CN110815491B - 3D (three-dimensional) freezing printing method of ceramic component - Google Patents
3D (three-dimensional) freezing printing method of ceramic component Download PDFInfo
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- CN110815491B CN110815491B CN201911132894.9A CN201911132894A CN110815491B CN 110815491 B CN110815491 B CN 110815491B CN 201911132894 A CN201911132894 A CN 201911132894A CN 110815491 B CN110815491 B CN 110815491B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B33Y10/00—Processes of additive manufacturing
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- 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
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Abstract
The invention relates to a 3D (three-dimensional) freezing and printing method of a ceramic component. The method comprises the following steps: (1) ball-milling ceramic powder, silica sol, polyethylene glycol and polyvinyl alcohol to obtain ceramic slurry; (2) cooling a printing cavity of the 3D printing device to 10 ℃ below zero to 60 ℃ below zero, then printing by adopting ceramic slurry, and adhering wet mud extruded from a nozzle to a printing bottom plate to form a first layer of mud; continuously printing, and continuously forming a second layer of pug and a third layer of pug on the first layer of pug by the wet pug extruded from the nozzle, wherein the layer is the Nth layer of pug; gradually fusing the formed pug layers, and gradually freezing and curing the inner part and the layers of the pug layers to obtain green bodies when the pug layers are printed to 4-10 layers; (3) and freeze-drying the green body, and then heating and sintering to obtain the ceramic component. The method provided by the invention is beneficial to realizing the integrity of the printing ceramic and improving the interlayer bonding strength.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to a 3D (three-dimensional) freezing printing method for a ceramic component.
Background
In recent years, 3D printing technology has been rapidly developed, and a preliminary industrial chain has been established for the preparation of organic and metallic materials. In contrast, the ceramic 3D printing technology is slowly developed and is still in the printing application stage based on the existing printing technology. At present, the existing ceramic 3D printing technology has the problems of low product density, large sintering shrinkage, insufficient mechanical properties, unfriendly environment and the like in ceramic preparation, and a new ceramic 3D printing way is urgently needed to be researched and developed.
The water-based ceramic slurry has no environmental pollution in the whole process of ceramic green body forming, drying, sintering and the like, and is a green and environment-friendly ceramic raw material. The water-based slurry is used for solid free-forming type 3D printing, the component collocation of the ceramic ink is not limited, and the technology expansion and application are easy. Therefore, the water-based ceramic slurry is used for 3D printing and is a new generation ceramic 3D printing technology. However, ceramic slurries are difficult to obtain in 3D printing technology applications with self-strength support to complex structural prototypes, and freezing is the simplest and most effective way to achieve water-based slurry solidification. The freezing forming is used as a common ceramic preparation technology, and the main process steps are that ceramic slurry is firstly frozen to be below a eutectic point at low temperature, so that water in the slurry is changed into solid ice, and then the ice is directly sublimated into water vapor and removed under a proper vacuum environment, so that a ceramic blank with certain strength is obtained.
However, at present, research on the aspect is less, the interlayer strength is difficult to meet the actual requirement, and how to overcome the ice crystal expansion stress between the layers in the freezing process and realize the interlayer combination with high strength becomes the technical problem to be solved.
Disclosure of Invention
The invention provides a novel interlayer printing 3D printing method, aiming at the technical problems that the interlayer bonding strength is not high in the existing ceramic product 3D printing process, and the interlayer expansion stress of ice crystals is difficult to overcome in the freezing process so as to realize high-strength interlayer bonding.
In order to solve the technical problems, the invention provides the following technical scheme:
a method of 3D cryo-printing of ceramic components, the method comprising the steps of:
(1) ball-milling ceramic powder, silica sol, polyethylene glycol and polyvinyl alcohol to obtain ceramic slurry;
(2) cooling a printing cavity of the 3D printing device to 10 ℃ below zero to 60 ℃ below zero, then printing by adopting the ceramic slurry obtained in the step (1), and adhering wet mud extruded from a nozzle to a printing bottom plate to form a first layer of mud; continuously printing, and continuously forming a second layer of pug and a third layer of pug on the first layer of pug by the wet pug extruded from the nozzle, wherein the layer is the Nth layer of pug; gradually fusing the formed pug layers, and gradually freezing and curing the inner part and the layers of the pug layers to obtain green bodies when the pug layers are printed to 4-10 layers;
(3) and (3) freeze-drying the green body obtained after printing in the step (2), and then heating and sintering to obtain the ceramic component.
