Preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup

Abstract

The invention discloses a preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup. The steps are as follows: preparing 3D printing slurry: the slurry includes ceramic clay, pulp and water; the components of the ceramic clay include ceramic powder, pore-forming agent and additive; printing the cup body; printing the heat-insulating structure: printing the 3D printing slurry into a cross-grid structure to obtain the heat-insulating structure; bonding: bonding the heat-insulating structure to the outer wall of the cup body through the 3D printing slurry; firing. The invention adopts 3D printing slurry with a specific formula, and makes a porous lightweight ceramic material through 3D printing technology. The ceramic cup body and heat-insulating structure made thereof can reduce their weight while ensuring good strength. The heat-insulating structure with a cross-grid structure arranged on the surface of the cup body can effectively solve the problem of heat insulation of the cup wall of the ceramic cup, and enriches the diversity of the ceramic cup, and can realize the rapid and large-scale industrial production of lightweight heat-insulating ceramic cups with complex structures.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing ceramic materials, and particularly to a preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup. Background Art

[0002] Traditional ceramic cups have poor heat-insulating effects. Therefore, it is usually necessary to set handles on the ceramic cups to avoid scalding hands when boiling water is contained in the cups. However, the single handle setting is difficult to meet the diverse needs of consumers for ceramic cups, and it is still difficult to solve the problem of the heat-insulating property of the cup wall of the ceramic cup when only handles are set, and there is still a risk of scalding when accidentally touching the cup wall. The reason why existing ceramic cups do not have a more complex heat-insulating structure on the cup wall is that, on the one hand, the density of ceramic materials is large, and setting a complex heat-insulating structure will cause the cup body to be relatively heavy, which is not conducive to use; on the other hand, when making ceramic cups at present, traditional manual potter's wheel forming technology is generally adopted, and setting a more complex heat-insulating structure will lead to complex processing technology, which is not conducive to large-scale industrial production.

[0003] 3D printing technology is an additive manufacturing method that can quickly generate ceramic bodies with complex structures. Compared with traditional ceramic forming technology, this technology can be unrestricted by mold making or processing technology, providing a way for the forming of complex ceramic products, greatly reducing the processing procedures, and shortening the processing cycle. The printing material is one of the key factors restricting the development of ceramic 3D printing technology. When preparing ceramic products by 3D printing technology, on the one hand, it is necessary to ensure that the ceramic slurry has a certain fluidity to meet the forming requirements of 3D printing; on the other hand, it is also necessary to ensure that the formed product has a small shrinkage and deformation rate after firing, and the fired product is not prone to cracks and defects. Therefore, developing a preparation method of a lightweight ceramic material that can be formed by 3D printing can solve the problem that it is difficult to set a heat-insulating structure on the surface of a ceramic cup in the prior art, improve the use performance of the ceramic cup, and enrich its diversity. Summary of the Invention

[0004] The present invention aims to overcome the problems of large weight and poor heat-insulating performance of ceramic cups in the prior art, and provides a preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup. By using a 3D printing slurry with a specific formula and through 3D printing technology, a porous lightweight ceramic material is prepared. The ceramic cup body and heat-insulating structure made of it can reduce its weight while ensuring good strength. The heat-insulating structure with a cross-grid structure arranged on the surface of the cup body can effectively solve the problem of the heat-insulating property of the cup wall of the ceramic cup, and enrich the diversity of the ceramic cup, and can realize the rapid and large-scale industrial production of lightweight heat-insulating ceramic cups with complex structures.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] A preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup, comprising the following steps:

[0007] (1) Prepare 3D printing slurry: Mix ceramic mud and pulp evenly, add water and stir until the water content is 25-30wt%, to obtain the 3D printing slurry. The mass ratio of the ceramic mud to the pulp is 100:10-15; the preparation method of the ceramic mud is: dissolve the pore-forming agent in water to obtain a ball-milling liquid, add the ceramic powder and the additive to the ball-milling liquid for ball-milling; then obtain the ceramic mud after pressure filtration, vacuum clay kneading, aging, and drying;

[0008] The preparation method of the additive is: A) React decanediamine with dimethyl maleate to obtain aspartic acid ester; B) React the obtained aspartic acid ester with polyethylene glycol monomethyl ether to obtain the additive;

[0009] (2) Cup body printing: Print the prepared 3D printing slurry through 3D printing to form a cup body;

[0010] (3) Heat-insulating structure printing: Print the prepared 3D printing slurry through 3D printing into a cross-grid structure to obtain a heat-insulating structure;

[0011] (4) Bonding: Bond the printed heat-insulating structure on the outer wall of the cup body through 3D printing slurry to obtain a ceramic cup blank; (5) Firing: Fire the ceramic cup blank to obtain the lightweight 3D printed heat-insulating and anti-slip ceramic cup.

