Zirconium silicate composite ceramic glaze, preparation method and application thereof

Abstract

The application belongs to the technical field of ceramic manufacturing, and particularly relates to a zirconium silicate composite ceramic glaze as well as a preparation method and application thereof. The hyperbranched polysiloxane is grafted to the surface of zirconium silicate through covalent bond, so as to reduce the surface energy of zirconium silicate and the interfacial tension between zirconium silicate and glaze melt, inhibit high-temperature agglomeration of zirconium silicate particles, make the glaze surface more uniform and smooth, and reduce defects such as pinholes and spots; the mercapto mesoporous silica is bridged to the surface of the modified zirconium silicate, a core-shell structure is formed, and a synergistic effect is generated, so that the zirconium silicate is released in a gradient when the glaze melts, and the local high concentration of zirconium ions is avoided to cause the dramatic increase of the viscosity of the glaze; after the mesoporous silica is dissolved, the outer hyperbranched polysiloxane continues to play a steric hindrance effect, prevents the further approach of the zirconium silicate particles, maintains the stable viscosity of the glaze, and further improves the glaze surface quality.

Description

Technical Field

[0001] This invention belongs to the field of ceramic manufacturing technology, specifically relating to a zirconium silicate composite ceramic glaze, its preparation method, and its application. Background Technology

[0002] Zirconium silicate is an indispensable opacifier in modern ceramic glazes. With a refractive index between 1.92 and 1.97 and a Mohs hardness of 7.5, zirconium silicate possesses high hardness and a high refractive index, ensuring not only the opacifying effect of the glaze but also its high mechanical properties, good corrosion resistance, wear resistance, hydrolysis resistance, and whitening ability. Currently, the most commonly used glaze in sanitary ceramics production is raw zirconium opacified glaze. Its advantages include strong production stability, reduced sensitivity to firing atmosphere, a lower coefficient of thermal expansion, and abundant resources. These advantages determine that raw zirconium opacified glaze will inevitably become an important material in sanitary ceramics production.

[0003] The opacifying properties of zirconium silicate determine the glaze's covering power and color rendering intensity, affecting the glaze's performance and decorative effect, ultimately impacting product quality and cost. Many companies increase the amount of zirconium silicate used to improve the wear resistance of ceramic glazes; currently, its usage has increased to 10%. However, the high-temperature viscosity of zirconium silicate rises sharply with its addition to opacified glazes, leading to excessive glaze viscosity, insufficient surface smoothness, poor visual appearance, and noticeable defects such as pinholes and spots. This not only affects the overall appearance quality of the glaze but also directly impacts its stain resistance and ease of cleaning. Summary of the Invention

[0004] The purpose of this invention is to provide a zirconium silicate composite ceramic glaze, its preparation method, and its application, in order to solve the above-mentioned technical problems.

[0005] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows: A zirconium silicate composite ceramic glaze, by weight, comprises the following components: 30-40 parts potassium feldspar, 20-25 parts quartz, 8-12 parts kaolin, 10-12 parts calcite, 5-8 parts dolomite, 3-5 parts zinc oxide, 2-4 parts talc, 5-8 parts modified zirconium silicate, 2-4 parts spodumene, and 0.2-0.3 parts carboxymethyl cellulose.

[0006] As a further improvement, the preparation method of the modified zirconium silicate includes the following steps: hyperbranched polysiloxane-grafted zirconium silicate, mercaptoized mesoporous silica microspheres, silane coupling agent KH560, and anionic dispersant are mixed and dispersed in ethylene glycol, triethylamine is added, and the mixture is stirred at high speed at 60~100℃ for 2~4h using a suspension blending method. After the reaction is completed, the mixture is filtered, washed, and vacuum dried to obtain the modified zirconium silicate.

[0007] As a further improvement, by weight, it includes 50-60 parts of hyperbranched polysiloxane-grafted zirconium silicate, 15-20 parts of mercaptoized mesoporous silica microspheres, 2-3 parts of silane coupling agent KH560, 1-2 parts of anionic dispersant and 0.5-1 parts of triethylamine.