Preferably, the ceramic powder is selected from any one or more of alumina, silicon oxide, silicon nitride, aluminum nitride, zirconia and silicon carbide; preferably, the particle size of the ceramic powder has the following gradation: the powder with particle size less than 200nm accounts for 3-5%, the powder with particle size of 200nm-1.0 μm accounts for 10-15%, the powder with particle size of 1-10 μm accounts for 30-40%, the powder with particle size of 10-30 μm accounts for 20-30%, and the powder with particle size greater than 30 μm accounts for 10-20%.
Preferably, the silica sol is an acidic silica sol with a solid content of 15-30%; preferably, the mass of the silica sol is 25 to 50% of the mass of the ceramic powder.
Preferably, the mass of the polyethylene glycol is 0.2-3% of the mass of the ceramic powder.
Preferably, the mass of the polyvinyl alcohol is 0.5-3% of the mass of the ceramic powder.
Preferably, the ceramic slurry is a ceramic slurry with a solid content of 55-75%.
Preferably, the print cavity is cooled by liquid nitrogen refrigeration.
Preferably, the freeze-drying is carried out under the temperature condition of minus 2 ℃ to minus 5 ℃ and the pressure condition of 0.02 to 0.09MPa of vacuum degree; preferably, the freeze-drying time is 5-15 h.
Preferably, the heating is performed at a temperature of 50-80 ℃; preferably, the heating time is 3-6 h.
Preferably, the sintering is performed at a temperature of 1200-.
Advantageous effects
The technical scheme of the invention has the following advantages:
according to the invention, the technological process of interlayer fusion and freezing solidification is adopted, wet pug extruded from a nozzle of the 3D printing device is adhered to the printing bottom plate layer by layer, the newly extruded pug layer is fused with the previous layer of pug under stress but is not frozen and solidified, and the fused pug is gradually frozen and solidified along with the extension of the printing time. The process is favorable for realizing the integrity of the printing ceramic and improving the interlayer bonding strength.
The silica sol used in the preparation of the water-based slurry can generate a gelling reaction to generate Si-O-Si bonds, so that the interlayer bonding strength can be further improved.
The addition of the polyethylene glycol and the polyvinyl alcohol can improve the plasticity of the paste, overcome the bleeding of the paste and ensure that the paste is kept stable in the extrusion printing process.
And in the printing process, the printing cavity is cooled to the subzero temperature, and the temperature of the printing environment is kept stable.
The 3D printing raw material used by the invention is water-based slurry, has no pollution and is a green printing technology; the water-based slurry is used for solid free-forming type 3D printing, the component collocation of ceramic 'ink' is not limited, and the technology expansion and application are easy; moreover, the water has lower viscosity and surface tension, the ceramic powder can reach solid content of more than 55 wt% after being freely dispersed in the water, and the ceramic green body has higher density, which is beneficial to reducing the shrinkage rate in the subsequent drying and sintering processes.
The temperature of the printing cavity is controlled to be 10 ℃ below zero to 60 ℃ below zero, so that the pug layer extruded from the printing cavity is not solidified as soon as being extruded, but is frozen and solidified by water into ice after a period of time, and the pug layer is fused with the previous pug layer in the period of time, thereby ensuring the bonding strength of the printing material.
The ceramic slurry used in the invention is ceramic slurry with solid content of 55-75%, and the solid content is relatively high, so that the ceramic member with excellent strength can be obtained. In addition, when the solid content of the ceramic slurry is increased, the linear shrinkage of the ceramic product obtained after sintering is reduced. Therefore, the green body produced using the ceramic slurry of the present invention having such a higher solid content has a smaller linear shrinkage after sintering.
