A modular method for preparing ceramic materials by combining photocuring 3D printing with traditional ceramic processing technology

Abstract

A method for modularly preparing ceramic materials by collaboratively utilizing photocuring 3D printing and traditional ceramic processing technology. This method relates to a modular collaborative manufacturing method for photocuring 3D printed ceramics and traditional ceramic processing technology. The method provides a low-cost, high-efficiency modular collaborative manufacturing method for ceramic materials by collaboratively utilizing photocuring 3D printing and traditional ceramic processing technology. The method of the present invention utilizes a ceramic printing slurry prepared using a solvent-responsive polymer resin as a substrate, uses a DLP printer to print and form multiple ceramic green modules, utilizes n-butyl acetate as a solvent to stimulate and activate the surface of the green modules, and welds them together with ceramic modules manufactured using traditional technology. After undergoing a degreasing and sintering process, a ceramic material with a complete integrated structure is obtained. This method reduces the total cost of ceramic printing and can be used in the field of ceramic preparation.

Description

Technical Field

[0001] The present invention relates to a modular collaborative manufacturing method for light-cured 3D printed ceramics and traditional ceramic processing technology. Specifically, the present invention relates to a modular construction method for realizing the collaboration between light-cured 3D printed ceramics and traditional ceramics to manufacture ceramic materials. Background Art

[0002] 3D-printed ceramics, a booming emerging technology, has broken through the limitations of traditional ceramic processing technology's reliance on molds. By employing a layer-by-layer construction approach, it achieves greater freedom in forming complex ceramic structures, significantly enhancing the freedom of structural design and paving the way for the further development and application of modern ceramic materials in many fields. Of course, we should also be aware that 3D-printed ceramics and traditional ceramic processing technologies are not mutually exclusive. Traditional ceramic processing technologies are capable of mass-producing simpler ceramic materials on a large scale, while 3D printing technology is currently limited by printer efficiency and cannot achieve large-scale production. Therefore, the combination and complementarity of these two manufacturing technologies will be an important direction for the future development of ceramic manufacturing.

[0003] However, barriers exist between established traditional manufacturing technologies and emerging 3D printing technologies, preventing them from complementing each other. This problem has limited both the large-scale adoption of 3D printing ceramics in ceramic production and the further development and upgrading of traditional manufacturing technologies. Therefore, building upon existing light-curing 3D printing ceramics technology, a low-cost, high-efficiency modular ceramic material manufacturing technology combining these two technologies is needed. 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 collaboratively combining photocuring 3D printing with traditional ceramic processing technology. Based on a ceramic printing slurry prepared with a solvent-responsive polymer resin as a base, 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 then welded to a ceramic module manufactured by traditional technology into a whole. After a degreasing and sintering process, an integrated ceramic material with a complete structure is obtained.

[0005] The modular method for preparing ceramic materials by combining photocuring 3D printing with traditional ceramic processing technology is carried out in 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 to a ball mill and mixing them evenly to obtain a ceramic slurry;

[0008] Second, use software on a computer to split the target large-scale ceramic model into interconnected simple structure modules and complex structure modules, leaving smooth flat connection surfaces between the modules for easy contact and assembly;

[0009] 3. Use traditional ceramic processing technology to prepare simple structure 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 and start the light-curing 3D printing to obtain the complex structure module green body; remove the complex structure module green body from the printing platform, clean the residual slurry on the surface of the module with water, and then 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 structural module, and apply pressure on both sides of the interface to make the structural module tightly attached and maintain for 10 to 30 minutes, and connect the modules into one to obtain a prefabricated body with the ceramic module and the green body module connected as one.

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

[0013] Furthermore, the acrylate monomer 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% by mass of the acrylate monomer to the acrylate monomer, mixing evenly, and performing light-curing 3D printing with a DLP printer to obtain the polymerized acrylate.

[0015] Furthermore, the ceramic powder in step 1 is alumina or zirconia ceramic powder.

