Photocurable printing silicon carbide and method of making the same

Abstract

This invention provides a photocurable printing silicon carbide and its preparation method, relating to the field of additive manufacturing technology. The preparation method of photocurable printing silicon carbide provided by this invention includes the following steps: submicron green silicon carbide is sequentially subjected to granulation by ball pressing, curing, airflow crushing, modification, heat treatment, and fumigation bleaching to obtain silicon carbide powder with a composite structure; a printing paste containing the silicon carbide powder is then photocured and sintered to obtain photocurable printing silicon carbide. This invention prepares silicon carbide powder with a composite structure by subjecting submicron green silicon carbide powder to a series of treatments. During the paste mixing process, the composite structure of the silicon carbide powder does not disperse, and the modified liquid phase layer is not easily detached. This overcomes the problems of severe light absorption and difficulty in printing by fine-particle-size silicon carbide powder, and low sintering activity and low green density of coarse-particle-size powder. The resulting photocurable printing silicon carbide has the advantages of easy photocuring, fewer defects, easy sintering, and high finished product density.

Description

Technical Field

[0001] This invention relates to the field of additive manufacturing technology, and more specifically, to a photocurable silicon carbide printing method and its preparation method. Background Technology

[0002] Silicon carbide's high strength, high hardness, high wear and corrosion resistance, and high thermal conductivity make it widely used in aerospace, mechanical seals, photovoltaic semiconductors, pharmaceuticals, chemicals, and metallurgy. However, silicon carbide has a high sintering temperature and is difficult to manufacture. Ordinary molding methods can only produce products with simple structures and single characteristics, and the molding and sintering of complex silicon carbide parts presents significant challenges. Currently, complex part molding technologies include injection molding, slip casting, sol-gel injection molding, and additive manufacturing, each with its own advantages and disadvantages. Among them, additive manufacturing technology, broadly referring to 3D printing technology, differs from other molding technologies in that it eliminates the limitations of molds on products, enabling significant breakthroughs in spatial structure and size, and can basically achieve net-size machining. It has great advantages and development potential in the production of large and complex structural devices.

[0003] Currently, 3D printing technologies are mainly classified according to their principles, including direct injection molding, laser printing, fused deposition modeling, and photopolymerization. Different 3D printing technologies have different advantages and disadvantages. Among them, photopolymerization utilizes changes in the molecular structure of photosensitive substances to trigger a chemical reaction that solidifies the material. It boasts advantages such as high automation, high surface quality, high smoothness, and high dimensional accuracy of the finished product, making it a promising molding method. However, during the photopolymerization process, unavoidable adverse factors such as ineffective absorption and scattering of the light source by the material are unavoidable. Therefore, photopolymerization printing technology is often used for printing whitish materials such as alumina, silicon dioxide, zirconium oxide, and silicon nitride. In whitish or lightly colored materials, the photosensitive resin can absorb more light energy for rapid curing, deepening the curing depth, ensuring the strength of the blank, and reducing interlayer cracking. However, for black raw materials such as boron carbide and graphite, the ineffective absorption and scattering of the light source by the material makes photopolymerization printing technology unsuitable. For silicon carbide materials, using submicron silicon carbide as raw material results in severe absorption and scattering of light sources, leading to problems such as low curing depth, interlayer cracking, high defect rate, and low green density in photopolymerized silicon carbide printing. To overcome the problem of ineffective absorption and scattering of light sources by the material, large-particle coarse green silicon carbide is usually used. However, using coarse-particle silicon carbide as raw material presents problems such as low sintering activity and sintering difficulties. Therefore, it is urgent to solve the problems of low powder particle density, low curing depth, low sintering activity, and low finished product density caused by the severe absorption of light sources by fine-particle silicon carbide powder and the low sintering activity of coarse-particle powder. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a photocurable silicon carbide for printing and its preparation method. The silicon carbide obtained has the advantages of easy photocuring, few defects, easy sintering, and high finished product density, while also possessing excellent properties such as high strength, high hardness, high wear and corrosion resistance, and high thermal conductivity.

