CN114150201A - Preparation method of superhard CoWB-Co hard alloy - Google Patents
Preparation method of superhard CoWB-Co hard alloy Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- 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
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- B22F2003/1042—Sintering only with support for articles to be sintered
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Abstract
The invention discloses a preparation method of superhard CoWB-Co hard alloy, belonging to the technical field of novel material preparation, and comprising the following steps: mixing the W powder and the B powder, ball-milling, placing in a graphite crucible, and reacting at 1200-1600 ℃ for 1-4h to obtain WB powder; mixing WB powder and Co powder, ball-milling, placing in a graphite crucible, and reacting at 1200-1600 ℃ for 1-4h to obtain ternary CoWB ceramic powder; taking ternary CoWB ceramic powder and Co powder as raw materials, adding a forming agent, and wet-grinding for 20-72 h; drying the slurry subjected to wet grinding in the step (5), and pressing into a block-shaped green body; and (3) placing the block-shaped blank on a graphite plate, sintering at 1300-1550 ℃, and preserving heat for 1-4h to obtain the superhard CoWB-Co hard alloy, wherein the phase purity of a material system can be ensured, and the porosity of a hard alloy material can be greatly reduced.
Description
Technical Field
The invention relates to the technical field of novel material preparation, in particular to a preparation method of superhard CoWB-Co hard alloy.
Background
The WC-Co hard alloy has high hardness, high wear resistance, high deformation resistance, high impact resistance, high pressure resistance, high corrosion resistance and other performance, and may find its wide application in metal cutting, rock drilling tool, timber processing, forming mold, rolling mill, mine digging and other fields. However, with rapid progress of science and technology and continuous improvement of the technical level of modern industry, complex service environments such as high-temperature, high-salt, dry cutting, high-speed cutting and the like put higher demands on the service performance of WC-Co series hard alloy materials, and the hardness, wear resistance, oxidation resistance and heat conductivity of the traditional WC-Co hard alloy cannot meet the performance requirements of high-end application fields on the materials.
The microhardness of the ternary boride ceramic CoWB reaches 44GPa, the microhardness of the WC ceramic is only 17GPa, the CoWB has higher microhardness and better wear resistance than WC, the CoWB ceramic also has better heat conductivity and oxidation resistance than WC, and in addition, the wettability of CoWB and metal Co and the wettability of WC and Co are both 0 degree at high temperature and are completely wetted. Therefore, how to develop and design the CoWB-Co hard alloy is a difficult problem in the field, and the problem of solving the technical barrier of the traditional WC-Co hard alloy in the high-end application field is solved.
Disclosure of Invention
According to the invention, the ceramic phase CoWB and the metal phase Co are respectively used as the hard phase and the binder phase of the hard alloy material component, and the novel superhard CoWB-Co hard alloy with controllable design process is used for solving the problem that the traditional WC-Co hard alloy cannot be in service for a long time under severe working conditions such as high-temperature, dry cutting and high-speed cutting.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of superhard CoWB-Co hard alloy, which comprises the following steps:
(1) mixing the W powder and the B powder, and performing ball milling;
(2) placing the W powder and the B powder which are subjected to ball milling and mixing in a graphite crucible, and reacting for 1-4h at 1200-1600 ℃ to obtain WB powder;
(3) mixing the WB powder and the Co powder, and carrying out ball milling;
(4) putting the WB powder and the Co powder which are mixed by ball milling into a graphite crucible, and reacting for 1-4h at 1200-1600 ℃ to obtain ternary CoWB ceramic powder;
(5) taking the ternary CoWB ceramic powder and Co powder as raw materials, adding a forming agent, and wet-grinding for 20-72 h;
(6) drying the slurry subjected to wet grinding in the step (5), and pressing into a block-shaped green body;
(7) and (3) placing the block-shaped blank on a graphite plate, sintering at 1300-1550 ℃, and preserving heat for 1-4h to obtain the superhard CoWB-Co hard alloy.
Further, the molar ratio of the W powder to the B powder in the step (1) is 1:1, ball milling balls are hard alloy balls of WC-8Co, the ball material mass ratio is 3:1, and the ball milling time is 6-24 hours.
Further, the inner wall of the graphite crucible in the step (2) is coated with BN powder.
Further, the molar ratio of WB powder to Co powder in the step (3) is 1:1, ball milling balls are hard alloy balls of WC-8Co, the ball material mass ratio is 3:1, and the ball milling time is 4-36 h.