[0008] As a further improvement, the preparation method of the hyperbranched polysiloxane-grafted zirconium silicate includes the following steps: toluene and anhydrous ethanol are mixed at a mass ratio of 1:5 as solvents, activated zirconium silicate is slowly added to the solvent, and after stirring evenly, hyperbranched polysiloxane is added. After ultrasonic dispersion and mixing evenly, p-toluenesulfonic acid and deionized water are added. The mixture is reacted under reflux for 8 hours in an oil bath at 85~90℃ with stirring. After high-speed centrifugation and filtration, the mixture is washed successively with toluene and anhydrous ethanol, and then vacuum dried at 60℃ to obtain hyperbranched polysiloxane-grafted zirconium silicate.

[0009] As a further improvement, by weight, it includes 100-120 parts activated zirconium silicate, 5-8 parts hyperbranched polysiloxane, 0.05-0.1 parts p-toluenesulfonic acid and 0.5-1 parts deionized water.

[0010] As a further improvement, the preparation method of the hyperbranched polysiloxane includes the following steps: under a nitrogen atmosphere, silane coupling agent KH560 is mixed with diethylene glycol at a molar ratio of 1:1.8~2, heated to 120°C, and then the mixture is gradually heated from 120°C to 150°C at a heating rate of 1°C / min, and kept at 150°C for 30 min. Then, it is heated to 160°C and the reaction continues for 1 h. After the reaction is completed, hyperbranched polysiloxane is obtained.

[0011] As a further improvement, the method for preparing activated zirconium silicate includes the following steps: dispersing zirconium silicate powder in 1-2 mol / L dilute hydrochloric acid at a mass ratio of 1:5, stirring and reacting at 400 rpm and 60-80℃ for 2-4 hours, filtering, washing with deionized water until neutral, and drying to obtain activated zirconium silicate.

[0012] As a further improvement, the preparation method of the mercapto-modified mesoporous silica microspheres includes the following steps: adding mesoporous silica microspheres to an ethanol-water solution at a mass ratio of 1:10~15, dispersing by ultrasonication at 300W, adjusting the pH to 4~5, adding silane coupling agent KH590 dropwise, dispersing at high speed for 10 min, stirring and reacting at 60~80℃ for 8~10 h, after the reaction is complete, cooling, filtering, ultrasonically washing three times with anhydrous ethanol, and vacuum drying at 80℃ to constant weight to obtain mercapto-modified mesoporous silica microspheres; the amount of silane coupling agent KH590 used is 10~15wt% of the mesoporous silica microspheres; in the ethanol-water solution, the mass ratio of ethanol to water is 3:1.

[0013] This invention also provides a method for preparing a zirconium silicate composite ceramic glaze, comprising the following steps: Modified zirconium silicate was mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder. Potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc were mixed, ball-milled, and passed through a 250-mesh sieve to obtain the base glaze raw material. Carboxymethyl cellulose was added to water, stirred and dissolved, and then the base glaze raw material was added. After stirring at high speed for 30 minutes, the mixed powder was added, and the mixture was stirred at low speed for 20 minutes to obtain zirconium silicate composite ceramic glaze. The mass ratio of the total mass of the base glaze raw material and the mixed powder to the mass of water was 2:5.

[0014] This invention also provides the application of zirconium silicate composite ceramic glaze in the preparation of ceramic products.

[0015] Due to the adoption of the above technical solution, the beneficial effects of the present invention are as follows: 1. Using p-toluenesulfonic acid as a catalyst, a hydrolysis-condensation reaction is catalyzed between hyperbranched polysiloxane and the silanol groups on the surface of zirconium silicate to form Si-O-Si covalent bonds. This reduces the interfacial tension between zirconium silicate particles and the high-temperature glaze melt, making it easier for the zirconium silicate surface to integrate into the glass phase. It also lowers the surface energy of zirconium silicate, reduces the driving force for particle agglomeration, prevents excessive agglomeration of zirconium silicate at high temperatures, reduces the high-temperature viscosity of the glaze melt, reduces defects such as pinholes and spots on the glaze surface, and improves the anti-fouling and easy-to-clean properties of the glaze surface. This helps to promote the optimization and upgrading of the ceramic and other building materials industries.

