CN114230346A - Silicon carbide composite powder for additive manufacturing and preparation method thereof - Google Patents
Silicon carbide composite powder for additive manufacturing and preparation method thereof Download PDFInfo
- Publication number
- CN114230346A CN114230346A CN202111607563.3A CN202111607563A CN114230346A CN 114230346 A CN114230346 A CN 114230346A CN 202111607563 A CN202111607563 A CN 202111607563A CN 114230346 A CN114230346 A CN 114230346A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- powder
- composite
- curing agent
- additive manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of additive manufacturing, and provides silicon carbide composite powder for additive manufacturing and a preparation method thereof, wherein the silicon carbide composite powder comprises 50-99 parts of silicon carbide powder, 1-50 parts of composite binder, 1-5 parts of composite curing agent, 0-40 parts of carbon source and 0-40 parts of solvent by mass, the particle morphology of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is more than or equal to 0.9, and the particle size is 60-250 mu m. According to the invention, the sintering density and mechanical property of the silicon carbide product are improved by controlling the particle size and morphology of the silicon carbide composite powder; by adopting the composite binder, the strength of the 3D printing biscuit is improved, and the probability of damage of the 3D printing product in the manufacturing and transferring processes is reduced; by adopting the composite curing agent, the high-temperature stability of the 3D printing biscuit is improved, the shrinkage of the biscuit in the sintering process is reduced, and the biscuit is prevented from deforming and even collapsing in the sintering process. The silicon carbide composite powder disclosed by the invention is particularly suitable for additive manufacturing of large-size and heavy-weight silicon carbide products.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to silicon carbide composite powder for additive manufacturing and a preparation method thereof.
Background
The silicon carbide ceramic has the excellent performances of strong oxidation resistance, good wear resistance, high hardness, good thermal stability, high-temperature strength, small thermal expansion coefficient, high thermal conductivity, thermal shock resistance, chemical corrosion resistance and the like, can be made into various accessories and devices such as a bearing, a nozzle, an impeller, a sealing element, a cutting tool, a turbine blade, a turbocharger rotor, a reflector and the like, and is suitable for being applied to extreme environments and special working conditions such as high temperature, high pressure, high frequency friction, high radiation, strong acid and strong alkali and the like. However, the advantages of high strength and high hardness of silicon carbide ceramics are the biggest obstacles in the processes of forming and processing devices and accessories. Especially for special-shaped parts with complex structures and shapes, the conventional forming processing mode is difficult to realize, so that the manufacturing of complex silicon carbide ceramic devices is difficult, and the wider and deeper application of the complex silicon carbide ceramic devices is severely restricted.
Additive manufacturing techniques (3D printing techniques) can utilize 3D model data to build objects by connecting materials in a layer-by-layer, stacked, cumulative manner. Therefore, the ceramic part blank with a complex shape can be directly printed and molded by using an additive manufacturing technology, a plurality of complex procedures such as die manufacturing, ceramic machining and the like can be omitted, the manufacturing period is shortened, and the material development and manufacturing cost is reduced. Meanwhile, the additive manufacturing technology has relatively simple forming process and obvious economic benefit, and the ceramic part produced by the additive manufacturing technology has great development prospect.
The additive manufacturing of the silicon carbide composite material can not only give play to the inherent performance advantages of the silicon carbide ceramic, but also realize the manufacture and application of the silicon carbide ceramic in structurization, complication, differentiation and even intellectualization. However, the additive manufacturing technology is an emerging material production processing manufacturing technology, and the related technology and production manufacturing process are not complete. The 3D printing technology for special engineering ceramics, particularly silicon carbide composite materials, is still in the preliminary research stage, and a great deal of blank exists particularly for the ceramic raw material preparation technology suitable for the 3D printing technology. The silicon carbide ceramic powder prepared by the conventional process can be applied to a three-dimensional printing process by introducing the binder. The patent CN 106083061A, a preparation method of laser sintering rapid prototyping silicon carbide ceramics, discloses a powder material prepared by materials such as silicon carbide powder, phenolic resin, carbon black, polyvinyl alcohol and acetone; CN 105837219 a patent discloses a powder material prepared from silicon carbide powder, boron powder, carbon powder and single organic binder. However, the powders prepared by the prior patents and the processes thereof have many drawbacks. For example: the density of the printed biscuit is low, so that the sintered silicon carbide composite material is low in density, poor in mechanical property, incapable of being commercialized and widely applied; the high-temperature stability of the printed biscuit is poor, so that the biscuit is large in shrinkage and easy to deform in the sintering process, and the process stability and quality control of the silicon carbide composite material are not facilitated; the strength of the printed biscuit is low, the biscuit is easy to break in the manufacturing and transferring processes, the biscuit is difficult to carry particularly for large-size and heavy products, the product yield of the silicon carbide composite material is low, and the large-scale production is not facilitated.
