CN114406256B - Method for preparing three-dimensional structure hard alloy by adopting photo-curing 3D printing - Google Patents
Method for preparing three-dimensional structure hard alloy by adopting photo-curing 3D printing Download PDFInfo
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- CN114406256B CN114406256B CN202210239428.6A CN202210239428A CN114406256B CN 114406256 B CN114406256 B CN 114406256B CN 202210239428 A CN202210239428 A CN 202210239428A CN 114406256 B CN114406256 B CN 114406256B
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The method for preparing the three-dimensional hard alloy by adopting the photocuring 3D printing is provided, water-soluble tungsten salt is used as a tungsten source, water-soluble cobalt salt is used as a cobalt source to prepare printable ink, a blank of the three-dimensional structure is molded by adopting the photocuring 3D printing, and the blank is treated by combining a high-temperature post-treatment process, so that the three-dimensional hard alloy is finally obtained. The preparation method is ingenious in preparation strategy, high in surface quality of the hard alloy subjected to 3D printing, low in raw material requirement and low in cost, and is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to a method for preparing a three-dimensional structure hard alloy by adopting photo-curing 3D printing.
Background
Cemented carbides are multiphase composites with one or more refractory metal carbides (e.g., WC or TiC) as the matrix and transition metals (e.g., fe, co, ni, and alloys thereof) as the binder phase. Because of its high hardness, strength, elastic modulus, toughness and wear resistance, and excellent combination properties such as good corrosion resistance and thermal shock resistance, the application of cemented carbide has been expanded from metal cutting of processing tools to many fields such as petroleum drilling, mining engineering and electronic communication, and has taken up an important role for a long time, and has been known as "industrial teeth".
At present, hard alloy is mainly produced by adopting a powder metallurgy method, namely, raw material powder is firstly mixed and ground, then a part blank is pressed and formed, then glue is discharged, sintering and densification are carried out to obtain a hard alloy part, and finally, a sintered body is polished, eroded or polished according to the requirements of the appearance and the precision of the product, so that a hard alloy finished product is obtained. The method is mature and stable, is used for mass production, but is only suitable for preparing products with simpler shapes and structures. In addition, the die adopted in the powder metallurgy process is designed and processed according to the appearance and the size of the product. This results in lengthy product development and production cycles and dramatically increases as the complexity of the product shape increases. For some products with complicated heterogeneity, the preparation of complex moulds is extremely difficult or even impossible. However, with expansion of the application field of cemented carbide, more and more cemented carbide special-shaped products with complex structures are proposed due to application environments and use requirements.
The advent of 3D Printing technology (3D Printing) provides a solution for the manufacture of complex shaped cemented carbide products. At present, the method for researching the 3D printing of the hard alloy mainly comprises the following steps: laser selective melting (Selective Laser Melting, SLM)/laser selective sintering (Selective Laser Sintering, SLS)/laser engineered net shaping (Laser Engineered Net Shaping, LENS) based on high energy beams; fuse fabrication based on extrusion (Fused Filament Fabrication, FFF)/direct write molding (Direct Ink Writing, DIW); and spray printing (Binder Jet Printing, BJP) based on the sprayed adhesive.
However, these 3D printing methods have various problems. For example:
the methods such as SLM/SLS/LENS based on high energy beams have high requirements on the performance of raw material powder (such as high purity, small particle size, narrow particle size distribution, high sphericity, good fluidity, high apparent density and the like), and the WC phase is extremely easy to be changed into W by the irradiation of high energy beams in the printing process 2 C causes phase impurity;
hard alloy printed on the basis of DIW and FFF3D formed by extrusion is poor in surface quality, has detailed interlayer marks, and has discontinuous large holes and dispersed small holes in the local interior;
as with the high energy beam based SLS/SLM method, the spray based BJP method also has requirements for cemented carbide powder properties and the shaped cemented carbide part is simple in shape.
Thus, a new method for preparing a three-dimensional hard alloy by 3D printing is needed to solve the above technical problems.