[0016] 2. Thiol-modified mesoporous silica microspheres are bridged by thiol groups and epoxy groups at the ends of hyperbranched polysiloxanes, forming a composite structure with zirconium silicate as the core and hyperbranched polysiloxane-thiolized mesoporous silica as the shell, producing a dual synergistic effect: During the glaze melting process, the melt first contacts the mesoporous silica and gradually melts its pore walls, and the modified zirconium silicate is released in a gradient rather than participating in the reaction all at once, avoiding a sharp increase in glaze viscosity and glaze surface defects caused by excessively high local zirconium ion concentration; After the modified zirconium silicate loses the protection of mesoporous silica, the hyperbranched polysiloxane exerts a steric hindrance effect, continuing to prevent further approach between zirconium silicate particles and reducing the increase in glaze viscosity. Attached Figure Description

[0017] Figure 1 Infrared spectrum of hyperbranched polysiloxane; Figure 2 Here is a SEM image of the surface of the ceramic product obtained in Comparative Example 3; Figure 3 Here is a SEM image of the surface of the ceramic product obtained in Comparative Example 4; Figure 4 This is a SEM image of the surface of the ceramic product obtained in Example 6. Detailed Implementation

[0018] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0019] Example 1: A zirconium silicate composite ceramic glaze, comprising the following components: by weight, 30 parts potassium feldspar, 20 parts quartz, 8 parts kaolin, 10 parts calcite, 5 parts dolomite, 3 parts zinc oxide, 2 parts talc, 5 parts modified zirconium silicate, 2 parts spodumene, and 0.2 parts carboxymethyl cellulose.

[0020] The preparation method of the above-mentioned zirconium silicate composite ceramic glaze is as follows: 1. Under a nitrogen atmosphere, γ-glycidoxypropyltrimethoxysilane (KH560) and diethylene glycol were added to a four-necked round-bottom flask equipped with a thermometer, mechanical stirrer, and distillation apparatus at a molar ratio of 1:1.8. The mixture was heated to 120°C, and then gradually increased to 150°C at a rate of 1°C / min. The mixture was held at 150°C for 30 min, and then heated to 160°C for another 1 h. After the reaction was complete, a pale yellow transparent liquid hyperbranched polysiloxane was obtained in the round-bottom flask. The infrared spectrum of the synthesized hyperbranched polysiloxane is shown below. Figure 1 As shown.

[0021] 2. Disperse zirconium silicate powder in 1 mol / L dilute hydrochloric acid at a mass ratio of 1:5. Stir at 400 rpm and 60°C for 2 hours. Then, filter to separate the solid and liquid phases. Wash with deionized water until neutral and dry at 80°C for 4 hours to obtain activated zirconium silicate.

[0022] 3. Toluene and anhydrous ethanol were mixed at a mass ratio of 1:5 and added to a three-necked flask equipped with a mechanical stirrer, thermometer, water separator, and reflux condenser. 100 parts by weight of activated zirconium silicate were slowly added to the solvent and stirred at 400 rpm until homogeneous. 5 parts of hyperbranched polysiloxane were added, and the mixture was ultrasonically dispersed at 600 W for 30 min. Finally, 0.05 parts of p-toluenesulfonic acid and 0.5 parts of deionized water were added. A water separator and reflux apparatus was set up, and the reaction was carried out at 500 rpm and 85℃ in an oil bath for 8 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a suspension. The mass ratio of activated zirconium silicate to solvent was 1:3.

[0023] 4. Centrifuge the suspension at 8000 rpm for 10 min, separate and discard the supernatant, wash 3 times with toluene and 2 times with anhydrous ethanol, and then dry under vacuum at 60℃ and 0.15 MPa for 4 h to obtain hyperbranched polysiloxane-grafted zirconium silicate.