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

[0017] Furthermore, the photoinitiator in step 1 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 V1 of the ceramic powder in the ceramic slurry is 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 the powder metallurgy method is as follows:

[0024] (1) Raw material preparation: Ceramic raw material powders are mixed and a binder and a lubricant are added to obtain a mixed powder;

[0025] (2) Molding: The mixed powder is pressed into shape using a mold. 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 for preparing a simple structure ceramic module by the laser sintering method is as follows:

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

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

[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 light-curing 3D printing ceramics and traditional ceramic processing technology, breaking through the collaborative barriers between light-curing 3D printing ceramic technology and traditional ceramic processing and manufacturing technology. It uses a DLP printer to print ceramic slurry into multiple ceramic green modules; one or more ceramic green modules are connected to ceramic modules sintered and processed using traditional manufacturing methods by solvent welding to form their interfaces into one body to obtain a preform; the preform is degreased and sintered to obtain an integrated complete ceramic. The process flow diagram is shown below. Figure 1 As shown. The present invention uses DLP printing to form multiple small-volume ceramic green sheets with complex structures and formed ceramics 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 an external solvent, the printed green sheet forms a highly fluid gel layer at the interface, and the gel layer diffuses to the surface of the formed ceramic material to form a tightly connected layer. At this interface, the ceramic powder and the surface of the ceramic material are in a microscopically close contact state. Subsequently, after degreasing, accompanied by the decomposition of the polymer components, the green sheet material undergoes an inward shrinkage process based on the connection surface. This shrinkage 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 powder and the ceramic microcrystalline structure are closely fitted together enough 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 on a macroscopic level.

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

[0038] 1. It increases the configuration possibilities of 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 printing efficiency of light-curing 3D printed ceramics. Since some modules can be mass-produced using traditional manufacturing technology, the workload of 3D printing is effectively saved and work efficiency is improved.

[0040] 3. Breaking through the size limitations of stereolithography printers, enabling them to print across multiple sizes. Large ceramic structures can be broken down into multiple modules for batch printing, and some large, simple components can be manufactured using traditional production methods. This allows stereolithography printers to mold ceramic materials beyond their printable size range using traditional manufacturing techniques.

[0041] 4. Achieve cross-temporal collaboration in ceramic printing. Ceramic modules can be produced in areas equipped with traditional ceramic production centers, and green modules can be produced in areas equipped with printers. The modules are then sealed and sent to the same location for connection, followed by debinding and sintering to produce an integrated ceramic material.

[0042] 5. Improve the fault tolerance of ceramic photolithography printing and reduce the total printing cost. Traditional methods have extremely low tolerance for printing ceramic materials. If defects or equipment problems occur during the printing process, the entire print will be scrapped. With this method, some modules are produced and processed using more stable traditional manufacturing technologies. 3D printing only needs to be responsible for a portion of the components, improving fault tolerance. Traditional manufacturing has lower mass production costs, so the processing of some modules is shared with it, reducing 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 Flowchart showing the modular preparation of ceramic materials using photocuring 3D printing and traditional ceramic processing technology. 1 represents a simple structure ceramic module, 2 represents a complex structure module, 3 represents n-butyl acetate, 4 represents a 3D printer, and 5 represents a large-scale ceramic material.

[0045] Figure 2 This 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 of the step 6 of Example 1 after being kept at 120° C. for 2 hours;

[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 demonstrated with the following examples.

[0050] Example 1: The modular method for preparing ceramic materials by combining photocuring 3D printing with traditional ceramic processing technology is carried out as follows:

[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 BYK dispersant, and 0.3 g of 819 photoinitiator were weighed, added to a ball mill at room temperature, and ball milled for 4 hours to obtain a ceramic slurry. The polymerized isobornyl acrylate was prepared by adding 0.5 g of TPO photoinitiator to 100 g of isobornyl acrylate, mixing well, and then 3D printing using a DLP printer via light-curing. The mass content of alumina ceramic powder in the ceramic slurry was 81.5%.

[0052] Second, use software on a computer to split the target large-scale 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] 4. 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 from the printing platform, clean the residual slurry on the surface of the module with water, and then dry it naturally after cleaning;

[0055] 5. Assemble a simple structure pure alumina ceramic material module and a complex structure module green body together, apply n-butyl acetate on the connecting surface of the two structural modules, and apply pressure on both sides of the interface to make the structural modules stick together and maintain it for 10 minutes to connect the two modules into one, thereby obtaining a prefabricated body with the ceramic module and green body module connected as one.

