Antibacterial ceramic glaze and preparation method thereof

Abstract

The present invention belongs to the technical field of ceramic glazes and specifically discloses an antibacterial ceramic glaze and a preparation method thereof. The ceramic glaze comprises the following components, measured by mass: 60-75 parts of a base glaze, 1-3 parts of nano-titanium dioxide, 2-6 parts of a cosolvent, 0.5-3 parts of ochre, 5-10 parts of curcumin, 1-3 parts of a stabilizer, 1-5 parts of a rare earth antibacterial agent, 1-3 parts of sodium polyacrylate, and 1-6 parts of a composite additive. The present invention adopts the above-mentioned antibacterial ceramic glaze and a preparation method thereof to improve the antibacterial properties, glossiness, and smoothness of the glaze surface. The introduction of rare earth ions can refine the crystal structure of the glaze, enhance the hardness of the glaze surface, and effectively improve the wear resistance of ceramic products. The special chemical properties of the rare earth elements form stable chemical bonds in the glaze, enhancing the glaze surface's resistance to chemicals such as acids and alkalis, thereby improving the chemical corrosion resistance of the ceramic glaze.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glazes, in particular to an antibacterial ceramic glaze and a preparation method thereof. Background Art

[0002] Ceramic glaze is a thin, colorless or colored, glassy layer that covers the surface of ceramic products. It's made by mixing mineral and chemical raw materials in a specific ratio, grinding them into a glaze slurry, and then applying it to the ceramic body and calcining it. The glaze layer makes the product impermeable, smooth, and stain-resistant, while also improving its mechanical strength, electrical properties, and chemical stability. Colored glazes also have aesthetic and decorative properties.

[0003] With the continuous development of society and the gradual improvement of living standards, people's demands for quality of life are becoming increasingly higher, and the concept of hygiene, antimicrobial health care has also become deeply rooted in people's minds. To meet people's hygiene standards, antimicrobial ceramics have emerged and have experienced rapid development. Antimicrobial ceramics refer to a type of ceramic product that maintains the original functional and decorative effects of ceramic products while adding disinfection, sterilization, and chemical degradation functions. These antimicrobial ceramic products are widely used in industries such as hygiene, medical care, home living, and civil or industrial construction. In addition to adding relevant antimicrobial ingredients to ceramic blanks, applying certain antimicrobial ingredients to ceramic glazes is also an option. However, the introduction of antimicrobial ingredients also presents some problems that need to be addressed. For example, some antimicrobial ceramics have poor antimicrobial efficacy, poor glaze gloss, and poor glaze smoothness. Therefore, it is necessary to explore ceramic glazes with good comprehensive effects. Summary of the Invention

[0004] The purpose of the present invention is to provide an antibacterial ceramic glaze and a preparation method thereof, so as to improve the antibacterial performance, glossiness and flatness of the glaze surface.

[0005] To achieve the above objectives, the present invention provides an antibacterial ceramic glaze comprising the following components in parts by mass: 60-75 parts of a base glaze, 1-3 parts of nano-titanium dioxide, 2-6 parts of a cosolvent, 0.5-3 parts of ochre, 5-10 parts of curcumin, 1-3 parts of a stabilizer, 1-5 parts of a rare earth antibacterial agent, 1-3 parts of sodium polyacrylate, and 1-6 parts of a composite additive.

[0006] Preferably, the basic glaze comprises albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0007] Preferably, the co-solvent is at least one of zirconium silicate, sodium carbonate and borax.

[0008] Preferably, the stabilizer is at least one of calcium silicate, calcium phosphate, and zirconium phosphate.

[0009] Preferably, the rare earth antibacterial agent is at least one of lanthanum chloride and cerium chloride.

[0010] Preferably, the rare earth antibacterial agents are lanthanum chloride and cerium chloride, and the mass ratio of lanthanum chloride to cerium chloride is 1:1.