[0012] In the present invention, the ceramic powder, pore-forming agent, and additive are ball-milled to make ceramic mud, and the ceramic mud and pulp are mixed and then water is added to make 3D printing slurry. During the firing process, the pore-forming agent, additive, and pulp can be decomposed and removed, forming pores in the ceramic product, to obtain a ceramic cup body and heat-insulating structure with a porous structure. The formation of the porous structure can effectively reduce the density of the ceramic product and reduce its weight. Using this porous lightweight ceramic material to make a heat-insulating structure with a cross-grid structure and setting it on the surface of the ceramic cup body can effectively improve the heat-insulating performance and anti-slip performance of the cup body without making the weight of the ceramic cup too heavy, and avoid scalding when the hand directly contacts the cup wall; at the same time, the setting of the heat-insulating structure can also enrich the surface decoration of the ceramic cup and meet the diverse needs of consumers. The ceramic cup body and heat-insulating structure of the present invention are prepared by 3D printing technology, which can be unrestricted by mold making or processing technology, is suitable for the forming of complex heat-insulating structures, greatly reduces the processing procedures, shortens the processing cycle, and can realize the large-scale industrial production of heat-insulating ceramic cups.

[0013] However, the formation of the porous structure will reduce the density of the ceramic product, increase the shrinkage and deformation rate of the green body, and the fired product is prone to cracks and defects. Therefore, pulp is added to the slurry in the present invention, and the ceramic powder is ball-milled; the fibers in the pulp can reduce the shrinkage and deformation rate of the green body, making the fired product not easily cracked and deformed; ball-milling can reduce the fineness of the ceramic powder, improve the plasticity of the mud and the density of the green body. In order to further improve the quality of the green body, a specific structure additive is also added during the ball-milling process in the present invention. During the preparation process of the additive used in the present invention, first, through the Michael addition reaction of sebac diamine and dimethyl maleate, an aspartic acid ester with a hydrophobic aliphatic carbon chain in the middle and four ester groups at both ends is prepared; then, through the transesterification reaction of the ester group with the hydroxyl group in polyethylene glycol monomethyl ether, a hydrophilic chain segment is connected to the four end groups of the aspartic acid ester to obtain an aspartic acid ester with a specific length of hydrophobic chain segment in the middle of the molecular chain and hydrophilic chain segments extending outward at both ends; when used as a ball-milling additive, during the ball-milling process, the hydrophobic chain segment adsorbs on the surface of the powder, and the hydrophilic chain segment extends outward, which can reduce the surface energy of the powder, prevent the agglomeration of the powder, reduce the viscosity of the slurry, improve its fluidity, and improve the ball-milling efficiency; at the same time, the polymer molecular chains at the end groups of the additive wrapped on the surface of the powder can be intertwined with each other, play a bridging role between the powders, form a three-dimensional network structure, make the powder particles more closely combined, thereby improving the density and strength of the green body, and the fired product is not easily cracked, deformed and formed with defects, improving the quality of the ceramic cup.

[0014] Preferably, the reaction method of step A) is: mixing sebac diamine with sodium methoxide catalyst, then heating to 70 - 90 °C, dropping dimethyl maleate under nitrogen protection, and keeping the temperature for reaction for 12 - 24 h to obtain aspartic acid ester; the molar ratio of sebac diamine to dimethyl maleate is 1:2 - 2.2, and the addition amount of sodium methoxide catalyst is 0.5 - 1% of the total mass of sebac diamine and dimethyl maleate.

[0015] Preferably, the reaction method of step B) is: mixing the obtained aspartic acid ester and polyethylene glycol monomethyl ether, adding sodium methoxide catalyst, and reacting at 130 - 150 °C for 5 - 8 h to obtain the additive; the molecular weight of polyethylene glycol monomethyl ether is 300 - 500, the mass ratio of aspartic acid ester to polyethylene glycol monomethyl ether is 1:3 - 5, and the addition amount of sodium methoxide catalyst is 0.5 - 1% of the total mass of aspartic acid ester and polyethylene glycol monomethyl ether.

[0016] Preferably, the pore-forming agent in step (1) is starch.

[0017] Preferably, the mass ratio of the ceramic powder, pore-forming agent and additive in step (1) is 100:5 - 8:3 - 5.

