Degradable ceramic clay and its manufacturing method

Abstract

The present invention relates to a degradable ceramic green mud and a manufacturing method thereof, belonging to the technical field of ceramics. The method comprises the following steps: grinding and crushing calcined talc, wollastonite, phlogopite and yttria-stabilized zirconia, screening, adding stearic acid and carboxymethyl chitosan solution and ball milling, adding polyhydroxycitronellal and anhydrous ethanol under a nitrogen atmosphere and stirring at a constant temperature, filtering out the solvent and drying, adding isobutanol and an aluminum zirconium coupling agent and continuing to stir, filtering, washing, vacuum drying, adding a binder and deionized water and stirring, standing, pressing and molding, vacuum drying and calcining. Polyvinyl alcohol is selected as a green binder. Its excellent bonding properties enhance the molding efficiency of the mud and are harmless to the environment. Polyhydroxycitronellal and carboxymethyl chitosan enhance the modification of the stone surface and its uniform distribution, thereby improving the microstructure of the material. The addition of an environmentally friendly dispersant and a binder reduces environmental pollution and achieves a dual improvement in performance and green ecology.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramics and relates to a degradable ceramic clay and a manufacturing method thereof. Background Art

[0002] Ceramic container blanks are typically made from a mixture of clay, quartz, feldspar, and other raw materials in specific proportions. These blanks are then formed into the desired shape through processes such as wheel throwing and slip casting. After drying and bisque firing, the blanks become hard and strong ceramic embryos. Finally, they are glazed and fired at high temperatures to create decorative and practical ceramic containers.

[0003] Patent publication number CN103771829A discloses a ceramic product comprising the following raw materials in parts by weight: 20-23 parts quartz sand, 30-34 parts potassium feldspar, 10-12 parts hard kaolin, 50-55 parts potash clay, 23-25 ​​parts bentonite, 5-10 parts wollastonite powder, 3-4 parts zinc oxide, 4-5 parts magnesium oxide, 20-24 parts loess powder, and 5-6 parts additives. The additives are also comprised of the following raw materials in parts by weight: 2-3 parts brown corundum powder, 5-6 parts sodium tripolyphosphate, 4-5 parts jade powder, 2 parts silane coupling agent KH-5501-2 parts, 4-5 parts silicon carbide powder, and 8-10 parts aluminum hydroxide. The ceramic product is prepared by mixing the raw materials and grinding and dispersing them uniformly. The advantage of this patent document is that hard kaolin, bentonite, wollastonite powder and other raw materials are added to the raw material formula, which enhances the strength and toughness of the embryo, increases the plasticity, and promotes the bonding of the raw materials, so that the prepared ceramic products have good strength and bending resistance, and a fine and dense texture. Summary of the Invention

[0004] The object of the present invention is to provide a degradable ceramic clay and a method for manufacturing the same. The ceramic clay of the present invention is suitable for producing ceramic products. The products have high hardness and strength, good degradability and mechanical properties, a wide range of raw materials, and low production costs.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing degradable ceramic clay comprises the following steps:

[0007] S1. Grind and crush burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia, and sieve to obtain a composite stone;

[0008] S2. The composite stone, stearic acid and carboxymethyl chitosan solution are ball-milled and mixed. Under a nitrogen atmosphere, polyhydroxycitronellal and anhydrous ethanol are added and stirred at a constant temperature. After filtering off the solvent and drying, isobutanol and aluminum zirconium coupling agent are added and continued to stir. The mixture is filtered, washed and vacuum-dried to obtain a slurry.

[0009] S3. Add a binder and deionized water to the slurry, stir, let it stand, press into shape, vacuum dry and then calcine to obtain.

[0010] As a preferred technical solution of the present invention, in step S1, the mass ratio of the calcined talc, wollastonite, phlogopite and yttria-stabilized zirconia is 10-12:7-8:3-5:1.2-1.5; and the screening is through a 200-mesh sieve.

[0011] As a preferred technical solution of the present invention, in step S2, the ball milling mixing time is 1.5-2.0 hours; the constant temperature stirring is stirring at a temperature of 50-60°C for 4-5 hours; and the continued stirring is stirring at a speed of 500-600 r / min for 3-4 hours.

[0012] As a preferred technical solution of the present invention, in step S2, the washing is washing three times with anhydrous ethanol; and the vacuum drying is drying at a temperature of 80° C. to a constant weight.

