Method for preparing ceramic material through cooperation and modularization of photocuring 3D printing and traditional ceramic processing technology

Abstract

The invention discloses a method for preparing a ceramic material in a modularized mode through cooperation of photocuring 3D printing and a traditional ceramic processing technology, and relates to a modularized cooperation manufacturing method of photocuring 3D printing ceramic and the traditional ceramic processing technology. According to the method, low-cost and high-efficiency photo-curing 3D printing and traditional ceramic processing technology cooperation modularization preparation of the ceramic material is provided, based on ceramic printing slurry prepared by taking solvent response high-molecular polymer resin as a substrate, a DLP printer is used for printing and forming a plurality of ceramic green body modules; an n-butyl acetate solvent is adopted to stimulate and activate the surface of a green body module, the green body module and a ceramic module manufactured through a traditional technology are welded into a whole, and the integrated ceramic material with the complete structure is obtained after degreasing and sintering procedures. The method reduces the total ceramic printing cost and can be used in the field of ceramic preparation.

Description

Technical Field

[0001] The present invention relates to a modular collaborative manufacturing method of photocuring 3D printed ceramics and traditional ceramic processing technology, and specifically to manufacturing ceramic materials by realizing the collaboration between photocuring 3D printed ceramics and traditional ceramics through a modular construction method. Background Art

[0002] As a booming emerging technology, 3D printing ceramics has broken through the limitations of traditional ceramic processing technology that relies on mold forming. It uses a layer-by-layer construction method to obtain a more free ceramic complex structure forming capability, fully improves the freedom of structural design, and broadens the way for the further development and application of modern ceramic materials in many fields of human beings. Of course, we should also be clearly aware that 3D printing ceramic technology and traditional ceramic processing technology are not mutually exclusive. Traditional ceramic processing technology has the ability to mass-produce ceramic materials with simpler structures on a large scale, while 3D printing technology is limited by the working efficiency of the printer and cannot currently achieve large-scale production. Therefore, the combination and complementarity of the two manufacturing technologies will be an important direction for the future development of ceramic manufacturing.

[0003] However, there are barriers to collaboration between the mature traditional manufacturing technology and the new 3D printing technology, and they cannot be combined in a complementary way. This problem not only restricts the large-scale use of 3D printing ceramic technology in the field of ceramic production, but also restricts the further development and upgrading of traditional manufacturing technology. Therefore, it is necessary to develop a low-cost, high-efficiency modular ceramic material manufacturing technology that combines the old and new technologies based on the existing light-curing 3D printing ceramic technology. Summary of the invention

[0004] The purpose of the present invention is to provide a low-cost, high-efficiency method for modular preparation of ceramic materials by cooperating with photocuring 3D printing and traditional ceramic processing technology. Based on a ceramic printing slurry prepared with a solvent-responsive polymer resin as a substrate, a DLP printer is used to print and form multiple ceramic green modules, the surface of the green modules is activated by solvent stimulation, and the ceramic modules manufactured by traditional technology are welded into a whole, and after a degreasing and sintering process, an integrated ceramic material with a complete structure is obtained.

[0005] The method for preparing ceramic materials by modularization of light-curing 3D printing and traditional ceramic processing technology is carried out according to the following steps:

[0006] 1. Preparation of ceramic slurry for 3D printing:

[0007] Weighing acrylate monomer, polymerized acrylate, ceramic powder, dispersant, and photoinitiator, adding them into a ball mill and mixing them evenly to obtain a ceramic slurry;

[0008] Second, use software on the computer to split the target large-size ceramic model into simple structural modules and complex structural modules that are interconnected, leaving smooth flat connecting surfaces between the modules for easy contact and assembly;

[0009] 3. Use traditional ceramic processing technology to prepare simple structural ceramic modules;

[0010] 4. Import the 3D model of the complex structure module into the DLP printer, then inject the ceramic slurry into the material tank of the DLP printer, start the light-curing 3D printing, and obtain the complex structure module green body; remove the complex structure module green body on the printing platform, clean the residual slurry on the surface of the module with water; clean and dry it;