[0018] Preferably, by weight, the components of the ceramic powder in step (1) include: 60-65 parts of purple gold clay, 25-35 parts of kaolin, 3-5 parts of iron oxide, and 5-8 parts of calcined kaolin; the preparation method of the calcined kaolin is: placing the kaolin in a calcination device, heating from room temperature to 300 °C in 50-70 min, then heating to 600 °C in 100-130 min and stopping the fire, and taking it out after cooling to room temperature to obtain the calcined kaolin. In the present invention, adding calcined kaolin to the ceramic powder can improve the plasticity of the ceramic powder and is beneficial to reducing the cracking of ceramic products.

[0019] Preferably, during ball milling in step (1), the mass ratio of ball stones, ceramic powder and water is 2-3:1:0.5-1, and the ball milling time is 10-15 h.

[0020] Preferably, during 3D printing in step (2), the nozzle diameter is 0.4-0.6 mm, the layer height is 0.3-0.5 mm, and the air pump air pressure is 5-6 MPa.

[0021] Preferably, during 3D printing in step (3), the nozzle diameter is 0.4-0.6 mm, the layer height is 0.8-1 mm, the number of printed layers is 2-10 layers, and the air pump air pressure is 5-6 MPa. When manufacturing the heat insulation structure in the present invention, by increasing the printing layer height, the heat insulation structure with a cross-grid structure can form a fluctuating surface, which can better fit the curvature of the cup body surface.

[0022] Preferably, the firing method in step (5) is: first heating from room temperature to 950-1000 °C in 4-6 h; then heating to 1050-1100 °C and holding for 1-2 h; then continuing to heat to 1280-1300 °C in 3-5 h; finally heating to 1300-1310 °C and holding for 40-50 min, and then cooling naturally and taking out of the kiln.

[0023] Therefore, the present invention has the following beneficial effects:

[0024] (1) Setting a heat insulation structure with a cross-grid structure on the surface of the ceramic cup body can improve the heat insulation and anti-slip performance of the cup body and enrich the decoration on the cup body surface;

[0025] (2) The ceramic cup body and the heat insulation structure are prepared by 3D printing technology, which can be unrestricted by mold making or processing technology, is suitable for the forming of complex heat insulation structures, greatly reduces the processing procedures, shortens the processing cycle, and can realize the large-scale industrial production of heat insulation ceramic cups;

[0026] (3) By removing the pore-forming agent, additives, and pulp decomposition, a ceramic cup body with a porous structure and a heat insulation structure can be obtained. The formation of the porous structure can effectively reduce the density of the ceramic product, reduce its weight, and ensure that the ceramic cup body with the heat insulation structure is not overly heavy.

[0027] (4) Adding pulp to the slurry and adding additives with a specific structure during the ball milling process of preparing the ceramic clay can reduce the shrinkage and deformation rate of the porous green body, making the fired product less prone to cracking and deformation, and improving the quality of the ceramic cup. Description of the Drawings

[0028] Figure 1 It is a physical diagram of the heat insulation structure in Embodiment 1 of the present invention. Detailed Embodiments

[0029] The present invention will be further described below in conjunction with the drawings and specific embodiments.

[0030] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in this industry. The methods in the following embodiments, unless otherwise specified, are conventional methods in this field.

[0031] General Embodiment

[0032] A preparation method of a lightweight 3D printed heat insulation and anti-slip ceramic cup includes the following steps:

[0033] (1) Prepare calcined kaolin: Place the kaolin in an electric kiln, heat it from room temperature to 300 °C in 50 - 70 min, then heat it to 600 °C in 100 - 130 min and stop firing, and take it out after cooling to room temperature to obtain the calcined kaolin;

[0034] (2) Prepare additives: A) Mix decanediamine with a sodium methoxide catalyst, then heat it to 70 - 90 °C, and dropwise add dimethyl maleate under nitrogen protection, and keep the reaction for 12 - 24 h to obtain aspartic acid ester; the molar ratio of decanediamine to dimethyl maleate is 1:2 - 2.2, and the addition amount of the sodium methoxide catalyst is 0.5 - 1% of the total mass of decanediamine and dimethyl maleate; B) Mix the obtained aspartic acid ester with methoxypolyethylene glycol, add a sodium methoxide catalyst, and react at 130 - 150 °C for 5 - 8 h to obtain the additive; the molecular weight of methoxypolyethylene glycol is 300 - 500, the mass ratio of aspartic acid ester to methoxypolyethylene glycol is 1:3 - 5, and the addition amount of the sodium methoxide catalyst is 0.5 - 1% of the total mass of aspartic acid ester and methoxypolyethylene glycol;