Disclosure of Invention
Therefore, the invention provides a method for preparing a three-dimensional hard alloy by adopting photo-curing 3D printing, wherein water-soluble tungsten salt is used as a tungsten source, water-soluble cobalt salt is used as a cobalt source to prepare printable ink, a blank with a three-dimensional structure is formed by photo-curing 3D printing, and then the blank is treated by combining a high-temperature post-treatment process, so that the three-dimensional hard alloy is finally obtained.
The invention provides a method for preparing a three-dimensional structure hard alloy by photo-curing 3D printing, which comprises the following steps:
(1) Preparing ink: mixing a solvent, water-soluble tungsten salt, water-soluble cobalt salt, an organic functional monomer and a photoinitiator according to a certain proportion to prepare printing ink;
(2) Photo-curing 3D printing: filling the printing ink prepared in the step (1) into a photocuring 3D printer for photocuring 3D printing to obtain a precursor with a three-dimensional structure;
(3) And (3) drying post-treatment: drying the three-dimensional structure precursor obtained in the step (3) to obtain a dried precursor;
(4) High-temperature post-treatment: and (3) carrying out high-temperature post-treatment on the dried precursor obtained in the step (4) to obtain the WC-Co hard alloy.
Wherein said step (1) is performed at room temperature.
Wherein in the step (1), the solvent includes water.
Wherein in the step (1), the concentration of the water-soluble tungsten salt is 0.01-70wt%, preferably 0.1-50%, more preferably 1-40%, still more preferably 10-35%; the addition amount of the water-soluble cobalt salt is calculated according to the proportion of the cemented carbide tungsten cobalt; the addition amount of the organic functional monomer is 0.1% -50% of the mass of the ink, preferably 1% -40%, more preferably 5% -35%, still more preferably 10% -30%; the addition amount of the photoinitiator is 0.01% -50%, preferably 0.1% -30%, more preferably 0.5% -20%, still more preferably 1% -10% of the mass of the organic functional monomer.
Wherein in the step (1), the water-soluble tungsten salt comprises one or more of sodium tungstate, ammonium paratungstate and ammonium metatungstate.
Wherein in the step (1), the water-soluble cobalt salt comprises one or more of cobalt nitrate, cobalt carbonate and cobalt acetate.
Wherein in the step (1), the organic functional monomer comprises one or more of maleic acid, acrylamide, methacrylamide, N' -methylenebisacrylamide, methylolacrylamide, acrylic acid, methacrylic acid, methoxy polyethylene glycol methacrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, alkyl alkoxy acrylate, alkyl alkoxy methacrylate, methyl hydroxyethyl acrylate, methyl hydroxypropyl acrylate, methyl propenyl acrylate and polyethylene glycol dimethacrylate.
Wherein in the step (1), the photoinitiator comprises one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (2959), 2-hydroxy-2-methyl-1-phenylpropanone (1173), 1-hydroxycyclohexylphenyl ketone (184), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate (TPO-L), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819).
In the step (1), after the printing ink is obtained, the printing ink is stored in a dark place.
In the step (2), the printing ink prepared in the step (1) is filled into a trough of a photo-curing 3D printer.
In the step (2), the photo-curing 3D printer is a 3D printer based on photo-initiator polymerization, and the type of the photo-curing 3D printer includes at least one of SLA (stereolithography technology), DLP (digital light processing technology), CLIP (continuous liquid interface extraction technology), and HRAP (large area rapid printing technology).
Wherein in the step (3), the drying mode comprises one or more of oven drying or freeze drying.
Wherein, in the step (3), in the drying process of the oven, the humidity range is controlled to be 20-90%, and the temperature range is controlled to be less than 100 ℃.
Wherein, in the step (3), the freezing temperature is controlled to be less than or equal to-70 ℃ in the freeze drying process, the drying temperature is in the range of 1-30 ℃, and the vacuum degree is more than 0.001MPa.
In the step (4), in the high-temperature post-treatment stage, the organic matters in the dry precursor are decomposed/cracked, the tungsten salt is decomposed and carbonized into WC, the cobalt salt is decomposed and reduced into Co, and finally the WC-Co hard alloy is sintered and densified.
Wherein in the step (4), the atmosphere of the high-temperature post-treatment comprises one or more of a reducing atmosphere, a vacuum and an inert atmosphere; wherein the reducing atmosphere comprises one or more of hydrogen, carbon monoxide or propionitrile; the inert atmosphere comprises one or more of nitrogen, argon or helium.