[0013] As a preferred technical solution of the present invention, in step S2, the mass ratio of the composite stone, stearic acid, carboxymethyl chitosan solution, polyhydroxycitronellal, anhydrous ethanol, isobutanol and aluminum zirconium coupling agent is 100-110:12-14:160-170:3.2-3.6:40-50:130-140:2.8-3.0; the aluminum zirconium coupling agent is aluminum zirconium coupling agent TL-3A; the preparation of the polyhydroxycitronellal includes the following steps: after mixing 30 parts by weight of isobutanol and 2 parts by weight of citronellal, adding 1.5 parts by weight of thioglycerol and 0.08 parts by weight of photoinitiator 1173, irradiating with ultraviolet light at a wavelength of 365nm for 6 hours, and then removing the solvent by rotary evaporation to obtain the product.

[0014] As a preferred technical solution of the present invention, in step S2, the carboxymethyl chitosan solution is prepared by mixing carboxymethyl chitosan, acetic acid and deionized water in a mass ratio of 2.0-2.2:0.3-0.4:80-85.

[0015] As a preferred technical solution of the present invention, in step S3, the stirring time is 2-3 hours; the standing time is 24 hours at room temperature; and the vacuum drying is vacuum drying at 85°C to constant weight.

[0016] As a preferred technical solution of the present invention, in step S3, the calcination is carried out at a temperature of 1080-1200° C. for 5-6 hours.

[0017] As a preferred technical solution of the present invention, in step S3, the mass ratio of the slurry, the binder and the deionized water is 90-100:3.8-4.3:90-100; and the binder is polyvinyl alcohol.

[0018] The invention discloses degradable ceramic clay prepared by the above preparation method.

[0019] Beneficial effects of the present invention:

[0020] (1) The ceramic clay of the present invention is suitable for producing ceramic products. The products have high hardness and strength, good degradability and mechanical properties, a wide range of raw materials, and low production costs.

[0021] (2) The present invention uses polyvinyl alcohol as a green binder. Its excellent bonding properties enhance the slurry's molding efficiency and are environmentally friendly. This process significantly enhances the mechanical strength, density, and crack resistance of the ceramic slurry while also improving its environmental performance.

[0022] (3) Polyhydroxycitronellal and carboxymethyl chitosan enhance the surface modification and uniform distribution of the stone, thereby improving the microstructure of the material. The addition of environmentally friendly dispersants and binders reduces environmental pollution, achieving a dual improvement in performance and green ecology. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0024] Example 1

[0025] A method for preparing degradable ceramic clay comprises the following steps:

[0026] S1. Grind and crush burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia, and sieve to obtain a composite stone; the mass ratio of the burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia is 10:7:3:1.2; and the sieving is to pass through a 200-mesh sieve;

[0027] S2. The composite stone, stearic acid and carboxymethyl chitosan solution are ball-milled and mixed. In a nitrogen atmosphere, polyhydroxycitronellal and anhydrous ethanol are added and stirred at a constant temperature. After filtering off the solvent and drying, isobutanol and aluminum zirconium coupling agent are added and continued stirring is performed. The mixture is filtered, washed and vacuum-dried to obtain a slurry. The ball-milling mixing time is 1.5 h. The constant temperature stirring is stirring at 50° C. for 4 h. The continued stirring is stirring at a speed of 500 r / min for 3 h. The washing is washing three times with anhydrous ethanol. The vacuum drying is drying at 80° C. to constant weight. The mass ratio of the composite stone, stearic acid, carboxymethyl chitosan solution, polyhydroxycitronellal, anhydrous ethanol, isobutanol and aluminum zirconium coupling agent is 100:12:160:3.2:40:130:2.8. The carboxymethyl chitosan solution is prepared by mixing carboxymethyl chitosan, acetic acid and deionized water in a mass ratio of 2.0:0.3:80.

[0028] S3. Add a binder and deionized water to the slurry, stir, let it stand, press into shape, vacuum dry and then calcine to obtain; the stirring time is 2 hours; the standing time is 24 hours at room temperature; the vacuum drying is vacuum drying at 85°C to constant weight; the calcination is calcining at 1080°C for 5 hours; the binder is polyvinyl alcohol; the mass ratio of the slurry, binder and deionized water is 90:3.8:90.

