Photocuring printing silicon carbide and preparation method thereof

Abstract

The invention provides light-cured printing silicon carbide and a preparation method thereof, and relates to the technical field of additive manufacturing. The preparation method of the light-cured printing silicon carbide provided by the invention comprises the following steps: sequentially carrying out ball pressing granulation, curing, airflow crushing, modification, heat treatment, fumigation bleaching treatment and the like on submicron green silicon carbide to obtain silicon carbide powder with a composite structure; the printing paste containing the silicon carbide powder is subjected to photocuring printing and sintering, and photocuring printing silicon carbide is obtained. The submicron green silicon carbide powder is subjected to a series of treatment to prepare the silicon carbide powder with a composite structure, in the paste mixing process, the composite structure of the silicon carbide powder is not dispersed, a modified liquid phase layer is not prone to falling off, and the defects that silicon carbide powder with the fine particle size severely absorbs a light source and is not prone to falling off are overcome. And the prepared photocuring printing silicon carbide has the advantages of easiness in photocuring, few defects, easiness in sintering and high finished product density.

Description

Technical Field

[0001] The present invention relates to the technical field of additive manufacturing, and in particular to a photocuring printed silicon carbide and a preparation method thereof. Background Art

[0002] Silicon carbide's high strength, high hardness, high wear and corrosion resistance, high thermal conductivity and other properties make it widely used in aerospace, mechanical seals, photovoltaic semiconductors, pharmaceutical chemicals, smelting and other fields. However, the sintering temperature of silicon carbide is high and it is difficult to prepare. Ordinary molding methods can only produce products with simple structures and single features. The molding and sintering of complex silicon carbide parts are very difficult. At present, the molding technologies for complex parts include injection molding, grouting, sol-gel injection, additive manufacturing, etc. Each of these molding technologies has its own advantages and disadvantages. Among them, additive manufacturing technology, which generally refers to 3D printing technology, is different from other molding technologies. It can abandon the restrictions of molds on products, can achieve great breakthroughs in spatial structure and size, and can basically achieve net size processing. It has great advantages and development space in the production of large and complex structural devices.

[0003] At present, 3D printing technology is mainly divided into direct injection printing, laser printing, melt printing, photocuring printing, etc. according to the principle. Different 3D printing technologies have different advantages and disadvantages. Among them, photocuring printing is a technology that uses the molecular structure of photosensitive substances to change, thereby inducing chemical reactions to solidify the materials. It has the advantages of high process automation, good surface quality of molded products, high finish, and high dimensional accuracy. It is a more promising molding method. However, in the photocuring process, unfavorable factors such as the ineffective absorption and scattering of the light source by the material are inevitable. Therefore, photocuring printing technology is often used to print materials with white color such as aluminum oxide, silicon oxide, zirconium oxide, and silicon nitride. In white or light-colored materials, photosensitive resins can absorb more light energy for rapid curing, deepen the curing depth, ensure the strength of the blank, and reduce interlayer cracking. For black raw materials such as boron carbide and graphite, due to unfavorable factors such as the ineffective absorption and scattering of the light source by the material, photocuring printing technology cannot be used for printing. As for silicon carbide materials, submicron silicon carbide is used as the raw material. Due to the serious absorption and scattering of the light source, the photocuring printing of silicon carbide has problems such as low curing depth, interlayer cracking, high defects, and low green density. In order to overcome the problem of ineffective absorption and scattering of the light source by the material, large-particle coarse-grained green silicon carbide is usually used. However, when using coarse-grained silicon carbide as the raw material to prepare silicon carbide, there are problems such as low sintering activity and difficulty in sintering; 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 serious absorption of light source by fine-particle silicon carbide powder and the low sintering activity of coarse-particle powder. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a photocurable printed silicon carbide and a preparation method thereof. The prepared silicon carbide has the advantages of easy photocuring, few defects, easy sintering and high finished product density, and also has excellent properties such as high strength, high hardness, high wear resistance and corrosion resistance, and high thermal conductivity.