Further, the inner wall of the graphite crucible in the step (4) is coated with BN powder.
Furthermore, the adding proportion of the CoWB powder in the ternary CoWB ceramic powder and Co powder in the step (5) is 75-94 wt%, and the adding proportion of the metal Co powder is 6-25 wt%; deionized water or alcohol is used as a ball milling medium, and the mass ratio of ball materials is 2:1-5: 1; the forming agent is PEG, and the addition amount of the forming agent is 1.0-2.0% of the total mass.
Further, the pressing pressure in the step (6) is 50-400 MPa.
Further, the drying in the step (6) adopts spray drying, the temperature of the air inlet is 180-260 ℃, and the temperature of the air outlet is 90-120 ℃.
Further, in the step (7), the surface of the graphite plate is coated with ZrO2-18％Y2O3。
Furthermore, the mass percentage purity of the W powder, the B powder and the Co powder is more than 99.8%; the Fisher size of W powder is 0.6-5 μm, the Fisher size of B powder is 0.8-3 μm, and the Fisher size of Co powder is 0.8-1.2 μm.
Further, both ball milling and wet milling are performed in a ball mill, which is a rolling tiltable ball mill.
Patent CN 109266939B discloses a method for preparing a high-density WC-WB-Co spherical powder hard-face material, which takes WC powder, WB powder and Co powder as raw materials, prepares the raw materials into spherical powder through the processes of batching, wet grinding, spray drying, pressing, sintering, mechanical crushing, sieving, high-temperature spheroidizing, re-sieving and the like, and prepares the powder into a hard alloy coating on the surface of a metal substrate by utilizing the processes of supersonic flame spraying, laser cladding, plasma surfacing and plasma spraying. The invention is different from the invention target and target components of patent CN 109266939B, firstly WB powder is synthesized, then WB powder and Co powder are prepared into CoWB powder, then CoWB powder and Co powder are used as raw materials, and the hard alloy with the material component of CoWB-Co is finally prepared by ball milling, drying, pressing and sintering processes, and the hard alloy can be directly applied to the fields of metal cutting, rock drilling tools, wood processing, forming dies, rolling mill rolls, mine excavation and the like.
The invention also provides application of the superhard CoWB-Co hard alloy prepared by the preparation method in metal cutting, rock drilling tools, wood processing, forming dies, rolling mill rolls and mine excavation.
The invention discloses the following technical effects:
(1) the invention designs a novel hard alloy material CoWB-Co, wherein ternary CoWB ceramic is used as a hard phase, metal Co is used as a binding phase, CoWB has higher hardness and better heat conductivity than WC, and the microhardness and wear resistance of the CoWB-Co hard alloy can be respectively improved by more than 20% and more than 40% compared with the traditional WC-Co hard alloy.
(2) According to the invention, WB powder is synthesized firstly, then the WB powder is utilized to synthesize the CoWB powder, and finally the CoWB-Co hard alloy is further prepared by taking the CoWB powder and the Co powder as raw materials.
(3) In the preparation process of WB powder and CoWB powder, BN powder is coated on the inner wall of the graphite crucible, so that the chemical reaction of C in the graphite crucible with W powder, B powder and Co powder can be effectively prevented, and the smooth preparation of the CoWB-Co target material is ensured.
(4) According to the invention, WC-8Co hard alloy balls are adopted in dry grinding in the WB powder and CoWB powder preparation process and wet grinding in the CoWB-Co alloy preparation process, so that impurity elements can be effectively prevented from being doped into a CoWB-Co material system, and the high purity of the CoWB-Co hard alloy material is ensured.
(5) ZrO is coated on the surface of the graphite plate adopted in the step of sintering the CoWB-Co hard alloy2-18％Y2O3The coating can prevent C element in the graphite plate from diffusing into a CoWB-Co system in the sintering process, and avoids the generation of impurity phase.