[0005] This invention provides a method for preparing photocurable silicon carbide, comprising the following steps:

[0006] S1. A mixture containing green silicon carbide, thermosetting resin, plasticizer and lubricant is sequentially subjected to ball granulation, curing, airflow crushing and sieving to obtain a first powder with a particle size of 5-8μm.

[0007] S2, Step S1: The first powder is dispersed in the first organic solvent to form a first mixed slurry; after the nano silicon carbide and nano aluminum powder are dispersed in the second organic solvent, ammonia is added to form a second mixed slurry; after the first mixed slurry and the second mixed slurry are mixed, they are filtered, sieved, and heat-treated to obtain the second powder;

[0008] S3, colorless yttrium aluminate and anhydrous ethanol are mixed evenly in a third organic solvent to obtain a mixed slurry; the mixed slurry is atomized onto the second powder in step S2, and granulation is performed at the same time; after granulation, it is sieved and solidified to obtain the third powder.

[0009] S4. The third powder in step S3 is subjected to fumigation and bleaching treatment to remove the dark part in the third powder to obtain silicon carbide powder. The silicon carbide powder has a composite structure, which includes a particle region, a nano-diffusion layer, and a liquid phase modification layer. The nano-diffusion layer wraps the particle region, and the outside of the nano-diffusion layer is covered by the liquid phase modification layer.

[0010] S5. The printing paste containing the silicon carbide powder and photosensitive resin described in step S4 is photocured and printed to obtain a silicon carbide green blank; the silicon carbide green blank is sintered to obtain photocured printed silicon carbide.

[0011] The method for preparing photocurable silicon carbide provided by this invention uses submicrocrystalline green silicon carbide, thermosetting resin, plasticizer, and release agent as raw materials. The process involves pelletizing, curing, airflow crushing, modification, heat treatment, and fumigation bleaching to obtain silicon carbide powder with a composite structure. During the paste mixing process, the composite structure of the silicon carbide powder remains intact, and the modified liquid phase layer is not easily detached. This overcomes the problems of severe light absorption by fine-particle-size silicon carbide powder and low sintering activity of coarse-particle-size powder. The prepared silicon carbide powder retains the sintering activity of small-particle-size silicon carbide powder while improving the powder particle density, photocuring depth, and sintered body density of photocurable silicon carbide. The prepared photocurable silicon carbide has the advantages of easy photocuring, fewer defects, easy sintering, and high finished product density.

[0012] In one possible implementation, the mass ratio of the green silicon carbide, thermosetting resin, plasticizer, and release agent is (90-93):(4-6):(2-3):1.

[0013] In one possible implementation, the green silicon carbide has a particle size of 0.2-0.5 μm.

[0014] In one possible implementation, the thermosetting resin in step S1 is one or more of epoxy resin, phenolic resin, and furan resin.

[0015] In one possible implementation, the plasticizer in step S1 is polyethylene glycol and / or glycerol.

[0016] In one possible implementation, the lubricant in step S1 is paraffin wax and / or oleic acid.

[0017] In one possible implementation, the pressure for granulation in step S1 is 20-30 MPa.

[0018] In one possible implementation, the particle size of the powder after granulation in step S1 is 0.5-1 mm.

[0019] In one possible implementation, the curing temperature in step S1 is 100-120°C and the time is 10-12 hours.

[0020] In one possible implementation, the mass ratio of the first powder to the first organic solvent in step S2 is (55-60):(40-45).

[0021] In one possible implementation, the solid content in the second slurry in step S2 is 50-55 wt%.

[0022] In one possible implementation, the mass ratio of nano-silicon carbide to nano-aluminum powder in step S2 is (45-50):(50-55).

[0023] In one possible implementation, the volume ratio of the second organic solvent to the ammonia in step S2 is (95-97):(3-5).

[0024] In one possible implementation, the concentration of the ammonia water in step S2 is 30-35%.

[0025] In one possible implementation, the particle size of the nano-silicon carbide powder in step S2 is 50-100 nm.

