Method for producing a ceramic-based composite material reinforced with metal particles
A method combining specific mixing and stereolithography printing with sintering produces a uniformly dispersed ceramic-metal composite with high density and mechanical strength, addressing the challenges of traditional fabrication techniques.
Patent Information
- Application Number
- JP2024565043
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2022-07-07
- Filing Date
- 2023-07-07
- Publication Date
- 2025-07-15
AI Technical Summary
Existing methods for producing ceramic-metal composites struggle with forming complex shapes and large dimensions due to the need for molds, high pressure, and non-uniform density, while 3D stereolithography is susceptible to oxygen inhibition and light scattering, leading to inhomogeneous products.
A method involving mixing specific ratios of ceramic powder, metal powder, organic monomers, solvent, and photoinitiator, followed by degassing and stereolithography printing, then sintering to produce a uniformly dispersed ceramic-metal composite with high density and mechanical strength.
The method achieves a ceramic-metal composite with uniform metal dispersion, high density, and excellent mechanical properties without molds, overcoming the limitations of traditional methods.
Smart Images
Figure 2025522264000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a method for manufacturing a ceramic-based composite material reinforced with metal particles by stereolithography (SLA) belonging to 3D printing technology.
Background Art
[0002] The biggest drawback of ceramic materials is their brittleness. To solve this problem, metal particles are introduced into the ceramic matrix to form a ceramic-metal composite material. The main advantage of the composite material over single-phase ceramics is its higher fracture toughness, which improves depending on the type, amount, particle size, and shape of the metal particles used. The metal phase can further affect the physical, mechanical, and thermal properties of the composite material (M. Chmielewski, J. Dutkiewicz, D. Kalinski, L. Litynska-Dobrzynska, K. Pietrzak, A. Strojny-Nedza, "Microstructure and properties of hot-pressed molybdenum-alumina composites," Archives of Metallurgy and Materials, 57, (3), pp. 686-693, 2015).
[0003] A ceramic-based composite material reinforced with metal particles is hereinafter referred to as a ceramic-metal composite. However, it should be noted that in the scientific literature related to this subject, metal-based composite materials reinforced with ceramic phases in the form of particles or fibers may also be referred to as ceramic-metal composites, or metal-ceramic composites. Due to their properties, ceramic-based composite materials reinforced with metal particles are used in numerous applications in various industries such as construction, transportation, and electronic devices as anti-rust coatings, thermal spray coatings, and orthopedic implants (K. Konopka, Particle-Reinforced Ceramic Matrix Composites - Selected Examples, "Journal of Composites Science, 6, (6), 2022).
[0004] There are several methods for fabricating ceramic-metal composites. One of them is the method of forming a ceramic-metal composite from powders. In this method, in the first stage, ceramic powders are mixed with metal powders or their oxides to prepare appropriate granules. Next, an additive (binder) is added to improve compressibility. This powder mixture is placed in a mold and compressed axially or isotropically. In the final stage, the compact is sintered. This method is generally popular because the process is simple, but the main drawback is that it is very difficult to form products with complex shapes and large dimensions (J. Zygmuntowicz, P. Falkowski, A. Miazga, K. Konopka, "Fabrication and characterization of ZrO2 / Ni composites," Journal of the Australian Ceramic Society, 54, (4), pp. 655 - 662, 2018). Furthermore, it is necessary to use high pressure, and the generally used metal molds wear out in a short period.
[0005] Ceramic-metal composites can also be obtained by a method using a slurry. An example of such a method is the casting molding method, in which a suspension of ceramic particles and metal particles in a solvent with a dispersant added is poured into a porous mold (usually made of gypsum) (M. Gizowska, K. Konopka, M. Szafran, "Properties of water-based slurries for fabrication of ceramic-metal composites by slip casting method", Archives of Metallurgy and Materials, 56, (4), pp. 1105 - 1110, 2011). The solvent diffuses through the pores of the mold by the action of capillary force. After drying, the product is removed from the mold and a sintering process is carried out. The advantage of the casting molding method is that it does not require special equipment, but the disadvantages are that a mold is required, the process takes a long time, and the density of the product is non-uniform.
