Artistic ceramic glaze and preparation method and application thereof

Abstract

The application discloses artistic ceramic glaze and a preparation method and application thereof, and belongs to the technical field of artistic ceramic glaze, and raw materials of the application include sericite 25-35%, silicon dioxide 18-30%, quartz 12-18%, dextrin 4-10%, calcium oxide 3-6%, dolomite 0.6-6%, chromium oxide 0.4-4%, barium carbonate 1-5%, kaolin 11-15% and antibacterial agent 0.5%-3%. Meanwhile, a silver-loaded carrier with a metal organic framework structure is self-assembled and synthesized, and the silver-loaded carrier with the metal organic framework is calcined at high temperature to obtain the antibacterial agent with a long-acting slow-release effect. The artistic ceramic glaze has the powder gold matt effect, uniform coloring and high ornamental value, and has the long-acting slow-release antibacterial effect; meanwhile, the artistic ceramic glaze has high adaptability to process conditions and simple process and is suitable for large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of art ceramic glaze technology, specifically relating to an art ceramic glaze, its preparation method, and its application. Background Technology

[0002] Glaze is a silicate. Glazes applied to ceramics are generally made from quartz, feldspar, and clay. These are ground, mixed with water, and applied to the surface of the ceramic body. After firing at a certain temperature, the glaze melts and, as the temperature drops, forms a thin, glassy layer on the ceramic surface. This layer increases the mechanical strength, thermal stability, and dielectric strength of the ceramic, prevents corrosion from liquids and gases, enhances its appearance, facilitates cleaning, and prevents dust accumulation. In recent years, with the improvement of people's aesthetic standards, the decorative requirements for ceramic products have also been continuously increasing. To meet these demands, and with advancements in technology, the quality of ceramics has been continuously improved. The market offers a wide variety of ceramic products, many of which are both practical and decorative. However, current ceramic decoration primarily focuses on innovative shapes, with relatively limited color options. Further innovation and enhancement of colored glazes are needed to meet creative and decorative needs.

[0003] Ceramic glaze is an essential raw material used in ceramic production, providing strong protection for the ceramic body. Currently, common ceramic glazes are typically applied directly by spraying the dye onto the ceramic body surface before applying a clear glaze. This often results in uneven coloring, affecting the ceramic's appearance. Meanwhile, household tableware and cups are the most frequently used ceramic products in daily life. A large number of bacteria adhere to the surfaces of these household ceramics, posing a health risk. Therefore, there is an urgent need for a glaze with long-lasting, slow-release antibacterial properties to enhance the antibacterial effect of ceramic glazes. Summary of the Invention

[0004] One of the objectives of this invention is to overcome the shortcomings of the prior art and provide an art ceramic glaze that solves the problem that ordinary ceramic glazes affect the aesthetics of art ceramics. This ceramic glaze has a powder gold matte effect and antibacterial properties.

[0005] The second objective of this invention is to provide a method for preparing artistic ceramic glazes. This method has a simple preparation process and a simple raw material processing technology, making it suitable for large-scale production.

[0006] The third objective of this invention is to provide a method for applying art ceramic glaze, that is, to apply the above-mentioned art ceramic glaze to the preparation of art ceramic products, so as to solve the technical problems such as poor matte effect of powder gold and poor antibacterial effect in existing art ceramic products.

[0007] Based on this, the present invention discloses an art ceramic glaze comprising the following raw materials by weight percentage: 25-35% sericite, 18-30% silica, 12-18% quartz, 4-10% dextrin, 3-6% calcium oxide, 0.6-6% dolomite, 0.4-4% chromium oxide, 1-5% barium carbonate, 13-17% kaolin, and 0.5%-3% antibacterial agent.

[0008] S1. Sericite, silica, quartz, calcium oxide, dolomite, chromium oxide, and barium carbonate are proportioned according to the above weight percentages, and then ground using a grinding mill to obtain component A;

[0009] S2. Synthesis of antibacterial agent: Glycerin and silver nitrate solution are added to a flask under oil bath heating, stirred and refluxed, and the temperature is gradually raised to 95°C. Sodium citrate solution and polyvinylpyrrolidone solution are quickly added, the heat source is removed, and the mixture is stirred at room temperature until cooled. After centrifugation, silver particles are obtained. 2-Methylimidazole and zinc nitrate hexahydrate and silver particles are added sequentially to a hexadecyltrimethylammonium bromide aqueous solution and incubated at room temperature (25-30°C) for 12 hours to self-assemble and grow into a semi-finished metal-organic framework silver carrier. The semi-finished metal-organic framework silver carrier is dried at 180°C, ground and pulverized, and then calcined in a calcining kiln at a high temperature of 650-750°C for 9-10 hours. After cooling to room temperature, the antibacterial agent is obtained.