[0035] (3) Preparation of ceramic mud: By weight, 60 - 65 parts of purple gold clay, 25 - 35 parts of kaolin, 3 - 5 parts of iron oxide, and 5 - 8 parts of calcined kaolin are mixed to obtain ceramic powder; The pore-forming agent starch is dissolved in water to obtain a ball-milling liquid, and the ceramic powder and additives are added to the ball-milling liquid for ball-milling. The mass ratio of the ceramic powder, starch, and additives is 100:5 - 8:3 - 5. When ball-milling, the mass ratio of the ball stones: ceramic powder: water is 2 - 3:1:0.5 - 1, and the ball-milling time is 10 - 15h; After ball-milling, it is subjected to pressure filtration, vacuum clay kneading, aging, and drying to obtain mud powder;

[0036] (4) Preparation of 3D printing slurry: The ceramic mud and pulp with a mass ratio of 100:10 - 15 are mixed, stirred evenly, and then water is added and stirred until the water content of the slurry is 25 - 30wt%, obtaining the 3D printing slurry;

[0037] (5) Cup body printing: The prepared 3D printing slurry is printed into shape with an LDM method 3D printer to obtain a cup body; When 3D printing, the nozzle diameter is 0.4 - 0.6mm, the layer height is set to 0.3 - 0.5mm, and the air pump air pressure is 5 - 6MPa;

[0038] (6) Heat insulation structure printing: The prepared 3D printing slurry is printed into a cross-grid structure with an LDM method 3D printer to obtain a heat insulation structure; When 3D printing, the nozzle diameter is 0.4 - 0.6mm, the layer height is set to 0.8 - 1mm, the number of printing layers is 2 - 10 layers, and the air pump air pressure is 5 - 6MPa;

[0039] (7) Bonding: The printed heat insulation structure is bonded to the outer wall of the cup body through the 3D printing slurry to obtain a ceramic cup blank; (8) Firing: The ceramic cup blank is fired to obtain the lightweight 3D printed heat insulation and anti-slip ceramic cup; The firing method is as follows: First, it is heated from room temperature to 950 - 1000°C in 4 - 6h; Then it is heated to 1050 - 1100°C and held for 1 - 2h; Then it is continuously heated to 1280 - 1300°C in 3 - 5h; Finally, it is heated to 1300 - 1310°C and held for 40 - 50min, and then taken out of the kiln after natural cooling.

[0040] Example 1:

[0041] A preparation method of a lightweight 3D printed heat insulation and anti-slip ceramic cup, comprising the following steps:

[0042] (1) Preparation of calcined kaolin: The Longquan kaolin is placed in an electric kiln, heated to 300°C in 60min, then heated to 600°C in 120min and the fire is stopped, and it is taken out after cooling to room temperature to obtain the calcined kaolin;

[0043] (2) Preparation of the additive: A) Mix decanediamine with sodium methoxide catalyst, then heat up to 80 °C, and dropwise add dimethyl maleate under nitrogen protection, and keep the temperature for reaction for 18 h to obtain aspartate; the molar ratio of decanediamine to dimethyl maleate is 1:2.1, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of decanediamine and dimethyl maleate; B) Mix the obtained aspartate with polyethylene glycol monomethyl ether (average molecular weight 350), add sodium methoxide catalyst, and react at 140 °C for 6 h to obtain the additive; the mass ratio of aspartate to polyethylene glycol monomethyl ether is 1:4, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of aspartate and polyethylene glycol monomethyl ether;

[0044] (3) Preparation of ceramic mud: By weight, mix 62 parts of Baoxi purple gold clay, 30 parts of Longquan kaolin, 3 parts of iron oxide and 5 parts of calcined kaolin to obtain ceramic powder; dissolve the pore-forming agent starch in water to obtain a ball-milling liquid, add the ceramic powder and the additive to the ball-milling liquid for ball-milling, the mass ratio of the ceramic powder, starch and additive is 100:6:4, and the mass ratio of the ball stones: ceramic powder: water during ball-milling is 2:1:0.8, and the ball-milling time is 12 h; after ball-milling, obtain the mud through pressure filtration, vacuum clay kneading, and aging; dry the mud to obtain mud powder;

[0045] (4) Preparation of 3D printing slurry: Mix the ceramic mud and pulp (water content 50 wt%) with a mass ratio of 100:12, stir evenly, and then add water and stir until the water content of the slurry is 30 wt% to obtain the 3D printing slurry;