[0011] 5. Assemble the simple structure ceramic module and the complex structure module green body together, apply n-butyl acetate on the connection surface of the structure module, and apply pressure on both sides of the interface to make the structure module stick tightly and keep it for 10 to 30 minutes, connect the modules together, and obtain a prefabricated body in which the ceramic module and the green body module are connected as one;

[0012] 6. Place the preform into a sintering furnace, heat it to 120-125°C at a heating rate of 0.2-2°C / min and keep it for 2-5 hours, then heat it to 150-155°C and keep it for 2-5 hours, and finally heat it to 600-620°C and keep it for 2-5 hours for degreasing; then sinter it at high temperature to obtain a large-sized ceramic material.

[0013] Furthermore, the acrylic acid ester monomer described in step 1 is isobornyl acrylate, isobornyl methacrylate, neobornyl acrylate, neobornyl methacrylate or isobornyl diester acrylate.

[0014] Furthermore, the preparation method of the polymerized acrylate described in step 1 is: adding a photoinitiator accounting for 0.3% to 8% of the mass of the acrylate monomer to the acrylate monomer, mixing evenly, and performing photocuring 3D printing with a DLP printer to obtain the polymerized acrylate.

[0015] Furthermore, the ceramic powder in step one is aluminum oxide or zirconium oxide ceramic powder.

[0016] Furthermore, the dispersant described in step 1 is BYK.

[0017] Furthermore, the photoinitiator described in step one is 819 or TPO photoinitiator.

[0018] Furthermore, the mass of the polymerized acrylate in step 1 is 3% to 15% of the mass of the acrylate monomer;

[0019] Furthermore, the amount of ceramic powder added in step 1 is to ensure that the volume percentage of the ceramic powder in the ceramic slurry is V 1 Greater than 40%.

[0020] Furthermore, the amount of the dispersant added in step 1 is 1% to 5% of the mass of the ceramic powder.

[0021] Furthermore, the amount of the photoinitiator added in step 1 is 0.3% to 8% of the sum of the mass of the acrylate monomer and the polymerized acrylate.

[0022] Furthermore, the method for processing the simple structure ceramic module described in step three is a non-3D printing ceramic manufacturing technology, which is powder metallurgy, gel injection molding or laser sintering.

[0023] Furthermore, the method for preparing a simple structure ceramic module by powder metallurgy is as follows:

[0024] (1) Raw material preparation: mixing ceramic raw material powders, and adding a binder and a lubricant to obtain a mixed powder;

[0025] (2) Molding: The mixed powder is pressed into shape using a mold, and the molding method is dry pressing, isostatic pressing or injection molding to obtain a ceramic body;

[0026] (3) Sintering: The ceramic body is sintered at high temperature to densify it and obtain a ceramic module.

[0027] Furthermore, the gel casting method is carried out according to the following steps:

[0028] (1) Sol preparation: ceramic powder is dispersed in water and sol is added to form a stable suspension;

[0029] (2) Molding: Pour the suspension into a mold and solidify it into shape through a gelation reaction.

[0030] (3) Drying and sintering: The solidified green body is dried and sintered at high temperature to finally obtain a ceramic product.

[0031] Furthermore, the method of preparing a simple structure ceramic module by laser sintering is as follows:

[0032] (1) Using a high-energy laser beam to sinter ceramic powder to form a dense ceramic structure;

[0033] (2) Laser cutting and drilling: Use laser beam to precisely cut and drill holes in sintered ceramic structures.

[0034] Furthermore, the ceramic components in the simple structure ceramic module described in step three are the same as the ceramic components in the complex structure module green body, and the content of the ceramic components in the simple structure ceramic module and the content of the same ceramic components in the complex structure module green body do not differ by more than 20%.

[0035] Furthermore, the high temperature sintering described in step five is sintering at a temperature of 1600-1700°C for 1-5 hours. The sintering temperature and time are determined according to the type of ceramic. For ceramics of different materials, the sintering temperature and time are determined according to the material with the highest sintering temperature.