In the step (4), the high-temperature post-treatment is divided into three stages, wherein a reducing atmosphere is adopted in the first stage, a vacuum atmosphere is adopted in the second stage, and an inert atmosphere is adopted in the third stage; in a first stage, heating from room temperature to a first temperature at a heating rate of 0.01-5 ℃/min, and in a second stage, heating from a temperature greater than the first temperature to a second temperature at a heating rate of 0.1-100 ℃/min; in the third stage, heating from a temperature greater than the second temperature to a third temperature at a heating rate of 0.1-100 ℃/min; wherein the first temperature is 400-600 ℃, the second temperature is 800-1500 ℃, and the third temperature is 1400-1800 ℃;
preferably, the temperature rising rate of the first stage is 0.1-2 ℃/min, the temperature rising rate of the second stage is 0.5-10 ℃/min, and the temperature rising rate of the third stage is 0.5-10 ℃/min; further preferably, the temperature rising rate of the first stage is 0.2-1 ℃/min, the temperature rising rate of the second stage is 1-5 ℃/min, and the temperature rising rate of the third stage is 5-10 ℃/min.
Wherein in the step (4), the highest temperature adopted in the high-temperature post-treatment is 1400-1800 ℃.
Therefore, the invention has the following beneficial technical effects:
the invention provides a simple and feasible method for printing hard alloy in 3D, wherein monomer polymerization in organic chemistry and metal reduction in inorganic chemistry are combined, tungsten salt, cobalt salt and the like are used as raw materials, a tungsten precursor blank is precisely formed by means of photo-curing 3D printing, and then the tungsten precursor blank is sintered and carbonized into the hard alloy at high temperature. The advantages are that:
(1) The preparation strategy is ingenious: the adopted organic matters are polymerized in the 3D printing forming process, so that the forming effect is achieved; and in the subsequent high-temperature sintering carbonization process, the organic matters can play a role of a carbon source.
(2) The surface quality of the 3D printed hard alloy is high: the tungsten-containing ink is adopted for printing and forming, so that the problem of surface quality which is difficult to solve by other hard alloy 3D printing methods is solved.
(3) The invention has low requirements on raw materials: the hard alloy is obtained by a conversion mode of high-temperature reduction of the tungsten compound, and the cobalt compound is reduced to be metallic cobalt, so that the high requirements of other 3D printing methods on powder are avoided.
(4) The invention has low cost and is suitable for industrial production and application: the invention can be applied to 3D printing based on photo-curing, such as SLA, DLP, CLIP, HRAP.
Brief description of the drawings
FIG. 1 is a photograph of the macrostructure of a three-dimensional structured cemented carbide 3D printed using the method of the present invention.
Fig. 2 is an XRD pattern of a three-dimensional structured cemented carbide 3D printed using the method of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these examples are for illustration only and are not intended to limit the scope of the invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims of the present application.
The invention provides a simple and feasible method for printing hard alloy in 3D, wherein monomer polymerization in organic chemistry and metal reduction in inorganic chemistry are combined, tungsten salt, cobalt salt and the like are used as raw materials, a tungsten precursor blank is precisely formed by means of photo-curing 3D printing, and then the tungsten precursor blank is sintered and carbonized into hard alloy-cobalt hard alloy at high temperature. The picture of the macrostructure of the three-dimensional structure hard alloy prepared by the method is shown in figure 1, and the XRD result is shown in figure 2.
Example 1
Sodium tungstate is used as tungsten salt, and photo-curing 3D printing is adopted to prepare the three-dimensional structure hard alloy:
photo-curable 3D printing ink was prepared by mixing deionized water (5 g), sodium tungstate (5 g), cobalt acetate (1 g), acrylic acid (5 g) and N, N' -methylenebisacrylamide (0.2 g) with a photoinitiator TPO (0.1 g) at room temperature, and magnetically stirring. The temperature of all operations was controlled to about 20 ℃.
Photo-curing 3D printing was then performed, the photo-curing 3D printing layer thickness being 0.01mm, and the exposure time per layer being 1s.