[0026] In one possible implementation, the particle size of the nano-aluminum powder in step S2 is 50-80 nm.

[0027] In one possible implementation, the volume ratio of the first slurry to the second slurry in step S2 is (85-90):(10-15).

[0028] In one possible implementation, in step S2, the first organic solvent and the second organic solvent are anhydrous ethanol.

[0029] In one possible implementation, the heat treatment in step S2 is performed at a temperature of 400-600°C for 8-12 hours.

[0030] In one possible implementation, the solid content in the mixed slurry in step S3 is 55-60 wt%.

[0031] In one possible implementation, the mass ratio of yttrium aluminate in step S3 to the second powder in step S2 is (10-15):(85-90).

[0032] In one possible implementation, the yttrium aluminate in step S3 has a particle size of 300-500 nm.

[0033] In one possible implementation, the volume ratio of anhydrous ethanol to the third organic solvent in step S3 is (95-97):(3-5).

[0034] In one possible implementation, the curing temperature in step S3 is 80-100°C and the time is 12 hours.

[0035] In one possible implementation, the third organic solvent in step S3 is one or more of acrylic resin and vinyl resin.

[0036] In one possible implementation, the bleaching agent used in the fumigation bleaching in step S4 is one or more of sulfur dioxide, chlorine, and ozone.

[0037] In one possible implementation, the photosensitive resin in step S5 is one or more of alkyl acrylate photosensitive resins, hydroxy acrylate photosensitive resins, and acrylamide photosensitive resins with cyclic structures.

[0038] In one possible implementation, the mass ratio of silicon carbide powder to photosensitive resin in step S5 is (70-80):(20-30).

[0039] Based on common knowledge in the field, the above-described embodiments can be combined arbitrarily.

[0040] The present invention also provides photocurable silicon carbide prepared by the above method.

[0041] The reagents and raw materials used in this invention are all commercially available.

[0042] The positive and progressive effects of this invention are as follows:

[0043] The method for preparing photocurable silicon carbide provided by this invention prepares silicon carbide powder with a composite structure suitable for printing through a series of powder processing processes, overcoming the difficulties of photocurable silicon carbide printing, and has the advantages of high powder particle density, high sintering activity, good quality of green body and high density of sintered body. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of a silicon carbide composite powder structure for photopolymerization printing.

[0045] 1-Particle region, 2-Nano diffusion layer, 3-Liquid phase modification layer Detailed Implementation

[0046] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the claims of the present invention.

[0047] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0048] Unless otherwise defined, all terms, symbols, and other scientific terms used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In some instances, terms having a conventional meaning are defined herein for clarification or ease of reference, and such definitions should not be construed as indicating a significant difference from conventional understanding in the art. The technical methods described or referenced herein are generally well understood by those skilled in the art and employed by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents, and instruments shall be performed according to the manufacturer's instructions and parameters. Example 1

[0049] This embodiment provides a photocurable printing silicon carbide, which is prepared by the following method:

[0050] (1) 90 parts by weight of green silicon carbide with a particle size of 0.2-0.5 μm were selected as raw materials and mixed with 6 parts by weight of epoxy resin, 3 parts by weight of polyethylene glycol and 1 part by weight of paraffin for 48 h. After the mixing was completed, the mixture was granulated by pressing. The pressure of granulation was 20 MPa. The particle size of the powder after granulation was 0.5-1 mm. Then, the mixture was extended at low temperature for 12 h and the curing temperature was 100 °C. After that, the mixture was subjected to airflow crushing and sieving to obtain the first powder with a particle size range of 5-8 μm.

[0051] (2) 55 parts by weight of the first powder were placed in 45 parts by weight of anhydrous ethanol solution and ultrasonically dispersed to form the first mixed slurry. 50 parts by weight of nano-silicon carbide with a particle size of 50-100 nm, 50 parts by weight of nano-aluminum powder with a particle size of 50-100 nm, and 95 parts by weight of anhydrous ethanol were ultrasonically stirred and dispersed. Then, 5 parts by weight of ammonia water with a concentration of 35% were added dropwise to form the second mixed slurry. Then, 10 parts by volume of the second mixed slurry were poured into 90 parts by volume of the first mixed slurry and ultrasonically stirred again. Then, the mixture was filtered and dried, and heat-treated in air at 400°C for 12 hours. After sieving, the second powder was obtained.