[0006] In the method of forming a ceramic material, due to the possibility of manufacturing precise and complex elements without using a mold, the interest in the additive manufacturing (AM) method is increasing. The additive manufacturing method can be effectively used both in continuous production and in the manufacture of single and unique elements. Different from conventional forming methods (such as injection molding, casting molding method, gel casting method, etc.), in the additive manufacturing (AM) method, it is not necessary to manufacture an expensive mold. Since the only process required before the printing process is to create a three-dimensional model with CAD (computer-aided design) software, the manufacturing cost of a single element can be significantly reduced.
[0007] The most common 3D printing method is stereolithography. This method involves selectively curing the surface of a ceramic dispersion containing a photocurable resin layer by layer using a light source in the ultraviolet region (F.Doreau, C.Chaput, T.Chartier, "Stereolithography for Manufacturing Ceramic Parts," Advanced Engineering Materials, 2, (8), pp.493-496, 2000). The curing mechanism for each layer is free radical photopolymerization. This reaction occurs rapidly at room temperature but tends to be susceptible to the so-called oxygen inhibition effect.
[0008] A photocurable suspension mainly composed of a mixture of ceramic powder, a solvent, a monomer or an organic monomer, a dispersant, and a photoinitiator is very important in the printing process of the stereolithography method. In order to effectively use the photocurable suspension in this process, it is necessary to meet many requirements. The ceramic particles need to be homogeneously and uniformly dispersed in the photopolymerization medium, and since the printing process takes several hours or, in the case of large products, several days, it is necessary to prevent sedimentation over a long period of time. If the suspension is unstable, the material of the manufactured part will be inhomogeneous, and as a result, anisotropy may occur in the finished product (M.L. Griffith, J.W. Halloran, "Freeform fabrication of ceramics via stereolithography," Journal of the American Ceramic Society, 79, (10), pp. 2601 - 2608, 1996). In the case of a ceramic suspension, rheological properties including viscosity and yield stress also play an important role, so it is very important to optimize the composition of the photocurable dispersion. The higher the volume fraction of the ceramic powder, the lower the shrinkage rate and the higher the density after sintering, resulting in higher mechanical strength. On the other hand, when the proportion of the powder is low, the viscosity of the suspension decreases. Furthermore, the higher the proportion of the ceramic powder in the suspension, the lower the curing depth, that is, the depth through which ultraviolet light can penetrate while supplying sufficient energy to initiate the polymerization reaction. This is related to the light scattering phenomenon by the ceramic particles. Light scattering occurs when the refractive indices (RIs) of two media are different, and it is possible to quantify the scattering of the light beam by the difference in the refractive indices. Depending on the refractive index, the ceramic powder scatters ultraviolet light in different ways. The higher the refractive index, the more scattered light there is and the lower the polymerization depth. The intensity of this phenomenon depends not only on the type and amount of the powder but also on the particle size.Ceramic powders with smaller particle sizes have a larger specific surface area, so stronger scattering is observed (Z.Chen, Z.Li, J.Li, C.Liu, C.Lao, Y.Fu, C.Liu, Y.Li, P.Wang, Y.He, "3D printing of ceramics: A review," Journal of the European Ceramic Society, 39, (4), pp.661-687, 2019). Also, when the refractive index of the suspension does not match the intensity of the light used for curing, the polymerization depth decreases, which may result in a structure with cracks, lower mechanical strength, and a rough surface. Furthermore, the prepared dispersion needs to be homogeneous to maintain the continuity of the ceramic phase in the polymerized product. Lack of homogeneity may cause cracks to form during sintering (S.A.Rasaki, D.Xiong, S.Xiong, F.Su, M.Idrees, Z.Chen, "Photopolymerization-based additive manufacturing of ceramics: A systematic review," Journal of Advanced Ceramics, 10, (3), pp.442-471, 2021).