[0011] Preferably, the composite additive comprises sodium butylbenzenesulfonate, carboxymethyl chitosan, and oxidized hyaluronic acid, and the mass ratio of sodium butylbenzenesulfonate, carboxymethyl chitosan, and oxidized hyaluronic acid is (2-4): (2-4): (1-3).

[0012] The present invention also provides a method for preparing an antibacterial ceramic glaze, comprising the following steps:

[0013] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0014] S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to 9-10 and the reaction temperature to 60-80° C., filter, wash, and dry, and then calcine at 500-700° C. for 2-3 hours to obtain a calcined product;

[0015] S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 2-4 hours to obtain a preliminary mixed slurry;

[0016] S4, mixing the calcined product of step S2 with deionized water to form a solution, slowly adding the prepared mixed solution dropwise to the preliminary mixed slurry under stirring in step S3, and continuing stirring for 1-2 hours to ensure that the rare earth ions are evenly dispersed in the slurry;

[0017] S5. Transfer the uniformly mixed slurry from step S4 to a sealed container and age it for 12-24 hours. Then, add ochre, curcumin, sodium polyacrylate, and composite additives, and stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze.

[0018] Preferably, in step S4, the calcined product is mixed with deionized water to form a solution with a mass concentration of 10-20%.

[0019] The advantages and beneficial effects of the present invention using the above-mentioned antibacterial ceramic glaze and its preparation method are:

[0020] 1. The introduction of rare earth ions in the present invention can refine the crystal structure of the glaze, enhance the hardness of the glaze surface, and effectively improve the wear resistance of ceramic products.

[0021] 2. The addition of rare earth chloride improves the glaze's melting properties and surface smoothness, significantly enhancing the gloss of the ceramic glaze and making the product more beautiful and bright. The unique chemical properties of rare earth elements form stable chemical bonds in the glaze, enhancing the glaze's resistance to acids, alkalis, and other chemicals, and improving the ceramic glaze's chemical resistance.

[0022] 3. The present invention improves the antibacterial properties of the glaze, protects the glaze from oxidative damage, improves the glossiness of the glaze surface, affects the safety and durability of the ceramic glaze, and adds ochre and curcumin as auxiliary rare earth antibacterial agents. Sodium polyacrylate and composite additives make the glaze less likely to delaminate, thereby improving the stability, uniformity and fluidity of the glaze.

[0023] The technical solution of the present invention is further described in detail below through examples. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further illustrated by the following examples.

[0025] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

[0026] Unless otherwise defined, the reagents and equipment used in the present invention are all commercially available. Example 1

[0027] An antibacterial ceramic glaze comprises the following components in parts by mass: 60 parts of a basic glaze, 1.5 parts of nano-titanium dioxide, 2 parts of a cosolvent, 1 part of ochre, 6 parts of curcumin, 1.5 parts of a stabilizer, 2 parts of a rare earth antibacterial agent, 1 part of sodium polyacrylate, and 2 parts of a composite additive.

[0028] The basic glaze includes albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0029] The cosolvent is zirconium silicate.

[0030] The stabilizer is calcium silicate.

[0031] The rare earth antibacterial agent is lanthanum chloride.

[0032] The composite additives include sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid, and the mass ratio of the sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid is 2:2:1.

[0033] A method for preparing an antibacterial ceramic glaze comprises the following steps:

[0034] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0035] S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to 9 and the reaction temperature to 60° C., filter, wash, and dry, and then calcine at 500° C. for 2 h to obtain a calcined product.