[0052] (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid content is 55wt%, the mass part of anhydrous ethanol in the liquid phase is 95 parts and the mass part of acrylic resin is 5 parts. The mixture is stirred and dispersed for 24h, and the mixed slurry is placed in a pressure atomizer. The second powder is placed in a disc granulator, the granulation disc is turned on, and the slurry is atomized onto the second powder for granulation. The mass ratio of yttrium aluminate to the second powder is 15:85. Then it is passed through a 400-mesh sieve and then cured at 80℃ for 12h to obtain the third powder.

[0053] (4) The third powder is uniformly fumigated and bleached with sulfur dioxide bleaching agent to remove the dark part of the third powder and obtain silicon carbide powder with composite structure.

[0054] (5) Silicon carbide powder and alkyl acrylate photosensitive resin are mixed in a mass ratio of 80:20 to form a printing paste, which is then photocured to form a green body and sintered to obtain photocured printing silicon carbide.

[0055] A schematic diagram of the composite structure of the silicon carbide powder prepared in step (4) of Example 1 is shown below. Figure 1 As shown, the interior of the composite structure is a highly dense particle region 1 composed of multiple particles, the periphery of the particle region is a nano-diffusion layer 2, and the exterior of the nano-diffusion layer is covered by a liquid phase modification layer 3.

[0056] For the printing paste in step (5) of Example 1, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 seconds, and its curing depth was measured to be 256 μm. The density of the photocurable printing silicon carbide prepared in Example 1 was 3.15 g / cm³.3 . Example 2

[0057] This embodiment provides a photocurable printing silicon carbide, which is prepared by the following method:

[0058] (1) 91 parts by weight of green silicon carbide with a particle size of 0.2-0.5 μm were selected as raw materials and mixed with 5 parts by weight of phenolic resin, 3 parts by weight of glycerol and 1 part by weight of oleic acid for 48 h. After the mixing was completed, the powder was granulated by pressing and pelletizing at a pressure of 30 MPa. The particle size of the powder after granulation was 0.5-1 mm. Then, the powder was extended and cured at low temperature for 12 h at a curing temperature of 120 °C. Subsequently, the powder was subjected to airflow crushing and sieving to obtain the first powder with a particle size range of 5-8 μm.

[0059] (2) 60 parts by weight of the first powder were placed in 40 parts by weight of anhydrous ethanol solution and ultrasonically dispersed to form the first mixed slurry. 45 parts by weight of nano-silicon carbide with a particle size of 50-100 nm, 55 parts by weight of nano-aluminum powder with a particle size of 50-100 nm, and 97 parts by weight of anhydrous ethanol were ultrasonically stirred and dispersed. Then, 3 parts by weight of ammonia water with a concentration of 30% were added dropwise to form the second mixed slurry. Then, 15 parts by volume of the second mixed slurry were poured into 85 parts by volume of the first mixed slurry and ultrasonically stirred. Then, the mixture was filtered and dried. The mixture was heat-treated in air at 400°C for 12 hours and then sieved to obtain the second powder.

[0060] (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid content is 55wt%, the mass part of anhydrous ethanol in the liquid phase is 95 parts and the mass part of acrylic resin is 5 parts. The mixture is stirred and dispersed for 24h, and the mixed slurry is placed in a pressure atomizer. The second powder is placed in a disc granulator, the granulation disc is turned on, and the slurry is atomized onto the second powder for granulation. The mass ratio of yttrium aluminate to the second powder is 10:90. Then it is passed through a 400-mesh sieve and then cured at 80℃ for 12h to obtain the third powder.

[0061] (4) The third powder is uniformly fumigated and bleached with sulfur dioxide bleaching agent to remove the dark part of the third powder and obtain silicon carbide powder with composite structure.