[0009] The paper "The fracture properties of metal-ceramic composites manufactured via stereolithography" by Bhargavi Mummaredda et al. (International Journal of Applied Ceramic Technology, 2020;17:413-423) discloses a method for manufacturing metal-ceramic composites by a two-step process. First, ceramic preforms made of a polymer resin containing SiO2 in particular are produced by stereolithography, followed by curing and sintering steps. Next, these test preforms are infiltrated with metal to produce metal-ceramic composites.
Summary of the Invention
Means for Solving the Problems
[0010] An object of the present invention is to develop a method for producing a ceramic-metal composite material having a complex shape, high density, and excellent mechanical properties from a dispersion containing both ceramic particles and metal particles by a single molding process without using a mold.
[0011] An object of the present invention is a method for producing a ceramic-metal composite material reinforced with metal particles, comprising: a) a step of mixing 2 to 15 parts by weight of a solvent with each of 2 to 15 parts by weight of two types of organic monomers and 1 to 5 parts by weight of a photopolymerization initiator based on the total weight of the organic monomers, wherein the photopolymerization initiator is selected from the group consisting of a mixture of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and ethyl (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl; b) a step of adding 0.2 to 5.0 parts by weight of a dispersant, 65 to 90 parts by weight of ceramic powder, and 0.1 to 10.0 parts by weight of metal powder and remixing, wherein the dispersant is selected from the group consisting of a copolymer of polyester and polyamine as a 50% solution in a trichloroethylene-ethanol azeotropic mixture and a copolymer of polyester and polyamine as a 50% solution in 2-butanone; c) a step of mixing and degassing the dispersion obtained in the step; d) a step of printing and forming a product by a 3D stereolithography printer according to a pre-prepared product design; and e) a step of sintering the formed product.
[0012] It is preferable that the step c) is carried out twice.
[0013] Preferably, 2-ethylhexanol is used as the solvent.
[0014] As the organic monomer, it is preferable to use triethylene glycol dimethacrylate and poly(1,3-propylene glycol) dimethacrylate.
[0015] The ceramic powder is preferably selected from the group consisting of Al2O3, ZrO2, and SiO2.
[0016] More preferably, Al2O3 has a particle size in the range of 150 nm to 2 μm.
[0017] More preferably, ZrO2 has a particle size in the range of 40 nm to 2 μm.
[0018] More preferably, SiO2 has a particle size in the range of 100 nm to 1.5 μm.
[0019] The metal powder is preferably selected from the group consisting of nickel and molybdenum.
[0020] The metal powder preferably has a particle size in the range of 3 μm to 15 μm.
[0021] The mixing step is preferably carried out at a rotational speed of 200 rpm to 400 rpm for 30 minutes to 120 minutes using a planetary ball mill.
[0022] The degassing step is preferably carried out at a rotational speed of 500 rpm to 2200 rpm for 1 minute to 15 minutes using a high-speed homogenizer.
[0023] The printing and forming step is preferably carried out using parameters consisting of a single-layer height in the range of 0.01 mm to 0.05 mm, a reference printing time in the range of 10 seconds to 60 seconds, an adhesion time in the range of 10 seconds to 60 seconds, and a light intensity in the range of 50% to 100%.
[0024] The sintering step is preferably carried out at a temperature of 1350°C to 1650°C for 1 to 5 hours in an argon-hydrogen reducing atmosphere.
[0025] As shown in the examples, in the method according to the present invention, by using a printing method of a 3D stereolithography method, it is possible to obtain a ceramic-metal composite material in which metal particles are uniformly dispersed in a ceramic matrix. This can be observed by an image of a scanning electron microscope equipped with an EDS detector (Fig. 1).
[0026] The suspension used for forming was characterized by having appropriately low viscosity and yield point. Further, these suspensions were rheologically stable and no precipitation was observed. After irradiation with a UV lamp, the dispersion was photopolymerized, and the obtained curing depth was suitable for printing by the stereolithography method.