[0005] The present invention provides a method for preparing photocured silicon carbide, comprising the following steps: S1, a mixture containing green silicon carbide, a thermosetting resin, a plasticizer and a lubricant is successively subjected to pelletizing, curing, air flow crushing and screening to obtain a first powder with a particle size of 5-8 μm; S2, step S1: the first powder is dispersed in a first organic solvent to form a first mixed slurry; after the nano-silicon carbide and nano-aluminum powder are dispersed in a second organic solvent, ammonia water is added to form a second mixed slurry; after the first mixed slurry and the second mixed slurry are mixed, the second powder is obtained by filtering, screening and heat treatment; S3, colorless yttrium aluminate and anhydrous ethanol are uniformly mixed 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, and after the granulation is completed, the third powder is obtained by screening and solidification; S4, fumigating and bleaching the third powder in step S3 to remove the dark part of the third powder to obtain silicon carbide powder, wherein the silicon carbide powder has a composite structure, and the composite structure includes a particle area, a nano diffusion layer, and a liquid phase modification layer, wherein the nano diffusion layer wraps the particle area, and the outside of the nano diffusion layer is coated by the liquid phase modification layer; S5, performing photocuring printing on the printing paste containing the silicon carbide powder and the photosensitive resin in step S4 to obtain a silicon carbide green body; after sintering the silicon carbide green body, a photocuring printed silicon carbide is obtained.

[0006] The preparation method of photocured silicon carbide provided by the present invention uses submicrocrystalline green silicon carbide, thermosetting resin, plasticizer and release agent as raw materials, and obtains silicon carbide powder with a composite structure through ball pressing and granulation, curing, air flow crushing, modification, heat treatment, fumigation and bleaching treatment, etc. During the mixing process, the composite structure of the silicon carbide powder does not disperse, and the modified liquid phase layer is not easy to fall off, thereby overcoming the problems of severe light source absorption by fine-grained silicon carbide powder and low sintering activity of coarse-grained powder. The prepared silicon carbide powder retains the sintering activity of small-grained silicon carbide powder, and improves the powder particle density, photocuring depth and sintered body density of the photocured silicon carbide. The prepared photocured silicon carbide has the advantages of easy photocuring, few defects, easy sintering and high finished product density.

[0007] 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.

[0008] In a possible implementation, the particle size of the green silicon carbide is 0.2-0.5 μm.

[0009] In a possible implementation manner, the thermosetting resin in step S1 is one or more of epoxy resin, phenolic resin and furan resin.

[0010] In a possible implementation, the plasticizer in step S1 is polyethylene glycol and / or glycerol.

[0011] In a possible implementation, the lubricant in step S1 is paraffin and / or oleic acid.

[0012] In a possible implementation manner, the pressure of the pelletizing process in step S1 is 20-30 MPa.

[0013] In a possible implementation, the particle size of the powder after the ball pressing and granulation in step S1 is 0.5-1 mm.

[0014] In a possible implementation manner, the curing temperature in step S1 is 100-120° C. and the curing time is 10-12 hours.

[0015] In a possible implementation manner, in step S2, the mass ratio of the first powder to the first organic solvent is (55-60):(40-45).

[0016] In a possible implementation, in step S2, the solid content of the second slurry is 50-55wt%.

[0017] In a possible implementation manner, the mass ratio of nano-silicon carbide and nano-aluminum powder in step S2 is (45-50):(50-55).

[0018] In a possible implementation manner, in step S2, the volume ratio of the second organic solvent to the ammonia water is (95-97):(3-5).

[0019] In a possible implementation manner, the concentration of the ammonia water in step S2 is 30-35%.

[0020] In a possible implementation manner, the particle size of the nano silicon carbide powder in step S2 is 50-100 nm.

[0021] In a possible implementation manner, the particle size of the nano aluminum powder in step S2 is 50-80 nm.

[0022] In a possible implementation, in step S2, the volume ratio of the first slurry to the second slurry is (85-90):(10-15).

[0023] In a possible implementation manner, in step S2, the first organic solvent and the second organic solvent are anhydrous ethanol.

[0024] In a possible implementation manner, the heat treatment in step S2 is performed at a temperature of 400-600° C. and for a time of 8-12 hours.

[0025] In a possible implementation, the solid content in the mixed slurry in step S3 is 55-60wt%.

[0026] In a possible implementation, the mass ratio of the yttrium aluminate in step S3 to the second powder in step S2 is (10-15): (85-90) In a possible implementation manner, the particle size of the yttrium aluminate in step S3 is 300-500 nm.

[0027] In a possible implementation manner, the volume ratio of the anhydrous ethanol and the third organic solvent in step S3 is (95-97):(3-5).