[0024] 5. By weight, 0.6 parts tetraethyl silicate, 0.6 parts 1,2-bis(triethoxysilyl)ethane, and 0.8 parts cyclohexane were mixed and dissolved in 60 parts anhydrous ethanol. 0.64 parts hexadecyltrimethylammonium bromide were added and mixed thoroughly. Then, 100 parts water were added and stirred at 300 rpm for 60 min. Then, 1 part concentrated ammonia was added and the reaction was continued for 2.5 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min, washed three times with anhydrous ethanol, resuspended in hydrochloric acid-ethanol solution, and refluxed for 12 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min. The precipitate was washed twice with anhydrous ethanol and twice with deionized water, and then freeze-dried at -50℃ to obtain mesoporous silica microspheres. In the hydrochloric acid-ethanol solution, the volume ratio of hydrochloric acid to anhydrous ethanol was 1:9.

[0025] 6. Mesoporous silica microspheres were added to an ethanol-water solution at a mass ratio of 1:10. After ultrasonic dispersion at 300W for 10 min, the mixture was transferred to a high-speed homogenizer. The pH was adjusted to 4 using hydrochloric acid solution. γ-mercaptopropyltrimethoxysilane (KH590) was added dropwise and dispersed at 8000 rpm for 10 min. The mixture was then transferred to a four-necked flask and stirred at 60℃ and 400 rpm for 8 h. After the reaction was complete, the mixture was cooled, filtered, and ultrasonically washed three times with anhydrous ethanol. It was then vacuum dried at 80℃ to constant weight to obtain mercapto-modified mesoporous silica microspheres. The amount of silane coupling agent KH590 was 10 wt% of the mesoporous silica microspheres. The mass ratio of ethanol to water in the ethanol-water solution was 3:1.

[0026] 7. By weight, take 50 parts of hyperbranched polysiloxane-grafted zirconium silicate, 15 parts of mercaptoized mesoporous silica microspheres, 2 parts of silane coupling agent KH560, and 1 part of anionic dispersant (BYK110), disperse them in ethylene glycol, add 0.5 parts of triethylamine, and use the suspension blending method to stir and react at 60℃ and 1000rpm for 2h. After the reaction is completed, filter the mixture, wash the product with anhydrous ethanol, and then vacuum dry it at 80℃ for 6h to obtain modified zirconium silicate.

[0027] 8. By weight, take 30 parts potassium feldspar, 20 parts quartz, 8 parts kaolin, 10 parts calcite, 5 parts dolomite, 3 parts zinc oxide, 2 parts talc, 5 parts modified zirconium silicate, 2 parts spodumene, and 0.2 parts carboxymethyl cellulose.

[0028] 9. Modified zirconium silicate is mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder; potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc are mixed, ball-milled, and passed through a 250-mesh sieve to obtain the basic glaze raw material; carboxymethyl cellulose is added to water, stirred and dissolved, then the basic glaze raw material is added, stirred at 1200 rpm for 30 min, then the mixed powder is added, and stirred at 300 rpm for 20 min to obtain zirconium silicate composite ceramic glaze; wherein, the mass ratio of the total mass of the basic glaze raw material and the mixed powder to the mass of water is 2:5.

[0029] Example 2: A zirconium silicate composite ceramic glaze, comprising the following components: by weight, 35 parts potassium feldspar, 23 parts quartz, 10 parts kaolin, 11 parts calcite, 6 parts dolomite, 4 parts zinc oxide, 3 parts talc, 6 parts modified zirconium silicate, 3 parts spodumene, and 0.3 parts carboxymethyl cellulose.

[0030] The preparation method of the above-mentioned zirconium silicate composite ceramic glaze is as follows: 1. Under a nitrogen atmosphere, silane coupling agent KH560 and diethylene glycol were added to a four-necked round-bottom flask equipped with a thermometer, mechanical stirrer and distillation apparatus at a molar ratio of 1:1.9. The mixture was heated to 120°C and gradually increased to 150°C at a heating rate of 1°C / min. The mixture was then kept at 150°C for 30 min and then heated to 160°C to continue the reaction for 1 h. After the reaction was completed, a pale yellow transparent liquid hyperbranched polysiloxane was obtained in the round-bottom flask.