Disclosure of Invention
The invention aims at solving the defects of the prior art and provides composite powder for manufacturing a silicon carbide material with high density, high strength and good high-temperature stability by additive manufacturing.
In order to solve the problems, the invention provides silicon carbide composite powder for additive manufacturing, which comprises 50-99 parts of silicon carbide powder, 1-50 parts of composite binder, 1-5 parts of composite curing agent, 0-40 parts of carbon source and 0-40 parts of solvent by mass, wherein the particle morphology of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is more than or equal to 0.9, and the particle size is 60-250 mu m.
Compared with the prior art, the method has the advantages that the loose packing density of the silicon carbide composite powder is favorably improved by controlling the particle size and the morphology of the silicon carbide composite powder, so that the density of single particles of the granulated silicon carbide composite powder is improved, the density of a biscuit of the 3D-printed silicon carbide composite powder is improved, and the sintering density and the mechanical property of the biscuit are finally improved; by adopting the composite binder, the strength of the 3D printing biscuit is greatly improved, and the probability of damage of the 3D printing product in the manufacturing and transferring processes is reduced; by adopting the composite curing agent, the high-temperature stability of the 3D printing biscuit is greatly improved, the shrinkage of the biscuit in the sintering process is reduced, the biscuit is prevented from deforming and even collapsing in the sintering process, and a supporting structure of the biscuit in the printing process can be simplified and even omitted.
Preferably, the silicon carbide powder consists of unimodal or multimodal small-particle size particles, medium-particle size particles and large-particle size particles, wherein the small-particle size particles of the silicon carbide powder range from 0.2 to 2 μm, the medium-particle size particles range from 5 to 20 μm, and the large-particle size particles range from 50 to 200 μm. By adopting the further optimized particle size distribution of the silicon carbide composite powder, the silicon carbide particles with large particle size, medium particle size and small particle size are matched with one another, and the silicon carbide particles with medium particle size and small particle size are filled among the silicon carbide particles with large particle size, so that the biscuit density and the sintering density of the silicon carbide composite powder are improved, and the mechanical property of the final 3D printing product is further improved.
Preferably, in the silicon carbide powder, the small-particle-size particles account for 10-20% of the total mass of the silicon carbide powder, the medium-particle-size particles account for 10-20% of the total mass of the silicon carbide powder, and the large-particle-size particles account for 70-80% of the total mass of the silicon carbide powder. By further optimizing the proportion of large-particle size, medium-particle size and small-particle size particles in the silicon carbide powder, gaps among the large-particle size silicon carbide particles can be more fully filled with the medium-particle size and small-particle size silicon carbide particles, and the biscuit density and the sintering density of the silicon carbide composite powder can be further improved.
Preferably, the composite binder is selected from two or more of epoxy resin, phenolic resin, novolac epoxy resin, furan resin or urea resin. By adopting two or more of epoxy resin, phenolic resin, novolac epoxy resin, furan resin or urea resin as the composite binder, in the 3D printing process, one single binder plays roles in binding powder and strength support under a specific 3D printing process condition, and the other single binder plays roles in binding powder and strength support under another specific 3D printing process condition. Therefore, the silicon carbide composite powder can be fully bonded together under various 3D printing process conditions, the bonding strength is superposed, the strength of the 3D printing biscuit is greatly improved, the probability of damage of the product in the manufacturing and transferring processes is reduced, and the transportation of the biscuit of large-size and heavy-weight products is particularly facilitated. The yield and the qualification rate of the silicon carbide composite material for 3D printing are ensured.