And taking the printed and molded green body out of the trough, and then placing the green body in the condition of 80% of humidity and 60 ℃ for heat preservation for 96 hours to completely dry the green body.
Finally, placing the blank body in hydrogen, raising the temperature to 500 ℃ at a heating rate of 0.5 ℃/min for 2 hours, raising the temperature to 900 ℃ at a heating rate of 2 ℃/min under vacuum, and finally raising the temperature to 1450 ℃ at a heating rate of 5 ℃/min in argon atmosphere for 2 hours.
Example 2
Preparation of three-dimensional hard alloy by using ammonium paratungstate as tungsten salt and adopting photocuring 3D printing
Photo-curable 3D printing ink was prepared by magnetically stirring deionized water (4 g), ammonium paratungstate (6 g), cobalt nitrate (1 g), acrylic acid (6 g) and ethyl methacrylate (0.3 g) with a photoinitiator 651 (0.1 g) at room temperature. The temperature of all operations was controlled to about 20 ℃.
Photo-curing 3D printing was then performed, the photo-curing 3D printing layer thickness being 0.01mm, and the exposure time per layer being 1s.
Taking out the formed green body from the trough, placing the green body in the condition of humidity of 80% and temperature of 70 ℃ for preserving heat for 48 hours, and completely drying the green body.
Finally, placing the blank body in hydrogen, raising the temperature to 400 ℃ at a heating rate of 0.5 ℃/min for 2 hours, raising the temperature to 1000 ℃ at a heating rate of 5 ℃/min under vacuum, and finally raising the temperature to 1450 ℃ at a heating rate of 10 ℃/min in argon atmosphere for 2 hours.
Example 3
Preparation of three-dimensional hard alloy by taking ammonium metatungstate as tungsten salt and adopting photocuring 3D printing
Photo-curing 3D printing ink was prepared by magnetically stirring deionized water (3 g), ammonium metatungstate (10 g), cobalt acetate (1.5 g), acrylic acid (6 g) and polyethylene glycol dimethacrylate (1 g) with a photoinitiator TPO-L (0.1 g) at room temperature. The temperature of all operations was controlled to about 20 ℃.
Photo-curing 3D printing was then performed, the photo-curing 3D printing layer thickness being 0.01mm, and the exposure time per layer being 1s.
Taking out the formed blank from the trough, placing the blank in a freeze dryer, cooling to-70 ℃, gradually heating to 20 ℃ and keeping the vacuum degree at 0.01MPa, and completely drying the blank.
Finally, placing the blank body in hydrogen, raising the temperature to 500 ℃ at a heating rate of 0.5 ℃/min for 2 hours, raising the temperature to 900 ℃ at a heating rate of 5 ℃/min under vacuum, and finally raising the temperature to 1450 ℃ at a heating rate of 5 ℃/min in argon atmosphere for 2 hours.
Example 4
Preparation of three-dimensional hard alloy by taking methacrylic acid as monomer and adopting photo-curing 3D printing
At room temperature, magnetically stirring deionized water (5 g), ammonium metatungstate (8 g), cobalt carbonate (1 g), methacrylic acid (5 g), and polyethylene glycol dimethacrylate (1 g) with a photoinitiator TPO-L (0.5 g) to prepare a photo-curable 3D printing ink. The temperature of all operations was controlled to about 20 ℃.
Photo-curing 3D printing was then performed, the photo-curing 3D printing layer thickness being 0.01mm, and the exposure time per layer being 1s.
Taking out the formed blank from the trough, placing the blank in a freeze dryer, cooling to-70 ℃, gradually heating to 20 ℃ and keeping the vacuum degree at 0.01MPa, and completely drying the blank.
Finally, placing the blank body in hydrogen, raising the temperature to 500 ℃ at a heating rate of 0.5 ℃/min for 2 hours, raising the temperature to 900 ℃ at a heating rate of 2 ℃/min under vacuum, and finally raising the temperature to 1450 ℃ at a heating rate of 5 ℃/min in argon atmosphere for 2 hours.