[0028] In a possible implementation manner, the curing temperature in step S3 is 80-100° C. and the curing time is 12 hours.

[0029] In a possible implementation, the third organic solvent in step S3 is one or more of acrylic resin and vinyl resin.

[0030] In a possible implementation, the bleaching agent used in the fumigation bleaching in step S4 is one or more of sulfur dioxide, chlorine and ozone.

[0031] In a possible implementation, the photosensitive resin in step S5 is one or more of an alkyl acrylate photosensitive resin, a hydroxy acrylate photosensitive resin, and an acrylamide photosensitive resin with a cyclic structure.

[0032] In a possible implementation, in step S5, the mass ratio of the silicon carbide powder to the photosensitive resin is (70-80):(20-30).

[0033] Based on the common knowledge in this field, the above-mentioned implementation modes can be combined arbitrarily.

[0034] The present invention also provides light-cured silicon carbide prepared by the method.

[0035] The reagents and raw materials used in the present invention are commercially available.

[0036] The positive and progressive effects of the present invention are: The method for preparing photocured silicon carbide provided by the present invention prepares silicon carbide powder of a composite structure suitable for printing through a series of powder processing processes, overcomes the difficulties of photocuring printing of silicon carbide, and has the advantages of high powder particle density, high sintering activity, good green product quality, and high sintered body density. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 Schematic diagram of the structure of silicon carbide composite powder printed by photocuring.

[0038] 1-particle area, 2-nano diffusion layer, 3-liquid phase modification layer DETAILED DESCRIPTION

[0039] In order to make the above-mentioned purposes, features and advantages of the present invention more obvious and easy to understand, the 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 method and typical parameters of the present invention, and are not used to limit the parameter range described in the present invention. Reasonable changes derived therefrom are still within the scope of protection of the claims of the present invention.

[0040] It should be noted that the endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0041] Unless otherwise defined, all terms, symbols and other scientific terms used herein are intended to have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. In some cases, terms with conventionally understood meanings are defined herein for the purpose of clarification or ease of reference, and such definitions herein should not be construed as indicating significant differences from conventional understandings in the art. The technical methods described or cited herein are generally well understood by those skilled in the art and are adopted by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents and instruments is carried out in accordance with the protocols and parameters given by the manufacturer. Example 1

[0042] This embodiment provides a photocurable printed silicon carbide, which is prepared by the following preparation method: (1) 90 parts by weight of green silicon carbide with a particle size of 0.2-0.5 um is selected as a raw material, 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 hours; after the mixing is completed, pelletizing is performed, and the pressure of the pelletizing is 20 MPa. The particle size of the powder after pelletizing is 0.5-1 mm, and then low-temperature extended curing is performed for 12 hours, and the curing temperature is 100°C, followed by air flow crushing and screening of the first powder with a particle size range of 5-8 um; (2) placing 55 parts by mass of the first powder in 45 parts by mass of anhydrous ethanol solution and ultrasonically dispersing it into a first mixed slurry, ultrasonically stirring and dispersing 50 parts of nano-silicon carbide with a particle size of 50-100 nm, 50 parts by mass of nano-aluminum powder with a particle size of 50-100 nm, and 95 parts by mass of anhydrous ethanol, and then dropping 5 parts by mass of 35% ammonia water to form a second mixed slurry, and then pouring 10 parts by volume of the second mixed slurry into 90 parts by volume of the first mixed slurry, continuing ultrasonic stirring, and then filtering and drying, heat-treating in air at 400°C for 12 hours, and sieving to obtain a second powder; (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid phase content is 55wt%, the mass portion of anhydrous ethanol in the liquid phase is 95 parts by mass, and the mass portion of acrylic resin is 5 parts by mass, and the mixture is stirred and dispersed for 24 hours to obtain a mixed slurry, which is then placed in a pressure atomizer, and the second powder is placed in a disc granulator, and the granulation disc is turned on, and the slurry is simultaneously atomized onto the second powder for granulation, wherein the mass ratio of yttrium aluminate to the second powder is 15:85, and then the mixture is passed through a 400 mesh sieve, and then cured at 80°C for 12 hours to obtain a third powder; (4) using sulfur dioxide bleaching agent to uniformly perform fumigation bleaching treatment on the third powder to remove the dark part of the third powder, thereby obtaining silicon carbide powder with a composite structure; (5) Silicon carbide powder and alkyl acrylate photosensitive resin are mixed into a printing paste in a mass ratio of 80:20, and photocuring is performed to print the green body, and then the green body is sintered to obtain photocuring printed silicon carbide.