[0062] (5) Silicon carbide powder and acrylic hydroxy ester photosensitive resin are mixed in a mass ratio of 95:20 to form a printing paste, which is then photocured to form a green blank, and sintered to obtain photocured printed silicon carbide.

[0063] For the printing paste in step (5) of Example 2, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 seconds, and its curing depth was measured to be 223 μm. The density of the photocurable printing silicon carbide prepared in Example 2 was 2.9 g / cm³. 3 . Example 3

[0064] (1) 93 parts by weight of green silicon carbide with a particle size of 0.2-0.5 μm was selected as raw material and mixed with 5 parts by weight of phenolic resin, 1 part by weight of glycerol and 1 part by weight of oleic acid for 48 h. After mixing, the mixture was granulated by pressing at a pressure of 30 MPa. The particle size of the granulated powder was 0.5-1 mm. Then, it was cured at low temperature for 12 h at a curing temperature of 120 °C. Subsequently, the first powder was subjected to air-jet crushing and sieving with a particle size range of 5-8 μm.

[0065] (2) 56 parts by mass of the first powder were placed in 44 parts by mass of anhydrous ethanol solution and ultrasonically dispersed to form the first mixed slurry. 46 parts by mass of nano-silicon carbide with a particle size of 50-100 nm, 54 parts by mass of nano-aluminum powder with a particle size of 50-100 nm, and 96 parts by mass of anhydrous ethanol were ultrasonically stirred and dispersed. Then, 4 parts by mass of ammonia water with a concentration of 30% were added dropwise to form the second mixed slurry. Then, 12 parts by volume of the second mixed slurry were poured into 88 parts by volume of the first mixed slurry and ultrasonically stirred again. After that, the mixture was filtered and dried. It was then heat-treated in air at 600°C for 8 hours and sieved to obtain the second powder.

[0066] (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid content is 55wt%, the mass part of anhydrous ethanol in the liquid phase is 95 parts and the mass part of acrylic resin is 5 parts. The mixture is stirred and dispersed for 24h, and the mixed slurry is placed in a pressure atomizer. The second powder is placed in a disc granulator, the granulation disc is turned on, and the slurry is atomized onto the second powder for granulation. The mass ratio of yttrium aluminate to the second powder is 12:88. Then it is passed through a 400-mesh sieve and then cured at 80℃ for 12h to obtain the third powder.

[0067] (4) The third powder is uniformly fumigated and bleached with chlorine bleaching agent to remove the dark part of the third powder and obtain silicon carbide powder with composite structure.

[0068] (5) Silicon carbide powder and acrylamide photosensitive resin with cyclic structure are mixed in a mass ratio of 85:15 to form a printing paste, which is then photocured and printed into a green body. After sintering, photocured printing silicon carbide is obtained.

[0069] For the printing paste in step (5) of implementation 3, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 seconds, and its curing depth was measured to be 212 μm. The density of the photocurable printing silicon carbide prepared in Example 3 was 3.0 g / cm³. 3 . Example 4

[0070] (1) 92 parts by weight of green silicon carbide with a particle size of 0.2-0.5 μm was selected as raw material and mixed with 4 parts by weight of phenolic resin, 3 parts by weight of glycerol and 1 part by weight of oleic acid for 48 h. After the mixing was completed, the mixture was granulated by pressing. The pressure of granulation was 30 MPa. The particle size of the powder after granulation was 0.5-1 mm. Then, it was extended and cured at low temperature for 12 h at a curing temperature of 120 °C. Then, the first powder with a particle size range of 5-8 μm was crushed by air and screened.