[0036] S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 4 hours to obtain a preliminary mixed slurry;

[0037] S4, the calcined product of step S2 is mixed with deionized water to prepare a solution with a mass concentration of 10%, and the prepared mixed solution is slowly added dropwise to the preliminary mixed slurry under stirring in step S3, and stirring is continued for 1.5 hours to ensure that the rare earth ions are evenly dispersed in the slurry;

[0038] S5. Transfer the uniformly mixed slurry from step S4 to a sealed container, age it for 18 hours, then add ochre, curcumin, sodium polyacrylate, and composite additives, and stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze. Example 2

[0039] An antibacterial ceramic glaze comprises the following components in parts by mass: 68 parts of basic glaze, 3 parts of nano-titanium dioxide, 4 parts of cosolvent, 1.5 parts of ochre, 5 parts of curcumin, 1 part of stabilizer, 3 parts of rare earth antibacterial agent, 2 parts of sodium polyacrylate, and 4 parts of composite additives.

[0040] The basic glaze includes albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0041] The cosolvent is sodium carbonate.

[0042] The stabilizer is zirconium phosphate.

[0043] The rare earth antibacterial agent is cerium chloride.

[0044] The composite additives include sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid, and the mass ratio of the sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid is 3:2:2.

[0045] A method for preparing an antibacterial ceramic glaze comprises the following steps:

[0046] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0047] S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to 9.5 and the reaction temperature to 70°C. After filtering, washing, and drying, calcining at 600°C for 2h to obtain a calcined product.

[0048] S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 2 hours to obtain a preliminary mixed slurry;

[0049] S4, mixing the calcined product of step S2 with deionized water to prepare a solution with a mass concentration of 15%, slowly adding the prepared mixed solution dropwise to the preliminary mixed slurry under stirring in step S3, and continuing stirring for 1 hour to ensure that the rare earth ions are evenly dispersed in the slurry;

[0050] S5. Transfer the uniformly mixed slurry from step S4 to a sealed container and age it for 15 hours. Then, add ochre, curcumin, sodium polyacrylate, and composite additives, and stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze. Example 3

[0051] An antibacterial ceramic glaze comprises the following components in parts by mass: 75 parts of a basic glaze, 1 part of nano-titanium dioxide, 2 parts of a cosolvent, 2 parts of ochre, 8 parts of curcumin, 2 parts of a stabilizer, 4 parts of a rare earth antibacterial agent, 3 parts of sodium polyacrylate, and 6 parts of a composite additive.

[0052] The basic glaze includes albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0053] The cosolvents are sodium carbonate and borax.

[0054] Stabilizers are calcium silicate and calcium phosphate.

[0055] The rare earth antibacterial agents are lanthanum chloride and cerium chloride, and the mass ratio of lanthanum chloride to cerium chloride is 1:1.

[0056] The composite additives include sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid, and the mass ratio of the sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid is 2.5:2:1.

[0057] A method for preparing an antibacterial ceramic glaze comprises the following steps:

[0058] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0059] S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to be 10 and the reaction temperature to be 80° C., filter, wash, and dry, and then calcine at 700° C. for 3 h to obtain a calcined product;

[0060] S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 3 hours to obtain a preliminary mixed slurry;

[0061] S4, the calcined product of step S2 is mixed with deionized water to prepare a solution with a mass concentration of 20%, and the prepared mixed solution is slowly added dropwise to the preliminary mixed slurry under stirring in step S3, and stirring is continued for 2 hours to ensure that the rare earth ions are evenly dispersed in the slurry;

[0062] S5. Transfer the uniformly mixed slurry from step S4 to a sealed container and age it for 24 hours. Then, add ochre, curcumin, sodium polyacrylate, and composite additives, and stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze.

[0063] Comparative Example 1

[0064] An antibacterial ceramic glaze comprises the following components in parts by mass: 60 parts of basic glaze, 1.5 parts of nano-titanium dioxide, 2 parts of cosolvent, 1.5 parts of stabilizer, 2 parts of rare earth antibacterial agent, 1 part of sodium polyacrylate, and 2 parts of composite additives.

[0065] The basic glaze includes albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0066] The cosolvent is zirconium silicate.

[0067] The stabilizer is calcium silicate.

[0068] The rare earth antibacterial agent is lanthanum chloride.