(6) The production process is controllable and pollution-free, and the developed novel CoWB-Co hard alloy is expected to be in service for a long time under severe working conditions such as high temperature, dry cutting and high speed cutting, and meets the performance requirements of high-end application fields on materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an SEM electron micrograph of a 94CoWB-6Co cemented carbide prepared in example 1 after polishing;
FIG. 2 is an SEM electron micrograph of the 88CoWB-12Co cemented carbide prepared in example 2 after polishing;
FIG. 3 is an SEM electron micrograph of the 83CoWB-17Co cemented carbide prepared in example 3 after polishing;
FIG. 4 is an XRD pattern of the 83CoWB-17Co cemented carbide made in example 3;
FIG. 5 is an SEM electron micrograph of a fracture in the 75CoWB-25Co cemented carbide prepared in example 4.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the embodiment of the invention, the mass percentage purity of the W powder, the B powder and the Co powder is more than 99.8%; the Fisher size of W powder is 0.6-5 μm, the Fisher size of B powder is 0.8-3 μm, and the Fisher size of Co powder is 0.8-1.2 μm.
Example 1
(1) Adding the W powder and the B powder into a ball milling tank according to the mol ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 24 hours.
(2) Placing the W powder and the B powder which are subjected to ball milling and mixing in a graphite crucible with the BN powder coated on the inner wall, then placing the W powder and the B powder together in a vacuum furnace, and synthesizing for 4 hours at a high temperature of 1200 ℃ to obtain WB powder.
(3) Adding the prepared WB powder and Co powder into a ball milling tank according to the molar ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and carrying out dry milling for 36 h.
(4) Putting the WB powder and the Co powder which are mixed by ball milling into a graphite crucible with the inner wall coated with BN powder, putting the graphite crucible and the WB powder into a vacuum furnace together, and synthesizing for 4 hours at a high temperature of 1200 ℃ to obtain the ternary CoWB ceramic powder.
(5) The preparation method comprises the steps of taking prepared CoWB ceramic powder and Co powder as raw materials, batching according to mass percentage, wherein the adding proportion of the CoWB powder is 94%, the adding proportion of the metal Co powder is 6%, PEG is selected as a forming agent, the adding amount of the PEG is 2.0% of the total mass, deionized water is used as a ball milling medium, the ball-milling time is 20 hours, and the ball-milling mass ratio is controlled within the range of 5: 1.
(6) And (3) carrying out spray drying on the slurry after wet grinding by using a pressure type spray drying tower, and then pressing the prepared powder into a block blank at the pressure of 400MPa by using a powder press for later use.
(7) Placing the obtained block-shaped blank body on the surface coated with ZrO2-18％Y2O3Then sintering the graphite plate by a vacuum furnace within the temperature range of 1550 ℃, and keeping the temperature for 1 h. And sintering to obtain the superhard CoWB-Co hard alloy, which is marked as 94CoWB-6Co hard alloy. The porosity was 0.06%, and the SEM image of the 94CoWB-6Co cemented carbide prepared in this example after polishing is shown in FIG. 1.
Example 2
(1) Adding the W powder and the B powder into a ball milling tank according to the mol ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 12 hours.
(2) Placing the W powder and the B powder which are subjected to ball milling and mixing in a graphite crucible with the BN powder coated on the inner wall, then placing the W powder and the B powder together in a vacuum furnace, and synthesizing for 3 hours at a high temperature of 1350 ℃ to obtain WB powder.
(3) Adding the prepared WB powder and Co powder into a ball milling tank according to the molar ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 25 hours.
(4) Putting the WB powder and the Co powder which are mixed by ball milling into a graphite crucible with the inner wall coated with BN powder, putting the graphite crucible and the WB powder into a vacuum furnace together, and synthesizing for 3 hours at the high temperature of 1300 ℃ to obtain the ternary CoWB ceramic powder.
(5) The preparation method comprises the steps of taking prepared CoWB ceramic powder and Co powder as raw materials, batching according to mass percentage, wherein the adding proportion of the CoWB powder is 88%, the adding proportion of the metal Co powder is 12%, PEG is selected as a forming agent, the adding amount of the PEG is 1.5% of the total mass, deionized water is used as a ball milling medium, the ball-milling time is 40 hours, and the ball-milling mass ratio is controlled within the range of 4: 1.
(6) And (3) carrying out spray drying on the slurry after wet grinding by using a pressure type spray drying tower, and then pressing the prepared powder into a block blank at the pressure of 300MPa by using a powder press for later use.
(7) Placing the obtained block-shaped blank body on the surface coated with ZrO2-18％Y2O3Then sintering the graphite plate by a vacuum furnace at 1450 ℃ for 2 h. And sintering to obtain the superhard CoWB-Co hard alloy, wherein the porosity is 0.04% and the SEM electron microscope image of the polished 88CoWB-12Co hard alloy in the embodiment is shown in figure 2.