[0071] (2) 58 parts by weight of the first powder were placed in 42 parts by weight of anhydrous ethanol solution and ultrasonically dispersed to form the first mixed slurry. 48 parts by weight of nano-silicon carbide with a particle size of 50-100 nm, 52 parts by weight of nano-aluminum powder with a particle size of 50-100 nm, and 96 parts by weight of anhydrous ethanol were ultrasonically stirred and dispersed. Then, 4 parts by weight of ammonia water with a concentration of 30% were added dropwise to form the second mixed slurry. Then, 15 parts by weight of the second mixed slurry were poured into 85 parts by weight of the first mixed slurry and ultrasonically stirred again. Then, the mixture was filtered and dried, and heat-treated in air at 500°C for 10 h. After sieving, the second powder was obtained.

[0072] (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid content is 55wt%, the mass part of anhydrous ethanol in the liquid phase is 95 parts and the mass part of acrylic resin is 5 parts. The mixture is stirred and dispersed for 24h, and the mixed slurry is placed in a pressure atomizer. The second powder is placed in a disc granulator, the granulation disc is turned on, and the slurry is atomized onto the second powder for granulation. The mass ratio of yttrium aluminate to the second powder is 13:87. Then it is passed through a 400-mesh sieve and then cured at 80℃ for 12h to obtain the third powder.

[0073] (4) The third powder is uniformly fumigated and bleached with ozone bleaching agent to remove the dark part of the third powder and obtain silicon carbide powder with composite structure.

[0074] (5) Silicon carbide powder and alkyl acrylate photosensitive resin are mixed in a mass ratio of 80:20 to form a printing paste, which is then photocured to form a green body and sintered to obtain photocured printing silicon carbide.

[0075] For the printing paste in step (5) of Example 4, irradiation with ultraviolet light at a wavelength of 405 nm for 20 s was used, and its curing depth was measured to be 235 μm. The density of the photocurable printing silicon carbide prepared in Example 4 was 3.0 g / cm³. 3 .

[0076] Comparative Example 1

[0077] Comparative Example 1 provides a photocurable printing silicon carbide. The difference between Comparative Example 1 and Example 1 is that the photocurable printing silicon carbide preparation method of Comparative Example 1 does not use the ball-forming process in step (1).

[0078] For the printing paste in step (5) of Comparative Example 1, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 s, and its curing depth was measured to be 153 μm. The density of the photocurable printing silicon carbide prepared in Comparative Example 1 was 2.4 g / cm³. 3 .

[0079] Comparative Example 2

[0080] Comparative Example 2 provides a photocurable printing silicon carbide. The difference between Comparative Example 2 and Example 1 is that the second slurry is not used in step (2) of the preparation method of photocurable printing silicon carbide in Comparative Example 2.

[0081] For the printing paste in step (5) of Comparative Example 2, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 s, and its curing depth was measured to be 116 μm. The density of the photocurable printing silicon carbide prepared in Comparative Example 2 was 2.1 g / cm³. 3 .

[0082] Comparative Example 3

[0083] Comparative Example 3 provides a photocurable printed silicon carbide. The difference between Comparative Example 3 and Example 1 is that the photocurable printed silicon carbide preparation method of Comparative Example 3 does not include step (3).

[0084] For the printing paste in step (5) of Comparative Example 3, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 s, and its curing depth was measured to be 86 μm. The density of the photocurable printing silicon carbide prepared in Comparative Example 3 was 1.7 g / cm³. 3 .

[0085] Comparative Example 4

[0086] Comparative Example 4 provides a photocurable printed silicon carbide. The difference between Comparative Example 4 and Example 1 is that the photocurable printed silicon carbide preparation method of Comparative Example 4 does not include step (4).

[0087] For the printing paste in step (5) of Comparative Example 4, it was irradiated with ultraviolet light at a wavelength of 405 nm for 20 s, and its curing depth was measured to be 174 μm. The density of the photocurable printing silicon carbide prepared in Comparative Example 4 was 2.5 g / cm³. 3 .