Preferably, the composite curing agent is selected from two or more of acid curing agent, amine curing agent, anhydride curing agent and ester curing agent; the acid curing agent is selected from at least one of oxalic acid, monochloroacetic acid, benzoic acid, phthalic acid and dodecenylsuccinic acid; the amine curing agent is selected from at least one of diethylenetriamine, tetrahydrophthalimide, hexamethylenetetramine and low-molecular polyamide; the acid anhydride curing agent is at least one selected from tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, succinic anhydride and dodecenyl succinic anhydride; the ester curing agent is at least one selected from glycerol methacrylate, dimethyl butene dicarboxylate and diethyl butene dicarboxylate. By adopting two or more of acid curing agent, amine curing agent, anhydride curing agent and ester curing agent as curing agents in the silicon carbide composite material, the requirements of the silicon carbide composite material on the curing agents in different stages of 3D printing, different external conditions (such as illumination or heating) and the like can be met, and the type matching of the proper curing agents can be selected according to different processing process conditions of the 3D printing.
Preferably, the carbon source is selected from at least one of a graphite-based carbon source and an amorphous carbon-based carbon source; the graphite carbon source is selected from at least one of graphite, graphene and graphite alkyne; the amorphous carbon-based carbon source is at least one selected from charcoal, carbon black, activated carbon, coke and sugar char.
Preferably, the solvent is selected from at least one of water, methanol, ethanol, acetone, ethylene glycol, xylene, ethyl acetate, petroleum ether.
The invention also discloses a preparation method of the silicon carbide composite powder for additive manufacturing, which comprises the following steps:
s1, weighing: weighing silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent according to set mass;
s2, premixing: putting the silicon carbide powder and the carbon source in the step S1 into a mixer, mixing for 2-5h, and heating the materials to 120-150 ℃ at the speed of 1 ℃/min in the premixing process;
s3, mixing: adding the composite binder and the solvent in the step S1 into the mixer in the step S2, continuously mixing for 4-9h at the medium mixing temperature of 120-150 ℃, and then naturally reducing the temperature to 90-110 ℃;
s4, final mixing: adding the composite curing agent obtained in the step S1 into the mixer obtained in the step S3, continuously mixing for 8-12 hours at the final mixing temperature of 90-110 ℃, and naturally reducing the temperature to room temperature to obtain mixed slurry;
s5, granulating: drying and crushing or spraying and granulating the mixed slurry obtained in the step S4 to obtain silicon carbide composite powder for additive manufacturing; the working temperature adopted by the spray granulation is 60-110 ℃.
The preparation method of the silicon carbide composite powder for additive manufacturing adopts main process flows of premixing, middle mixing, final mixing and granulation, and can select corresponding mixing temperature and mixing time according to the characteristics of different raw materials; premixing, so that the silicon carbide powder with various sizes and a carbon source are fully and uniformly mixed; the silicon carbide powder and the carbon source which are uniformly mixed are wrapped by the binder at a specific mixing temperature and time to form a pseudo aggregate; final mixing, namely introducing a curing agent at a lower temperature, and fully and uniformly mixing the curing agent and the pseudo aggregate; granulating to optimize and improve the appearance of the mixed powder, obtaining powder with inconsistent particle size after granulation, and mixing the powder with multi-particle size distribution, thereby being beneficial to improving the bulk density of the powder and improving the fluidity of the powder; and further improve the density of the 3D printing silicon carbide composite material biscuit.
In conclusion, the silicon carbide composite powder for additive manufacturing disclosed by the invention has the advantages of high density of the blank after 3D printing, high strength of the blank, good stability of the blank, small shrinkage and small high-temperature deformation in the sintering process, and the sintered silicon carbide composite material has the advantages of high density, strong mechanical property, excellent overall performance and huge application prospect. Particularly for large-size and heavy-weight silicon carbide products, the silicon carbide composite powder for additive manufacturing disclosed by the invention can meet the high requirements of biscuit on indexes such as strength, stability, sintering shrinkage and deformation. Meanwhile, the preparation method of the composite powder for the additive manufacturing of the silicon carbide material adopts specific process steps, so that different raw materials can be fully and uniformly mixed, the composite binder and the composite curing agent cannot lose effectiveness due to advanced reaction, and the preparation method is a high-quality and high-efficiency preparation method, is suitable for large-scale production and has wide development space.
Drawings
Fig. 1 is a pictorial view of a silicon carbide composite powder for additive manufacturing prepared in example 4.
FIG. 2 is a schematic representation of a large-size complex-structured silicon carbide product prepared in example 5.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
The embodiment provides silicon carbide composite powder for additive manufacturing, which comprises silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent, wherein the mass part ratio of the silicon carbide powder to the composite binder to the composite curing agent to the carbon source to the solvent is 50:1:3:20:10, the particle morphology of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is greater than or equal to 0.9, and the particle size is 60-200 mu m.