Example 3
(1) Adding the W powder and the B powder into a ball milling tank according to the mol ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 18 h.
(2) Placing the W powder and the B powder which are subjected to ball milling and mixing in a graphite crucible with the BN powder coated on the inner wall, then placing the W powder and the B powder together in a vacuum furnace, and synthesizing for 2 hours at a high temperature of 1450 ℃ to obtain WB powder.
(3) Adding the prepared WB powder and Co powder into a ball milling tank according to the molar ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 16 h.
(4) Putting the WB powder and the Co powder which are mixed by ball milling into a graphite crucible with the inner wall coated with BN powder, then putting the graphite crucible and the WB powder into a vacuum furnace together, and synthesizing for 2 hours at a high temperature of 1400 ℃ to obtain the ternary CoWB ceramic powder.
(5) The preparation method comprises the steps of taking the prepared CoWB ceramic powder and Co powder as raw materials, batching according to mass percentage, wherein the adding proportion of the CoWB powder is 83%, the adding proportion of the metal Co powder is 17%, PEG is selected as a forming agent, the adding amount of the PEG is 1.5% of the total mass, edible alcohol is used as a ball milling medium, the ball-milling time is 48 hours, and the ball-milling mass ratio is controlled within the range of 3: 1.
(6) And (3) carrying out spray drying on the slurry after wet grinding by using a pressure type spray drying tower, and then pressing the prepared powder into a block blank at the pressure of 200MPa by using a powder press for later use.
(7) Placing the obtained block-shaped blank body on the surface coated with ZrO2-18％Y2O3Then sintering the graphite plate by a vacuum furnace within the temperature range of 1380 ℃, and keeping the temperature for 3 hours. And sintering to obtain the superhard CoWB-Co hard alloy, wherein the porosity is 0.02% and is recorded as 83CoWB-17Co hard alloy, SEM electron microscope images of the polished 83CoWB-17Co hard alloy prepared in the embodiment are shown in figure 3, and XRD patterns of the 83CoWB-17Co hard alloy are shown in figure 4.
Example 4
(1) Adding the W powder and the B powder into a ball milling tank according to the mol ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 6 hours.
(2) Placing the W powder and the B powder which are subjected to ball milling and mixing in a graphite crucible with the BN powder coated on the inner wall, then placing the W powder and the B powder together in a vacuum furnace, and synthesizing for 1h at a high temperature of 1600 ℃ to obtain WB powder.
(3) Adding the prepared WB powder and Co powder into a ball milling tank according to the molar ratio of 1:1, wherein the ball milling ball is WC-8Co hard alloy ball with the ball material mass ratio of 3:1, and performing dry milling for 4 hours.
(4) Putting the WB powder and the Co powder which are mixed by ball milling into a graphite crucible with the inner wall coated with BN powder, putting the graphite crucible and the WB powder into a vacuum furnace together, and synthesizing for 1h at a high temperature of 1600 ℃ to obtain the ternary CoWB ceramic powder.
(5) The preparation method comprises the steps of taking prepared CoWB ceramic powder and Co powder as raw materials, batching according to mass percentage, wherein the adding proportion of the CoWB powder is 75%, the adding proportion of the metal Co powder is 25%, PEG is selected as a forming agent, the adding amount of the PEG is 1.0% of the total mass, edible alcohol is used as a ball milling medium, the ball-milling time is 72 hours, and the ball-milling mass ratio is controlled within the range of 2: 1.
(6) And (3) carrying out spray drying on the slurry after wet grinding by using a pressure type spray drying tower, and then pressing the prepared powder into a block blank at the pressure of 50MPa by using a powder press for later use.
(7) Placing the obtained block-shaped blank body on the surface coated with ZrO2-18％Y2O3Sintering the graphite plate in a vacuum furnace at the temperature of 1300 ℃ for 4 hours. And sintering to obtain the superhard CoWB-Co hard alloy, wherein the porosity is 0.03 percent and is marked as 75CoWB-25Co hard alloy, and SEM electron microscope images of fractures of the 75CoWB-25Co hard alloy prepared in the embodiment are shown in FIG. 5.
As can be seen from the XRD pattern and SEM electron microscope image of the hard alloy prepared by the method, the novel CoWB-Co hard alloy can be successfully prepared by the method, and has the advantages of uniform phase distribution, uniform grain size, compact tissue structure and basically no pores.
