Preparation method of ceramic photocuring 3D printing slurry with recycled green bodies

Abstract

The invention relates to a preparation method of 3D printing slurry, in particular to a preparation method of ceramic photocuring 3D printing slurry with recycled green bodies. The technical problem that according to an existing ceramic 3D printing method, the cost is increased due to discarding of defective green bodies is solved. The method comprises the following steps: calculating the mass of resin and the mass of ceramic powder contained in a circulating green body according to the mass of the to-be-circulated green body; calculating the mass of the acrylate monomer required for dissolving the circulating green body; the mass of the ceramic powder needing to be supplemented is calculated according to the formula; the preparation method comprises the following steps: crushing a to-be-recycled green body, adding to-be-recycled green body powder into an acrylate monomer, dissolving, finally adding ceramic powder, a dispersing agent and a photoinitiator, and carrying out uniform ball milling to obtain the 3D printing slurry for recycling the green body. And the slurry has the same printing integrity as the slurry without the to-be-circulated green body, and the degreased and sintered ceramic product has the same mechanical strength and appearance quality. The method can be used in the 3D printing field.

Description

Technical Field

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

[0002] Ceramic materials with complex geometric shapes and various sizes of multiple materials are used in various fields of social production and life. Compared with traditional manufacturing technology, 3D printing technology can flexibly and efficiently build complex and precise structures without relying on molds and most supports due to its layer-by-layer manufacturing method, and fully improve the degree of design freedom, playing an increasingly important role in the field of ceramic manufacturing. Among them, photocuring printing ceramic technology, as a 3D printing ceramic technology with great research value and potential, is increasingly used in the field of ceramic manufacturing. However, there are still certain problems and limitations in 3D printing ceramic technology, such as: incomplete printing or damage of green blanks is very likely to occur during the printing process and sampling from the printing platform, or the printed green blanks cannot meet the requirements due to design problems. Due to the above reasons, the defective green blanks that cannot enter the subsequent degreasing and sintering steps can only be destroyed and discarded, which greatly wastes ceramic powder and the resin material therein, and increases the cost of 3D printing ceramics. Therefore, it is necessary to develop a low-cost, green printing method that can effectively recycle such defective green blank materials. Summary of the invention

[0003] The present invention aims to solve the technical problem of the existing 3D printing ceramic method that the cost is increased due to the discarding of defective green bodies, and provide a method for preparing a ceramic photocuring 3D printing slurry with recycled green bodies.

[0004] The method for preparing the ceramic photocuring 3D printing slurry for recycling green body 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 green body are calculated; wherein the mass A of the resin in the green body is the sum of the masses of the acrylate monomer and the polymerized acrylate added during the preparation of the green body;

[0006] 2. Calculate the mass C of the acrylic ester 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 milling is performed to mix them evenly to obtain 3D printing slurry for green body recycling.

[0009] Furthermore, 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.

[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 450-500 nm;

[0011] Furthermore, the dispersant described 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 photocuring 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; wherein the preparation method of the polymerized acrylate is: add 0.3 to 0.5 grams of photoinitiator to 100 grams of acrylate monomer, mix well, and perform photocuring 3D printing with 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 with 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 photocurable 3D printing slurry, which is polymerized acrylate and acrylate monomer to form a thermoplastic resin component, the thermoplastic resin component is ball-milled with ceramic powder, dispersant and photoinitiator to obtain ceramic photocurable slurry, and the slurry is printed and formed into a green body using a DLP printer, wherein the defective green body can be dissolved in the polymer monomer by heating and stirring, and then an appropriate amount of ceramic powder, dispersant and photoinitiator are added thereto, and ball-milled to obtain a new ceramic photocurable slurry, which can be used for 3D printing again. The flow chart is as follows Figure 1 As shown. The slurry with recycled green body and the slurry without recycled green body have the same printing integrity during printing. After degreasing and sintering, the 3D printed alumina ceramic products have the same mechanical strength and appearance quality. Repeating the above process allows the defective green body produced in each printing to be recycled, successfully realizing the recycling of ceramic powder and resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a process flow chart of preparing a ceramic photocurable 3D printing slurry for recycling green body of the present invention; in the figure, 1 is a 3D printer, 2 is a green body 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 verified by the following examples.

[0022] Embodiment 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 dispersant BYK, and 0.3 g of 819 photoinitiator; wherein the preparation method of polymerized isobornyl acrylate is as follows: add 0.5 g of 819 photoinitiator to 100 g of isobornyl acrylate monomer, mix well, and then perform photocuring 3D printing with a DLP printer;

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

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

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

[0027] 5. First, according to 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 body, 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 dispersant BYK, 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 milling is performed to mix them evenly to obtain 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 obtained in step 8 is injected into the material tank of the DLP printer for 3D photocuring printing to obtain a recycled green body. Comparing the recycled green body with the qualified green body in step 4, it is found that the two green bodies have 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 for 2h, then heated to 150℃ for 2h, and then heated to 600℃ for 2h for degreasing; finally, the temperature was raised to 1600℃ for high temperature sintering 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. 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 show that the recycling of defective green materials in the printing cycle reduces the cost of ceramic photocuring printing and saves components such as ceramic powder and resin. The defective green materials in the general printing process can be reused after processing, which avoids material waste to a limited extent. In addition, compared with the defective green materials in the general printing process, which contain difficult-to-degrade thermosetting polymer components and are difficult to handle, causing environmental pollution, the green materials prepared with thermoplastic resin components in this embodiment can be recycled and effectively protect 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. First, 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 recycled green body; 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 acrylic ester 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; 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; 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 milling is performed to mix them evenly to obtain 3D printing slurry for green body recycling.

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

4. The method for preparing a ceramic photocurable 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 photocurable 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 photocurable 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.

7. The method for preparing a ceramic photocurable 3D printing slurry for recycling green body according to claim 1 or 2, characterized in that: The green body to be recycled in step 1 is a defective product produced after 3D light-curing printing, and its 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 preparation method of the polymerized acrylate is: add 0.3-0.5 g of photoinitiator to 100 g of acrylate monomer, mix well, and perform photocuring 3D printing with a DLP printer; 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; 3. Mixing the thermoplastic polymer resin with the ceramic powder, adding a dispersant and a photoinitiator, and mixing them evenly with 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 billets to be recycled.

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