[0043] The schematic diagram of the composite structure of the silicon carbide powder prepared in step (4) of Example 1 is as follows Figure 1 As shown, the interior of the composite structure is a highly dense particle region 1 composed of a plurality of particles, the periphery of the particle region is a nano diffusion layer 2, and the exterior of the nano diffusion layer is coated by a liquid phase modification layer 3.

[0044] For the printing paste in step (5) of Example 1, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 256 μm. The density of the photocurable printed silicon carbide prepared in Example 1 is 3.15 g / cm 3 . Example 2

[0045] This embodiment provides a photocurable printed silicon carbide, which is prepared by the following preparation method: (1) 91 parts by weight of green silicon carbide with a particle size of 0.2-0.5 μm was selected as a raw material, and mixed with 5 parts by weight of phenolic resin, 3 parts by weight of propylene glycol, and 1 part by weight of oleic acid for 48 hours; after the mixing was completed, pelletizing was performed, the pressure of pelletizing was 30 MPa, and the particle size of the powder after pelletizing was 0.5-1 mm, and then low-temperature extended curing was performed for 12 hours, and the curing temperature was 120° C., and then air flow crushing and screening were performed to obtain a first powder with a particle size range of 5-8 μm; (2) placing 60 parts by mass of the first powder in 40 parts by mass of anhydrous ethanol solution and ultrasonically dispersing the mixture into a first mixed slurry, ultrasonically stirring and dispersing 45 parts of nano-silicon carbide with a particle size of 50-100 nm, 55 parts by mass of nano-aluminum powder with a particle size of 50-100 nm, and 97 parts by mass of anhydrous ethanol, and then dropping 3 parts by mass of 30% ammonia water to form a second mixed slurry, and then pouring 15 parts by volume of the second mixed slurry into 85 parts by volume of the first mixed slurry, continuing ultrasonic stirring, and then filtering and drying, heat-treating in air at 400° C. for 12 h, and sieving to obtain a second powder; (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid phase content is 55wt%, the mass portion of anhydrous ethanol in the liquid phase is 95 parts, and the mass portion of acrylic resin is 5 parts. The mixture is stirred and dispersed for 24 hours to obtain a mixed slurry, which 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, wherein the mass ratio of yttrium aluminate to the second powder is 10:90. The mixture is then sieved through a 400-mesh sieve and then cured at 80°C for 12 hours to obtain a third powder. (4) using sulfur dioxide bleaching agent to uniformly perform fumigation bleaching treatment on the third powder to remove the dark part of the third powder, thereby obtaining silicon carbide powder with a composite structure; (5) Silicon carbide powder and acrylic hydroxyl ester photosensitive resin are mixed into a printing paste in a mass ratio of 95:20, and photocuring is performed to print a green body, and then sintering is performed to obtain photocuring printed silicon carbide.

[0046] For the printing paste in step (5) of Example 2, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 223 μm. The density of the photocurable printed silicon carbide prepared in Example 2 is 2.9 g / cm 3 . Example 3