[0031] 2. Disperse zirconium silicate powder in 1.5 mol / L dilute hydrochloric acid at a mass ratio of 1:5. Stir at 400 rpm and 70°C for 3 hours. After solid-liquid separation by filtration, wash with deionized water until neutral and dry at 80°C for 4 hours to obtain activated zirconium silicate.

[0032] 3. Toluene and anhydrous ethanol were mixed at a mass ratio of 1:5 and added to a three-necked flask equipped with a mechanical stirrer, thermometer, water separator, and reflux condenser. 150 parts by weight of activated zirconium silicate were slowly added to the solvent and stirred evenly at 400 rpm. 6 parts of hyperbranched polysiloxane were added and ultrasonically dispersed at 600 W for 30 min. Finally, 0.08 parts of p-toluenesulfonic acid and 0.8 parts of deionized water were added. A water separation and reflux apparatus was set up, and the reaction was carried out at 500 rpm and 88℃ in an oil bath for 8 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a suspension. The mass ratio of activated zirconium silicate to solvent was 1:3.

[0033] 4. Centrifuge the suspension at 8000 rpm for 10 min, separate and discard the supernatant, wash 3 times with toluene and 2 times with anhydrous ethanol, and then dry under vacuum at 60℃ and 0.15 MPa for 4 h to obtain hyperbranched polysiloxane-grafted zirconium silicate.

[0034] 5. By weight, 0.6 parts tetraethyl silicate, 0.6 parts 1,2-bis(triethoxysilyl)ethane, and 0.8 parts cyclohexane were mixed and dissolved in 60 parts anhydrous ethanol. 0.64 parts hexadecyltrimethylammonium bromide were added and mixed thoroughly. Then, 100 parts water were added and stirred at 300 rpm for 60 min. Then, 1 part concentrated ammonia was added and the reaction was continued for 2.5 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min, washed three times with anhydrous ethanol, resuspended in hydrochloric acid-ethanol solution and refluxed for 12 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min. The precipitate was washed twice with anhydrous ethanol and twice with deionized water, and then freeze-dried at -50℃ to obtain mesoporous silica microspheres. In the hydrochloric acid-ethanol solution, the volume ratio of hydrochloric acid to anhydrous ethanol was 1:9.

[0035] 6. Mesoporous silica microspheres were added to an ethanol-water solution at a mass ratio of 1:13. After ultrasonic dispersion at 300W for 10 min, the mixture was transferred to a high-speed homogenizer. The pH was adjusted to 5 using hydrochloric acid solution. Silane coupling agent KH590 was added dropwise, and the mixture was dispersed at 8000 rpm for 10 min. The mixture was then transferred to a four-necked flask and stirred at 70℃ and 400 rpm for 9 h. After the reaction was complete, the mixture was cooled, filtered, and ultrasonically washed three times with anhydrous ethanol. It was then vacuum dried at 80℃ to constant weight to obtain mercapto-modified mesoporous silica microspheres. The amount of silane coupling agent KH590 used was 13 wt% of the mesoporous silica microspheres. The mass ratio of ethanol to water in the ethanol-water solution was 3:1.

[0036] 7. By weight, take 55 parts of hyperbranched polysiloxane-grafted zirconium silicate, 18 parts of mercaptoized mesoporous silica microspheres, 3 parts of silane coupling agent KH560, and 2 parts of anionic dispersant (BYK110), disperse them in ethylene glycol, add 0.8 parts of triethylamine, and use the suspension blending method to stir and react at 80℃ and 1250rpm for 3h. After the reaction is completed, filter the mixture, wash the product with anhydrous ethanol, and then vacuum dry it at 80℃ for 6h to obtain modified zirconium silicate.

[0037] 8. By weight, take 35 parts potassium feldspar, 23 parts quartz, 10 parts kaolin, 11 parts calcite, 6 parts dolomite, 4 parts zinc oxide, 3 parts talc, 6 parts modified zirconium silicate, 3 parts spodumene, and 0.3 parts carboxymethyl cellulose.