[0010] S3. Heat and mix at 600-800℃. Add the ground and pulverized raw material mixture to the mixer, then add dextrin and stir at 550-1000 r / min for 20-30 min. Then add antibacterial agent and continue stirring for 12-16 min to obtain the color base.

[0011] S4. Add kaolin to the color base and grind it to obtain the glaze.

[0012] Furthermore, in S2, the volume ratio of glycerol, silver nitrate solution, sodium citrate solution, polyvinylpyrrolidone solution, hexadecyltrimethylammonium bromide aqueous solution, 2-methylimidazole solution, and zinc nitrate hexahydrate solution is 200:20:5:5:20:3:3.

[0013] Further, the concentrations of silver nitrate solution, sodium citrate solution, hexadecyltrimethylammonium bromide aqueous solution, 2-methylimidazolium solution, and zinc nitrate hexahydrate solution in S2 are 0.1 mol / L, 0.25 mol / L, 0.2 mol / L, and 1.32 x 10⁻⁶ mol / L, respectively. -2 mol / L, 2.4x10 -2 The mass concentration of the polyvinylpyrrolidone solution is 1 g / mL.

[0014] This invention also discloses a method for applying an art ceramic glaze, which involves applying the aforementioned art ceramic glaze to the preparation of ceramic products, including the following application steps:

[0015] After the porcelain blank is bisque-fired at 850℃ for 5 hours and then naturally cooled, glaze is applied to the surface of the green blank, and it is then fired and shaped in the following three stages:

[0016] Heating phase: In an oxidizing atmosphere, the temperature is uniformly increased from room temperature to 1280℃-1310℃ within 8-10 hours;

[0017] High-temperature insulation stage: Insulate at 1280℃-1310℃ for 1-2 hours;

[0018] Cooling phase: The temperature drops from 1310℃ to 780℃ at a rate of 10℃-12℃ per minute.

[0019] Finally, the ceramic product is brought out of the kiln and allowed to cool naturally to room temperature, resulting in an art ceramic product with a matte pink-gold glaze.

[0020] The beneficial effects of this invention are:

[0021] (1) The matte gold glaze provided by the present invention uses sericite, silicon dioxide, dextrin, calcium oxide, zinc oxide and dolomite as the base glaze, introduces chromium oxide as crystals and uses barium carbonate as a colorant to form a matte gold glaze; avoiding the method of directly spraying dyes on the surface of ceramic body, the body is uniformly colored after glazing, and has a soft satin luster under light conditions, with a delicate appearance. Combined with the pink formed by barium carbonate, it has artistic appreciation value.

[0022] (2) The present invention synthesizes a metal-organic framework silver carrier with a large specific surface area and pore adsorption capacity through self-assembly. After high-temperature calcination, it forms a spherical zinc oxide silver carrier antibacterial agent, which gives the glaze a long-lasting slow-release antibacterial and bactericidal effect.

[0023] (3) The art ceramic glaze of the present invention and its preparation and application process are simple and highly adaptable to process conditions. It will not become other glazes due to changes in process conditions, thus avoiding product waste. It can meet more creative and decorative needs. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0025] Example 1

[0026] Synthesis of antibacterial agents:

[0027] Under oil bath heating, 200 mL of glycerol and 20 mL of 0.1 mol / L AgNO3 solution were added to a three-necked flask. The mixture was stirred and refluxed at 150 rpm, and the temperature was gradually increased to 95 °C. 5 mL of 0.25 mol / L sodium citrate solution and 5 mL of 1 g / mL polyvinylpyrrolidone solution were quickly added. The oil bath heating was removed, and the mixture was stirred at room temperature for 1.5 h. After centrifugation, excess glycerol was removed to obtain silver particles. 3 mL of 1.32 x 10⁻⁶ ppm glycerol solution was added sequentially to 20 mL of 0.2 mol / L hexadecyltrimethylammonium bromide aqueous solution. -2 mol / L 2-methylimidazole, 3 mL 2.4 x 10 -2 Zinc nitrate hexahydrate and silver particles were incubated at room temperature (25-30℃) for 12 hours to self-assemble and grow into a semi-finished silver carrier with a metal-organic framework structure. The semi-finished silver carrier was dried at 180℃, ground and pulverized, and then placed in a calcining kiln for high-temperature shaping. The temperature was controlled at 680℃ and the calcination time was 9 hours. After cooling to room temperature, spherical zinc oxide silver-loaded antibacterial agent was obtained.

[0028] Examples 2-7

[0029] Examples 2-7 of this invention describe an art ceramic glaze, the raw material composition of which is sericite, silicon dioxide, quartz, dextrin, calcium oxide, dolomite, chromium oxide, barium carbonate, kaolin, and an antibacterial agent. The raw material composition of each example is shown in Table 1.