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for producing photocured printed silicon carbide, characterized by, Includes the following steps: S1. A mixture containing green silicon carbide, thermosetting resin, plasticizer and lubricant is sequentially subjected to granulation by ball pressing, curing, airflow crushing and sieving to obtain a first powder with a particle size of 5-8 μm; wherein the particle size of the green silicon carbide is 0.2-0.5 μm; S2, Step S1: The first powder is dispersed in the first organic solvent to form a first mixed slurry; after the nano silicon carbide and nano aluminum powder are dispersed in the second organic solvent, ammonia is added to form a second mixed slurry; after the first mixed slurry and the second mixed slurry are mixed, they are filtered, sieved, and heat-treated to obtain the second powder; S3, colorless yttrium aluminate and anhydrous ethanol are mixed evenly in a third organic solvent to obtain a mixed slurry; the mixed slurry is atomized onto the second powder in step S2, and granulation is performed at the same time; after granulation, it is sieved and solidified to obtain the third powder. S4. The third powder in step S3 is subjected to fumigation and bleaching treatment to remove the dark part in the third powder and obtain silicon carbide powder. The silicon carbide powder has a composite structure, which includes a particle region (1), a nano-diffusion layer (2), and a liquid phase modification layer (3). The nano-diffusion layer (2) wraps the particle region (1), and the outside of the nano-diffusion layer is covered by the liquid phase modification layer (3). S5. The printing paste containing the silicon carbide powder and photosensitive resin described in step S4 is photocured and printed to obtain a silicon carbide green blank; the silicon carbide green blank is sintered to obtain photocured printed silicon carbide.

2. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, The mass ratio of green silicon carbide, thermosetting resin, plasticizer and lubricant in step S1 is (90-93):(4-6):(2-3):

1.

3. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, The thermosetting resin mentioned in step S1 is at least one of epoxy resin, phenolic resin and furan resin; And / or, the plasticizer in step S1 is polyethylene glycol and / or glycerol; And / or, the lubricant in step S1 is paraffin and / or oleic acid.

4. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, The pressure for granulation in step S1 is 20-30 MPa; And / or, the particle size of the powder after granulation by ball pressing in step S1 is 0.5-1 mm; And / or, the curing temperature in step S1 is 100-120℃ and the time is 10-12h.

5. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, In step S2, the mass ratio of the first powder to the first organic solvent is (55-60):(40-45); And / or, in step S2, the solid content in the second mixed slurry is 50-55 wt%; And / or, the mass ratio of nano-silicon carbide to nano-aluminum powder in step S2 is (45-50):(50-55); And / or, in step S2, the mass ratio of the second organic solvent to the ammonia is (95-97):(3-5); And / or, the concentration of the ammonia solution in step S2 is 30-35%; And / or, the particle size of the nano-silicon carbide powder in step S2 is 50-100 nm; And / or, the particle size of the nano-aluminum powder in step S2 is 50-80 nm; And / or, in step S2, the volume ratio of the first mixed slurry to the second mixed slurry is (85-90):(10-15).

6. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, In step S2, the first organic solvent and the second organic solvent are anhydrous ethanol; And / or, the heat treatment in step S2 is performed at a temperature of 400-600℃ for 8-12 hours.

7. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, The solid content in the mixed slurry described in step S3 is 55-60 wt%; And / or, the mass ratio of yttrium aluminate in step S3 to the second powder in step S2 is (10-15):(85-90); And / or, the yttrium aluminate particle size in step S3 is 300-500 nm; And / or, the volume ratio of anhydrous ethanol to the third organic solvent in step S3 is (95-97):(3-5); And / or, the curing temperature in step S3 is 80-100℃ and the time is 12h; And / or, the third organic solvent in step S3 is one or more of acrylic resin and vinyl resin.

8. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, The bleaching agent used in the fumigation and bleaching process described in step S4 is one or more of sulfur dioxide, chlorine, and ozone.

9. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that, The photosensitive resin mentioned in step S5 is one or more of alkyl acrylate photosensitive resin, hydroxy acrylate photosensitive resin, and acrylamide photosensitive resin with a cyclic structure; And / or, the mass ratio of silicon carbide powder to photosensitive resin in step S5 is (80-90):(10-20).

10. A photocurable silicon carbide printing method, characterized in that, The silicon carbide is prepared by the method for preparing photocurable printing silicon carbide according to any one of claims 1 to 9.

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