Preparation method of green body recycled ceramic photocuring 3D printing paste

Abstract

The application discloses a preparation method of a green body recycling ceramic photocuring 3D printing slurry, and relates to a 3D printing slurry preparation method. The application aims to solve the technical problem of cost increase caused by the discarding of defective green bodies in the existing 3D printing ceramic method. The method comprises the following steps: calculating the mass of resin and the mass of ceramic powder contained in the recycled green body according to the quality of the recycled green body; calculating the mass of acrylic ester monomer required for dissolving the recycled green body; calculating the mass of ceramic powder required for supplementing according to the mass of acrylic ester monomer; crushing the recycled green body; adding the recycled green body powder into the acrylic ester monomer for dissolving; and finally adding ceramic powder, a dispersing agent and a photoinitiator and uniformly ball milling to obtain the 3D printing slurry for green body recycling. The slurry with the recycled green body has the same printing integrity, and the mechanical strength and appearance quality of the ceramic product after debinding and sintering are the same. The application can be used in the field of 3D printing.

Description

Technical Field

[0001] The invention relates to a method for preparing a 3D printing slurry. Background Art

[0002] Ceramics with complex geometries, multiple materials, and various sizes are used in various fields of life and production. Compared to traditional manufacturing techniques, 3D printing technology, due to its layer-by-layer construction method, can flexibly and efficiently construct complex and precise structures without relying on molds and most supports, greatly enhancing design freedom and playing an increasingly important role in ceramic manufacturing. Among them, photocuring ceramic printing technology, as a 3D printing technology with great research value and potential, is increasingly being used in ceramic manufacturing. However, current 3D printing ceramic technology still has certain problems and limitations. For example, during the printing process and sampling from the print platform, green bodies are prone to incomplete printing or damage, and printed green bodies fail to meet design requirements. Due to these reasons, defective green bodies that cannot proceed to the subsequent debinding and sintering steps must be destroyed and discarded, which greatly wastes ceramic powder and the resin material contained therein, and increases the cost of 3D printing ceramics. Therefore, there is a need to develop low-cost, green printing methods that can effectively recycle these defective green materials. Summary of the Invention

[0003] The present invention aims to solve the technical problem of increased costs caused by discarding defective green bodies in existing 3D printing ceramic methods, and to provide a method for preparing a ceramic light-cured 3D printing slurry that can recycle green bodies.

[0004] The method for preparing the green body recycled photocurable 3D printing slurry of the present invention is carried out according to the following steps:

[0005] First, the mass G of the green body to be recycled is weighed, and the mass A of the resin and the mass B of the ceramic powder contained in the recycled green body are calculated; the mass A of the resin in the recycled green body is the sum of the masses of the acrylate monomer and the polymerized acrylate added during the preparation of the recycled green body;

[0006] 2. Calculate the mass C of the acrylate monomer required to dissolve the recycled green body, where C = A / (3% to 5%); and calculate the mass D of the ceramic powder that needs to be replenished based on this. Where E% is the solid content of the 3D printing slurry;

[0007] 3. Weigh C mass of acrylate monomer, G mass of green body to be recycled, D mass of ceramic powder, (1% to 1.5%) mass of dispersant D, and (0.3% to 0.5%) mass of (C + A) photoinitiator;

[0008] 4. After the green body to be recycled is crushed, the green body powder to be recycled is added to the acrylate monomer and stirred at a temperature of 90-110°C until the recycled green body powder is dissolved and dispersed in the acrylate monomer; finally, ceramic powder, dispersant and photoinitiator are added and ball milled to mix them evenly to obtain 3D printing slurry for green body recycling.

[0009] Furthermore, the acrylate monomer in step 1 is one or a combination of isobornyl acrylate, isobornyl methacrylate, neobornyl acrylate, neobornyl methacrylate and isobornyl diester acrylate.

[0010] Furthermore, the ceramic powder in step 3 is zirconium oxide or aluminum oxide ceramic powder, and the average particle size of the powder is 450 to 500 nm;

[0011] Furthermore, the dispersant in step three is BYK.

[0012] Furthermore, the photoinitiator described in step three is 819 photoinitiator.

[0013] Furthermore, the green body to be recycled in step 1 is a defective product produced after 3D light-stereolithography printing, and its specific production process is as follows:

[0014] Weigh 100 grams of acrylate monomer, 3 to 5 grams of polymerized acrylate, 400 to 500 grams of ceramic powder, 10 to 15 grams of dispersant, and 0.3 to 0.5 grams of photoinitiator; the polymerized acrylate is prepared by adding 0.3 to 0.5 grams of photoinitiator to 100 grams of acrylate monomer, mixing well, and performing light-curing 3D printing using a DLP printer;

[0015] 2. First, add the polymerized acrylate to the acrylate monomer, heat to 95-110° C. and stir to dissolve the polymerized acrylate in the acrylate monomer to obtain a thermoplastic polymer resin;

[0016] 3. Mixing the thermoplastic polymer resin with the ceramic powder, adding a dispersant and a photoinitiator, and mixing them evenly using a ball mill to obtain a ceramic slurry;

[0017] 4. Inject the ceramic slurry into the material tank of the DLP printer and perform 3D light-curing printing to obtain a green body; collect the defective green body materials that cannot enter the subsequent degreasing and sintering steps during the printing process to obtain the green body to be recycled.