[0047] (1) 93 parts by weight of green silicon carbide with a particle size of 0.2-0.5 um is selected as a raw material, and mixed with 5 parts by weight of phenolic resin, 1 part by weight of propylene glycol, and 1 part by weight of oleic acid for 48 hours; after the mixing, pelletizing is performed at a pressure of 30 MPa, and the particle size of the powder after pelletizing is 0.5-1 mm, and then low-temperature extended curing is performed for 12 hours at a curing temperature of 120°C, followed by air flow crushing and screening of the first powder with a particle size range of 5-8 um (2) placing 56 parts by mass of the first powder in 44 parts by mass of anhydrous ethanol solution and ultrasonically dispersing the mixture into a first mixed slurry; dispersing 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 by ultrasonic stirring; and then dropping 4 parts by mass of 30% ammonia water to form a second mixed slurry; and then pouring 12 parts by volume of the second mixed slurry into 88 parts by volume of the first mixed slurry, continuing ultrasonic stirring, and then filtering and drying the mixture, heat-treating the mixture in air at 600° C. for 8 h, and sieving the mixture to obtain a second powder; (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid phase content is 55wt%, the mass portion of anhydrous ethanol in the liquid phase is 95 parts by mass, and the mass portion of acrylic resin is 5 parts by mass, and the mixture is stirred and dispersed for 24 hours to obtain a mixed slurry, which is then placed in a pressure atomizer, and the second powder is placed in a disc granulator, and the granulation disc is turned on, and the slurry is simultaneously atomized onto the second powder for granulation, wherein the mass ratio of yttrium aluminate to the second powder is 12:88, and then the mixture is passed through a 400 mesh sieve, and then cured at 80°C for 12 hours to obtain a third powder; (4) using chlorine bleach to evenly bleach the third powder, removing the dark part of the third powder, and obtaining silicon carbide powder with a composite structure; (5) Silicon carbide powder and acrylamide photosensitive resin with a ring structure are mixed into a printing paste in a mass ratio of 85:15, and photocuring is performed to print the green body, and then sintering is performed to obtain photocuring printed silicon carbide.

[0048] For the printing paste in step (5) of implementation 3, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 212 μm. The density of the photocurable printed silicon carbide prepared in Example 3 is 3.0 g / cm 3 . Example 4

[0049] (1) 92 parts by weight of green silicon carbide with a particle size of 0.2-0.5 μm is selected as a raw material, and mixed with 4 parts by weight of phenolic resin, 3 parts by weight of propylene glycol, and 1 part by weight of oleic acid for 48 hours; after the mixing is completed, pelletizing is performed, and the pressure of the pelletizing is 30 MPa. The particle size of the powder after pelletizing is 0.5-1 mm, and then the low-temperature extended curing is performed for 12 hours, and the curing temperature is 120°C, followed by air flow crushing and screening of the first powder with a particle size range of 5-8 μm; (2) 58 parts by weight of the first powder is ultrasonically dispersed in 42 parts by weight of anhydrous ethanol solution to form a 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 are ultrasonically dispersed, and 4 parts by weight of 30% ammonia water is added dropwise to form a second mixed slurry, and then 15 parts by weight of the second mixed slurry is poured into 85 parts by weight of the first mixed slurry, and ultrasonic stirring is continued, followed by filtering and drying, and heat-treating in air at 500° C. for 10 hours, and sieving to obtain a second powder; (3) Yttrium aluminate with a particle size of 300-500 nanometers, anhydrous ethanol and acrylic resin are mixed, wherein the solid phase content is 55wt%, the mass portion of anhydrous ethanol in the liquid phase is 95 parts by mass, and the mass portion of acrylic resin is 5 parts by mass, and the mixture is stirred and dispersed for 24 hours to obtain a mixed slurry, which is then placed in a pressure atomizer, and the second powder is placed in a disc granulator, and the granulation disc is turned on, and the slurry is simultaneously atomized onto the second powder for granulation, wherein the mass ratio of yttrium aluminate to the second powder is 13:87, and then the mixture is passed through a 400 mesh sieve, and then cured at 80°C for 12 hours to obtain a third powder; (4) using ozone bleaching agent to uniformly perform fumigation bleaching treatment on the third powder to remove the dark part of the third powder, thereby obtaining silicon carbide powder with a composite structure; (5) Silicon carbide powder and alkyl acrylate photosensitive resin are mixed into a printing paste in a mass ratio of 80:20, and photocuring is performed to print the green body, and then the green body is sintered to obtain photocuring printed silicon carbide.

[0050] For the printing paste in step (5) of Example 4, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 235 μm. The density of the photocurable printed silicon carbide prepared in Example 4 is 3.0 g / cm 3 .

[0051] Comparative Example 1 Comparative Example 1 provides a photocurable printed silicon carbide. The difference between Comparative Example 1 and Example 1 is that the ball pressing and granulation process is not used in step (1) of the preparation method of the photocurable printed silicon carbide in Comparative Example 1.

[0052] For the printing paste in step (5) of comparative example 1, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 153 μm. The density of the photocured printed silicon carbide prepared in comparative example 1 was 2.4 g / cm 3 .

[0053] Comparative Example 2 Comparative Example 2 provides a photocurable printed 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 the photocurable printed silicon carbide in Comparative Example 2.