[0036] The present invention successfully realizes the modular collaborative manufacturing of ceramics by photocuring 3D printing ceramics and traditional ceramic processing technology, breaking through the collaborative barriers between photocuring 3D printing ceramic technology and traditional ceramic processing and manufacturing technology. A DLP printer is used to print ceramic slurry into multiple ceramic green modules; one or more ceramic green modules are connected to a ceramic module sintered and processed by a traditional manufacturing method by a solvent welding method to obtain a preform; the preform is degreased and sintered to obtain an integrated complete ceramic. The process flow diagram is shown in the figure. Figure 1 As shown. The present invention uses DLP printing to form multiple small-volume ceramic green bodies and formed ceramics with complex structures as building modules to make large-volume ceramic preforms, and degrease and sinter them into large-volume complete ceramics. The interface connection principle is as follows: under the stimulation of external solvents, the printed green body forms a gel layer with high fluidity at the interface, and the gel layer diffuses to the surface of the formed ceramic material to form a tightly connected layer. On the interface, the ceramic powder and the surface of the ceramic material are in a microscopic tight contact state. After degreasing, accompanied by the decomposition of the polymer components, the green body material undergoes an inward contraction process based on the connection surface. This contraction process makes the ceramic powder at the connection surface more closely fit on the microscopic crystal structure of the ceramic material. Finally, during the high-temperature sintering process, at the microscopic level, because the close fit between the powder and the ceramic microscopic crystal structure is sufficient to cross the energy barrier, the powder grows on the crystal structure of the ceramic material to produce a new ceramic crystal structure, and finally realizes the connection and forming of the new ceramic material printed by 3D printing and the ceramic material sintered and formed by the old traditional manufacturing method at the macroscopic level.

[0037] The method of the present invention has the following advantages and beneficial effects:

[0038] 1. It increases the configuration possibilities for traditional ceramic manufacturing technology, so that simple ceramic materials produced in traditional batches can be connected into materials with various configurations through specially printed modules.

[0039] 2. Improved the printing efficiency of light-curing 3D printed ceramics. Since some modules can be mass-produced through traditional manufacturing technology, the workload of 3D printing is effectively saved and work efficiency is improved.

[0040] 3. Break through the size limitation of photocuring printers, so that photocuring printers have the ability to print across sizes. Large-sized ceramic structures can be split into multiple modules for batch printing, and some large simple parts can be manufactured by traditional production methods, so that photocuring printers can use traditional manufacturing technology to form ceramic materials that exceed their printing size range.

[0041] 4. Realize the cross-time and space cooperation capability of ceramic printing. Ceramic modules can be produced in the area of ​​​​the traditional ceramic production and manufacturing center, and green modules can be produced in the area of ​​​​the printer production. Then the modules are sealed and stored and sent to the same place for connection, and then degreased and sintered to obtain integrated ceramic materials.

[0042] 5. Improve the fault tolerance of ceramic photocuring printing and reduce the total printing cost. The traditional method has a very low tolerance for printing ceramic materials. Once defects or equipment problems occur during the printing process, the entire print will be scrapped. With this method, some modules are produced and processed by more stable traditional manufacturing technology. 3D printing only needs to be responsible for some components, which improves fault tolerance. In addition, the mass production cost of traditional manufacturing is lower, so it can share the processing of some modules and reduce the total printing cost.

[0043] The method of the present invention can be used in the field of 3D printing ceramics. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 Flow chart of the modular preparation of ceramic materials by the collaboration of photocuring 3D printing and traditional ceramic processing technology of the present invention; wherein 1 is a simple structure ceramic module, 2 is a complex structure module, 3 is n-butyl acetate, 4 is a 3D printer, and 5 is a large-size ceramic material;

[0045] Figure 2 is a scanning electron microscope photograph of the preform in which the ceramic module and the green module are integrated in step 5 of Example 1;

[0046] Figure 3 This is a scanning electron microscope photograph after being kept at 120° C. for 2 hours in step 6 of Example 1;

[0047] Figure 4 This is a scanning electron microscope photograph of the step 6 of Example 1 after degreasing at 600° C. for 2 hours;

[0048] Figure 5 This is a scanning electron microscope photograph of the large-sized ceramic material obtained after sintering at 1600° C. for 3 hours in Example 1. DETAILED DESCRIPTION

[0049] The beneficial effects of the present invention are verified by the following examples.

[0050] Embodiment 1: The method of preparing ceramic materials by modularization using photocuring 3D printing and traditional ceramic processing technology in this embodiment is carried out in the following steps:

[0051] 1. Preparation of ceramic slurry for 3D printing: 100 g of isobornyl acrylate monomer, 3 g of polymerized isobornyl acrylate, 500 g of alumina ceramic powder, 10 g of dispersant BYK, and 0.3 g of 819 photoinitiator were weighed, added into a ball mill at room temperature, and ball milled for 4 hours to obtain ceramic slurry; wherein the preparation method of polymerized isobornyl acrylate is as follows: 0.5 g of TPO photoinitiator was added to 100 g of isobornyl acrylate, mixed evenly, and then obtained by photocuring 3D printing with a DLP printer; the mass content of alumina ceramic powder in the ceramic slurry was 81.5%;

[0052] Second, use software on the computer to split the target large-size ceramic model into a simple structure module and a complex structure module that are connected to each other, leaving a smooth flat connection surface between the two modules for easy contact and assembly;

[0053] 3. Purchase pure alumina ceramic material modules with simple structures prepared by traditional ceramic processing technology;

[0054] Fourth, import the 3D model of the complex structure module into the DLP printer, then inject the ceramic slurry prepared in step 1 into the material tank of the DLP printer, start the light-curing 3D printing, and obtain the complex structure module green body; remove the complex structure module green body on the printing platform, clean the residual slurry on the surface of the module with water, and dry it naturally after cleaning;

[0055] 5. Assemble the pure alumina ceramic material module of the simple structure and the green body of the complex structure module together, apply n-butyl acetate on the connection surface of the two structural modules, and apply pressure on both sides of the interface to make the structural modules stick together and keep them for 10 minutes to connect the two modules into one, so as to obtain a prefabricated blank in which the ceramic module and the green body module are connected as one;

[0056] 6. Place the preform into a sintering furnace, heat it to 120°C at a heating rate of 1°C / min and keep it for 2 hours, then heat it to 150°C and keep it for 2 hours, then heat it to 600°C and keep it for 2 hours for degreasing; finally heat it to 1600°C and sinter it for 3 hours to obtain a large-sized ceramic material.

[0057] The scanning electron microscope photograph of the preform in which the ceramic module and the green module are integrated in step 5 of this embodiment is as follows: Figure 2 As shown, from Figure 2It can be seen that there is an obvious connection interface between the ceramic module and the green body module, and the powder in the green body is tightly packed on the microscopic interface of the ceramic material.

[0058] Figure 3 This is a scanning electron microscope photo of the step 6 of this embodiment after being kept at 120°C for 2 hours. Figure 4 is a scanning electron microscope photograph of the step 6 of this embodiment after degreasing at 600°C for 2h; Figure 3 and Figure 4 It can be seen that during the heating and degreasing process, as the temperature increases, the powder and ceramic interface are more densely packed.

[0059] Figure 5 is a scanning electron microscope photograph of the large-sized ceramic material obtained after sintering at 1600°C for 3 hours in this embodiment. Figure 5 It can be seen that after sintering, the ceramic module and the green module have become a ceramic material connected as one.

[0060] Comparative Example 1: This comparative example is different from Example 1 in that step 1 is replaced by the following operation:

[0061] 1. Preparation of ceramic slurry for 3D printing: weigh 100 g of isobornyl acrylate monomer, 3 g of polymerized isobornyl acrylate, 350 g of alumina ceramic powder, 10 g of dispersant BYK, and 0.3 g of 819 photoinitiator, add them into a ball mill at room temperature, and ball mill for 4 hours to obtain ceramic slurry; wherein the preparation method of polymerized isobornyl acrylate is as follows: add 0.5 g of TPO photoinitiator to 100 g of isobornyl acrylate, mix well, and then use a DLP printer to obtain it by photocuring 3D printing; the mass percentage of alumina ceramic powder in the ceramic slurry is 75.5%;

[0062] The other steps and parameters are the same as those in Example 1.