The embodiment also provides a preparation method of the silicon carbide composite powder for additive manufacturing, which comprises the following specific steps:
s1, weighing: weighing various raw materials according to the mass part ratio of silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent of 50:1:3:20: 10;
wherein the silicon carbide powder is weighed according to the proportion that small-particle-size particles account for 20 percent of the total mass of the silicon carbide powder, medium-particle-size particles account for 10 percent of the total mass of the silicon carbide powder, and large-particle-size particles account for 70 percent of the total mass of the silicon carbide powder;
the composite binder is prepared by mixing epoxy resin, phenolic epoxy resin and urea resin according to the mass ratio of 1:1:1: 1;
wherein the composite curing agent is prepared by mixing benzoic acid, diethylenetriamine and methyl tetrahydrophthalic anhydride according to the mass ratio of 1:1: 1;
wherein the carbon source is formed by mixing graphite and charcoal according to the mass ratio of 1: 1;
wherein the solvent is water and acetone in a ratio of 2: 1;
s2, premixing: putting the silicon carbide powder and the carbon source weighed in the step S1 into a mixer, mixing for 3h, and heating the materials to 130 ℃ at the speed of 1 ℃/min in the premixing process;
s3, mixing: adding the compounded binding agent and the solvent weighed in the step S1 into a mixer, continuously mixing for 7 hours at the mixing temperature of 130 ℃, and then self-heating to reduce the temperature to 105 ℃;
s4, final mixing: adding the compound curing agent weighed and prepared in the step S1 into a mixer, continuously mixing for 10 hours at the final mixing temperature of 105 ℃, and naturally reducing the temperature to room temperature to obtain sand-yellow mixed slurry;
s5, granulating: and S4, drying and crushing the mixed slurry, sieving with a 60-mesh sieve, and taking the sieved product to obtain the silicon carbide composite powder for additive manufacturing.
Example 2
The embodiment provides silicon carbide composite powder for additive manufacturing, which comprises silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent, wherein the silicon carbide powder, the composite binder, the composite curing agent, the carbon source and the solvent are mixed according to the mass part ratio of 50:50:5:5:40, the particle morphology of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is greater than or equal to 0.9, and the particle size is 100-250 mu m.
The embodiment also provides a preparation method of the silicon carbide composite powder for additive manufacturing, which comprises the following specific steps:
s1, weighing: weighing various raw materials according to the mass part ratio of silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent of 50:50:5:5: 40;
wherein the silicon carbide powder is weighed according to the proportion that small-particle-size particles account for 10 percent of the total mass of the silicon carbide powder, medium-particle-size particles account for 10 percent of the total mass of the silicon carbide powder, and large-particle-size particles account for 80 percent of the total mass of the silicon carbide powder;
wherein the composite binder is formed by mixing phenolic resin and furan resin according to the mass ratio of 1: 1;
wherein the composite curing agent is formed by mixing low molecular polyamide and dimethyl butene diformate according to the mass ratio of 1: 1;
wherein the carbon source is formed by mixing graphite and carbon black according to the mass ratio of 1: 1;
wherein the solvent is ethyl acetate and hydrolysate, and the proportion of ethyl acetate to hydrolysate is 2: 1.
S2, premixing: putting the silicon carbide powder and the carbon source weighed in the step S1 into a mixer, mixing for 5 hours, and heating the materials to 150 ℃ at the speed of 1 ℃/min in the premixing process;
s3, mixing: adding the compounded binding agent and the solvent weighed in the step S1 into a mixer, continuously mixing for 9 hours at the medium mixing temperature of 150 ℃, and then self-heating to reduce the temperature to 110 ℃;
s4, final mixing: adding the compound curing agent weighed and prepared in the step S1 into a mixer, continuously mixing for 8 hours at the final mixing temperature of 110, and naturally reducing the temperature to room temperature to obtain brown mixed slurry;
s5, granulating: and S4, performing spray granulation on the mixed slurry at the working temperature of 110 ℃ to obtain the silicon carbide composite powder for additive manufacturing.
Example 3
The embodiment provides silicon carbide composite powder for additive manufacturing, which comprises silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent, wherein the mass part ratio of the silicon carbide powder to the composite binder to the composite curing agent to the carbon source to the solvent is 99:20:1:40:0, the particle morphology of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is greater than or equal to 0.9, and the particle size is 80-250 micrometers.