Drawings
FIG. 1 is a schematic flow diagram of a method provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a 3D (three-dimensional) freezing and printing method of a ceramic component, which comprises the following steps as shown in figure 1:
(1) ball-milling ceramic powder, silica sol, polyethylene glycol and polyvinyl alcohol to obtain ceramic slurry;
(2) cooling a printing cavity of the 3D printing device to 10 ℃ below zero to 60 ℃ below zero, then printing by adopting the ceramic slurry obtained in the step (1), and adhering wet mud extruded from a nozzle to a printing bottom plate to form a first layer of mud; continuously printing, and continuously forming a second layer of pug, a third layer of pug and an Nth layer of pug on the first layer of pug by using the wet pug extruded from the nozzle (wherein N is used for representing the number of layers of the pug layer and is a natural number more than 10); gradually fusing the formed pug layers, and gradually freezing and curing the inner part and the layers of the pug layers to obtain green bodies when the pug layers are printed to 4-10 layers;
(3) and (3) freeze-drying the green body obtained after printing in the step (2), and then heating and sintering to obtain the ceramic component.
The 3D printing method provided by the invention adopts the process flow of firstly fusing the layers and then freezing and solidifying, the wet pug extruded from the nozzle of the 3D printing device is adhered to the printing bottom plate layer by layer, the newly extruded pug layer can be fused with the previous layer of pug under stress but can not be frozen and solidified, and the fused pug can be gradually frozen and solidified along with the extension of the printing time. The process is favorable for realizing the integrity of the printing ceramic and improving the interlayer bonding strength. In addition, the silica sol used in the preparation of the water-based slurry can generate a gelling reaction to generate Si-O-Si bonds, so that the interlayer bonding strength can be further improved; the addition of the polyethylene glycol and the polyvinyl alcohol can improve the plasticity of the paste, overcome the bleeding of the paste and ensure that the paste is kept stable in the extrusion printing process; and in the printing process, the printing cavity is cooled to the subzero temperature, and the temperature of the printing environment is kept stable.
In order to ensure that the newly extruded pug layer has enough time to be fused with the pug layer on the upper layer, the temperature of the printing cavity is controlled to be 10 ℃ below zero to 60 ℃ below zero, for example, the temperature can be-10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃. This temperature range is comparatively suitable for the pug layer of extruding from the printing cavity is not just once extrudeing just solidification, but just can realize freezing solidification for ice by the water knot after a period of time, and in this period of time, the pug layer can fuse with last one deck pug layer, thereby has guaranteed printing material's bonding strength. In some preferred embodiments, the printing cavity is cooled by liquid nitrogen refrigeration, the printing cavity is cooled to-10 ℃ to-60 ℃, and the printing process can be started after the temperature is stabilized.
In addition to controlling the temperature of the printing cavity, the ceramic slurry used for printing is optimized, and the ceramic slurry suitable for 3D (three-dimensional) frozen printing is provided.
In some preferred embodiments, the ceramic powder is selected from any one or more of alumina, silica, silicon nitride, aluminum nitride, zirconia, and silicon carbide. More preferably, the particle size of the ceramic powder has the following gradation: the powder with the particle size less than 200nm accounts for 3-5%; powder of 200nm-1.0 μm accounts for 10-15%; 30-40% of powder with the particle size of 1-10 μm; 20-30% of powder with the particle size of 10-30 μm; the powder with the particle size larger than 30 μm accounts for 10-20%; the sum of the powders with various particle diameters is 100 percent. The inventor finds that when the grain diameter of the ceramic powder is less than 200nm, the viscosity of the slurry is greatly improved by the ceramic powder, and the doping amount is difficult to ensure; when the particle size of the ceramic powder is more than 30 μm, the activity of the ceramic powder is too low to form a high-strength matrix after sintering. The ceramic powder with a certain grain size grading can ensure that the viscosity of slurry is not too high and the activity is relatively high under the condition of fully ensuring the solid content of the powder.
In some preferred embodiments, the silica sol is an acidic silica sol having a solid content (as a mass percentage) of 15-30% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%) may be used. The solid content silica sol can improve the viscosity of the slurry and is beneficial to interlayer adhesion. When the solid content of the silica sol is too high, the viscosity of the silica sol is too high, so that the subsequent powder doping amount is not high, and finally the ceramic green body density is low. In some preferred embodiments, the mass of the silica sol is 25 to 50% of the mass of the ceramic powder, and may be, for example, 25%, 30%, 35%, 40%, 45%, or 50%.
In some preferred embodiments, the mass of the polyethylene glycol is 0.2 to 3% of the mass of the ceramic powder, and for example, may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%.