[0046] (5) Cup body printing: Print the prepared 3D printing slurry with an LDM method 3D printer to form a cup body; when 3D printing, the nozzle diameter is 0.5 mm, the layer height is set to 0.4 mm, and the air pump air pressure is 5 MPa;

[0047] (6) Heat insulation structure printing: Print the prepared 3D printing slurry with an LDM method 3D printer into a cross-grid structure to obtain the heat insulation structure as shown in Figure 1 ; when 3D printing, the nozzle diameter is 0.5 mm, the layer height is set to 1 mm, the number of printing layers is 9 layers, and the air pump air pressure is 5 MPa;

[0048] (7) Bonding: Bond the printed heat insulation structure to the outer wall of the cup body through the 3D printing slurry to obtain a ceramic cup blank; (8) Firing: Fire the ceramic cup blank to obtain the lightweight 3D printed heat insulation and anti-slip ceramic cup; the firing method is: first heat up to 980 °C in 5 h; then heat up to 1080 °C and keep the temperature for 1.5 h; then continue to heat up to 1290 °C in 4 h; finally heat up to 1300 °C and keep the temperature for 40 min, and then cool down naturally and take out of the kiln.

[0049] Example 2:

[0050] A preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup, comprising the following steps:

[0051] (1) Prepare calcined kaolin: Place Longquan kaolin in an electric kiln, heat it to 300 °C in 60 min, then heat it to 600 °C in another 120 min and stop firing, take it out after cooling to room temperature to obtain the calcined kaolin;

[0052] (2) Prepare an additive: A) Mix sebac diamine with sodium methoxide catalyst, then heat it to 80 °C, and dropwise add dimethyl maleate under nitrogen protection, keep the temperature for reaction for 18 h to obtain aspartic acid ester; the molar ratio of sebac diamine to dimethyl maleate is 1:2.1, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of sebac diamine and dimethyl maleate; B) Mix the obtained aspartic acid ester with polyethylene glycol monomethyl ether (average molecular weight 350), add sodium methoxide catalyst, and react at 140 °C for 6 h to obtain the additive; the mass ratio of aspartic acid ester to polyethylene glycol monomethyl ether is 1:4, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of aspartic acid ester and polyethylene glycol monomethyl ether;

[0053] (3) Prepare ceramic mud: By weight, mix 60 parts of Baoxi purple gold clay, 25 parts of Longquan kaolin, 3 parts of iron oxide and 5 parts of calcined kaolin to obtain ceramic powder; dissolve the pore-forming agent starch in water to obtain a ball-milling liquid, add the ceramic powder and the additive to the ball-milling liquid for ball-milling, the mass ratio of the ceramic powder, starch and additive is 100:5:3, the mass ratio of ball stones: ceramic powder: water during ball-milling is 2:1:0.8, and the ball-milling time is 12 h; after ball-milling, obtain mud through pressure filtration, vacuum clay refining and aging; dry the mud to obtain mud powder;

[0054] (4) Prepare 3D printing slurry: Mix ceramic mud and pulp (water content 50 wt%) with a mass ratio of 100:15, stir evenly and then add water and stir until the water content of the slurry is 25 wt% to obtain 3D printing slurry;

[0055] (5) Print the cup body: Use an LDM method 3D printer to print and form the prepared 3D printing slurry to obtain the cup body; the nozzle diameter during 3D printing is 0.5 mm, the layer height is set to 0.4 mm, and the air pump air pressure is 5 MPa;

[0056] (6) Print the heat-insulating structure: Use an LDM method 3D printer to print the prepared 3D printing slurry into a cross-grid structure to obtain the heat-insulating structure; the nozzle diameter during 3D printing is 0.5 mm, the layer height is set to 1 mm, the number of printed layers is 9 layers, and the air pump air pressure is 5 MPa;

[0057] (7) Bonding: Bond the printed heat-insulating structure to the outer wall of the cup body with 3D printing slurry to obtain a ceramic cup blank; (8) Firing: Fire the ceramic cup blank to obtain the lightweight 3D printed heat-insulating and anti-slip ceramic cup; The firing method is as follows: First, heat up to 980 °C in 5 h; then heat up to 1080 °C and keep warm for 1.5 h; then continue to heat up to 1290 °C in 4 h; finally heat up to 1300 °C and keep warm for 40 min, and then cool down naturally and take out of the kiln.