The embodiment also provides a preparation method of the silicon carbide composite powder for additive manufacturing, which comprises the following specific steps:
s1, weighing: weighing various raw materials according to the mass part ratio of the silicon carbide powder, the composite binder, the composite curing agent and the carbon source of 99:20:1: 40;
wherein the silicon carbide powder is weighed according to the proportion that small-particle-size particles account for 10 percent of the silicon carbide powder, medium-particle-size particles account for 15 percent of the total mass of the silicon carbide powder, and large-particle-size particles account for 75 percent of the total mass of the silicon carbide powder;
wherein the composite binder is prepared by mixing epoxy resin, phenolic resin and urea-formaldehyde resin according to the mass ratio of 1:1: 1;
wherein the composite curing agent is prepared by mixing oxalic acid, hexamethylenetetramine and succinic anhydride according to the mass ratio of 1:1: 1;
wherein the carbon source is carbon black;
s2, premixing: putting the silicon carbide powder and the carbon source weighed in the step S1 into a mixer, mixing for 2h, and heating the materials to 120 ℃ at the speed of 1 ℃/min in the premixing process;
s3, mixing: adding the compounded binding agent and the solvent weighed in the step S1 into a mixer, continuously mixing for 4 hours at the medium-mixing temperature of 120 ℃, and then self-heating to reduce the temperature to 90 ℃;
s4, final mixing: adding the compound curing agent weighed and prepared in the step S1 into a mixer, continuously mixing for 12 hours at the final mixing temperature of 90 ℃, and naturally reducing the temperature to room temperature to obtain dark green mixed slurry;
s5, granulating: and S4, drying and crushing the mixed slurry, sieving with a 60-mesh sieve, and taking the sieved product to obtain the silicon carbide composite powder for additive manufacturing.
Example 4
The embodiment provides silicon carbide composite powder for additive manufacturing, which comprises silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent, wherein the mass part ratio of the silicon carbide powder to the composite binder to the composite curing agent to the carbon source to the solvent is 75:15:2:10:15, the particle morphology of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is greater than or equal to 0.9, and the particle size is 60-250 micrometers.
The embodiment also provides a preparation method of the silicon carbide composite powder for additive manufacturing, which comprises the following specific steps:
s1, weighing: weighing various raw materials according to the mass part ratio of silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent of 75:15:2:10: 15;
wherein the silicon carbide powder is weighed according to the proportion that small-particle-size particles account for 15 percent of the total mass of the silicon carbide powder, medium-particle-size particles account for 10 percent of the total mass of the silicon carbide powder, and large-particle-size particles account for 75 percent of the total mass of the silicon carbide powder.
The composite adhesive is prepared by mixing epoxy resin, phenolic resin and novolac epoxy resin according to the mass ratio of 1:1: 1;
wherein the composite curing agent is formed by mixing phthalic acid and diethylenetriamine according to the mass ratio of 1: 1;
wherein the carbon source is graphite;
wherein the solvent is ethanol;
s2, premixing: putting the silicon carbide powder and the carbon source weighed in the step S1 into a mixer, mixing for 3h, and heating the materials to 130 ℃ at the speed of 1 ℃/min in the premixing process;
s3, mixing: adding the prepared composite binder and the solvent weighed in the step S1 into a mixer, continuously mixing for 6 hours at the medium mixing temperature of 130 ℃, and then self-heating and reducing the temperature to the final mixing temperature of 100 ℃;
s4, final mixing: adding the compound curing agent weighed and prepared in the step S1 into a mixer, continuously mixing for 10 hours at the final mixing temperature of 100 ℃, and naturally reducing the temperature to room temperature to obtain grey-black mixed slurry;
s5, granulating: and S4, performing spray granulation on the mixed slurry at the working temperature of 85 ℃ to obtain the silicon carbide composite powder for additive manufacturing.
The green density and sintered density of the silicon carbide composite powder provided in this example are shown in table 1, and the morphology of the silicon carbide composite powder is shown in fig. 1.
Example 5
In this embodiment, the silicon carbide composite powder for additive manufacturing produced and prepared in embodiment 4 is conveyed to a 3D printing device, and is subjected to main processes such as three-dimensional drawing design introduction, 3D printing, sintering and the like, so that a large-size silicon carbide product with a complex structure is finally obtained, mass production is realized, a blank support structure is not required in the 3D printing process, and the prepared large-size silicon carbide product with a complex structure is a real object as shown in fig. 2, which is not deformed under a high-temperature condition.
