.2-0.3) to (0.8-1.2)).
In other embodiments of the present invention, the polycrystalline composite material is a polycrystalline cubic boron nitride compact.
In other embodiments of the invention, the amount of the titanium-aluminum-chromium-nitrogen nano powder used in the preparation process of the polycrystalline composite material is 10% of the mass of the mixture.
In other embodiments of the present invention, in the preparation process of the titanium aluminum chromium nitrogen nano powder used in the polycrystalline composite material, the amounts of argon, hydrogen and nitrogen may be adjusted, but the volume ratios of the argon, the hydrogen and the nitrogen are (10-15): (1-5): (8-12).
Comparative example
The preparation method of the stirring head of the comparative example is basically the same as that of the example 1, except that the titanium-aluminum-chromium-nitrogen nano powder is not added.
Test example 1
In this test example, the welding performance of the stirring heads of example 1 and the comparative example was tested under the following specific test conditions: the rotating speed of the stirring head of the friction stir welding is 1000rpm, and the advancing speed is 30 mm/min. The test result shows that the stirring head of the comparative example generates obvious abrasion and cracks when the linear welding length exceeds 10 m; the stirring head of example 1 had significant wear and tear at a linear weld length of 15 m. The test result shows that the stirring head added with the titanium-aluminum-chromium-nitrogen nano powder has better wear resistance.
Claims (9)
1. A polycrystalline composite material is characterized by being prepared from a superhard material and a metal composite binder; the superhard material is cubic boron nitride; the metal composite bonding agent comprises metal and titanium-aluminum-chromium-nitrogen nano powder.
2. The polycrystalline composite material according to claim 1, wherein the titanium-aluminum-chromium-nitrogen nanopowder has an atomic ratio of titanium to aluminum to chromium to nitrogen of 1: (0.2-0.5): (0.2-0.3): (0.9-1.2).
3. The polycrystalline composite material according to claim 1 or 2, wherein the titanium-chromium-aluminum-nitrogen nanopowder is synthesized by a direct current arc plasma method, and during synthesis, titanium-aluminum-chromium alloy is used as an anode target material, and argon, hydrogen and nitrogen are used as plasma working gases.
4. The polycrystalline composite material according to claim 3, wherein the current used in the synthesis of the titanium chromium aluminum nitrogen nanopowder by the direct current arc plasma method is 90-120A.
5. The polycrystalline composite material according to claim 3, wherein the volume ratio of the argon gas to the hydrogen gas to the nitrogen gas is (10-15): (1-5): (8-12).
6. The polycrystalline composite material according to claim 1 or 2, wherein the mass of the titanium-aluminum-chromium-nitrogen nanopowder is 5-10% of the total mass of the superhard material and the metal in the metal composite binder.
7. The polycrystalline composite material according to claim 1 or 2, wherein the mass ratio of the superhard material to the metal in the metal composite binder is (7-9): (3-1).
8. The polycrystalline composite material according to claim 1 or 2, wherein the metal is at least two of titanium, aluminum, cobalt, chromium, niobium.
9. The polycrystalline composite material according to claim 1 or 2, wherein the polycrystalline composite material is a friction stir welding tool, a polycrystalline cubic boron nitride compact.
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| CN202010286907.4A CN111411282B (en) | 2020-04-13 | 2020-04-13 | Polycrystalline composite material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125287A (en) * | 2020-09-11 | 2020-12-25 | 昆明理工大学 | Refractory metal nano nitride and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168229A (en) * | 2006-10-27 | 2008-04-30 | 河南富耐克超硬材料有限公司 | Method for manufacturing ultra-hard composite blade |
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2020
- 2020-04-13 CN CN202010286907.4A patent/CN111411282B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168229A (en) * | 2006-10-27 | 2008-04-30 | 河南富耐克超硬材料有限公司 | Method for manufacturing ultra-hard composite blade |
Non-Patent Citations (2)
| Title |
|---|
| 戴达煌: "《功能薄膜及其沉积制备技术》", 31 January 2013 * |
| 翟光辉等: "《超硬材料烧结体制造》", 30 June 1993 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125287A (en) * | 2020-09-11 | 2020-12-25 | 昆明理工大学 | Refractory metal nano nitride and preparation method thereof |
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| CN111411282B (en) | 2021-08-20 |
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