[0038] 9. Modified zirconium silicate is mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder; potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc are mixed, ball-milled, and passed through a 250-mesh sieve to obtain the basic glaze raw material; carboxymethyl cellulose is added to water, stirred and dissolved, then the basic glaze raw material is added, stirred at 1200 rpm for 30 min, then the mixed powder is added, and stirred at 300 rpm for 20 min to obtain zirconium silicate composite ceramic glaze; wherein, the mass ratio of the total mass of the basic glaze raw material and the mixed powder to the mass of water is 2:5.

[0039] Example 3: A zirconium silicate composite ceramic glaze, comprising the following components: by weight, 40 parts potassium feldspar, 25 parts quartz, 12 parts kaolin, 12 parts calcite, 8 parts dolomite, 5 parts zinc oxide, 4 parts talc, 8 parts modified zirconium silicate, 4 parts spodumene, and 0.3 parts carboxymethyl cellulose.

[0040] The preparation method of the above-mentioned zirconium silicate composite ceramic glaze is as follows: 1. Under a nitrogen atmosphere, silane coupling agent KH560 and diethylene glycol were added to a four-necked round-bottom flask equipped with a thermometer, mechanical stirrer and distillation apparatus at a molar ratio of 1:2. The mixture was heated to 120°C and gradually increased to 150°C at a heating rate of 1°C / min. The mixture was then held at 150°C for 30 min and then heated to 160°C to continue the reaction for 1 h. After the reaction was completed, a pale yellow transparent liquid hyperbranched polysiloxane was obtained in the round-bottom flask.

[0041] 2. Disperse zirconium silicate powder in 2 mol / L dilute hydrochloric acid at a mass ratio of 1:5. Stir at 400 rpm and 80°C for 4 hours. After solid-liquid separation by filtration, wash with deionized water until neutral and dry at 80°C for 4 hours to obtain activated zirconium silicate.

[0042] 3. Toluene and anhydrous ethanol were mixed at a mass ratio of 1:5 and added to a three-necked flask equipped with a mechanical stirrer, thermometer, water separator, and reflux condenser. 120 parts by weight of activated zirconium silicate were slowly added to the solvent and stirred at 400 rpm until homogeneous. 8 parts of hyperbranched polysiloxane were added and ultrasonically dispersed at 600 W for 30 min. Finally, 0.1 parts of p-toluenesulfonic acid and 1 part of deionized water were added. A water separator and reflux apparatus was set up, and the reaction was carried out at 500 rpm and 90℃ in an oil bath for 8 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a suspension. The mass ratio of activated zirconium silicate to solvent was 1:3.

[0043] 4. Centrifuge the suspension at 8000 rpm for 10 min, separate and discard the supernatant, wash 3 times with toluene and 2 times with anhydrous ethanol, and then dry under vacuum at 60℃ and 0.15 MPa for 4 h to obtain hyperbranched polysiloxane-grafted zirconium silicate.

[0044] 5. By weight, 0.6 parts tetraethyl silicate, 0.6 parts 1,2-bis(triethoxysilyl)ethane, and 0.8 parts cyclohexane were mixed and dissolved in 60 parts anhydrous ethanol. 0.64 parts hexadecyltrimethylammonium bromide were added and mixed thoroughly. Then, 100 parts water were added and stirred at 300 rpm for 60 min. Then, 1 part concentrated ammonia was added and the reaction was continued for 2.5 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min, washed three times with anhydrous ethanol, resuspended in hydrochloric acid-ethanol solution and refluxed for 12 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min. The precipitate was washed twice with anhydrous ethanol and twice with deionized water, and then freeze-dried at -50℃ to obtain mesoporous silica microspheres. In the hydrochloric acid-ethanol solution, the volume ratio of hydrochloric acid to anhydrous ethanol was 1:9.