[0069] The composite additives include sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid, and the mass ratio of the sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid is 2:2:1.

[0070] A method for preparing an antibacterial ceramic glaze comprises the following steps:

[0071] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0072] S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to 9 and the reaction temperature to 60° C., filter, wash, and dry, and then calcine at 500° C. for 2 h to obtain a calcined product.

[0073] S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 4 hours to obtain a preliminary mixed slurry;

[0074] S4, the calcined product of step S2 is mixed with deionized water to prepare a solution with a mass concentration of 10%, and the prepared mixed solution is slowly added dropwise to the preliminary mixed slurry under stirring in step S3, and stirring is continued for 1.5 hours to ensure that the rare earth ions are evenly dispersed in the slurry;

[0075] S5. Transfer the uniformly mixed slurry from step S4 to a sealed container, age it for 18 hours, then add sodium polyacrylate and composite additives, stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze.

[0076] Comparative Example 2

[0077] An antibacterial ceramic glaze comprises the following components in parts by mass: 60 parts of basic glaze, 1.5 parts of nano-titanium dioxide, 2 parts of cosolvent, 1.5 parts of stabilizer, 1 part of sodium polyacrylate, and 2 parts of composite additives.

[0078] The basic glaze includes albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0079] The cosolvent is zirconium silicate.

[0080] The stabilizer is calcium silicate.

[0081] The composite additives include sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid, and the mass ratio of the sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid is 2:2:1.

[0082] A method for preparing an antibacterial ceramic glaze comprises the following steps:

[0083] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0084] S2, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 4 hours to obtain a preliminary mixed slurry;

[0085] S3. Transfer the uniformly mixed slurry from step S2 into a sealed container, age it for 18 hours, then add sodium polyacrylate and composite additives, stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze.

[0086] Comparative Example 3

[0087] An antibacterial ceramic glaze comprises the following components in parts by mass: 60 parts of basic glaze, 1.5 parts of nano-titanium dioxide, 2 parts of cosolvent, 1 part of ochre, 6 parts of curcumin, 1.5 parts of stabilizer, and 2 parts of rare earth antibacterial agent.

[0088] The basic glaze includes albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:1.

[0089] The cosolvent is zirconium silicate.

[0090] The stabilizer is calcium silicate.

[0091] The rare earth antibacterial agent is lanthanum chloride.

[0092] A method for preparing an antibacterial ceramic glaze comprises the following steps:

[0093] S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size;

[0094] S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to 9 and the reaction temperature to 60° C., filter, wash, and dry, and then calcine at 500° C. for 2 h to obtain a calcined product.

[0095] S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 4 hours to obtain a preliminary mixed slurry;

[0096] S4, the calcined product of step S2 is mixed with deionized water to prepare a solution with a mass concentration of 10%, and the prepared mixed solution is slowly added dropwise to the preliminary mixed slurry under stirring in step S3, and stirring is continued for 1.5 hours to ensure that the rare earth ions are evenly dispersed in the slurry;

[0097] S5. Transfer the uniformly mixed slurry from step S4 to a sealed container, age it for 18 hours, then add ochre and curcumin, stir and mix them uniformly, and obtain a rare earth antibacterial ceramic glaze.

[0098] The rare earth antibacterial ceramic glazes prepared in Examples 1-3 and Comparative Examples 1-3 were coated on ceramic green bodies, and the glaze layers formed after firing were tested for various properties of the formed glaze layers. The test results are shown in Table 1.

[0099] ;

[0100] As can be seen from Table 1, the rare earth antibacterial ceramic glaze of the present invention has an easy-to-clean performance of less than 0.45 g / cm 2 The antibacterial rates against Staphylococcus aureus and Escherichia coli are as high as 99.99%, the Vickers hardness is much higher than that of the comparative example, and the glossiness is good. The easy-to-clean performance, antibacterial rates against Staphylococcus aureus and Escherichia coli, Vickers hardness, and glossiness of the rare earth antibacterial ceramic glazes prepared in comparative examples 1, 2, and 3 are not as ideal as those in examples 1-3.