[0056] 6. Place the preform in a sintering furnace, heat it to 120°C at a heating rate of 1°C / min and keep it there for 2 hours, then heat it to 150°C and keep it there for 2 hours, then heat it to 600°C and keep it there 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 module, and the powder in the green module is tightly packed on the microscopic interface of the ceramic material.

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

[0059] Figure 5 This is a scanning electron microscope photo of the large-sized ceramic material obtained after sintering at 1600°C for 3 hours. 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 differs from Example 1 in that step 1 is replaced by the following operation:

[0061] 1. Preparation of 3D printing ceramic slurry: Weigh 100 g of isobornyl acrylate monomer, 3 g of polymerized isobornyl acrylate, 350 g of alumina ceramic powder, 10 g of BYK dispersant, and 0.3 g of 819 photoinitiator, add them to a ball mill at room temperature, and ball mill for 4 hours to obtain a ceramic slurry. The polymerized isobornyl acrylate is prepared by adding 0.5 g of TPO photoinitiator to 100 g of isobornyl acrylate, mixing well, and then printing the mixture by light-curing 3D printing using a DLP printer. The weight percentage of alumina ceramic powder in the ceramic slurry is 75.5%.

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

[0063] The large-scale ceramic material prepared under the conditions of Comparative Example 1 exhibits a 75.5% alumina ceramic powder content in the ceramic slurry in Step 1, while the purchased pure alumina ceramic material module contains 100% alumina. This significant difference in alumina content between the 3D-printed complex structure module green body and the pure alumina ceramic material module is 24.5%. This excessive difference results in stress deformation during sintering, severe deformation of the sintered ceramic, and even cracking of the contact surface. Therefore, the alumina content in the complex structure module green body and the pure alumina ceramic material module must be controlled within a 20% range to ensure the successful preparation of large-scale ceramic materials.

Claims

1. A modular method for preparing ceramic materials by combining photocuring 3D printing with 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 to a ball mill and mixing them evenly to obtain a ceramic slurry; Second, use software on a computer to split the target large-scale ceramic model into interconnected simple structure modules and complex structure modules, leaving smooth flat connection surfaces between the modules for easy contact and assembly; 3. Use traditional ceramic processing technology to prepare simple structure 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 and start the light-curing 3D printing to obtain the complex structure module green body; remove the complex structure module green body from the printing platform, clean the residual slurry on the surface of the module with water, and then 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 structural module, and apply pressure on both sides of the interface to make the structural module tightly attached and maintain for 10 to 30 minutes, and connect the modules into one to obtain a prefabricated body with the ceramic module and the green body module connected as one.

6. Place the preform in a sintering furnace, heat it to 120-125°C at a heating rate of 0.1-2°C / min and keep it warm for 2-5 hours, then heat it to 150-155°C and keep it warm for 2-5 hours, and finally heat it to 600-620°C and keep it warm for 2-5 hours for degreasing; then sinter it at high temperature to obtain a large-sized ceramic material.

2. The method for modularly preparing ceramic materials by combining photocuring 3D printing with traditional ceramic processing technology according to claim 1, characterized in that: The acrylate monomer described in step 1 is isobornyl acrylate, isobornyl methacrylate, neobornyl acrylate, neobornyl methacrylate or isobornyl diester acrylate.

3. The method for modularly preparing ceramic materials by combining photocuring 3D printing with 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% by mass of the acrylate monomer to the acrylate monomer, mixing evenly, and performing light-curing 3D printing with a DLP printer to obtain the polymerized acrylate.

4. The method for modularly preparing ceramic materials by combining photocuring 3D printing with traditional ceramic processing technology according to claim 1 or 2, characterized in that: The ceramic powder in step 1 is aluminum oxide or zirconium oxide ceramic powder.

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

8. The method for modularly preparing ceramic materials by combining photo-curing 3D printing with 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 combining photo-curing 3D printing with 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 combining photo-curing 3D printing with 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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