[0030] Table 1

[0031]

[0032]

[0033] The preparation method of the powder gold matte glaze in the above embodiments of the present invention comprises the following steps:

[0034] S1. The sericite, silica, quartz, calcium oxide, dolomite, chromium oxide, and barium carbonate are ground and pulverized using a grinding mill; the raw materials are proportioned according to the above Examples 2-7.

[0035] S2.680℃ heating and mixing, adding the ground and pulverized raw material mixture to the mixer, then adding dextrin and stirring at 750 r / min for 25 min, then adding the synthesized antibacterial agent and continuing to stir for 15 min, thereby obtaining the chromosome;

[0036] S3. Add kaolin to the color base and grind to obtain the glaze.

[0037] The application of the powder gold matte glaze in the above embodiments of the present invention is carried out through the following steps:

[0038] After the porcelain blank is bisque-fired at 850℃ for 4-6 hours and then naturally cooled, glaze is applied to the surface of the green blank, and it is then fired and shaped in the following three stages:

[0039] Heating phase: In an oxidizing atmosphere, the temperature is uniformly increased from room temperature to 1280℃-1310℃ within 8-10 hours;

[0040] High-temperature insulation stage: Insulate at 1280℃-1310℃ for 1-2 hours;

[0041] Cooling phase: The temperature drops from 1310℃ to 780℃ at a rate of 10℃-12℃ per minute.

[0042] Finally, the ceramic product is brought out of the kiln and allowed to cool naturally to room temperature, resulting in an art ceramic product with a matte pink-gold glaze.

[0043] The process parameters for each embodiment are shown in Table 2.

[0044] Table 2

[0045]

[0046]

[0047] The art ceramic products obtained by applying the matte pink gold glaze in the above embodiments of the present invention have a soft glaze surface, and the colors can range from light pink to cherry blossom pink to peach pink. The appearance of the matte pink gold glaze in each embodiment is shown in Table 3.

[0048] Table 3

[0049] Appearance / Example color Example 2 Cherry blossom pink Example 3 Peach pink Example 4 light pink Example 5 Cherry blossom pink Example 6 Peach pink Example 7 light pink

[0050] Comparative Examples 1-2

[0051] Evaluation of the slow-release antibacterial effect of an art ceramic glaze in ceramic products.

[0052] The art ceramic glaze, its preparation method, and its application method in ceramic products in this comparative example are all based on Example 2, except that:

[0053] In Comparative Example 1, the antibacterial agent was replaced with zinc oxide, while the remaining raw materials and preparation process remained the same as in Example 2.

[0054] In Comparative Example 2, the antibacterial agent was replaced with a 1:1 mixture of zinc oxide and silver oxide, while the remaining raw materials and preparation process remained the same as in Example 2.

[0055] The art ceramic products obtained from Example 2 and Comparative Examples 1-2 were subjected to a sustained-release antibacterial test. The experimental bacteria were *Escherichia coli* and *Staphylococcus aureus*. Fresh cultures (20 h) from the third-generation nutrient agar slant of the bacterial strain were collected at 0, 6, 12, 18, and 24 months, washed away the bacterial growth, mixed thoroughly by shaking, and diluted to 10% with sterile physiological saline. 6 -10 7 CFU / mL was prepared for use. Samples (5cm x 5cm) of the different ceramic products obtained in month 0 from Examples 2 and Comparative Examples 1-2 were placed in 500mL Erlenmeyer flasks. 95mL of PBS and 5mL of bacterial suspension were added to each flask. The flasks were fixed on a shaking table and shaken at 300rpm for 15 hours. The samples were then rinsed three times with PBS. Afterward, the rinsed ceramic samples were placed in 50mL of PBS and ultrasonically washed away the bacteria adhering to the surface of the ceramic samples. Finally, 5mL of the PBS solution containing the surface-adhered bacteria was evenly spread on a culture plate for observation and counting. The same batch of ceramic products from Examples 2 and Comparative Example 1 obtained in month 0 were aseptically stored, and antibacterial effects were tested at 6, 12, 18, and 24 months.

[0056] Table 4

[0057]

[0058] The results are shown in Table 4. It can be seen that the addition of antibacterial agents in both Comparative Examples 1 and 2 imparted a certain degree of antibacterial activity to the ceramic glaze, but this activity gradually decreased over time, failing to provide a long-lasting, sustained-release antibacterial effect. In Experimental Example 2, the ceramic glaze prepared with the addition of a self-assembled spherical zinc oxide-loaded silver antibacterial agent exhibited a long-lasting, sustained-release antibacterial effect. The number of *Escherichia coli* and *Staphylococcus aureus* on the surface of the ceramic product was significantly lower than in the comparative examples, and the antibacterial performance was more stable. Therefore, the artistic ceramic glaze of this invention possesses a long-lasting, sustained-release antibacterial effect.