[0101] Therefore, the present invention adopts the above-mentioned antibacterial ceramic glaze and its preparation method to improve the antibacterial performance, glossiness and smoothness of the glaze. The introduction of rare earth ions can refine the crystal structure of the glaze, enhance the hardness of the glaze, and effectively improve the wear resistance of ceramic products. The special chemical properties of rare earth elements form stable chemical bonds in the glaze, enhance the glaze's resistance to acids, alkalis and other chemical substances, and improve the chemical corrosion resistance of the ceramic glaze.

[0102] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. An antibacterial ceramic glaze, characterized in that: The invention comprises the following components in parts by mass: 60-75 parts of basic glaze, 1-3 parts of nano titanium dioxide, 2-6 parts of cosolvent, 0.5-3 parts of ochre, 5-10 parts of curcumin, 1-3 parts of stabilizer, 1-5 parts of rare earth antibacterial agent, 1-3 parts of sodium polyacrylate, and 1-6 parts of composite additives; The stabilizer is at least one of calcium silicate, calcium phosphate, and zirconium phosphate; The composite additive comprises sodium butylbenzene sulfonate, carboxymethyl chitosan and oxidized hyaluronic acid; A method for preparing an antibacterial ceramic glaze comprises the following steps: S1. Crush and grind the components of the base glaze separately, and pass them through a 200-mesh sieve to obtain a powder with uniform particle size; S2. Dissolve the rare earth antibacterial agent in an aqueous solution of aluminum nitrate to prepare a mixed solution. Slowly add a sodium hydroxide solution dropwise to the mixed solution under stirring, control the pH value of the solution to 9-10 and the reaction temperature to 60-80° C., filter, wash, and dry, and then calcine at 500-700° C. for 2-3 hours to obtain a calcined product; S3, adding the basic glaze treated in step S1, nano titanium dioxide, cosolvent, and stabilizer into a ball mill, adding deionized water and ball milling for 2-4 hours to obtain a preliminary mixed slurry; S4, mixing the calcined product of step S2 with deionized water to form a solution, slowly adding the prepared mixed solution dropwise to the preliminary mixed slurry under stirring in step S3, and continuing stirring for 1-2 hours to ensure that the rare earth ions are evenly dispersed in the slurry; S5. Transfer the uniformly mixed slurry from step S4 to a sealed container and age it for 12-24 hours. Then, add ochre, curcumin, sodium polyacrylate, and composite additives, and stir and mix them uniformly to obtain a rare earth antibacterial ceramic glaze.

2. The antibacterial ceramic glaze according to claim 1, characterized in that: The basic glaze comprises albite, limestone, kaolin and zinc oxide, and the mass ratio of albite, limestone, kaolin and zinc oxide is 5:3:2:

1.

3. The antibacterial ceramic glaze according to claim 1, characterized in that: The co-solvent is at least one of zirconium silicate, sodium carbonate and borax.

4. The antibacterial ceramic glaze according to claim 1, characterized in that: The rare earth antibacterial agent is at least one of lanthanum chloride and cerium chloride.

5. The antibacterial ceramic glaze according to claim 4, characterized in that: The rare earth antibacterial agents are lanthanum chloride and cerium chloride, and the mass ratio of lanthanum chloride to cerium chloride is 1:

1.

6. The antibacterial ceramic glaze according to claim 1, characterized in that: The mass ratio of sodium butylbenzenesulfonate, carboxymethyl chitosan and oxidized hyaluronic acid is (2-4): (2-4): (1-3).

7. The antibacterial ceramic glaze according to claim 1, characterized in that: In step S4, the calcined product is mixed with deionized water to form a solution with a mass concentration of 10-20%.