The density of the hard alloy is detected according to GB/T3850-1983, the relative magnetic saturation of the hard alloy is detected according to GB/T23369-2009, the bending strength of the hard alloy is detected according to GB/T3851-2015, the microhardness of the hard alloy is detected according to GB/T7997-2014, and the thermal conductivity of the hard alloy is detected according to ASTM-E1530. The results of performance measurements of the CoWB-Co cemented carbides prepared in examples 1-4 and the conventional WC-10Co cemented carbides are shown in Table 1.
TABLE 1 EXAMPLES 1-4 Performance test data for CoWB-Co cemented carbide and conventional WC-10Co cemented carbide prepared
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of superhard CoWB-Co hard alloy is characterized by comprising the following steps:
(1) mixing the W powder and the B powder, and performing ball milling;
(2) placing the W powder and the B powder which are subjected to ball milling and mixing in a graphite crucible, and reacting for 1-4h at 1200-1600 ℃ to obtain WB powder;
(3) mixing the WB powder and the Co powder, and carrying out ball milling;
(4) putting the WB powder and the Co powder which are mixed by ball milling into a graphite crucible, and reacting for 1-4h at 1200-1600 ℃ to obtain ternary CoWB ceramic powder;
(5) taking the ternary CoWB ceramic powder and Co powder as raw materials, adding a forming agent, and wet-grinding for 20-72 h;
(6) drying the slurry subjected to wet grinding in the step (5), and pressing into a block-shaped green body;
(7) and (3) placing the block-shaped blank on a graphite plate, sintering at 1300-1550 ℃, and preserving heat for 1-4h to obtain the superhard CoWB-Co hard alloy.
2. The method according to claim 1, wherein the molar ratio of the W powder to the B powder in the step (1) is 1:1, ball milling balls are hard alloy balls of WC-8Co, the ball material mass ratio is 3:1, and the ball milling time is 6-24 hours.
3. The production method according to claim 1, wherein the inner wall of the graphite crucible in the step (2) is coated with BN powder.
4. The method according to claim 1, wherein the molar ratio of WB powder to Co powder in the step (3) is 1:1, ball milling balls are hard alloy balls of WC-8Co, the ball material mass ratio is 3:1, and the ball milling time is 4-36 h.
5. The production method according to claim 1, wherein the inner wall of the graphite crucible in the step (4) is coated with BN powder.
6. The preparation method according to claim 1, wherein the adding proportion of the ternary CoWB ceramic powder and CoWB powder in the Co powder in the step (5) is 75-94 wt%, and the adding proportion of the metal Co powder is 6-25 wt%; deionized water or alcohol is used as a ball milling medium, and the mass ratio of ball materials is 2:1-5: 1.
7. The method according to claim 1, wherein the pressing pressure in the step (6) is 50 to 400 Mpa; spray drying is adopted for drying, the temperature of an air inlet is 180-260 ℃, and the temperature of an air outlet is 90-120 ℃.
8. The method according to claim 1, wherein in the step (7), the graphite plates are coated with ZrO on the surfaces thereof2-18％Y2O3。
9. The preparation method according to claim 1, wherein the mass percentage purity of the W powder, the B powder and the Co powder is more than 99.8%; the Fisher size of W powder is 0.6-5 μm, the Fisher size of B powder is 0.8-3 μm, and the Fisher size of Co powder is 0.8-1.2 μm.
10. Use of the superhard CoWB-Co cemented carbide prepared by the method of any one of claims 1 to 9 in metal cutting, rock drilling tools, wood working, forming dies, rolling mill rolls or mining.
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| CN109553112A (en) * | 2018-11-12 | 2019-04-02 | 北京工业大学 | A kind of preparation method of single-phase WCoB powder |
| CN109266939A (en) * | 2018-12-05 | 2019-01-25 | 株洲江钨博大硬面材料有限公司 | A kind of high-densit WC-WB-Co spherical powder hard material and preparation method thereof |
| CN110819866A (en) * | 2019-10-09 | 2020-02-21 | 西安理工大学 | WC-Co-B4Preparation method of C hard alloy |
| CN112063905A (en) * | 2020-08-28 | 2020-12-11 | 南京航空航天大学 | High-performance WC-WCoB-Co complex phase hard alloy and preparation method thereof |
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