[0063] The large-sized ceramic material prepared under the conditions of this comparative example 1, because the content of alumina ceramic powder in the ceramic slurry in step 1 is 75.5%, and the alumina of the purchased pure alumina ceramic material module is 100%, the difference between the alumina content in the green body of the complex structure module printed by 3D and the alumina content in the pure alumina ceramic material module is 24.5%, the difference is too large, resulting in stress deformation during the sintering of the ceramic, severe deformation of the sintered ceramic, and even cracking of the contact surface. Therefore, the alumina content in the green body of the complex structure module and the alumina content in the pure alumina ceramic material module must be controlled within the range of 20% to ensure the successful preparation of large-sized ceramic materials.

Claims

1. A method for modular preparation of ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology, characterized in that The method proceeds as follows:

1. Preparation of ceramic slurry for 3D printing: Weighing acrylate monomer, polymerized acrylate, ceramic powder, dispersant, and photoinitiator, adding them into a ball mill and mixing them evenly to obtain a ceramic slurry; Second, use software on the computer to split the target large-size ceramic model into simple structural modules and complex structural modules that are interconnected, leaving smooth flat connecting surfaces between the modules for easy contact and assembly; 3. Use traditional ceramic processing technology to prepare simple structural ceramic modules; 4. Import the 3D model of the complex structure module into the DLP printer, then inject the ceramic slurry into the material tank of the DLP printer, start the light-curing 3D printing, and obtain the complex structure module green body; remove the complex structure module green body on the printing platform, clean the residual slurry on the surface of the module with water; clean and dry it; 5. Assemble the simple structure ceramic module and the complex structure module green body together, apply n-butyl acetate on the connection surface of the structure module, and apply pressure on both sides of the interface to make the structure module stick tightly and keep it for 10 to 30 minutes, connect the modules together, and obtain a prefabricated body in which the ceramic module and the green body module are connected as one; 6. Place the preform into a sintering furnace, heat it to 120-125°C at a heating rate of 0.1-2°C / min and keep it for 2-5 hours, then heat it to 150-155°C and keep it for 2-5 hours, and finally heat it to 600-620°C and keep it for 2-5 hours for degreasing; then sinter it at high temperature to obtain a large-sized ceramic material.

2. The method for preparing ceramic materials by modularization of light-curing 3D printing and traditional ceramic processing technology according to claim 1, characterized in that: The acrylic acid ester monomer described in step 1 is isobornyl acrylate, isobornyl methacrylate, neobornyl acrylate, neobornyl methacrylate or isobornyl diester acrylate.

3. The method for preparing ceramic materials by modularization of light-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The preparation method of the polymerized acrylate described in step 1 is: adding a photoinitiator accounting for 0.3% to 8% of the mass of the acrylate monomer to the acrylate monomer, mixing evenly, and performing photocuring 3D printing with a DLP printer to obtain the polymerized acrylate.

4. The method for modularly preparing ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The ceramic powder described in step 1 is aluminum oxide or zirconium oxide ceramic powder.

5. The method for preparing ceramic materials by modularization by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The dispersant described in step 1 is BYK.

6. The method for modularly preparing ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The photoinitiator described in step 1 is 819 or TPO photoinitiator.

7. The method for modularly preparing ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The mass of the polymerized acrylate described in step 1 is 3% to 15% of the mass of the acrylate monomer.

8. The method for modularly preparing ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The amount of ceramic powder added in step 1 is to ensure that the volume content V1 of the ceramic powder in the ceramic slurry is greater than 40%.

9. The method for modularly preparing ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The amount of the photoinitiator added in step 1 is 0.3% to 8% of the sum of the mass of the acrylate monomer and the polymerized acrylate.

10. The method for modularly preparing ceramic materials by using photo-curing 3D printing and traditional ceramic processing technology according to claim 1 or 2, characterized in that: The ceramic components in the simple structure ceramic module described in step 3 are the same as the ceramic components in the complex structure module green body, and the difference between the ceramic component content in the simple structure ceramic module and the ceramic component content in the complex structure module green body does not exceed 20%.

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