In some preferred embodiments, the mass of the polyvinyl alcohol is 0.5 to 3% of the mass of the ceramic powder, and for example, may be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%.
In some preferred embodiments, the ceramic slurry is a ceramic slurry having a solid content (in mass%) of 55-75% (e.g., 55%, 60%, 65%, 70%, 75% is possible). It can be seen that the ceramic slurry used in the process of the present invention has a large solid content, and thus a ceramic member having excellent strength can be obtained. In addition, when the solid content of the ceramic slurry is increased, the linear shrinkage of the ceramic product obtained after sintering is reduced. Therefore, the green body produced using the ceramic slurry of the present invention having such a higher solid content has a smaller linear shrinkage after sintering. In addition, the solid content is not too high, the ceramic slurry with the solid content characteristic can ensure that the newly extruded pug layer has sufficient time to be fused with the previous pug layer and then is gradually solidified after being matched with the temperature of the printing cavity for use during printing, but when the solid content is too high, the change time of water becoming ice is not ideal, and the extruded pug cannot ensure that the extruded pug has sufficient time to be fused. The ceramic slurry with the solid content can be obtained to a certain extent through the control of the ball milling process, for example, the ball milling time is controlled to be 5-20h, for example, 5h, 10h, 15h and 20h in some preferred embodiments of the invention. The ball milling may be carried out using conventional ball milling equipment, such as planetary ball mills.
In some preferred embodiments, the freeze-drying is performed under temperature conditions of-2 ℃ to-5 ℃ (e.g., may be-2 ℃, -3 ℃, -4 ℃, -5 ℃) and pressure conditions of 0.02 to 0.09MPa (e.g., may be 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa) vacuum degree; preferably, the freeze-drying time is 5-15h, for example, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h may be used.
In some preferred embodiments, the heating is performed under temperature conditions of 50-80 ℃ (e.g., may be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃); preferably, the heating time is 3-6h, for example, 3h, 4h, 5h, 6 h.
In some preferred embodiments, the sintering is performed at a temperature of 1200-. The sintering condition can ensure that the sintered ceramic product has smaller linear shrinkage rate without the phenomenon of product cracking.
More generally, the method provided by the invention comprises the following steps:
(1) ball-milling ceramic powder, silica sol, polyethylene glycol and polyvinyl alcohol to obtain ceramic slurry; the ceramic powder is selected from any one or more of alumina, silicon oxide, silicon nitride, aluminum nitride, zirconia and silicon carbide; the grain diameter of the ceramic powder has the following grading: the powder with particle size less than 200nm accounts for 3-5%, the powder with particle size 200nm-1.0 μm accounts for 10-15%, the powder with particle size 1-10 μm accounts for 30-40%, the powder with particle size 10-30 μm accounts for 20-30%, and the powder with particle size greater than 30 μm accounts for 10-20%; the silica sol is acidic silica sol with the solid content of 15-30%; the mass of the silica sol is 25-50% of that of the ceramic powder; the mass of the polyethylene glycol is 0.2-3% of that of the ceramic powder; the mass of the polyvinyl alcohol is 0.5-3% of that of the ceramic powder; the ceramic slurry has a solid content of 55-75%;
(2) cooling a printing cavity of the 3D printing device to 10-60 ℃ below zero through liquid nitrogen refrigeration, then printing by adopting the ceramic slurry obtained in the step (1), and adhering wet mud extruded from a nozzle to a printing bottom plate to form a first layer of mud; continuously printing, and continuously forming a second layer of pug and a third layer of pug on the first layer of pug by the wet pug extruded from the nozzle, wherein the layer is the Nth layer of pug; gradually fusing the formed pug layers, and gradually freezing and curing the inner part and the layers of the pug layers to obtain green bodies when the pug layers are printed to 4-10 layers;
(3) freeze-drying the green body obtained after printing in the step (2), and then heating and sintering to obtain the ceramic component; wherein, the freeze drying is carried out under the temperature condition of minus 2 ℃ to minus 5 ℃ and the pressure condition of 0.02MPa to 0.09MPa of vacuum degree, and the freeze drying time is 5 hours to 15 hours; heating at 50-80 deg.C for 3-6 h; the sintering is carried out at a temperature of 1200 ℃ and 1700 ℃. Through detection, the ceramic green body prepared by the method has good mechanical strength, and the compressive strength reaches 0.5 MPa; after drying and sintering, the line shrinkage of the product is only 5-10%.
In summary, the method provided by the present invention has the following advantages:
adopt the process flow of fusing earlier between the layer, freezing solidification afterwards, the wet mud material successive layer that extrudes from 3D printing device's nozzle bonds on printing the bottom plate, and the mud material layer of newly extruding can fuse together but still can not freeze solidification with the previous layer mud material under stress, and along with the extension of printing time, the mud material of fusing together also can freeze solidification step by step. The process is favorable for realizing the integrity of the printing ceramic and improving the interlayer bonding strength.
The silica sol used in the preparation of the water-based slurry can generate a gelling reaction to generate Si-O-Si bonds, so that the interlayer bonding strength can be further improved.
The addition of the polyethylene glycol and the polyvinyl alcohol can improve the plasticity of the paste, overcome the bleeding of the paste and ensure that the paste is kept stable in the extrusion printing process.
And in the printing process, the printing cavity is cooled to the subzero temperature, and the temperature of the printing environment is kept stable.
The 3D printing raw material used by the invention is water-based slurry, has no pollution and is a green printing technology; the water-based slurry is used for solid free-forming type 3D printing, the component collocation of ceramic 'ink' is not limited, and the technology expansion and application are easy; moreover, water has lower viscosity and surface tension, the solid content of the ceramic powder which can be freely dispersed in the water is generally higher than 72 wt%, and the ceramic green body has higher density, which is beneficial to reducing the shrinkage rate in the subsequent drying and sintering processes.
The temperature of the printing cavity is controlled to be 10 ℃ below zero to 60 ℃ below zero, so that the pug layer extruded from the printing cavity is not solidified as soon as being extruded, but is frozen and solidified by water into ice after a period of time, and the pug layer is fused with the previous pug layer in the period of time, thereby ensuring the bonding strength of the printing material.
The ceramic slurry used in the invention is ceramic slurry with solid content of 55-75%, and the solid content is relatively high, so that the ceramic member with excellent strength can be obtained. In addition, when the solid content of the ceramic slurry is increased, the linear shrinkage of the ceramic product obtained after sintering is reduced. Therefore, the green body produced using the ceramic slurry of the present invention having such a higher solid content has a smaller linear shrinkage after sintering.
The following are examples of the present invention.
Example 1
Firstly, dispersing alumina ceramic powder with the grain size grading of less than 200nm accounting for 5%, 200nm-1.0 μm accounting for 10%, 1-10 μm accounting for 40%, 10-30 μm accounting for 30% and more than 30 μm accounting for 15% into silica sol with the solid content of 15%, adding 0.2% of polyethylene glycol and 0.5% of polyvinyl alcohol, and carrying out ball milling for 5h to obtain ceramic pug with the solid content of 55%, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-10 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fourth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the ceramic green body obtained by printing at the temperature of-2 ℃ and the vacuum degree of 0.02MPa for 5 hours, and then drying in an oven at the temperature of 50 ℃ for 3 hours. And finally, sintering at 1500 ℃ to obtain the ceramic member.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 7.0 percent through detection.
Example 2
Firstly, dispersing 3 percent of powder with the grain size grading of less than 200nm, 10 percent of powder with the grain size grading of 200nm-1.0 mu m, 40 percent of powder with the grain size grading of 1-10 mu m, 30 percent of powder with the grain size grading of 10-30 mu m and 17 percent of powder with the grain size grading of more than 30 mu m into silica sol with the solid content of 20 percent, adding 0.2 percent of polyethylene glycol and 0.5 percent of polyvinyl alcohol, and then carrying out ball milling for 5 hours to obtain ceramic pug with the solid content of 60 percent, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-10 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fourth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the ceramic green body obtained by printing at the temperature of-2 ℃ and the vacuum degree of 0.02MPa for 5 hours, and then drying in an oven at the temperature of 50 ℃ for 3 hours. And finally, sintering at 1500 ℃ to obtain the ceramic member.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 6.3 percent through detection.
Example 3
Firstly, dispersing 3 percent of powder with the grain size grading of less than 200nm, 10 percent of powder with the grain size grading of 200nm-1.0 mu m, 40 percent of powder with the grain size grading of 1-10 mu m, 30 percent of powder with the grain size grading of 10-30 mu m and 17 percent of powder with the grain size grading of more than 30 mu m into silica sol with the solid content of 25 percent, adding 0.5 percent of polyethylene glycol and 1 percent of polyvinyl alcohol, and then carrying out ball milling for 8 hours to obtain ceramic pug with the solid content of 65 percent, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-10 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fourth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the ceramic green body obtained by printing at the temperature of-2 ℃ and the vacuum degree of 0.02MPa for 5 hours, and then drying in an oven at the temperature of 50 ℃ for 3 hours. And finally, sintering at 1300 ℃ to obtain the ceramic component.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 5.0 percent through detection.
Example 4
Firstly, dispersing 3 percent of powder with the grain size grading of less than 200nm, 10 percent of powder with the grain size grading of 200nm-1.0 mu m, 40 percent of powder with the grain size grading of 1-10 mu m, 30 percent of powder with the grain size grading of 10-30 mu m and 17 percent of powder with the grain size grading of more than 30 mu m into silica sol with the solid content of 25 percent, adding 0.5 percent of polyethylene glycol and 1 percent of polyvinyl alcohol, and then carrying out ball milling for 8 hours to obtain ceramic pug with the solid content of 65 percent, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-40 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fourth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the ceramic green body obtained by printing at the temperature of-3 ℃ and the vacuum degree of 0.02MPa for 5 hours, and then drying in an oven at the temperature of 50 ℃ for 3 hours. And finally, sintering at 1300 ℃ to obtain the ceramic component.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 5.5 percent through detection.
Example 5
Firstly, dispersing 3 percent of powder with the grain size grading of less than 200nm, 10 percent of powder with the grain size grading of 200nm-1.0 mu m, 40 percent of powder with the grain size grading of 1-10 mu m, 30 percent of powder with the grain size grading of 10-30 mu m and 17 percent of powder with the grain size grading of more than 30 mu m into silica sol with the solid content of 25 percent, adding 0.5 percent of polyethylene glycol and 1 percent of polyvinyl alcohol, and then carrying out ball milling for 8 hours to obtain ceramic pug with the solid content of 65 percent, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-40 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fifth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the ceramic green body obtained by printing for 5 hours at the temperature of-4 ℃ and the vacuum degree of 0.05MPa, and then drying in an oven at the temperature of 50 ℃ for 3 hours. And finally, sintering at 1300 ℃ to obtain the ceramic component.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 5.6 percent through detection.
Example 6
Firstly, dispersing 3 percent of powder with the grain size grading of less than 200nm, 10 percent of powder with the grain size grading of 200nm-1.0 mu m, 40 percent of powder with the grain size grading of 1-10 mu m, 30 percent of powder with the grain size grading of 10-30 mu m and 17 percent of powder with the grain size grading of more than 30 mu m into silica sol with the solid content of 25 percent, adding 0.5 percent of polyethylene glycol and 1 percent of polyvinyl alcohol, and then carrying out ball milling for 8 hours to obtain ceramic pug with the solid content of 65 percent, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-40 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fifth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the printed ceramic green body for 10 hours at the temperature of-4 ℃ and the vacuum degree of 0.05MPa, and then drying in an oven at the temperature of 60 ℃ for 3 hours. And finally, sintering at 1300 ℃ to obtain the ceramic component.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 5.6 percent through detection.
Example 7
Firstly, dispersing silicon nitride ceramic powder with the grain size grading of less than 200nm accounting for 3%, 200nm-1.0 μm accounting for 10%, 1-10 μm accounting for 40%, 10-30 μm accounting for 30% and more than 30 μm accounting for 17% into silica sol with the solid content of 25%, adding 0.5% of polyethylene glycol and 1% of polyvinyl alcohol, and carrying out ball milling for 8h to obtain ceramic pug with the solid content of 65%, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-40 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fifth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the printed ceramic green body for 10 hours at the temperature of-4 ℃ and the vacuum degree of 0.05MPa, and then drying in an oven at the temperature of 80 ℃ for 5 hours. And finally, sintering is carried out at the sintering temperature of 1700 ℃, and the ceramic component is obtained.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 8.0 percent through detection.
Example 8
Firstly, dispersing 3 percent of powder with the grain size grading of less than 200nm, 10 percent of powder with the grain size grading of 200nm-1.0 mu m, 40 percent of powder with the grain size grading of 1-10 mu m, 30 percent of powder with the grain size grading of 10-30 mu m and 17 percent of powder with the grain size grading of more than 30 mu m into silica sol with the solid content of 25 percent, adding 0.5 percent of polyethylene glycol and 1 percent of polyvinyl alcohol, and then carrying out ball milling for 8 hours to obtain ceramic pug with the solid content of 65 percent, wherein the ceramic pug is used for 3D (three-dimensional) freezing printing. Then, the printing cavity is cooled to-40 ℃ by liquid nitrogen refrigeration. And then, extruding the prepared ceramic pug out of the nozzle through a motor, and bonding the wet pug on a printing bottom plate to start printing. In the printing process, the wet pug forms a plurality of layers of pugs which are sequentially overlapped on the printing bottom plate and are respectively named as a first layer of pug, a second layer of pug and a third layer of pug, wherein the layer is the Nth layer of pug. The newly extruded pug will fuse with the previous layer of pug under a certain stress. When the printing is carried out on the fifth layer or above, the first layer, the second layer of pug and the layers of the pug are frozen and solidified, and then the pugs of the rest layers are gradually frozen and solidified along with the printing, so that the ceramic green body is finally obtained. And then, carrying out freeze drying on the ceramic green body obtained by printing at-4 ℃ and the vacuum degree of 0.09MPa for 10 hours, and then drying in an oven at 70 ℃ for 8 hours. And finally, sintering at 1800 ℃ to obtain the ceramic member.
The linear shrinkage rate of the ceramic component obtained by freeze drying, heating and sintering the ceramic green body is 9.2% by detection.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A method of 3D cryo-printing of ceramic components, the method comprising the steps of:
(1) ball-milling ceramic powder, silica sol, polyethylene glycol and polyvinyl alcohol to obtain ceramic slurry;
(2) cooling a printing cavity of the 3D printing device to 10 ℃ below zero to 60 ℃ below zero, then printing by adopting the ceramic slurry obtained in the step (1), and adhering wet mud extruded from a nozzle to a printing bottom plate to form a first layer of mud; continuously printing, and continuously forming a second layer of pug and a third layer of pug on the first layer of pug by the wet pug extruded from the nozzle, wherein the layer is the Nth layer of pug; gradually fusing the formed pug layers, and gradually freezing and curing the inner part and the layers of the pug layers to obtain green bodies when the pug layers are printed to 4-10 layers; cooling the printing cavity through liquid nitrogen refrigeration;
(3) freeze-drying the green body obtained after printing in the step (2), and then heating and sintering to obtain the ceramic component;
the ceramic powder is selected from any one or more of alumina, silicon oxide, silicon nitride, aluminum nitride, zirconia and silicon carbide; the grain diameter of the ceramic powder has the following grading: the powder with particle size less than 200nm accounts for 3-5%, the powder with particle size 200nm-1.0 μm accounts for 10-15%, the powder with particle size 1-10 μm accounts for 30-40%, the powder with particle size 10-30 μm accounts for 20-30%, and the powder with particle size greater than 30 μm accounts for 10-20%;
the silica sol is acidic silica sol with the solid content of 15-30%; the mass of the silica sol is 25-50% of that of the ceramic powder;
the mass of the polyethylene glycol is 0.5-3% of that of the ceramic powder;
the mass of the polyvinyl alcohol is 1-3% of the mass of the ceramic powder.
2. The method of claim 1, wherein the ceramic slurry is a 55-75% solids ceramic slurry.
3. The method according to claim 1, wherein the freeze-drying is performed under a temperature condition of-2 ℃ to-5 ℃ and a pressure condition of a vacuum degree of 0.02 to 0.09 MPa; the freeze drying time is 5-15 h.
4. The method according to claim 1, wherein the heating is performed at a temperature of 50-80 ℃; the heating time is 3-6 h.
5. The method as claimed in any one of claims 1 to 4, wherein the sintering is carried out at a temperature of 1200 ℃ and 1700 ℃.
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