[0018] The present invention provides a low-cost, green ceramic light-curing 3D printing slurry. The thermoplastic resin component is formed by polymerizing acrylate and acrylate monomer. The thermoplastic resin component is mixed with ceramic powder, dispersant and photoinitiator by ball milling to obtain ceramic light-curing slurry. The slurry is printed into green bodies using a DLP printer. The defective green bodies can be dissolved in the polymer monomer by heating and stirring. Then, an appropriate amount of ceramic powder, dispersant and photoinitiator are added to the green bodies and ball milled to obtain new ceramic light-curing slurry, which can be used for 3D printing again. The flow chart is as follows. Figure 1 As shown in the figure, the slurry containing recycled greenware and the slurry without recycled greenware achieved the same print integrity during printing. After degreasing and sintering, the resulting 3D-printed alumina ceramic products had the same mechanical strength and appearance quality. Repeating this process allowed any defective greenware produced during each print to be recycled, successfully achieving the recycling of ceramic powder and resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a process flow chart for preparing a ceramic light-cured 3D printing slurry for recycling green compacts of the present invention; in the figure, 1 is a 3D printer, 2 is a green compact to be recycled, and 3 is a ceramic slurry;

[0020] Figure 2 This is a photo of the 3D printed alumina ceramic product obtained after sintering the qualified green body in step 4 of Example 1 and the recycled green body. DETAILED DESCRIPTION

[0021] The beneficial effects of the present invention are demonstrated with the following examples.

[0022] Example 1: The preparation method of the green body recycled ceramic light-cured 3D printing slurry of this embodiment is carried out according to the following steps:

[0023] 1. First, weigh 100 g of isobornyl acrylate monomer, 4 g of polymerized isobornyl acrylate, 500 g of alumina ceramic powder with an average particle size of 500 nm, 10 g of BYK dispersant, and 0.3 g of 819 photoinitiator; the polymerized isobornyl acrylate is prepared by adding 0.5 g of 819 photoinitiator to 100 g of isobornyl acrylate monomer, mixing well, and then performing light-curing 3D printing using a DLP printer;

[0024] 2. First, add polymerized isobornyl acrylate to isobornyl acrylate monomer, heat to 100° C. and stir to dissolve the polymerized isobornyl acrylate in the isobornyl acrylate monomer to obtain a thermoplastic polymer resin;

[0025] 3. Mixing thermoplastic polymer resin with alumina ceramic powder, adding dispersant BYK and 819 photoinitiator, and mixing them evenly using a ball mill to obtain ceramic slurry;

[0026] Fourth, the ceramic slurry is injected into the material tank of the DLP printer and 3D light-curing printing is performed to obtain a green body; and the defective green body materials that cannot enter the subsequent degreasing and sintering steps during the printing process are collected as the green bodies to be recycled;

[0027] 5. First, based on the mass G of the green body to be recycled, G = 50 grams, calculate the mass A of the resin and the mass B of the alumina ceramic powder contained in the recycled green body, where A = 8.5 grams and B = 40.7 grams;

[0028] 6. Calculate the mass C of the isobornyl acrylate monomer required to dissolve the recycled green compact, where C = A / 4% = 212.5 g; and calculate the mass D of the ceramic powder that needs to be replenished based on this. Where E% is the solid content of the 3D printing slurry, E% = 81.4%; D = 926.5 grams;

[0029] 7. Weigh 212.5 grams of isobornyl acrylate monomer, 50 grams of green body to be recycled, 926.5 grams of alumina ceramic powder with an average particle size of 500 nm, 9.3 grams of BYK dispersant, and 0.9 grams of 819 photoinitiator;

[0030] 8. After the green body to be recycled is crushed, the green body powder to be recycled is added to the isobornyl acrylate monomer and stirred at a temperature of 90-110°C until the recycled green body powder is dissolved and dispersed in the isobornyl acrylate monomer; finally, alumina ceramic powder, dispersant BYK and 819 photoinitiator are added and ball milled to mix them evenly to obtain a 3D printing slurry for green body recycling.

[0031] The solid content of the 3D printing slurry obtained in step eight of this embodiment is 81.4%.

[0032] The recycled 3D printing slurry from step 8 was injected into the DLP printer's hopper for 3D photocuring printing to produce a recycled green body. Comparing the recycled green body with the qualified green body from step 4 revealed that both had the same printing integrity.