The green density and sintered density of the 3D printed silicon carbide product are shown in Table 1, with a green density of 1.41 g-cm-3The biscuit has high strength and can be transferred by hoisting; no collapse in the sintering process, the sintering shrinkage rate is less than 0.2 percent, and the sintering density is 3.02g cm-3. The silicon carbide composite material product manufactured by the additive produced by the powder material of the invention has excellent comprehensive performance.
Comparative example 1
The difference between this example and example 5 is that the particle size and particle morphology of the silicon carbide composite powder used were not controlled, the particle size of the silicon carbide powder used for preparing the silicon carbide composite powder was not optimized, and the other examples are the same as example 5. Specifically, the particle size of the silicon carbide powder was 13 to 60 μm, and the green density and sintered density of the silicon carbide product provided in this comparative example are shown in table 1.
TABLE 1 biscuit and sintered densities of silicon carbide products prepared in example 5 and comparative example 1
| Density of biscuit g cm-3 | Sintered density g.cm-3 | |
| Comparative example 1 | 1.20 | 2.90 |
| Example 4 | 1.41 | 3.02 |
Comparative example 2
This example is different from example 5 in that the silicon carbide composite powder used contains only one curing agent phthalic acid, and does not contain a composite curing agent, and the other steps are the same as example 5. In the 3D printing process, a blank support structure needs to be adopted, and the prepared silicon carbide product with a large size and a complex structure is easy to deform under a high temperature condition.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (8)
1. The silicon carbide composite powder for additive manufacturing comprises, by mass, 50-99 parts of silicon carbide powder, 1-50 parts of a composite binder, 1-5 parts of a composite curing agent, 0-40 parts of a carbon source and 0-40 parts of a solvent, wherein the particle appearance of the silicon carbide composite powder is spherical or ellipsoidal, the sphericity is greater than or equal to 0.9, and the particle size is 60-250 mu m.
2. The silicon carbide composite powder for additive manufacturing according to claim 1, wherein the silicon carbide powder consists of unimodal or multimodal distribution of small-particle size particles, medium-particle size particles and large-particle size particles, the small-particle size particles of the silicon carbide powder have a particle size of 0.2-2 μm, the medium-particle size particles have a particle size of 5-20 μm, and the large-particle size particles have a particle size of 50-200 μm.
3. The silicon carbide composite powder for additive manufacturing according to claim 2, wherein the small-particle-size particles account for 10 to 20% of the total mass of the silicon carbide powder, the medium-particle-size particles account for 10 to 20% of the total mass of the silicon carbide powder, and the large-particle-size particles account for 70 to 80% of the total mass of the silicon carbide powder.
4. The silicon carbide composite powder for additive manufacturing according to claim 1, wherein the composite binder is selected from two or more of epoxy resin, phenol-formaldehyde epoxy resin, furan resin, and urea-formaldehyde resin.
5. The silicon carbide composite powder for additive manufacturing according to claim 1, wherein the composite curing agent is selected from two or more of an acid curing agent, an amine curing agent, an anhydride curing agent, and an ester curing agent; the acid curing agent is selected from at least one of oxalic acid, monochloroacetic acid, benzoic acid, phthalic acid and dodecenylsuccinic acid; the amine curing agent is selected from at least one of diethylenetriamine, tetrahydrophthalimide, hexamethylenetetramine and low-molecular polyamide; the anhydride curing agent is at least one selected from tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, succinic anhydride and dodecenyl succinic anhydride; the ester curing agent is at least one selected from glycerol methacrylate, dimethyl butene dicarboxylate and diethyl butene dicarboxylate.
6. The silicon carbide composite powder for additive manufacturing according to claim 1, wherein the carbon source is selected from at least one of a graphite-based carbon source and an amorphous carbon-based carbon source; the graphite carbon source is selected from at least one of graphite, graphene and graphite alkyne; the amorphous carbon-based carbon source is at least one selected from charcoal, carbon black, activated carbon, coke and sugar char.
7. The silicon carbide composite powder for additive manufacturing according to claim 1, wherein the solvent is at least one selected from the group consisting of water, methanol, ethanol, acetone, ethylene glycol, xylene, ethyl acetate, and petroleum ether.