[0054] For the printing paste in step (5) of comparative example 2, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 116 μm. The density of the photocured printed silicon carbide prepared in comparative example 2 was 2.1 g / cm 3 .

[0055] Comparative Example 3 Comparative Example 3 provides a photocurable printed silicon carbide. The difference between Comparative Example 3 and Example 1 is that the preparation method of the photocurable printed silicon carbide in Comparative Example 3 does not include step (3).

[0056] For the printing paste in step (5) of comparative example 3, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 86 μm. The density of the photocured printed silicon carbide prepared in comparative example 3 was 1.7 g / cm 3 .

[0057] Comparative Example 4 Comparative Example 4 provides a photocurable printed silicon carbide. The difference between Comparative Example 4 and Example 1 is that the preparation method of the photocurable printed silicon carbide in Comparative Example 4 does not include step (4).

[0058] For the printing paste in step (5) of comparative example 4, ultraviolet light with a wavelength of 405 nm was used for 20 seconds, and the curing depth was measured to be 174 μm. The density of the photocured printed silicon carbide prepared in comparative example 4 was 2.5 g / cm 3 .

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing photocurable printed silicon carbide, characterized in that: The following steps are involved: S1, a mixture containing green silicon carbide, a thermosetting resin, a plasticizer and a lubricant is successively subjected to pelletizing, curing, air flow crushing and screening to obtain a first powder with a particle size of 5-8 μm; S2, step S1: the first powder is dispersed in a first organic solvent to form a first mixed slurry; after the nano-silicon carbide and nano-aluminum powder are dispersed in a second organic solvent, ammonia water is added to form a second mixed slurry; after the first mixed slurry and the second mixed slurry are mixed, the second powder is obtained by filtering, screening and heat treatment; S3, colorless yttrium aluminate and anhydrous ethanol are uniformly mixed 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, and after the granulation is completed, the third powder is obtained by screening and solidification; S4, fumigating and bleaching the third powder in step S3 to remove the dark part of the third powder, thereby obtaining silicon carbide powder, wherein the silicon carbide powder has a composite structure, the composite structure comprising a particle area (1), a nano diffusion layer (2), and a liquid phase modified layer (3), the nano diffusion layer (2) wrapping the particle area (1), and the outside of the nano diffusion layer being coated by the liquid phase modified layer (3); S5, performing photocuring printing on the printing paste containing the silicon carbide powder and the photosensitive resin in step S4 to obtain a silicon carbide green body; after sintering the silicon carbide green body, a photocuring printed silicon carbide is obtained.

2. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that: The mass ratio of the green silicon carbide, thermosetting resin, plasticizer and release agent 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 particle size of the green silicon carbide in step S1 is 0.2-0.5 μm; And / or, the thermosetting resin 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 of the pelletizing process in step S1 is 20-30 MPa; And / or, the particle size of the powder after the spherical granulation in step S1 is 0.5-1 mm; And / or, the curing temperature in step S1 is 100-120° C. and the curing time is 10-12 hours.

5. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that: 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 of the second slurry is 50-55wt%; And / or, the mass ratio of nano-silicon carbide and 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 aqueous ammonia is (95-97):(3-5); And / or, the concentration of the ammonia water 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 slurry to the second slurry is (85-90):(10-15).

6. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that: Step S2: the first organic solvent and the second organic solvent are anhydrous ethanol; And / or, the heat treatment temperature in step S2 is 400-600° C. and the time is 8-12 hours.

7. The method for preparing photocurable printed silicon carbide according to claim 1, characterized in that: The solid content of the mixed slurry in step S3 is 55-60wt%; And / or, the mass ratio of the yttrium aluminate in step S3 to the second powder in step S2 is (10-15):(85-90); And / or, the particle size of the yttrium aluminate in step S3 is 300-500 nm; And / or, the volume ratio of the anhydrous ethanol and the third organic solvent in step S3 is (95-97):(3-5); And / or, the curing temperature in step S3 is 80-100° C. and the curing time is 12 hours; 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 bleaching 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 in step S5 is one or more of an alkyl acrylate photosensitive resin, a hydroxy acrylate photosensitive resin, and an acrylamide photosensitive resin with a cyclic structure; And / or, in step S5, the mass ratio of the silicon carbide powder to the photosensitive resin is (80-90):(10-20).

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

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