[0029] Example 2

[0030] A method for preparing degradable ceramic clay comprises the following steps:

[0031] S1. Grind and crush burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia, and sieve to obtain a composite stone; the mass ratio of the burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia is 11:7.5:4:1.4; the sieving is to pass through a 200-mesh sieve;

[0032] S2. The composite stone, stearic acid and carboxymethyl chitosan solution are ball-milled and mixed. In a nitrogen atmosphere, polyhydroxycitronellal and anhydrous ethanol are added and stirred at a constant temperature. After filtering off the solvent and drying, isobutanol and aluminum zirconium coupling agent are added and continued stirring is performed. The mixture is filtered, washed and vacuum-dried to obtain a slurry. The ball-milling mixing time is 1.8 h. The constant temperature stirring is stirring at 55° C. for 4.5 h. The continued stirring is stirring at a speed of 550 r / min for 3.5 h. The washing is washing three times with anhydrous ethanol. The vacuum drying is drying at 80° C. to constant weight. The mass ratio of the composite stone, stearic acid, carboxymethyl chitosan solution, polyhydroxycitronellal, anhydrous ethanol, isobutanol and aluminum zirconium coupling agent is 105:13:165:3.4:45:135:2.9. The carboxymethyl chitosan solution is prepared by mixing carboxymethyl chitosan, acetic acid and deionized water in a mass ratio of 2.1:0.35:82.

[0033] S3. Add a binder and deionized water to the slurry, stir, let it stand, press into shape, vacuum dry and then calcine to obtain; the stirring time is 2.5 hours; the standing time is 24 hours at room temperature; the vacuum drying is vacuum drying at 85°C to constant weight; the calcination is calcining at 1140°C for 5.5 hours; the binder is polyvinyl alcohol; the mass ratio of the slurry, binder and deionized water is 95:4:95.

[0034] Example 3

[0035] A method for preparing degradable ceramic clay comprises the following steps:

[0036] S1. Grind and crush burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia, and sieve to obtain a composite stone; the mass ratio of burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia is 12:8:5:1.5; the sieving is to pass through a 200-mesh sieve;

[0037] S2. The composite stone, stearic acid and carboxymethyl chitosan solution are ball-milled and mixed. In a nitrogen atmosphere, polyhydroxycitronellal and anhydrous ethanol are added and stirred at a constant temperature. After filtering off the solvent and drying, isobutanol and aluminum zirconium coupling agent are added and continued stirring is performed. The mixture is filtered, washed and vacuum-dried to obtain a slurry. The ball-milling mixing time is 2.0 h. The constant temperature stirring is stirring at 60° C. for 5 h. The continued stirring is stirring at a speed of 600 r / min for 4 h. The washing is washing three times with anhydrous ethanol. The vacuum drying is drying at 80° C. to constant weight. The mass ratio of the composite stone, stearic acid, carboxymethyl chitosan solution, polyhydroxycitronellal, anhydrous ethanol, isobutanol and aluminum zirconium coupling agent is 110:14:170:3.6:50:140:3.0. The carboxymethyl chitosan solution is prepared by mixing carboxymethyl chitosan, acetic acid and deionized water in a mass ratio of 2.2:0.4:85.

[0038] S3. Add a binder and deionized water to the slurry, stir, let it stand, press into shape, vacuum dry and then calcine to obtain; the stirring time is 3 hours; the standing time is 24 hours at room temperature; the vacuum drying is vacuum drying at 85°C to constant weight; the calcination is calcining at 1200°C for 6 hours; the binder is polyvinyl alcohol; the mass ratio of the slurry, binder and deionized water is 100:4.3:100.

[0039] Comparative Example 1

[0040] Compared with Example 3, Comparative Example 1 is different in that carboxymethyl chitosan is not used, and the other components, preparation steps and parameters are the same.

[0041] Comparative Example 2

[0042] Compared with Example 3, Comparative Example 2 is different in that citronellal replaces polyhydroxycitronellal, and the other components, preparation steps and parameters are the same.

[0043] Comparative Example 3

[0044] Compared with Example 3, Comparative Example 3 is different in that polyhydroxycitronellal is not used, and the other components, preparation steps and parameters are the same.

[0045] Comparative Example 4

[0046] Compared with Example 3, Comparative Example 4 is different in that aluminate coupling agent DL-411D is used instead of aluminum zirconium coupling agent, and the other components, preparation steps and parameters are the same.

[0047] Comparative Example 5

[0048] Compared with Example 3, Comparative Example 5 is different in that tetra-n-propyl zirconate is used instead of the aluminum zirconium coupling agent, and the other components, preparation steps and parameters are the same.

[0049] Comparative Example 6

[0050] Compared with Example 3, Comparative Example 6 is different in that no aluminum-zirconium coupling agent is used, and the remaining components, preparation steps and parameters are the same.