[0027] The printed molded body reproduced well the previously prepared design in terms of both shape and size. The product after sintering was characterized by having very good compressibility (almost 100% of the theoretical density during non-pressure sintering), which had a favorable effect on the mechanical properties.
Brief Description of the Drawings
[0028] The present invention is shown in the following drawings.
Figure 1
Mode for Carrying Out the Invention
[0029] The subject matter of the present invention will be described in detail in the following examples.
Examples
[0030] A ceramic dispersion was prepared. As the ceramic powder, with a density of 3.98 g / cm 3, 35.82 g (equivalent to 45% by volume and 77.18 parts by weight of the solid phase) of alumina (Al2O3) with an average particle size of 150 nm (trade name: TM-DAR, Dainippon Chemical Industry Co., Ltd., Japan) was used. As the metal phase, the density is 8.71 g / cm 3 , 0.8711 g of nickel (Ni) powder with an average particle size of 9.3 μm (Createc, Poland) in the form was introduced. As the monomers, two types were used: 3.53 g of triethylene glycol dimethacrylate and 3.53 g of poly(1,3-propylene glycol) dimethacrylate. As the solvent, 3.53 g of 2-ethylhexanol was used, and as the dispersant, 1.07 g of a copolymer of polyester and polyamine (trade name: KD1) as a 50% solution in a trichloroethylene-ethanol azeotropic mixture was used. As the photoinitiator, 0.21 g of the compound Omnirad 2100 (trade name), which is a mixture of ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate and bis-(2,4,6 trimethylbenzoyl)phenylphosphine oxide, was used.
[0031] A mixture of monomer, solvent, and photoinitiator was mixed by a Retsch PM200 planetary ball mill at 300 rpm for 15 minutes. Next, a dispersant, ceramic powder, and metal powder were added. After mixing the dispersion in the mill at 300 rpm for 30 minutes, the mixing speed was increased to 350 rpm and mixing was continued for an additional 15 minutes. Next, the suspension was placed in a Thinky ARE-250 high-speed homogenizer to simultaneously mix and degas the suspension. The dispersion was mixed at 800 rpm for 2 minutes and then degassed at 1800 rpm for 2 minutes to remove bubbles. This cycle was performed twice. In the next step, after preparing the design with Autodesk Fusion 360 graphic software and selecting the printing parameters, a cylindrical product was fabricated by stereolithography printing using a FlashForge Hunter printer. The height of a single layer was 0.02 mm, the reference printing time was 20 seconds, the adhesion time was 30 seconds, the number of layers was 250, and the light intensity was 65%. The sample was sintered at 1550 °C in an argon-hydrogen reduction atmosphere (heated to 1550 °C at a heating rate of 5 °C / min, maintained at 1550 °C for 1 hour, and cooled to room temperature at a rate of 5 °C / min).
[0032] The dispersion of the sample had a viscosity of approximately 11 Pa·s (Pascal seconds) at a shear rate of 1 s -1 and a viscosity of approximately 0.8 Pa·s at a shear rate of 50 s -1 a yield point of approximately 9.0 Pa, and a curing depth of 0.15 mm. With the obtained parameters, a green body could be fabricated by stereolithography printing.
[0033] A homogeneous sample with a relative density of 63.8% was obtained in the state of the green body. No defects were observed on the surface of the sample. The relative density of the sintered sample was 98.7%. Analysis of the microstructure of the sample showed that the alumina (Al2O3) matrix was sufficiently densified and the nickel particles were uniformly dispersed in the matrix.