Example 5
Preparation of three-dimensional hard alloy by taking acrylamide as monomer and adopting photo-curing 3D printing
Photo-curable 3D printing ink was prepared by magnetically stirring deionized water (4 g), ammonium paratungstate (10 g), cobalt nitrate (1 g), acrylamide (7 g) and N, N' -methylenebisacrylamide (0.25 g) with photoinitiator 2959 (0.05 g) at room temperature. The temperature of all operations was controlled to about 20 ℃.
Photo-curing 3D printing was then performed, the photo-curing 3D printing layer thickness being 0.01mm, and the exposure time per layer being 1s.
Taking out the formed green body from the trough, placing the green body in the condition of humidity of 80% and temperature of 70 ℃ for heat preservation for 72 hours, and completely drying the green body.
Finally, placing the blank body in hydrogen, raising the temperature to 500 ℃ at a heating rate of 0.5 ℃/min for 2 hours, raising the temperature to 900 ℃ at a heating rate of 2 ℃/min under vacuum, and finally raising the temperature to 1450 ℃ at a heating rate of 5 ℃/min in argon atmosphere for 2 hours.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. A method for preparing a three-dimensional structure hard alloy by photo-curing 3D printing, comprising:
(1) Preparing ink: mixing a solvent, water-soluble tungsten salt, water-soluble cobalt salt, an organic functional monomer and a photoinitiator according to a certain proportion to prepare printing ink;
(2) Photo-curing 3D printing: filling the printing ink prepared in the step (1) into a photocuring 3D printer for photocuring 3D printing to obtain a precursor with a three-dimensional structure;
(3) And (3) drying post-treatment: drying the three-dimensional structure precursor obtained in the step (3) to obtain a dried precursor;
(4) High-temperature post-treatment: carrying out high-temperature post-treatment on the dried precursor obtained in the step (4) to obtain WC-Co hard alloy;
wherein in the step (1), the organic functional monomer comprises one or more of maleic acid, acrylamide, methacrylamide, N' -methylenebisacrylamide, methylolacrylamide, acrylic acid, methacrylic acid, methoxy polyethylene glycol methacrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, alkyl alkoxy acrylate, alkyl alkoxy methacrylate, methyl hydroxyethyl acrylate, methyl hydroxypropyl acrylate, methyl propenyl acrylate and polyethylene glycol dimethacrylate;
wherein in the step (4), the high-temperature post-treatment is divided into three stages, wherein in the first stage, a reducing atmosphere is adopted, and the temperature is heated from room temperature to a first temperature at a heating rate of 0.1-2 ℃/min; heating from a temperature greater than the first temperature to a second temperature at a heating rate of 0.5-10 ℃/min using a vacuum atmosphere in the second stage; in the third stage, adopting inert atmosphere, and heating from a temperature higher than the second temperature to a third temperature at a heating rate of 0.5-10 ℃/min; wherein the first temperature is 400-600 ℃, the second temperature is 800-1500 ℃, and the third temperature is 1400-1800 ℃.
2. The method for preparing a three-dimensional hard alloy by photocuring 3D printing according to claim 1, wherein in the step (1), the concentration of the water-soluble tungsten salt is 0.01-70 wt%; the addition amount of the organic functional monomer is 0.1-50% of the mass of the ink; the addition amount of the photoinitiator is 0.01-50% of the mass of the organic functional monomer.
3. The method for preparing a three-dimensional hard alloy by photocuring 3D printing according to claim 1, wherein in the step (1), the water-soluble tungsten salt comprises one or more of sodium tungstate, ammonium paratungstate and ammonium metatungstate; the water-soluble cobalt salt comprises one or more of cobalt nitrate, cobalt carbonate and cobalt acetate.
4. The method for preparing a cemented carbide with a three-dimensional structure by photo-curing 3D printing according to claim 1, wherein in the step (1), the photoinitiator comprises one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
5. The method for preparing a cemented carbide with a three-dimensional structure by photo-curing 3D printing according to claim 1, wherein in the step (2), the type of the photo-curing 3D printer comprises at least one of SLA, DLP, CLIP, HRAP.
6. The method for preparing a cemented carbide with a three-dimensional structure by photo-curing 3D printing according to claim 1, wherein in the step (3), the drying mode comprises one or more of oven drying or freeze drying.
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