8. The method of preparing the silicon carbide composite powder for additive manufacturing of claim 1, comprising the steps of:
s1, weighing: weighing silicon carbide powder, a composite binder, a composite curing agent, a carbon source and a solvent according to set mass;
s2, premixing: putting the silicon carbide powder and the carbon source in the step S1 into a mixer, mixing for 2-5h, and heating the materials to 120-150 ℃ at the speed of 1 ℃/min in the premixing process;
s3, mixing: adding the composite binder and the solvent in the step S1 into the mixer in the step S2, continuously mixing for 4-9h at the medium mixing temperature of 120-150 ℃, and then naturally reducing the temperature to 90-110 ℃;
s4, final mixing: adding the composite curing agent obtained in the step S1 into the mixer obtained in the step S3, continuously mixing for 8-12 hours at the final mixing temperature of 90-110 ℃, and naturally reducing the temperature to room temperature to obtain mixed slurry;
s5, granulating: drying and crushing or spraying and granulating the mixed slurry obtained in the step S4 to obtain silicon carbide composite powder for additive manufacturing; the working temperature adopted by the spray granulation is 60-110 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111607563.3A CN114230346B (en) | 2021-12-27 | 2021-12-27 | Silicon carbide composite powder for additive manufacturing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111607563.3A CN114230346B (en) | 2021-12-27 | 2021-12-27 | Silicon carbide composite powder for additive manufacturing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114230346A true CN114230346A (en) | 2022-03-25 |
| CN114230346B CN114230346B (en) | 2023-03-24 |
Family
ID=80763037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111607563.3A Active CN114230346B (en) | 2021-12-27 | 2021-12-27 | Silicon carbide composite powder for additive manufacturing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114230346B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116409997A (en) * | 2023-01-18 | 2023-07-11 | 潍坊华美智能科技有限公司 | Silicon carbide composite ceramic and preparation method thereof |
| CN115611631B (en) * | 2022-10-21 | 2023-09-08 | 中国科学院上海硅酸盐研究所 | Silicon carbide composite powder and preparation method and application thereof |
| CN116947463A (en) * | 2023-03-16 | 2023-10-27 | 十维(广东)科技有限公司 | High-precision photo-curing 3D printing ceramic slurry and preparation method thereof |
| CN117550898A (en) * | 2023-11-23 | 2024-02-13 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing reaction sintering silicon carbide by using phenolic epoxy resin gel casting |
| CN118561599A (en) * | 2024-08-01 | 2024-08-30 | 中国科学院上海硅酸盐研究所 | A method for strengthening laser 3D printing of SiC blanks based on a dual binder system |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289319A (en) * | 2008-06-03 | 2008-10-22 | 浙江东新密封有限公司 | Reaction sintering silicon carbide ceramic and production method thereof |
| CN104446487A (en) * | 2014-10-31 | 2015-03-25 | 青岛店集润健泽新材料科技有限公司 | Slurry and method for gelcasting pressureless sintered silicon carbide ceramics |
| CN106187195A (en) * | 2016-06-29 | 2016-12-07 | 华中科技大学 | Use the method that selective laser sintering technique prepares silicon carbide ceramics |
| CN107043259A (en) * | 2017-03-17 | 2017-08-15 | 宁波伏尔肯陶瓷科技有限公司 | A kind of reaction sintering silicon carbide ceramic selective laser sintering forming method |
| CN107098714A (en) * | 2017-04-26 | 2017-08-29 | 西安交通大学 | A kind of types of silicon carbide-based ceramics method for manufacturing parts based on 3DP increases material manufacturing technologies |
| CN110698211A (en) * | 2019-11-05 | 2020-01-17 | 宁波伏尔肯科技股份有限公司 | Additive manufacturing silicon carbide ceramic grate and preparation method thereof |
| US20210283801A1 (en) * | 2018-07-04 | 2021-09-16 | Politecnico Di Torino | In situ synthesis, densification and shaping of non-oxide ceramics by vacuum additive manufacturing technologies |
-
2021
- 2021-12-27 CN CN202111607563.3A patent/CN114230346B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289319A (en) * | 2008-06-03 | 2008-10-22 | 浙江东新密封有限公司 | Reaction sintering silicon carbide ceramic and production method thereof |
| CN104446487A (en) * | 2014-10-31 | 2015-03-25 | 青岛店集润健泽新材料科技有限公司 | Slurry and method for gelcasting pressureless sintered silicon carbide ceramics |
| CN106187195A (en) * | 2016-06-29 | 2016-12-07 | 华中科技大学 | Use the method that selective laser sintering technique prepares silicon carbide ceramics |