Example
[0034] A ceramic dispersion was prepared. As the ceramic powder, with a density of 3.98 g / cm 3, 35.82 g (equivalent to 45% by volume and 77.18 parts by weight of the solid phase) of alumina (Al2O3) with an average particle size of 150 nm (trade name: TM-DAR, Dainippon Chemical Industry Co., Ltd., Japan) was used. As the metal phase, the density was 9.81 g / cm 3 , 0.9814 g of molybdenum (Mo) powder in the form of an average particle size of 13.4 μm (Createc, Poland) was introduced. As the monomers, two types were used: 3.53 g of triethylene glycol dimethacrylate and 3.53 g of poly(1,3-propylene glycol) dimethacrylate. As the solvent, 3.53 g of 2-ethylhexanol was used, and as the dispersant, 1.07 g of a copolymer of polyester and polyamine (trade name: KD1) as a 50% solution in a trichloroethylene-ethanol azeotropic mixture was used. As the photoinitiator, 0.21 g of the compound Omnirad 2100 (trade name), which is a mixture of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinic acid ethyl and bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, was used.
[0035] A mixture of a monomer, a solvent, and a photoinitiator was mixed by a Retsch PM200 planetary ball mill at 300 rpm for 15 minutes. Next, a dispersant, ceramic powder, and metal powder were added. After the dispersion was mixed in the mill at 300 rpm for 30 minutes, the mixing speed was increased to 350 rpm and mixing was continued for an additional 15 minutes. Next, the suspension was placed in a Thinky ARE-250 high-speed homogenizer, and mixing and degassing of the suspension were performed simultaneously. The dispersion was mixed at 800 rpm for 2 minutes and then degassed at 1800 rpm for 2 minutes to remove bubbles. This cycle was performed twice. In the next step, after preparing the design with Autodesk Fusion 360 graphic software and selecting the printing parameters, a cylindrical product was fabricated by stereolithography printing using a FlashForge Hunter printer. The height of a single layer was 0.02 mm, the reference printing time was 20 seconds, the adhesion time was 30 seconds, the number of layers was 250 layers, and the light intensity was 65%. The test specimens were sintered at 1550 °C in an argon-hydrogen reduction atmosphere (heated to 1550 °C at a heating rate of 5 °C / min, maintained at 1550 °C for 1 hour, and cooled to room temperature at a rate of 5 °C / min).
[0036] The dispersion of the test specimens had a viscosity of approximately 11 Pa·s (Pascal seconds) at a shear rate of 1 s -1 and a viscosity of approximately 0.8 Pa·s at a shear rate of 50 s -1 a yield point of approximately 9.5 Pa, and a curing depth of 0.17 mm. With the obtained parameters, a molded body could be fabricated by stereolithography printing.
[0037] A homogeneous sample with a relative density of 61.2% was obtained in the state of the molded body. No defects were observed on the surface of the sample. The relative density of the sintered sample was 99.6%. Analysis of the microstructure of the sample showed that the alumina (Al2O3) matrix was sufficiently densified and the molybdenum particles were uniformly dispersed in the matrix.
[0038] Comparative Example 1 A ceramic dispersion was prepared. As the ceramic powder, a density of 3.98 g / cm 3, 35.82 g (equivalent to 45% by volume and 77.18 parts by weight of the solid phase) of alumina (Al2O3) with an average particle size of 150 nm (trade name: TM-DAR, Daimyo Chemical Industry Co., Ltd., Japan) was used. As the metal phase, with a density of 9.81 g / cm 3 , 0.9814 g of molybdenum (Mo) powder in the form of an average particle size of 13.4 μm (Createc, Poland) was introduced. As monomers, two types were used: 3.53 g of triethylene glycol dimethacrylate and 3.53 g of poly(1,3-propylene glycol) dimethacrylate. As the solvent, 3.53 g of 2-ethylhexanol was used, and as the dispersant, 1.07 g of a copolymer of polyester and polyamine (trade name: KD1) as a 50% solution in a trichloroethylene-ethanol azeotropic mixture was used. As the photoinitiator, 0.21 g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (trade name: Irgacure 2959) was used.
[0039] The mixture of monomer, solvent, and photoinitiator was mixed at 300 rpm for 15 minutes using a Retsch PM200 planetary ball mill. Next, the dispersant, ceramic powder, and metal powder were added. After mixing the dispersion at 300 rpm for 30 minutes with the mill, the mixing speed was increased to 350 rpm and mixing was continued for an additional 15 minutes. Next, the suspension was placed in a Thinky ARE-250 high-speed homogenizer, and mixing and degassing of the suspension were performed simultaneously. After mixing the dispersion at 800 rpm for 2 minutes, it was degassed at 1800 rpm for 2 minutes to remove bubbles. This cycle was performed twice.
[0040] In the next step, after preparing the design with Autodesk Fusion 360 graphic software, an attempt was made to produce a cylindrical product by stereolithography printing using a FlashForge Hunter printer. After irradiating the first layer of the dispersion, it was observed that it did not cure, so further 3D printing was impossible.
[0041] Comparative Example 2 A ceramic dispersion was prepared. As the ceramic powder, 35.82 g (equivalent to 45% by volume of the solid phase and 77.18 parts by weight) of alumina (Al2O3) (trade name: TM-DAR, Dainippon Chemical Industry Co., Ltd., Japan) with a density of 3.98 g / cm 3 and an average particle size of 150 nm was used. As the metal phase, 0.8711 g of nickel (Ni) powder in the form of (Createc, Poland) with a density of 8.71 g / cm 3 and an average particle size of 9.3 μm was introduced. As the monomers, 3.53 g of triethylene glycol dimethacrylate and 3.53 g of dimethacrylate poly(1,3-propylene glycol) were used. As the solvent, 3.53 g of 2-ethylhexanol was used, and as the dispersant, 0.1075 g of diammonium hydrogen citrate was used. As the photoinitiator, 0.21 g of a compound of Omnirad 2100 (trade name), which is a mixture of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, was used.
[0042] A mixture of the monomers, solvent, and photoinitiator was mixed at 300 rpm for 15 minutes using a Retsch PM200 planetary ball mill. Next, the dispersant, ceramic powder, and metal powder were added. After mixing the bulk at 300 rpm for 30 minutes with the mill, the mixing speed was increased to 350 rpm and mixing was continued for an additional 15 minutes. Next, the suspension was placed in a Thinky ARE-250 high-speed homogenizer, and mixing and degassing of the suspension were performed simultaneously. After mixing the bulk at 800 rpm for 2 minutes, it was degassed at 1800 rpm for 2 minutes to remove bubbles. This cycle was performed twice.
[0043] In the next step, after preparing the design in Autodesk Fusion 360 graphics software, an attempt was made to produce a cylindrical product by stereolithography printing using a FlashForge Hunter printer. The suspension was characterized by being too viscous (having a paste-like consistency) and was not even able to fill the gap between the bottom of the cuvette and the platform on which the subsequent layers of the product were formed. Therefore, it was not possible to produce the composite using stereolithography printing.
[0044] Comparative Example 3 A ceramic dispersion was prepared. The ceramic powder had a density of 3.98 g / cm. 3 Alumina (Al2O3) with an average particle size of 150 nm (product name: TM-DAR, Taimei Chemical Industry Co., Ltd., Japan) was used in an amount of 35.82 g (equivalent to 45 volume % of the solid phase, or 77.18 parts by weight). 3 0.9814 g of molybdenum (Mo) powder (Createc, Poland) with an average particle size of 13.4 μm was introduced. As monomers, two types were used: 3.53 g of triethylene glycol dimethacrylate and 3.53 g of poly(1,3-propylene glycol) dimethacrylate. As solvent, 3.53 g of 2-ethylhexanol was used, and as dispersant, a copolymer of polyester and polyamine (trade name: KD1) was used in powder form. As photoinitiator, 0.21 g of the compound Omnirad 2100 (trade name), which is a mixture of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, was used.
[0045] A mixture of monomer, solvent, and photoinitiator was mixed by a Retsch PM200 planetary ball mill at 300 rpm for 15 minutes. Next, a dispersant, ceramic powder, and metal powder were added. After the dispersion was mixed in the mill at 300 rpm for 30 minutes, the mixing speed was increased to 350 rpm and mixing was continued for an additional 15 minutes. Next, the suspension was placed in a Thinky ARE-250 high-speed homogenizer, and mixing and degassing of the suspension were performed simultaneously. The dispersion was mixed at 800 rpm for 2 minutes and then degassed at 1800 rpm for 2 minutes to remove bubbles. This cycle was performed twice.
[0046] In the next step, after preparing the design with Autodesk Fusion 360 graphic software, an attempt was made to produce a cylindrical product by stereolithography printing using a FlashForge Hunter printer. The suspension was characterized by being too viscous (having a paste-like consistency) and was unable to even fill the gap between the bottom of the cuvette and the platform on which subsequent layers of the product were to be formed. Therefore, it was not possible to produce the composite material using the stereolithography printing method.
Claims
1. A method for producing a ceramic-based composite material reinforced with metal particles, comprising: a) mixing 2 to 15 parts by weight of a solvent with each of 2 to 15 parts by weight of two types of organic monomers and 1 to 5 parts by weight of a photoinitiator based on the total weight of the organic monomers, wherein the photoinitiator is selected from the group consisting of a mixture of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl ester and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and ethyl (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl ester; the step of mixing; b) adding 0.2 to 5.0 parts by weight of a dispersant, 65 to 90 parts by weight of ceramic powder, and 0.1 to 10.0 parts by weight of metal powder and remixing, wherein the dispersant is selected from the group consisting of a copolymer of polyester and polyamine as a 50% solution in a trichloroethylene-ethanol azeotropic mixture and a copolymer of polyester and polyamine as a 50% solution in 2-butanone; the step of adding and remixing; c) mixing the dispersion obtained in the above step and degassing; d) printing and forming a product with a 3D stereolithography printer according to a pre-prepared product design; e) sintering the formed product A method, characterized by comprising the above steps.
2. The method according to claim 1, characterized in that the step c) is carried out twice.
3. The method according to claim 1, characterized in that 2-ethylhexanol is used as the solvent.
4. The method according to claim 1, characterized in that triethylene glycol dimethacrylate and poly(1,3-propylene glycol) dimethacrylate are used as the organic monomers.
5. In the method according to claim 1, the ceramic powder is selected from the group consisting of Al ２ O ３ and ZrO ２ and SiO ２ and is characterized by being selected from the group consisting of.
6. In the method according to claim 5, Al ２ O ３ has a particle size in the range of 150 nm to 2 μm, the method being characterized thereby.
7. In the method according to claim 5, ZrO ２ is characterized by having a particle size in the range of 40 nm to 2 μm, a method.
8. In the method according to claim 5, SiO ２ has a particle size in the range of 100 nm to 1.5 μm, the method being characterized thereby.
9. The method according to claim 1, characterized in that the metal powder is selected from the group consisting of nickel and molybdenum.
10. The method according to claim 9, characterized in that the metal powder has a particle size in the range of 3 μm to 15 μm.
11. The method according to claim 1, wherein the mixing step is carried out by a planetary ball mill at a rotational speed of 200 rpm to 400 rpm for 30 minutes to 120 minutes.
12. The method according to claim 1, wherein the degassing step is carried out by a high-speed homogenizer at a rotational speed of 500 rpm to 2200 rpm for 1 minute to 15 minutes.
13. The method according to claim 1, wherein the printing formation step is carried out using parameters consisting of a single-layer height in the range of 0.01 mm to 0.05 mm, a reference printing time in the range of 10 seconds to 60 seconds, an adhesion time in the range of 10 seconds to 60 seconds, and a light intensity in the range of 50% to 100%.
14. The method according to claim 1, wherein the sintering step is carried out at a temperature of 1350°C to 1650°C for 1 to 5 hours in an argon-hydrogen reducing atmosphere.