[0033] Then, the recycled green body and the qualified green body obtained in step 4 were heated to 120℃ at a heating rate of 1.5℃ / min and kept warm for 2h, then heated to 150℃ and kept warm for 2h, and then heated to 600℃ and kept warm for 2h for degreasing; finally, the temperature was raised to 1600℃ and sintered at high temperature for 2h to obtain a 3D printed alumina ceramic product. The photo of the 3D printed alumina ceramic product obtained after sintering the qualified green body in step 4 and the recycled green body is shown in the figure below. Figure 2 As shown, A is the alumina ceramic product prepared from the qualified green body in step 4, and B is the alumina ceramic product prepared from the recycled green body. Figure 2It can be seen that for the same complex structure, the curing and molding capabilities of the original slurry and the recycled slurry are the same, which also proves that the recycled slurry has the same ceramic printing and molding capabilities as the original slurry.

[0034] The examples demonstrate that recycling defective green materials during the printing cycle reduces the cost of photocuring ceramic printing and conserves components such as ceramic powder and resin. Defective green materials from conventional printing processes can be processed and reused, minimizing material waste. Furthermore, unlike conventional green materials, which contain difficult-to-degrade thermosetting polymer components and are difficult to handle, potentially causing environmental pollution, the green materials prepared using thermoplastic resin components in this example can be recycled, effectively protecting the natural environment.

Claims

1. A method for preparing a ceramic photocurable 3D printing slurry for recycling green body, characterized in that The method proceeds as follows:

1. Weigh the mass G of the green body to be recycled, and calculate the mass A of the resin and the mass B of the ceramic powder contained in the green body to be recycled; the mass A of the resin in the recycled green body is the sum of the masses of the acrylate monomer and the polymerized acrylate added during the preparation of the recycled green body; 2. Calculate the mass C of the acrylate monomer required to dissolve the recycled green body, where C = A / (3%~5%); and calculate the mass D of the ceramic powder that needs to be replenished based on this. ; Where E% is the solid content of 3D printing slurry; 3. Weigh C mass of acrylate monomer, G mass of green body to be recycled, D mass of ceramic powder, (1% to 1.5%) mass of dispersant D, and (0.3% to 0.5%) mass of photoinitiator (C + A); 4. After the green body to be recycled is crushed, the green body powder to be recycled is added to the acrylate monomer and stirred at a temperature of 90-110°C until the recycled green body powder is dissolved and dispersed in the acrylate monomer; finally, ceramic powder, dispersant and photoinitiator are added and ball milled to mix them evenly to obtain a 3D printing slurry for green body recycling; The green body to be recycled in step 1 is a defective product produced after 3D light-curing printing. The specific production process is as follows: (1) Weigh 100 g of acrylate monomer, 3-5 g of polymerized acrylate, 400-500 g of ceramic powder, 10-15 g of dispersant, and 0.3-0.5 g of photoinitiator; wherein the polymerized acrylate is prepared by adding 0.3-0.5 g of photoinitiator to 100 g of acrylate monomer, mixing well, and then performing photocuring 3D printing using a DLP printer; (2) First, add the polymerized acrylate to the acrylate monomer, heat it to 95-110°C and stir it to dissolve the polymerized acrylate in the acrylate monomer to obtain a thermoplastic polymer resin; (3) Mixing the thermoplastic polymer resin with the ceramic powder, adding a dispersant and a photoinitiator, and mixing them evenly using a ball mill to obtain a ceramic slurry; (4) Inject the ceramic slurry into the material tank of the DLP printer and perform 3D light-curing printing to obtain a green body; The defective green materials that cannot enter the subsequent degreasing and sintering steps during the printing process are collected to obtain green bodies to be recycled.

2. The method for preparing a ceramic light-cured 3D printing slurry for recycling green body according to claim 1, characterized in that: The acrylic acid ester monomer described in step 1 is one or a combination of isobornyl acrylate, isobornyl methacrylate, neobornyl acrylate, neobornyl methacrylate and isobornyl diester acrylate.

3. The method for preparing a ceramic light-cured 3D printing slurry for recycling green body according to claim 1 or 2, characterized in that: The ceramic powder in step three is zirconium oxide or aluminum oxide ceramic powder.

4. The method for preparing a ceramic light-cured 3D printing slurry for recycling green body according to claim 1 or 2, characterized in that: The average particle size of the ceramic powder described in step 3 is 450-500 nm.

5. The method for preparing a ceramic light-cured 3D printing slurry for recycling green body according to claim 1 or 2, characterized in that: The dispersant described in step 3 is BYK.

6. The method for preparing a ceramic light-cured 3D printing slurry for recycling green body according to claim 1 or 2, characterized in that: The photoinitiator described in step three is 819 photoinitiator.

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