| CN107043259A (en) * | 2017-03-17 | 2017-08-15 | 宁波伏尔肯陶瓷科技有限公司 | A kind of reaction sintering silicon carbide ceramic selective laser sintering forming method |
| CN107098714A (en) * | 2017-04-26 | 2017-08-29 | 西安交通大学 | A kind of types of silicon carbide-based ceramics method for manufacturing parts based on 3DP increases material manufacturing technologies |
| US20210283801A1 (en) * | 2018-07-04 | 2021-09-16 | Politecnico Di Torino | In situ synthesis, densification and shaping of non-oxide ceramics by vacuum additive manufacturing technologies |
| CN110698211A (en) * | 2019-11-05 | 2020-01-17 | 宁波伏尔肯科技股份有限公司 | Additive manufacturing silicon carbide ceramic grate and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611631B (en) * | 2022-10-21 | 2023-09-08 | 中国科学院上海硅酸盐研究所 | Silicon carbide composite powder and preparation method and application thereof |
| CN116409997A (en) * | 2023-01-18 | 2023-07-11 | 潍坊华美智能科技有限公司 | Silicon carbide composite ceramic and preparation method thereof |
| CN116947463A (en) * | 2023-03-16 | 2023-10-27 | 十维(广东)科技有限公司 | High-precision photo-curing 3D printing ceramic slurry and preparation method thereof |
| CN117550898A (en) * | 2023-11-23 | 2024-02-13 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing reaction sintering silicon carbide by using phenolic epoxy resin gel casting |
| CN118561599A (en) * | 2024-08-01 | 2024-08-30 | 中国科学院上海硅酸盐研究所 | A method for strengthening laser 3D printing of SiC blanks based on a dual binder system |
| CN118561599B (en) * | 2024-08-01 | 2024-12-03 | 中国科学院上海硅酸盐研究所 | A method for strengthening laser 3D printing of SiC blanks based on a dual binder system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114230346B (en) | 2023-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114230346B (en) | Silicon carbide composite powder for additive manufacturing and preparation method thereof | |
| CN110128129B (en) | Preparation method of low-loss garnet ferrite material | |
| CN101245227B (en) | A kind of epoxy conductive silver glue for LED and manufacture method thereof | |
| CN102875137A (en) | Tape casting slurry for laminated sheet type electronic component and preparation method for tape casting slurry | |
| CN103769586A (en) | Metal 3D printing product production method by means of low-power laser sintering | |
| CN105503191A (en) | Method for preparing boron carbide spray granulation powder | |
| CN107417280A (en) | A kind of normal pressure-sintered boron carbide ceramics preparation method | |
| CN113999019B (en) | Preparation method of silicon nitride ceramic granulation powder | |
| CN113354787B (en) | Environment-friendly furan resin for 3D sand mold printing and preparation method thereof | |
| CN1937097A (en) | Technology for making nuclear fuel element core by external gelatinization method | |
| CN102533071A (en) | Insulating paint for motor elements and electronic products | |
| CN115650728A (en) | Preparation method of graphite for single crystal thermal field | |
| CN104961471A (en) | Cast film slurry of ultrathin lamination flaky inductor and manufacturing method for cast film of ultrathin lamination flaky inductor | |
| CN107216155A (en) | Double film coated ceramic powders of a kind of PF/PVA for laser 3D printing/isostatic cool pressing composite molding and preparation method thereof | |
| CN101824157A (en) | Method for modifying cyanate ester resin by hydroxyl-terminated polybutadiene | |
| CN102151824A (en) | Method for preparing coarse particle molybdenum powder by preliminary compression granulation | |
| CN103627918A (en) | High-density boron carbide composite material and preparation method thereof | |
| CN103881611A (en) | Normal temperature conductive adhesive and preparation method thereof | |
| CN103691956A (en) | Preparation Technology of Annular Thin-Walled Al-NpO2 Dispersion Pellets | |
| CN105810812B (en) | A kind of assemble method of spherical high-temperature phase transition heat storage element and the heat accumulation element being consequently formed | |
| CN111875730B (en) | High-performance solid buoyancy material and preparation method thereof | |
| CN114478012A (en) | Carbon part manufacturing method and carbon part manufactured by same | |
| CN110921648A (en) | One-step preparation method of light high-strength microspheric phenolic resin-based carbon foam | |
| CN111499386A (en) | Composite ceramic material and preparation method thereof | |
| CN108948301A (en) | A kind of modification triethylamine cold box resin that moisture resistance is good and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |