CN112723890B - Preparation method of photocuring ceramic slurry and silicon carbide ceramic - Google Patents
Preparation method of photocuring ceramic slurry and silicon carbide ceramic Download PDFInfo
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Abstract
The application provides a photocuring ceramic slurry which comprises the following raw materials in percentage by mass: SiC @ SiO2Powder: 25% -60%; light-curing resin: 10% -40%; carbon source resin: 10% -40%; photoinitiator (2): 0.1% -2%; dispersing agent: 2 to 6 percent; wherein, SiC @ SiO2The powder comprises a SiC core body and SiO coated on the surface of the SiC core body2A shell layer; the carbon source resin has a carbon residue rate of 40% or more at 800 ℃. SiO 22The shell layer can react with carbon source resin to generate secondary phase SiC in the sintering process while improving the forming efficiency of the photocuring ceramic slurry, thereby reducing/eliminating the introduced SiO2And (4) shell layer. And the rapid manufacturing of the complex and fine SiC ceramic parts is realized through a reaction sintering process. The application also provides a preparation method of the silicon carbide ceramic.
Description
Technical Field
The application relates to the technical field of ceramic additive manufacturing, in particular to a preparation method of photocuring ceramic slurry and silicon carbide ceramic.
Background
The silicon carbide ceramic has the advantages of stable chemical property, good wear resistance, high hardness, high mechanical strength, chemical corrosion resistance and the like, and is widely applied to the fields of aerospace, semiconductors and nuclear industry. Compared with the traditional ceramic preparation process, the photocuring ceramic forming process has the advantages of high forming precision, short forming period, simple process and the like. However, the silicon carbide has strong absorption of ultraviolet light and the refractive index difference between the silicon carbide and the light-cured resin is large, so that the light-cured molding efficiency of the silicon carbide ceramic slurry is low. Therefore, it is necessary to provide a photo-curable ceramic slurry to solve the problem of poor photo-curing performance of the existing silicon carbide ceramic slurry.
Disclosure of Invention
In order to solve the problems, the application provides the photocuring ceramic slurry which has good photocuring forming efficiency, effectively shortens the photocuring forming time of silicon carbide ceramic, and the prepared silicon carbide ceramic has high strength, high density and high precision, so that the rapid manufacturing of complex and fine SiC ceramic parts can be realized. The application also provides a preparation method of the silicon carbide ceramic.
The application provides a photocuring ceramic slurry in a first aspect, which comprises the following raw materials in percentage by mass:
SiC@SiO2powder: 25% -60%;
light-curing resin: 10% -40%;
carbon source resin: 10% -40%;
photoinitiator (2): 0.1% -2%;
dispersing agent: 2 to 6 percent;
the SiC @ SiO2The powder comprises a SiC core body and SiO coated on the surface of the SiC core body2A shell layer; the carbon source resin has a carbon residue rate of 40% or more at 800 ℃.
The application coats SiO on the surface of SiC2The shell layer reduces the absorption of SiC to ultraviolet light, and the formed SiC @ SiO2The powder has lower refractive index, thereby effectively improving the transmission depth of ultraviolet light in the ceramic slurry, reducing the critical exposure energy of the ceramic slurry, increasing the curing thickness of the ceramic slurry in unit time, improving the photocuring efficiency and ensuring that the prepared silicon carbide ceramic has higher precision; the photocuring resin can realize the photocuring of the silicon carbide ceramic through the irradiation of ultraviolet light under the action of a photoinitiator; due to SiO2The introduction of the carbon source resin can reduce the high temperature resistance of the silicon carbide ceramic, and SiO can be eliminated by adding a certain content of carbon source resin2The carbon source resin has high carbon residue rate, and carbon formed by pyrolysis of the carbon source resin can be mixed with SiO in the sintering process of the ceramic2Reaction to form SiC, thereby increasingHigh temperature resistance of the silicon carbide ceramic. The dispersant can promote SiC @ SiO2The powder is uniformly dispersed in the slurry, the powder agglomeration is inhibited, the solid phase content of the slurry is improved, and the shrinkage rate of ceramic sintering is reduced.
Optionally, the SiC core bodies have a particle size of 0.1 μm to 30 μm. Further, the grain size of the SiC nucleus body is 3-20 μm.
Optionally, the SiO2The thickness of the shell layer is 20nm-2000 nm. Further, the SiO2The thickness of the shell layer is 30nm-1000 nm.
Optionally, the SiC @ SiO2The powder comprises a first SiC @ SiO2Powder and second SiC @ SiO2Powder; the first SiC @ SiO2The particle size of the powder is more than 0.1 μm and less than or equal to 5 μm; the second SiC @ SiO2The particle size of the powder is greater than 5 μm and less than or equal to 32 μm.
Optionally, the second SiC @ SiO2Powder and the first SiC @ SiO2The volume ratio of the powders is greater than 0 and less than or equal to 1.
Optionally, the SiC @ SiO2The powder is prepared by a high-temperature oxidation method; the high temperature oxidation process comprises: keeping the temperature of the SiC powder at 800-1200 ℃ for 1-20 h to obtain SiC @ SiO2And (5) crude powder. The SiC @ SiO2The powder crude product is post-processed to obtain SiC @ SiO2And (3) powder.
Optionally, the heating rate of the high-temperature oxidation method is 1 ℃/min-5 ℃/min.
Optionally, the post-treatment comprises crushing and sieving.
Optionally, the crushing comprises grinding, the grinding comprising wet ball milling.
Optionally, the material ball ratio of the wet ball milling is 1: 2-4.
Optionally, the ball milling time of the wet ball milling is 12h-48 h.
Optionally, the solvent for wet ball milling comprises ethanol, and the ethanol and the SiC @ SiO are mixed2The volume ratio of the powder crude product is 1: 1-19.
Optionally, the wet ball milling further comprises addingSilane coupling agent, said SiC @ SiO2The mass ratio of the crude powder to the silane coupling agent is 1: 0.005-0.1.
Optionally, the carbon source resin comprises a phenolic resin.
Optionally, the carbon source resin comprises one or more of novolac epoxy acrylate and benzoxazine.
Optionally, the light-curable resin comprises one or more of trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, and polydihexaacrylate.
Optionally, the photoinitiator comprises one or more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexyl phenyl methanone.
Optionally, the dispersant comprises one or more of an acrylate-based dispersant, a polyurethane-based dispersant, and a polyester-based dispersant.
Optionally, the viscosity of the photocurable ceramic slurry is 1Pa · s to 5Pa · s.
In a second aspect, the present application provides a method for preparing a silicon carbide ceramic, comprising the steps of:
the light-cured ceramic slurry is subjected to light-curing molding to obtain SiC @ SiO2A ceramic body; the light-cured ceramic slurry comprises the following raw materials in percentage by mass:
SiC@SiO2powder: 25% -60%;
light-curing resin: 10% -40%;
carbon source resin: 10% -40%;
photoinitiator (2): 0.1% -2%;
dispersing agent: 2% -6%;
the SiC @ SiO2The powder comprises an SiC nuclear body and SiO coated on the surface of the SiC nuclear body2A shell layer; the carbon source resin has a carbon residue rate of 40% or more at 800 ℃;
the SiC @ SiO2The ceramic body is heated by a program to carbonize the carbon source resin, and thenKeeping the temperature of 1000-1700 ℃ for 2-8h to ensure that SiO is generated2And carbonizing to generate SiC, thereby obtaining the silicon carbide ceramic.
Optionally, the condition of the programmed temperature rise is as follows: heating to 150-220 ℃ at a heating rate of not higher than 3 ℃/min, and keeping the temperature for 1-3 h; heating to 250-380 ℃ at a heating rate of not higher than 3 ℃/min, and keeping the temperature for 1-3 h; heating to 700-900 ℃ at a heating rate of not higher than 3 ℃/min, and preserving heat for 1-3 h.
Optionally, the preparation method further comprises: and mixing the SiC ceramic with silicon particles, and keeping the temperature at 1500-1650 ℃ for 10-60 min to obtain the densified silicon carbide ceramic.
Optionally, the equipment used for the light-curing molding includes any one of a three-dimensional light-curing molding machine and a digital light processing molding machine.
Optionally, when the stereolithography machine is used for stereolithography, the laser power of the stereolithography machine is 0.1w-3w, the scanning speed of the stereolithography machine is 1000mm/s-4000mm/s, and the layering thickness of the stereolithography machine is 10 μm-150 μm.
Optionally, when the digital light processing molding machine is used for performing photocuring molding, the laser power of the digital light processing molding machine is 7mw/cm2-100mw/cm2, the exposure time of the digital light processing molding machine is 1s-90s, and the layering thickness of the digital light processing molding machine is 10 μm-150 μm.
The preparation method of the silicon carbide ceramic provided by the second aspect of the application is simple and convenient to operate, simple in process, short in production period and suitable for industrial mass production; the silicon carbide ceramic with high precision and a complex structure can be prepared by a photocuring molding technology, and the obtained silicon carbide ceramic has high density, good high-temperature resistance and good application prospect.
Drawings
FIG. 1 is a flow chart of a process for preparing a photocurable ceramic slurry according to an embodiment of the present disclosure;
FIG. 2 is a flow chart illustrating a process for preparing a silicon carbide ceramic according to an embodiment of the present disclosure;
FIG. 3 shows SiC @ SiO solid particles obtained in example 1 of the present application2Scanning electron micrographs of the powder;
FIG. 4 shows SiC @ SiO solid particles obtained in example 2 of the present application2Scanning electron micrographs of the powder;
FIG. 5 is a graph comparing the photocuring efficiency tests of the photocuring ceramic slurries of examples 1-2 of the present application and comparative example 1;
FIG. 6 is a graph showing the cured thickness of the photo-curable ceramic pastes according to example 1 and comparative example 1 at an exposure time of 90s, wherein (a) in FIG. 6 is a graph showing the cured thickness of the photo-curable ceramic paste according to comparative example 1 at an exposure time of 90s, and (b) in FIG. 6 is a graph showing the cured thickness of the photo-curable ceramic paste according to example 1 at an exposure time of 90 s;
FIG. 7 is a graph showing the printing effect of photocuring of a photocurable ceramic paste according to example 1 of the present application, wherein FIG. 7 (a) is a three-dimensional model of a ceramic part according to example 4, and FIG. 7 (b) is SiC @ SiO solid of example 42Photo of the ceramic body.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a photocuring ceramic slurry which comprises the following raw materials in percentage by mass:
SiC@SiO2powder: 25% -60%;
light-curing resin: 10% -40%;
carbon source resin: 10% -40%;
photoinitiator (2): 0.1% -2%;
dispersing agent: 2 to 6 percent.
In the embodiment of the present application, SiC @ SiO2The powder comprises SiC core bodies and SiO coated on the surfaces of the SiC core bodies2And (4) shell layer. SiO 22Has a low refractive index, SiO2When the coating is coated on the surface of SiC, the absorption of SiC to ultraviolet light and the photocuring of the ultraviolet light can be effectively reducedThe refractive index difference between the resins improves the transmission depth of ultraviolet light in the slurry and the curing thickness of the ceramic layer in unit time, reduces the critical exposure energy, improves the photocuring performance of the photocuring ceramic slurry, and is beneficial to preparing the silicon carbide ceramic with higher structural precision and high density.
In the embodiment of the present application, the particle diameter of the SiC nucleus body is 0.1 μm to 30 μm. The particle size of the SiC nucleus can be specifically, but not limited to, 0.1. mu.m, 0.5. mu.m, 1. mu.m, 3. mu.m, 5. mu.m, 7. mu.m, 10. mu.m, 15. mu.m, or 30 μm. In the embodiments of the present application, SiO2The thickness of the shell layer is 20nm-2000 nm. SiO 22The thickness of the shell layer may be specifically, but not limited to, 20nm, 30nm, 50nm, 70nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1000nm, 1500nm or 2000 nm. In the embodiment of the application, the grain diameter of the SiC nucleus body and the SiO2The thickness ratio of the shell layers is 1 to (0.01-0.5). In some embodiments of the present application, the SiC core has a particle size and SiO2The thickness ratio of the shell layers is 1: 0.15. Controlling the grain diameter of SiC nucleus body and SiO2The thickness ratio of the shell layer in the above range can ensure SiO2The SiC core body is fully coated, so that the absorption of the SiC to ultraviolet light and the refractive index difference between the silicon carbide and the light curing resin are effectively reduced; and SiO2The content of SiC in the slurry is not influenced too much, and the silicon carbide ceramic is ensured to have higher hardness and high temperature resistance.
In the embodiment of the present application, SiC @ SiO2The particle size of the powder is 0.1-32 μm. In some embodiments of the present application, SiC @ SiO2The powder comprises a first SiC @ SiO2Powder and second SiC @ SiO2Powder of, wherein, first SiC @ SiO2The particle size of the powder is more than 0.1 μm and less than or equal to 5 μm, second SiC @ SiO2The particle size of the powder is greater than 5 μm and less than or equal to 32 μm. In the embodiment of the present application, the second SiC @ SiO2Powder and first SiC @ SiO2The volume ratio of the powders is greater than 0 and less than or equal to 1. By para-SiC @ SiO2The powder is subjected to particle grading to enable the SiC @ SiO with small particle size2The powder is fully filled in the SiC @ SiO with large grain diameter2The silicon carbide ceramic is ensured to have higher density among the powder; and is sinteredIn the process, the grain boundary and pore separation area can be reduced and the sintering temperature can be reduced by adopting grain grading, the abnormal growth of crystal grains can be reduced by reducing the sintering temperature, and the uniform distribution of the ceramic crystal grains is ensured, so that the structural strength of the silicon carbide ceramic is improved.
In the embodiment of the present application, SiC @ SiO2The powder accounts for 25 to 60 percent of the mass of the light-cured ceramic slurry. SiC @ SiO2The powder may be, but is not limited to, 25%, 30%, 40%, 50%, 55%, or 60% by mass of the photocurable ceramic slurry. Control of SiC @ SiO2The content of the powder in the above range can ensure that the photocurable ceramic slurry has a certain solid content and the slurry has good fluidity.
In the present application, the SiC surface is coated with SiO2The high temperature resistance of the silicon carbide ceramic is reduced, and the SiC and the SiO are used2Different thermal expansion coefficient, SiO in long-term use2The layer may separate from the SiC, resulting in cracking of the silicon carbide ceramic and poor structural stability of the ceramic. In order to solve the problems, the carbon source resin is added into the photo-curing ceramic slurry, and the carbon residue rate of the carbon source resin at 800 ℃ is more than or equal to 40%. The carbon source resin can generate carbon, SiC @ SiO through pyrolysis in the sintering process of the silicon carbide ceramic2SiO in powder2Can react with carbon to generate SiC, thereby eliminating SiO introduced by cladding SiC2And the silicon carbide ceramic is ensured to have good high temperature resistance and structural stability.
In the embodiment of the present application, SiC @ SiO2The mass ratio of the powder to the carbon source resin is 1: 0.2-1.6. SiC @ SiO2The mass ratio of the powder to the carbon source resin may specifically be, but not limited to, 1: 0.2, 1: 0.4, 1: 0.5, 1: 0.8, 1:1, 1: 1.3 or 1: 1.6. Control of SiC @ SiO2The mass ratio of the powder to the carbon source resin is within the above range to ensure that the carbon source resin and SiO are sufficiently mixed2Reacting to eliminate SiO in the ceramic body2。
In the application, the density and the structural precision of the silicon carbide ceramic can be improved by adopting the carbon source resin with high carbon residue rate. Specifically, the residual carbon rate of photocuring resin in the photocuring slurry is low, and the photocuring resin can produce more gas holes when being pyrolyzed and lead to the shrinkage of a ceramic blank, and the carbon source resin is added into the photocuring slurry in the photocuring slurry to reduce the curing shrinkage of the ceramic slurry in the sintering process, so that the density and the structural precision of the silicon carbide ceramic are improved. In the embodiment of the present application, the carbon source resin has a carbon residue ratio of 40% or more at 800 ℃. The carbon residue rate of the carbon source resin at 800 ℃ can be more than or equal to 50 percent, or more than or equal to 60 percent, and the higher the carbon residue rate of the carbon source resin is, the more favorable the ceramic part with high compactness and structure precision can be formed. In some embodiments of the present application, the carbon source resin is a phenolic resin. In some embodiments of the present application, the phenolic resin comprises one or more of novolac epoxy acrylate and benzoxazine. In some embodiments of the present application, phenolic resin type 2130 is used as the carbon source resin. In the embodiment of the application, the carbon source resin accounts for 10-40% of the mass of the photocuring ceramic slurry. The carbon source resin may be, but is not limited to, 10%, 20%, 30% or 40% by mass of the photocurable ceramic slurry.
In the application, the photoinitiator can generate free radicals, cations and the like under the irradiation of ultraviolet light, so that the photo-curing resin is catalyzed to be polymerized, crosslinked and cured, and the silicon carbide ceramic blank is cured and molded. In the embodiment of the application, when the structure of the carbon source resin contains an unsaturated functional group, the photoinitiator can also catalyze the carbon source resin to perform polymerization crosslinking curing, so that the photocuring efficiency of the slurry is improved. In some embodiments of the present application, the carbon source resin is novolac epoxy acrylate, and the photoinitiator can catalyze the carbon source resin and the photocurable resin to cure at the same time, so that the silicon carbide ceramic green body is cured and molded. In embodiments herein, the photoinitiator comprises one or more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexyl phenyl methanone. In the embodiment, the light-curable resin includes one or more of trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, and poly (di-hexaacrylate). The photocuring resin can ensure that the ceramic blank after photocuring has higher strength and hardness.
In the embodiment of the application, the mass percentage of the light-cured resin in the light-cured ceramic slurry is 10-40%. The mass percentage of the photocurable resin in the photocurable ceramic slurry may be, but is not limited to, 10%, 20%, 30%, or 40%. The control of the content of the light-cured resin can ensure that the ceramic body after light curing has higher light-curing precision. In the embodiment of the application, the photoinitiator accounts for 0.1-2% of the mass of the photocuring ceramic slurry. In the embodiment of the present application, the mass ratio of the photocurable resin to the photoinitiator is 1: (0.01-0.05). The mass ratio of the photocurable resin to the photoinitiator may specifically be, but not limited to, 1: 0.01, 1: 0.02, 1: 0.03, 1: 0.04, or 1: 0.05. The mass ratio of the light-cured resin to the photoinitiator is controlled, so that the ceramic slurry has moderate light-curing rate, and the finally prepared silicon carbide ceramic has stable performance.
In the application, the addition of the dispersing agent can ensure that SiC @ SiO2The powder is uniformly dispersed in the photocuring ceramic slurry, so that the stability of the ceramic slurry is improved. In the embodiment of the present application, the dispersant may be one or more of an acrylate dispersant, a polyurethane dispersant and a polyester dispersant. In some embodiments of the present application, the dispersant is available under the trademark KY 100. In the embodiment of the application, the dispersant accounts for 2-6% of the mass of the photo-curing ceramic slurry. The dispersant may be, but is not limited to, 2%, 3%, 4%, 5%, or 6% by mass of the photocurable ceramic slurry.
In the embodiment of the present application, the viscosity of the photocurable ceramic slurry is 1 pas-5 pas. The photocuring ceramic slurry has low viscosity and good fluidity, and is favorable for preparing silicon carbide ceramic with high precision and a complex structure.
The photocuring ceramic slurry provided by the application has high photocuring efficiency and good photocuring performance; the components of the photocuring ceramic slurry are uniform, and the stability is good; the silicon carbide ceramic prepared by the photocuring ceramic slurry has high structural precision, and good high-temperature resistance and structural strength.
The application also provides a preparation method of the photocuring ceramic slurry, which comprises the following steps: mixing SiC @ SiO2And uniformly mixing the powder, the light-cured resin, the carbon source resin, the photoinitiator and the dispersant to obtain the light-cured ceramic slurry. In some embodiments of the present application, the mixing process is: mixing SiC @ SiO2And mechanically stirring the powder, the light-cured resin, the carbon source resin, the photoinitiator and the dispersant, and then carrying out ball milling in a planetary ball mill to obtain the light-cured ceramic slurry. In some embodiments of the present application, the time of mechanical stirring is 20 to 40min, the rotational speed of ball milling is 200r/min to 500r/min, and the time of ball milling is 2h to 24 h.
In the embodiment of the present application, SiC @ SiO2The preparation method of the powder comprises a chemical vapor deposition method and a high-temperature oxidation method. In some embodiments of the present application, SiC @ SiO2The powder is prepared by a high-temperature oxidation method, and uniform and compact SiO can be formed on the surface of SiC particles by the high-temperature oxidation method2Layer of, in favor of SiO2The layer completely covers the SiC particles; and SiO2The layer can be tightly combined with SiC, thereby ensuring that the silicon carbide ceramic has good structural stability. In addition, the high-temperature oxidation method has lower cost and is beneficial to industrial production. In the embodiment of the present application, the principle of the high-temperature oxidation method is: under the atmospheric environment and high temperature condition, SiC can perform inactive oxidation reaction with oxygen in the air, thereby generating a layer of compact SiO on the SiC surface2Layer, namely SiC @ SiO2And (3) powder.
In some embodiments of the present application, the process for preparing the photocurable ceramic slurry comprises:
step 100: keeping the temperature of the SiC powder at 800-1200 ℃ for 1-20 h to obtain SiC @ SiO2A crude powder;
step 200: mixing SiC @ SiO2The powder crude product is post-processed to obtain SiC @ SiO2A powder;
step 300: mixing SiC @ SiO2And uniformly mixing the powder, the light-cured resin, the carbon source resin, the photoinitiator and the dispersant to obtain the light-cured ceramic slurry.
Referring to fig. 1, fig. 1 is a flow chart illustrating a process for preparing a photo-curing ceramic slurry according to an embodiment of the present disclosure. Wherein, the step 100 and the step 200 are SiC @ SiO2Preparation of the powder, SiC @ SiO2The powder is prepared by a high temperature oxidation process. In the embodiment of the application, the temperature of the high-temperature oxidation method is 800-1200 ℃, the heating rate of the high-temperature oxidation method is 1-5 ℃/min, and the reaction time of the high-temperature oxidation method is 1-20 h. The temperature of the high-temperature oxidation method may be, but is not limited to, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃. The temperature of the high-temperature oxidation method can be controlled to effectively adjust the SiC @ SiO2SiO in powder2The thickness of the shell layer ensures that the photocuring ceramic slurry has good photocuring performance.
In the application, SiC @ SiO obtained by high-temperature oxidation method2The grain size of the powder crude product is not uniform enough, and SiC @ SiO is needed2The crude powder is post-treated to obtain a good performance light-cured ceramic slurry. In the embodiment of the present application, SiC @ SiO2The work-up of the crude powder involves crushing and sieving. In the embodiment of the application, the equipment used in the crushing process can be one or more of a mechanical impact crusher, a jet mill, a ball mill, a vibration mill and a stirring mill. In some embodiments of the present application, the crushing is by wet ball milling.
In the embodiment of the application, the material ball ratio of the wet ball milling is 1 to (2-4), and the ball milling time of the wet ball milling is 12-48 h. In some embodiments of the present application, the solvent for wet ball milling is ethanol, ethanol and SiC @ SiO2The volume ratio of the powder crude product is 1: 1-19. When ethanol is used as a solvent, SiC @ SiO can be well shortened2The ball milling time of the powder crude product improves the ball milling efficiency. In some embodiments of the present application, a silane coupling agent, SiC @ SiO, is further added during the wet ball milling process2The mass ratio of the powder crude product to the silane coupling agent is 1: 0.005-0.1. The addition of the silane coupling agent in the ball milling process can improve the SiC @ SiO2The dispersibility of the powder in the photocuring ceramic slurry, the viscosity of the ceramic slurry is reduced, and the improvement of SiC @ SiO is facilitated2The structure precision of the ceramic body. Some of the present applicationIn an embodiment, the silane coupling agent has a designation of KH 570. In the embodiment of the application, after wet ball milling is finished, the mixture is filtered and dried to obtain SiC @ SiO2And (3) powder. In some embodiments of the present application, SiC @ SiO2The mesh number used for sieving the powder is 70-100 meshes.
The preparation method of the photocuring ceramic slurry is simple and convenient to operate and suitable for industrial mass production; in the preparation process of the slurry, the high-temperature oxidation method can effectively coat SiO on the SiC surface2Thereby effectively reducing the absorption of the SiC to ultraviolet light and reducing the refractive index difference between the SiC and the light-cured resin; the surface coating SiO can be adjusted by setting the oxidation process parameters2In accordance with SiO2The carbon source resin with proper content is added to control the components of the silicon carbide ceramic, so that the performance of the silicon carbide ceramic is adjusted.
Referring to fig. 2, fig. 2 is a flow chart of a process for preparing a silicon carbide ceramic according to an embodiment of the present disclosure. The preparation method of the silicon carbide ceramic comprises the following steps:
step S1: the light-cured ceramic slurry is subjected to light-curing molding to obtain SiC @ SiO2A ceramic body;
step S2: mixing SiC @ SiO2Heating the ceramic blank in a program to obtain SiC @ SiO2a/C ceramic body;
step S3: mixing SiC @ SiO2And the/C ceramic blank is subjected to heat preservation for 2 to 8 hours at the temperature of between 1000 and 1650 ℃ to obtain the silicon carbide ceramic.
In the embodiment of the present application, step S1 specifically includes: pouring the photocuring ceramic slurry into a trough of photocuring forming equipment, importing model data of a ceramic piece to be prepared, setting processing parameters, and processing by the equipment to obtain SiC @ SiO2A ceramic body. In some embodiments of the present application, the model data of the ceramic part to be prepared is obtained by designing a three-dimensional model of the ceramic part through three-dimensional modeling software and then performing data layering. In the embodiment of the present application, the light-curing molding device includes a Stereolithography (SLA) and a digital light processing molding machine(Digital Light Processing, DLP). In some embodiments of the present application, the light-curing molding apparatus is a three-dimensional light-curing molding machine, the laser power of the three-dimensional light-curing molding machine is 0.1w-3w, the scanning speed is 1000mm/s-4000mm/s, and the layer thickness among the processing parameters is 10 μm-150 μm. In some embodiments, the light-curing molding device is a digital light processing molding machine, the laser power of the digital light processing molding machine is 7mw/cm2-100mw/cm2, the exposure time of the digital light processing molding machine is 1s-90s, and the lamination thickness of the digital light processing molding machine is 10 μm-150 μm.
In step S2, the carbon source resin and the photocurable resin can be thermally decomposed to form carbon by temperature programming to obtain SiC @ SiO2a/C ceramic body. In the embodiment of the present application, the temperature conditions for the temperature programming are: heating to 150-220 ℃ at a heating rate of not higher than 3 ℃/min, and keeping the temperature for 1-3 h; heating to 250-380 ℃ at a heating rate of not higher than 3 ℃/min, and keeping the temperature for 1-3 h; heating to 700-900 ℃ at a heating rate of not higher than 3 ℃/min, and preserving heat for 1-3 h. In some embodiments of the present application, the temperature conditions for the temperature programming are: heating to 160 ℃ at a heating rate of 1-3 ℃/min, and keeping the temperature for 2 h; heating to 300 ℃ at a heating rate of 1-3 ℃/min, and keeping the temperature for 2 h; heating to 800 ℃ at the heating rate of 1-3 ℃/min, and keeping the temperature for 2 h. The impact of volume change caused by the change of ceramic components in the temperature rise process of the ceramic body can be relieved by controlling the temperature condition of the resin thermal decomposition process (the ceramic components comprise all raw materials in the slurry and also comprise carbon, CO and C generated by the pyrolysis of the resin and the dispersing agent in the sintering process2CH4, and H2O, etc.), thereby increasing the structural strength of the silicon carbide ceramic.
In this application, step S3 is SiO2By carbothermal reduction reaction, SiO on the SiC surface can be eliminated2Thereby obtaining the silicon carbide ceramic. In the embodiment of the application, the temperature of the carbothermic reduction reaction is 1000-1700 ℃, and the heat preservation time is 2-8 h. In some embodiments of the present application, the carbothermic reduction reaction is performed at 1050 ℃ to 1650 ℃ for 3 to 6 hours. The temperature of the carbothermic reduction reaction may be, but is not limited to, 1000 deg.C, 1050 deg.C, 1100 deg.C, 1200 deg.C, 1400 deg.C1500 ℃ or 1600 ℃. The temperature of the carbothermic reduction reaction can be controlled to ensure that SiO is ensured2The SiC can be effectively generated by reaction with carbon, the occurrence of side reaction is reduced, and other impurities are prevented from being introduced.
In some embodiments of the present application, after obtaining the silicon carbide ceramic, the silicon carbide ceramic may be further subjected to a silicon-carbon reaction to achieve densification of the silicon carbide ceramic. In the embodiment of the application, the silicon-carbon reaction process comprises the following steps: mixing the silicon carbide ceramic and the silicon particles, placing the mixture in a vacuum sintering furnace, and preserving the heat at 1500-1650 ℃ for 10-60 min to obtain the densified silicon carbide ceramic. The reaction temperature of the silicon carbon reaction may be, but is not limited to, 1500 ℃, 1550 ℃, 1600 ℃ or 1650 ℃. The reaction time of the silicon-carbon reaction can be specifically but not limited to 10min, 20min, 30min, 40min, 50min or 60 min. Under the above reaction conditions, the silicon particles may react sufficiently with the carbon in the silicon carbide ceramic to form a densified silicon carbide ceramic. In the embodiment of the present application, the particle size of the silicon particles is 1mm to 5 mm.
The preparation method of the silicon carbide ceramic is simple to operate, controllable in process, short in product preparation period, low in cost and suitable for industrial production.
The following further describes embodiments of the present application in terms of a number of examples.
Example 1
The light-cured ceramic slurry consists of raw materials in the mass ratio shown in Table 1.
Table 1 example 1 raw material composition of photocurable ceramic slurry
Wherein, SiC @ SiO2The preparation process of the powder comprises the following steps: SiC powder having a particle size of 10 μm was put into an atmospheric furnace and subjected to high-temperature oxidation. The oxidation temperature is 1200 ℃, the oxidation time is 2h, the heating rate is 5 ℃/min, and SiC @ SiO is obtained2A crude powder; mixing SiC @ SiO2The powder crude product is subjected to wet ball milling, filtering, drying and sieving to obtain SiC @ SiO2And (3) powder. Ethanol and SiC @ SiO in wet ball milling2The volume ratio of the powder crude product is 4:1, and the addition amount of the silane coupling agent KH570 is SiC @ SiO23 percent of the mass of the crude powder.
The preparation method of the photocuring ceramic slurry comprises the following steps:
weighing SiC @ SiO2And mechanically stirring the powder, 1, 6-hexanediol diacrylate, novolac epoxy acrylate, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide and a polyurethane dispersant for 30min, pouring the mixture into a ball milling tank, and ball milling the mixture in a planetary ball mill at the ball milling speed of 300r/min for 5h to obtain the photocuring ceramic slurry.
Example 2
A light-cured ceramic slurry and a preparation method thereof are disclosed, wherein the light-cured ceramic slurry is composed of raw materials in the mass ratio shown in Table 2.
Table 2 example 2 raw material composition of photocurable ceramic slurry
Wherein, SiC @ SiO2The preparation process of the powder comprises the following steps: SiC powder having a particle size of 5 μm was put into an atmospheric furnace and subjected to high-temperature oxidation. The oxidation temperature is 1100 ℃, the oxidation time is 2h, the heating rate is 5 ℃/min, and SiC @ SiO is obtained2A crude powder; mixing SiC @ SiO2The powder crude product is subjected to wet ball milling, filtering, drying and sieving to obtain SiC @ SiO2And (3) powder. Ethanol and SiC @ SiO in wet ball milling2The volume ratio of the powder crude product is 4:1, and the addition amount of the silane coupling agent KH570 is SiC @ SiO23 percent of the mass of the crude powder.
The preparation method of the photocuring ceramic slurry comprises the following steps:
weighing SiC @ SiO2Powder, 1, 6-hexanediol diacrylate, novolac epoxy acrylate, diphenyl (2,4, 6-trimethylbenzoyl) oxygenAnd (3) mechanically stirring the phosphine and the polyurethane dispersant for 30min, pouring the mixture into a ball milling tank, and performing ball milling on the mixture in a planetary ball mill at the ball milling rotation speed of 400r/min for 3h to obtain the photocuring ceramic slurry.
Example 3
A light-cured ceramic slurry and a preparation method thereof are disclosed, wherein the light-cured ceramic slurry is composed of raw materials in the mass ratio shown in Table 3.
Table 3 example 3 raw material composition of photocurable ceramic slurry
Wherein, SiC @ SiO2The powder is prepared by grading coarse and fine particles, wherein the particle size of the coarse particle powder is 5-30 μm, the particle size of the fine particle powder is 0.1-5 μm, and the volume ratio of the coarse particle powder to the fine particle powder is 1: 1.
The preparation method of the photocuring ceramic slurry comprises the following steps:
weighing SiC @ SiO2And mechanically stirring the powder, trimethylolpropane triacrylate, 2130 type phenolic resin, 2-dimethoxy-2-phenylacetophenone and an acrylate type dispersing agent for 20min, pouring into a ball milling tank, and ball milling in a planetary ball mill at the ball milling speed of 400r/min for 5h to obtain the photocuring ceramic slurry.
Example 4
A preparation method of silicon carbide ceramic comprises the following steps:
1) the photocurable ceramic slurry of example 1 was poured into the trough of a digital light processing DLP molding apparatus. Designing a three-dimensional model of the ceramic part by three-dimensional modeling software and guiding the three-dimensional model into a photocuring molding device at 7.79mw/cm2The power density, the exposure time of 15s and the layer thickness of 50 mu m are used for carrying out ceramic photocuring printing to obtain SiC @ SiO2A ceramic body;
2) mixing SiC @ SiO2Carrying out temperature programming on the ceramic blank, wherein the temperature programming conditions are as follows: heating to 200 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 350 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; at 1 ℃/min literRaising the temperature to 800 ℃ at a speed, and preserving the heat for 2 hours to obtain SiC @ SiO2a/C ceramic body; and continuously heating to generate a carbon thermal reduction reaction, wherein the heating process comprises the following steps: heating from 800 ℃ to 1500 ℃ at the heating rate of 1 ℃/min, and preserving the heat for 2h to obtain the silicon carbide ceramic.
Example 5
A preparation method of silicon carbide ceramic comprises the following steps:
1) the photocurable ceramic slurry of example 2 was poured into the trough of a digital light processing DLP molding apparatus. Designing a three-dimensional model of the ceramic part by three-dimensional modeling software and guiding the three-dimensional model into a photocuring molding device at 7.79mw/cm2The power density, the exposure time of 15s and the layering thickness of 20 mu m are adopted to carry out ceramic photocuring printing to obtain SiC @ SiO2A ceramic body;
2) mixing SiC @ SiO2Carrying out temperature programming on the ceramic blank, wherein the temperature programming conditions are as follows: heating to 200 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 350 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 800 ℃ at the heating rate of 1 ℃/min, and preserving heat for 2h to obtain SiC @ SiO2a/C ceramic body; and continuously heating to generate a carbon thermal reduction reaction, wherein the heating process comprises the following steps: heating from 800 ℃ to 1650 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2h to obtain the silicon carbide ceramic.
Example 6
A preparation method of silicon carbide ceramic comprises the following steps:
1) the photocurable ceramic slurry of example 3 was poured into the trough of a digital light processing DLP molding apparatus. Designing a three-dimensional model of the ceramic part by three-dimensional modeling software and guiding the three-dimensional model into a photocuring molding device at 7.79mw/cm2The power density, the exposure time of 15s and the layering thickness of 20 mu m are adopted to carry out ceramic photocuring printing to obtain SiC @ SiO2A ceramic body;
2) mixing SiC @ SiO2Carrying out temperature programming on the ceramic blank, wherein the temperature programming conditions are as follows: heating to 200 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 350 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 800 ℃ at the heating rate of 1 ℃/min, and preserving heat for 2h to obtain SiC @ SiO2a/C ceramic body;continuously heating to generate carbon thermal reduction reaction, wherein the heating process comprises the following steps: heating from 800 ℃ to 1650 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2h to obtain the silicon carbide ceramic.
3) And mixing the silicon carbide ceramic with silicon particles with the particle size of 5mm, placing the mixture in a vacuum sintering furnace, and preserving the heat for 30min at 1600 ℃ to obtain the densified silicon carbide ceramic.
Example 7
A preparation method of silicon carbide ceramic comprises the following steps:
1) the photocurable ceramic slurry of example 3 was poured into the trough of a stereo photocurable forming machine. Designing a three-dimensional model of the ceramic part by three-dimensional modeling software and guiding the three-dimensional model into a photocuring molding device, and performing photocuring printing on the ceramic part at the laser power of 2.5w, the scanning speed of 3000mm/s and the layering thickness of 20 mu m to obtain SiC @ SiO2A ceramic body;
2) mixing SiC @ SiO2Carrying out temperature programming on the ceramic blank, wherein the temperature programming conditions are as follows: heating to 200 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 350 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 2 h; heating to 800 ℃ at the heating rate of 1 ℃/min, and preserving heat for 2h to obtain SiC @ SiO2a/C ceramic body; and continuously heating to generate a carbon thermal reduction reaction, wherein the heating process comprises the following steps: heating from 800 ℃ to 1500 ℃ at the heating rate of 1 ℃/min, and preserving the heat for 2h to obtain the silicon carbide ceramic.
3) And mixing the silicon carbide ceramic with silicon particles with the particle size of 1mm, placing the mixture in a vacuum sintering furnace, and preserving the heat for 30min at 1600 ℃ to obtain the densified silicon carbide ceramic.
To highlight the advantageous effects of the present application, the following comparative examples were provided.
Comparative example 1
A light-cured ceramic slurry and a preparation method thereof are disclosed, wherein the light-cured ceramic slurry is composed of raw materials in the mass ratio shown in Table 4.
Table 4 comparative example 1 raw material composition of photocurable ceramic slurry
The preparation method of the photocuring ceramic slurry comprises the following steps:
and mechanically stirring the weighed SiC powder, 1, 6-hexanediol diacrylate, phenolic epoxy acrylate, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide and polyurethane dispersant for 30min, pouring the mixture into a ball milling tank, and performing ball milling on the mixture in a planetary ball mill at the ball milling rotation speed of 300r/min for 5h to obtain the photocuring ceramic slurry.
Effects of the embodiment
In order to verify the performance of the photocuring ceramic slurry and the photocuring ceramic prepared by the method, the method also provides an effect embodiment.
1) Scanning electron microscope is adopted to carry out the preparation of SiC @ SiO of example 1 and example 22The powder was morphologically characterized, referring to FIGS. 3 and 4, FIG. 3 shows SiC @ SiO obtained in example 1 of the present application2Scanning Electron microscopy of the powder, FIG. 4 is a graph of SiC @ SiO obtained in example 2 of the present application2Scanning electron micrographs of the powder. As can be seen from FIG. 3, SiC @ SiO in example 12The particle size of the powder is 1-20 μm. As can be seen from FIG. 4, SiC @ SiO in example 22The particle size of the powder is 1-40 μm.
2) The photo-curing efficiency test was performed on the photo-curing ceramic pastes of examples 1-2 and comparative example 1, referring to fig. 5 and 6, fig. 5 is a graph comparing photo-curing efficiency test of the photo-curing ceramic pastes of examples 1-2 and comparative example 1 of the present application, and fig. 6 is a graph comparing curing thickness of the photo-curing ceramic pastes of example 1 and comparative example 1 of the present application at an exposure time of 90s, wherein (a) in fig. 6 is a graph of curing thickness of the photo-curing ceramic paste of comparative example 1 at an exposure time of 90s, and (b) in fig. 6 is a graph of curing thickness of the photo-curing ceramic paste of example 1 at an exposure time of 90 s. As can be seen from fig. 5, the cured thickness of the photo-curable ceramic pastes of examples 1 and 2 was greater than that of the photo-curable ceramic paste of comparative example 1 at the same exposure time. As can be seen from (a) in FIG. 6, the cured thickness of the ceramic slurry of comparative example 1 was 44.7 μm at an exposure time of 90s, and as can be seen from (b) in FIG. 6, the cured thickness of the ceramic slurry of example 1 was 89.9 μm at an exposure time of 90s, i.e., the cured thickness of the ceramic slurry of example 1 was that of the ceramic slurry of comparative example 1Twice the cured thickness. It can be seen that SiO is used for SiC2The light-cured slurry obtained after coating has higher light-cured efficiency, and can effectively shorten the production period of the silicon carbide ceramic.
3) The photocuring printing performance of the photocuring ceramic slurry of example 1 was tested, and the specific printing conditions were as shown in example 4. Referring to FIG. 7, FIG. 7 is a photo-curing printing effect diagram of photo-curing ceramic slurry according to example 1 of the present application, wherein (a) in FIG. 7 is a three-dimensional model diagram of a ceramic part according to example 4, and (b) in FIG. 7 is a SiC @ SiO solid film of example 42Photo of the ceramic body. As can be seen from a comparison between fig. 7 (a) and fig. 7 (b), the ceramic green body prepared by using the photocurable ceramic slurry of example 1 has a complete structure and a high structural accuracy.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The photocuring ceramic slurry is characterized by comprising the following raw materials in percentage by mass:
SiC@SiO2powder: 25% -60%;
light-curing resin: 10% -40%;
carbon source resin: 10% -40%;
photoinitiator (2): 0.1% -2%;
dispersing agent: 2% -6%;
the SiC @ SiO2The powder comprises a SiC core body and SiO coated on the surface of the SiC core body2A shell layer; the particle diameter of the SiC core body is equal to that of the SiO2The thickness ratio of the shell layer is 1 (0.15-0.5); the SiC @ SiO2The powder is prepared by a high temperature oxidation process comprising: mixing SiC powder inKeeping the temperature at 800-1200 ℃ for 1-20 h to obtain SiC @ SiO2Powder crude product, and mixing the SiC @ SiO2Crushing and sieving the crude powder to obtain SiC @ SiO2Powder; the SiC @ SiO2The powder comprises a first SiC @ SiO2Powder and second SiC @ SiO2Powder; the first SiC @ SiO2The particle size of the powder is more than 0.1 μm and less than or equal to 5 μm; the second SiC @ SiO2The particle size of the powder is more than 5 μm and less than or equal to 32 μm; the second SiC @ SiO2Powder and the first SiC @ SiO2The volume ratio of the powder is greater than 0 and less than or equal to 1; the carbon source resin has a carbon residue rate of 40% or more at 800 ℃; the SiC @ SiO2The mass ratio of the powder to the carbon source resin is 1 (0.4-1).
2. The photocurable ceramic slurry of claim 1 wherein the SiC nuclei have a particle size of 0.1 μ ι η to 30 μ ι η; the SiO2The thickness of the shell layer is 20nm-2000 nm.
3. The photocurable ceramic slurry of claim 1, wherein the carbon source resin comprises a phenolic resin.
4. The photocurable ceramic paste of claim 1 wherein the photocurable resin comprises one or more of trimethylolpropane triacrylate, 1,6 hexanediol diacrylate, and polydihexaacrylate.
5. The photocurable ceramic paste of claim 1 wherein the photoinitiator comprises one or more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexyl phenyl ketone.
6. The photocurable ceramic paste according to claim 1, wherein the photocurable ceramic paste has a viscosity of 1-5 Pa-s.
7. A preparation method of silicon carbide ceramic is characterized by comprising the following steps:
the light-cured ceramic slurry is subjected to light-curing molding to obtain SiC @ SiO2A ceramic body; the light-cured ceramic slurry comprises the following raw materials in percentage by mass:
SiC@SiO2powder: 25% -60%;
light-curing resin: 10% -40%;
carbon source resin: 10% -40%;
photoinitiator (2): 0.1% -2%;
dispersing agent: 2% -6%;
the SiC @ SiO2The powder comprises a SiC core body and SiO coated on the surface of the SiC core body2A shell layer; the particle diameter of the SiC core body is equal to that of the SiO2The thickness ratio of the shell layer is 1 (0.15-0.5); the SiC @ SiO2The powder is prepared by a high temperature oxidation process comprising: keeping the temperature of the SiC powder at 800-1200 ℃ for 1-20 h to obtain SiC @ SiO2Powder crude product, and mixing the SiC @ SiO2Crushing and sieving the crude powder to obtain SiC @ SiO2A powder; the SiC @ SiO2The powder comprises a first SiC @ SiO2Powder and second SiC @ SiO2A powder; the first SiC @ SiO2The particle size of the powder is more than 0.1 μm and less than or equal to 5 μm; the second SiC @ SiO2The particle size of the powder is more than 5 μm and less than or equal to 32 μm; the second SiC @ SiO2Powder and the first SiC @ SiO2The volume ratio of the powder is greater than 0 and less than or equal to 1; the carbon source resin has a carbon residue rate of 40% or more at 800 ℃; the SiC @ SiO2The mass ratio of the powder to the carbon source resin is 1 (0.4-1);
the SiC @ SiO2The carbon source resin is carbonized by the programmed temperature rise of the ceramic body, and then the temperature is kept for 2 to 8 hours at the temperature of between 1000 and 1700 ℃ to ensure that SiO is generated2And carbonizing to generate SiC, thus obtaining the silicon carbide ceramic.
8. The method of claim 7, wherein the temperature-programmed conditions are: heating to 150-220 ℃ at a heating rate of not higher than 3 ℃/min, and keeping the temperature for 1-3 h; heating to 250-380 ℃ at a heating rate of not higher than 3 ℃/min, and keeping the temperature for 1-3 h; heating to 700-900 ℃ at a heating rate of not higher than 3 ℃/min, and preserving heat for 1-3 h.
9. The method of claim 7, further comprising: and mixing the silicon carbide ceramic with silicon particles, and keeping the temperature at 1500-1650 ℃ for 10-60 min to obtain the densified silicon carbide ceramic.
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| CN115838288B (en) * | 2021-09-18 | 2023-12-26 | 中国科学院上海硅酸盐研究所 | SiC ceramic photosensitive slurry for photo-curing 3D printing and preparation method thereof |
| CN115180955A (en) * | 2021-10-19 | 2022-10-14 | 中国科学院沈阳自动化研究所 | Silicon carbide ceramic slurry, preparation method thereof and pyrolysis process of photocuring formed body |
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| CN114436658A (en) * | 2022-02-21 | 2022-05-06 | 深圳职业技术学院 | Photocuring silicon carbide ceramic slurry and preparation method and application thereof |
| CN114956828B (en) * | 2022-05-17 | 2023-08-15 | 合肥商德应用材料有限公司 | Silicon carbide ceramic and preparation method and application thereof |
| CN115010877B (en) * | 2022-05-27 | 2023-11-24 | 深圳大学 | Carbon-oxygen-silicon ceramic precursor, thick compact ceramic piece and 3D printing preparation method thereof |
| EP4331841A1 (en) * | 2022-08-31 | 2024-03-06 | FACT Industries OÜ | A composition for preparing a ceramic product by stereolithography, a ceramic product, and a method of manufacturing a ceramic product |
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