[0058] Example 3:

[0059] A preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup, comprising the following steps:

[0060] (1) Preparation of calcined kaolin: Place Longquan kaolin in an electric kiln, heat up to 300 °C in 60 min, then heat up to 600 °C in 120 min and stop firing, take out after cooling to room temperature to obtain the calcined kaolin;

[0061] (2) Preparation of additives: A) Mix sebac diamine and sodium methoxide catalyst, then heat up to 80 °C, dropwise add dimethyl maleate under nitrogen protection, and keep warm for reaction for 18 h to obtain aspartic acid ester; The molar ratio of sebac diamine to dimethyl maleate is 1:2.2, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of sebac diamine and dimethyl maleate; B) Mix the obtained aspartic acid ester and polyethylene glycol monomethyl ether (average molecular weight 500), add sodium methoxide catalyst, and react at 140 °C for 6 h to obtain the additive; The mass ratio of aspartic acid ester to polyethylene glycol monomethyl ether is 1:5, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of aspartic acid ester and polyethylene glycol monomethyl ether;

[0062] (3) Preparation of ceramic mud: By weight, mix 65 parts of Baoxi purple gold clay, 35 parts of Longquan kaolin, 5 parts of iron oxide and 8 parts of calcined kaolin to obtain ceramic powder; Dissolve the pore-forming agent starch in water to obtain a ball-milling liquid, add the ceramic powder and additives to the ball-milling liquid for ball-milling, the mass ratio of ceramic powder, starch and additives is 100:8:5, the mass ratio of ball stones: ceramic powder: water during ball-milling is 2:1:0.8, and the ball-milling time is 12 h; After ball-milling, obtain mud through pressure filtration, vacuum clay refining and aging; Dry the mud to obtain mud powder;

[0063] (4) Preparation of 3D printing slurry: Mix ceramic mud and pulp (water content 50 wt%) with a mass ratio of 100:12, stir evenly, and then add water and stir until the water content of the slurry is 30 wt% to obtain 3D printing slurry;

[0064] (5) Cup body printing: The prepared 3D printing slurry is printed into shape using an LDM method 3D printer to obtain the cup body; during 3D printing, the nozzle diameter is 0.5 mm, the layer height is set to 0.4 mm, and the air pump air pressure is 5 MPa;

[0065] (6) Heat insulation structure printing: The prepared 3D printing slurry is printed into a cross-grid structure using an LDM method 3D printer to obtain the heat insulation structure; during 3D printing, the nozzle diameter is 0.5 mm, the layer height is set to 1 mm, the number of printed layers is 9 layers, and the air pump air pressure is 5 MPa;

[0066] (7) Bonding: The printed heat insulation structure is bonded to the outer wall of the cup body through 3D printing slurry to obtain the ceramic cup blank; (8) Firing: The ceramic cup blank is fired to obtain the lightweight 3D printed heat insulation and anti-slip ceramic cup; the firing method is as follows: first, heat up to 980 °C in 5 h; then heat up to 1080 °C and keep warm for 1.5 h; then continue to heat up to 1290 °C in 4 h; finally, heat up to 1300 °C and keep warm for 40 min, and then cool down naturally and take out of the kiln.

[0067] Comparative Example 1:

[0068] The difference between Comparative Example 1 and Example 1 is that when preparing the ceramic mud in step (3), no additive is added during ball milling, and the rest are the same as in Example 1.

[0069] Comparative Example 2:

[0070] The difference between Comparative Example 2 and Example 1 is that when preparing the ceramic mud in step (3), polyethylene glycol monomethyl ether is used as an additive during ball milling, and the rest are the same as in Example 1.

[0071] Comparative Example 3:

[0072] The difference between Comparative Example 3 and Example 1 is that the preparation method of the additive used in Comparative Example 3 is as follows: Mix decanediamine with sodium methoxide catalyst, then heat up to 80 °C, and dropwise add dimethyl maleate under nitrogen protection, keep warm and react for 18 h to obtain the additive; the molar ratio of decanediamine to dimethyl maleate is 1:2.1, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of decanediamine and dimethyl maleate; the rest are the same as in Example 1.

[0073] Comparative Example 4:

[0074] The difference between Comparative Example 4 and Example 1 lies in that the preparation method used in step (3) is as follows: A) Mix sebac diamine with sodium methoxide catalyst, then heat up to 80°C, and dropwise add dimethyl maleate under nitrogen protection, and keep the temperature for reaction for 18 h to obtain aspartic acid ester; the molar ratio of sebac diamine to dimethyl maleate is 1:2.1, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of sebac diamine and dimethyl maleate; B) Mix the obtained aspartic acid ester with methoxypolyethylene glycol (average molecular weight 350), add sodium methoxide catalyst, and react at 140°C for 6 h to obtain the additive; the mass ratio of aspartic acid ester to methoxypolyethylene glycol is 1:2, and the addition amount of sodium methoxide catalyst is 0.5% of the total mass of aspartic acid ester and methoxypolyethylene glycol; the rest are the same as in Example 1.