[0051] The ceramic green clays obtained in Examples 1-3 and Comparative Examples 1-6 were subjected to flexural strength tests using a HYK-DPK digital electric green clay flexural tester. The test results are shown in Table 1.

[0052] Table 1

[0053]

[0054]

[0055] From the test results in Table 1, it can be seen that compared with Comparative Examples 1-6, the ceramic clay prepared in Examples 1-3 has excellent flexural strength.

[0056] During the preparation of ceramic green clay, carboxymethyl chitosan, polyhydroxycitronellal and polyvinyl alcohol are added, and a Schiff base structure and multiple hydroxyl groups are introduced at the same time. This can form a network structure in the ceramic green clay, improve its plasticity and toughness, increase the density of the ceramic green clay, enhance the bonding force between particles, and optimize the microstructure. This helps to reduce the formation of cracks during the drying process and can significantly affect the performance of the final ceramic product during the calcination process. The Schiff base structure has good thermal stability. At high temperatures, they can form a stable skeleton structure, which helps to maintain the structural integrity of the ceramic material and prevent softening or deformation at high temperatures. The Schiff base structure can promote chemical bonding between ceramic particles, increase the internal bonding strength of the material by forming covalent bonds or other strong interaction forces, and thus improve the overall mechanical properties. The polyhydroxycitronellal contains multiple hydroxyl groups, which promote the bonding strength between the slurry and the binder, allowing it to react with the active sites on the ceramic surface at high temperatures, promote the formation of a liquid phase during the sintering process, accelerate the speed of particle rearrangement and pore removal, and improve the density of the ceramic green clay.

[0057] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any indirect modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing degradable ceramic clay, characterized in that: The following steps are involved: S1. Grind and crush burnt talc, wollastonite, phlogopite and yttria-stabilized zirconia, and sieve to obtain a composite stone; S2. The composite stone, stearic acid and carboxymethyl chitosan solution are ball-milled and mixed. Under a nitrogen atmosphere, polyhydroxycitronellal and anhydrous ethanol are added and stirred at a constant temperature. After filtering off the solvent and drying, isobutanol and aluminum zirconium coupling agent are added and continued to stir. The mixture is filtered, washed and vacuum-dried to obtain a slurry. S3, adding a binder and deionized water to the slurry, stirring, standing, pressing into shape, vacuum drying and then calcining to obtain; The preparation of the polyhydroxycitronellal comprises the following steps: mixing 30 parts by weight of isobutanol and 2 parts by weight of citronellal, adding 1.5 parts by weight of thioglycerol and 0.08 parts by weight of photoinitiator 1173, irradiating with ultraviolet light at a wavelength of 365 nm for 6 hours, and then removing the solvent by rotary evaporation to obtain the polyhydroxycitronellal.

2. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S1, the mass ratio of the calcined talc, wollastonite, phlogopite and yttria-stabilized zirconia is 10-12:7-8:3-5:1.2-1.5; and the sieving is through a 200-mesh sieve.

3. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S2, the ball milling mixing time is 1.5-2.0 hours; the constant temperature stirring is stirring at a temperature of 50-60° C. for 4-5 hours; and the continued stirring is stirring at a speed of 500-600 r / min for 3-4 hours.

4. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S2, the washing is performed by washing three times with anhydrous ethanol; and the vacuum drying is performed at a temperature of 80° C. to a constant weight.

5. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S2, the mass ratio of the composite stone, stearic acid, carboxymethyl chitosan solution, polyhydroxycitronellal, anhydrous ethanol, isobutanol and aluminum zirconium coupling agent is 100-110:12-14:160-170:3.2-3.6:40-50:130-140:2.8-3.0; the carboxymethyl chitosan solution is prepared by mixing carboxymethyl chitosan, acetic acid and deionized water in a mass ratio of 2.0-2.2:0.3-0.4:80-85.

6. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S3, the stirring time is 2-3 hours; the standing time is 24 hours at room temperature; and the vacuum drying is vacuum drying at 85° C. to constant weight.

7. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S3, the calcination is carried out at a temperature of 1080-1200° C. for 5-6 hours.

8. The method for preparing a degradable ceramic clay according to claim 1, wherein: In step S3, the mass ratio of the slurry, the binder and the deionized water is 90-100:3.8-4.3:90-100; the binder is polyvinyl alcohol.

9. A degradable ceramic clay prepared by the method according to any one of claims 1 to 8.

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