[0059] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0060] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. An art ceramic glaze, characterized in that, The raw materials include the following by weight percentage: 25-35% sericite, 18-30% silica, 12-18% quartz, 4-10% dextrin, 3-6% calcium oxide, 0.6-6% dolomite, 0.4-4% chromium oxide, 1-5% barium carbonate, 13-17% kaolin, and 0.5%-3% antibacterial agent; the antibacterial agent is prepared by the following steps: Glycerol and silver nitrate solution were added to a flask under heating conditions, stirred and refluxed, and the temperature was gradually increased to 95°C. Sodium citrate solution and polyvinylpyrrolidone solution were quickly added, the heat source was removed, and the mixture was stirred at room temperature until cooled. The mixture was then centrifuged to obtain silver particles. 2-Methylimidazole and zinc nitrate hexahydrate and silver particles were added sequentially to a hexadecyltrimethylammonium bromide aqueous solution and incubated at room temperature (25-30°C) for 12 hours to allow self-assembly and growth into a semi-finished metal-organic framework silver-loaded carrier. The semi-finished metal-organic framework silver-loaded carrier was dried at 180°C, ground and pulverized, and then calcined at high temperature in a calcining kiln for shaping. After cooling to room temperature, the antibacterial agent was obtained. The calcination temperature was 650-750°C, and the calcination time was 9-10 hours.

2. The method for preparing an art ceramic glaze according to claim 1, characterized in that, Includes the following steps: S1. Sericite, silica, quartz, calcium oxide, dolomite, chromium oxide, and barium carbonate are proportioned according to the above weight percentages, and then ground using a grinding mill to obtain component A; S2. Synthesis of antibacterial agent: Glycerol and silver nitrate solution were added to a flask under heating conditions, stirred and refluxed, and the temperature was gradually increased to 95°C. Sodium citrate solution and polyvinylpyrrolidone solution were quickly added, the heat source was removed, and the mixture was stirred at room temperature until cooled. After centrifugation, silver particles were obtained. 2-Methylimidazole, zinc nitrate hexahydrate and silver particles were added sequentially to a hexadecyltrimethylammonium bromide aqueous solution and incubated at room temperature (25-30°C) for 12 hours to self-assemble and grow into a semi-finished metal-organic framework silver carrier. The semi-finished metal-organic framework silver carrier was dried at 180°C, ground and pulverized, and then calcined in a calcining kiln at high temperature for shaping. After cooling to room temperature, the antibacterial agent was obtained. S3. Heat and mix: Add component A to the mixer, then add dextrin and stir for 20-30 minutes. Then add antibacterial agent and continue stirring for 12-16 minutes to obtain the chromophore. S4. Add kaolin to the color base and grind it to obtain the glaze.

3. The method for preparing an art ceramic glaze according to claim 2, characterized in that, In step S2, the volume ratio of glycerol, silver nitrate solution, sodium citrate solution, polyvinylpyrrolidone solution, hexadecyltrimethylammonium bromide aqueous solution, 2-methylimidazole solution, and zinc nitrate hexahydrate solution is 200:20:5:5:20:3:

3.

4. The method for preparing an art ceramic glaze according to claim 2, characterized in that, In step S2, the concentrations of silver nitrate solution, sodium citrate solution, hexadecyltrimethylammonium bromide aqueous solution, 2-methylimidazole solution, and zinc nitrate hexahydrate solution are 0.1 mol / L, 0.25 mol / L, 0.2 mol / L, and 1.32 x 10⁻⁶, respectively. -2 mol / L, 2.4 x 10 -2 The mass concentration of the polyvinylpyrrolidone solution is 1 g / mL.

5. The method for preparing an art ceramic glaze according to claim 2, characterized in that, In step S3, the heating temperature is 600-800℃ and the stirring speed is 550-1000r / min.

6. The application of an art ceramic glaze according to claim 1, characterized in that, Includes the following steps: A. After bisque-firing the ceramic green at 850℃ for 5 hours and allowing it to cool naturally, glaze is applied to the surface of the ceramic green, and it is then fired and shaped in the following three stages; B. Heating stage: In an oxidizing atmosphere, the temperature is uniformly increased from room temperature to 1280℃-1310℃ within 8-10 hours; C. High-temperature insulation stage: Insulate at 1280℃-1310℃ for 1-2 hours; D. Cooling phase: The temperature will decrease from 1310℃ to 780℃ at a rate of 10℃-12℃ per minute; E. After being removed from the kiln, the ceramic product is allowed to cool naturally to room temperature, resulting in an art ceramic product with a matte pink-gold glaze.

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