[0075] Comparative Example 5:

[0076] The difference between Comparative Example 5 and Example 1 lies in that no pulp is added when preparing the 3D printing slurry in step (4), and the rest are the same as in Example 1.

[0077] Comparative Example 6:

[0078] The difference between Comparative Example 6 and Example 1 lies in that no calcined kaolin is added when preparing the ceramic clay in step (3), and the rest are the same as in Example 1.

[0079] The properties of the obtained ceramic cups were tested, and the results are shown in Table 1;

[0080] Among them, the flexural strength was detected by an electronic universal strength tester;

[0081] The test method for thermal shock resistance is as follows: Place the ceramic cup specimen in an oven preheated to a temperature 130°C ± 2°C higher than the cold water temperature, and make the specimen temperature reach the preheated temperature within 5 min, start timing, and keep the temperature for 45 min at this temperature; take out the specimen and immediately immerse it in a water tank filled with flowing cold water for rapid cooling for 5 min, and this is one thermal shock cycle; after 3 cycles, check and record the damage conditions of each specimen during the thermal shock process.

[0082] Table 1: Test results of the properties of ceramic cups.

[0083] <![CDATA[Density (g / cm 3 )]]> Flexural strength (MPa) Resistance to thermal shock Example 1 2.12 57 No cracking after 3 cycles Example 2 2.08 54 No cracking after 3 cycles Example 3 2.06 52 No cracking after 3 cycles Comparative Example 1 1.81 44 Cracking occurred after 3 cycles Comparative Example 2 1.94 48 No cracking after 3 cycles Comparative Example 3 1.85 45 No cracking after 3 cycles Comparative Example 4 1.93 47 No cracking after 3 cycles Comparative Example 5 2.09 42 Cracking occurred after 3 cycles Comparative Example 6 1.94 47 Cracking occurred after 3 cycles

[0084] As can be seen from Table 1, the ceramic cups prepared by the method of the present invention in Examples 1 to 3 have high density and flexural strength, and good frost resistance and thermal shock resistance. In Comparative Example 1, when preparing the ceramic mud, the additive of the present invention was not added during ball milling, resulting in a decrease in the density of the cup body, and also a decrease in the flexural strength and thermal shock resistance. This shows that the additive of the present invention can effectively improve the ball milling efficiency, and enhance the plasticity of the ceramic powder, the density and strength of the green body. In Comparative Example 2, polyethylene glycol monomethyl ether was directly used as the additive without reacting it with aspartate ester, resulting in a decrease in the amphiphilicity of the additive and a decrease in the grinding aid effect; moreover, when polyethylene glycol monomethyl ether was used alone as the additive, the entanglement effect of the molecular chain was poor, which was not conducive to improving the density of the green body, leading to a significant decrease in the various properties of the ceramic compared with those in Example 1. In Comparative Example 3, aspartate ester was used as the additive without reacting it with polyethylene glycol monomethyl ether, so the additive did not have amphiphilicity and the molecular chain was also difficult to entangle, and the processing performance of the ceramic powder, the density and strength of the green body could not be effectively improved, and the various properties of the ceramic cup also decreased significantly compared with those in Example 1. In Comparative Example 4, the amount of polyethylene glycol monomethyl ether reacted with aspartate ester was changed to be lower than the range defined in the present invention, resulting in a decrease in the proportion of hydrophilic end groups in the additive molecular chain, and also a decrease in the density and strength of the ceramic cup, indicating that the type of additive has a significant impact on the properties of the ceramic mud after ball milling, and only by selecting an additive that matches the properties of the mud can the quality of the ceramic product be effectively improved. In Comparative Example 5, pulp was not added to the 3D printing slurry, resulting in an increase in the shrinkage and deformation rate of the green body, leading to a decrease in the strength and thermal shock resistance of the ceramic cup. In Comparative Example 6, calcined kaolin was not added during the preparation of the ceramic mud, resulting in a decrease in the plasticity of the ceramic powder, leading to a decrease in the density of the green body and a decrease in the strength of the ceramic cup.

Claims

1. A preparation method of a lightweight 3D printed heat-insulating and anti-slip ceramic cup, characterized in that, The steps include: (1) Ceramic mud and paper pulp are mixed evenly in a mass ratio of 100:10-15, and water is added and stirred until the moisture content reaches 25-30wt% to obtain 3D printing slurry; the preparation method of the ceramic mud is as follows: a porogen is dissolved in water to obtain a ball milling solution, ceramic powder and additives are added to the ball milling solution for ball milling; and then the ceramic mud is obtained after filter pressing, vacuum mud kneading, aging, and drying; The additive is prepared by: A) mixing decanediamine with a sodium methoxide catalyst, then heating the mixture to 70-90°C, adding dimethyl maleate dropwise under nitrogen protection, and allowing the mixture to react for 12-24 hours to obtain aspartic acid ester; the molar ratio of decanediamine to dimethyl maleate is 1:2-2.2; B) mixing the obtained aspartic acid ester with polyethylene glycol monomethyl ether, adding sodium methoxide catalyst, and allowing the mixture to react at 130-150°C for 5-8 hours to obtain the additive; the molecular weight of the polyethylene glycol monomethyl ether is 300-500, and the mass ratio of aspartic acid ester to polyethylene glycol monomethyl ether is 1:3-5; (2) Printing the prepared 3D printing slurry into a shape by 3D printing to obtain a cup body; (3) Printing the prepared 3D printing slurry into a cross-grid structure through 3D printing to obtain a thermal insulation structure; (4) The printed insulation structure is bonded to the outer wall of the cup body through 3D printing slurry to obtain a ceramic cup body; (5) The ceramic cup body is fired to obtain the lightweight 3D printed heat-insulating and non-slip ceramic cup.

2. The preparation method of the lightweight 3D printed heat-insulating and anti-slip ceramic cup according to claim 1, characterized in that, In step A), the amount of sodium methoxide catalyst added is 0.5-1% of the total mass of decanediamine and dimethyl maleate.

3. The method for preparing a lightweight 3D printed heat-insulating and non-slip ceramic cup according to claim 1, characterized in that: In step B), the amount of sodium methoxide catalyst added is 0.5-1% of the total mass of aspartic acid ester and polyethylene glycol monomethyl ether.

4. The preparation method of the lightweight 3D printed heat-insulating and anti-slip ceramic cup according to claim 1, characterized in that, The porogen described in step (1) is starch.

5. The method for preparing a lightweight 3D printed heat-insulating and non-slip ceramic cup according to claim 1 or 4, characterized in that: The mass ratio of the ceramic powder, porogen and additive described in step (1) is 100:5~8:3~5.

6. The preparation method of the lightweight 3D printed heat-insulating and anti-slip ceramic cup according to claim 1, characterized in that, In parts by weight, the components of the ceramic powder described in step (1) include: 60-65 parts of purple clay, 25-35 parts of kaolin, 3-5 parts of iron oxide, and 5-8 parts of calcined kaolin; the preparation method of the calcined kaolin is: placing the kaolin in a calcining device, heating it from room temperature to 300°C in 50-70 minutes, then heating it to 600°C in 100-130 minutes, stopping the heating, cooling it to room temperature, and then taking it out to obtain the calcined kaolin.

7. The method for preparing a lightweight 3D printed heat-insulating and non-slip ceramic cup according to claim 1, characterized in that: During the ball milling in step (1), the mass ratio of the ball stone, ceramic powder and water is 2~3:1:0.5~1, and the ball milling time is 10~15h.

8. The method for preparing a lightweight 3D printed heat-insulating and non-slip ceramic cup according to claim 1, characterized in that: In step (2), the nozzle diameter during 3D printing is 0.4~0.6mm, the layer height is 0.3~0.5mm, and the air pump pressure is 5~6MPa.

9. The preparation method of the lightweight 3D printed heat-insulating and anti-slip ceramic cup according to claim 1, characterized in that, In step (3), the nozzle diameter during 3D printing is 0.4~0.6mm, the layer height is 0.8~1mm, the number of printing layers is 2~10, and the air pump pressure is 5~6MPa.

10. The preparation method of the lightweight 3D printed heat-insulating and anti-slip ceramic cup according to claim 1, characterized in that, The firing method in step (5) is as follows: first, heat from room temperature to 950 - 1000 °C in 4 - 6 h; then heat to 1050 - 1100 °C and keep warm for 1 - 2 h; then continue to heat to 1280 - 1300 °C in 3 - 5 h; finally, heat to 1300 - 1310 °C, keep warm for 40 - 50 min, and then cool naturally and take out of the kiln.

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