[0045] 6. Mesoporous silica microspheres were added to an ethanol-water solution at a mass ratio of 1:15. After ultrasonic dispersion at 300W for 10 min, the mixture was transferred to a high-speed homogenizer. The pH was adjusted to 5 using hydrochloric acid solution. Silane coupling agent KH590 was added dropwise, and the mixture was dispersed at 8000 rpm for 10 min. The mixture was then transferred to a four-necked flask and stirred at 80℃ and 400 rpm for 10 h. After the reaction was complete, the mixture was cooled, filtered, and ultrasonically washed three times with anhydrous ethanol. It was then vacuum dried at 80℃ to constant weight to obtain mercapto-modified mesoporous silica microspheres. The amount of silane coupling agent KH590 used was 15 wt% of the mesoporous silica microspheres. The mass ratio of ethanol to water in the ethanol-water solution was 3:1.

[0046] 7. By weight, take 60 parts of hyperbranched polysiloxane-grafted zirconium silicate, 20 parts of mercaptoized mesoporous silica microspheres, 3 parts of silane coupling agent KH560, and 2 parts of anionic dispersant (BYK110), disperse them in ethylene glycol, add 1 part of triethylamine, and use the suspension blending method to stir and react at 100℃ and 1500rpm for 4h. After the reaction is completed, filter the product, wash it with anhydrous ethanol, and then vacuum dry it at 80℃ for 6h to obtain modified zirconium silicate.

[0047] 8. By weight, take 40 parts potassium feldspar, 25 parts quartz, 12 parts kaolinite, 12 parts calcite, 8 parts dolomite, 5 parts zinc oxide, 4 parts talc, 8 parts modified zirconium silicate, 4 parts spodumene, and 0.3 parts carboxymethyl cellulose.

[0048] 9. Modified zirconium silicate is mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder; potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc are mixed, ball-milled, and passed through a 250-mesh sieve to obtain the basic glaze raw material; carboxymethyl cellulose is added to water, stirred and dissolved, then the basic glaze raw material is added, stirred at 1200 rpm for 30 min, then the mixed powder is added, and stirred at 300 rpm for 20 min to obtain zirconium silicate composite ceramic glaze; wherein, the mass ratio of the total mass of the basic glaze raw material and the mixed powder to the mass of water is 2:5.

[0049] Example 4: Application of a zirconium silicate composite ceramic glaze in the preparation of ceramic products, comprising the following steps: 1. The zirconium silicate composite ceramic glaze prepared in Example 1 was uniformly sprayed onto the body by spraying. The glaze layer thickness was 0.3 mm. After drying at 80°C for 30 min, it was fired. The firing regime was as follows: the temperature was increased from room temperature to 300°C at a heating rate of 3°C / min; then increased to 600°C at a heating rate of 2°C / min and held for 10 min; then increased to 800°C at a heating rate of 4°C / min and held for 15 min; then increased to 1050°C at a heating rate of 5°C / min; then increased to 1200°C at a heating rate of 2°C / min and held for 20 min; then cooled to 800°C at a cooling rate of 5°C / min; then cooled to 700°C at a cooling rate of 5°C / min and held at 500°C for 15 min. Finally, the ceramic was removed from the kiln and allowed to cool naturally to room temperature.

[0050] Example 5: Application of a zirconium silicate composite ceramic glaze in the preparation of ceramic products, comprising the following steps: 1. The zirconium silicate composite ceramic glaze prepared in Example 2 was uniformly sprayed onto the body by spraying. The glaze layer thickness was 0.4 mm. After drying at 80°C for 30 min, it was fired. The firing regime was as follows: the temperature was increased from room temperature to 300°C at a heating rate of 3°C / min; then increased to 650°C at a heating rate of 2°C / min and held for 10 min; then increased to 850°C at a heating rate of 4°C / min and held for 15 min; then increased to 1100°C at a heating rate of 5°C / min; then increased to 1200°C at a heating rate of 2°C / min and held for 25 min; then cooled to 825°C at a cooling rate of 5°C / min; then cooled to 700°C at a cooling rate of 5°C / min and held at 500°C for 15 min. Finally, the ceramic was removed from the kiln and allowed to cool naturally to room temperature.

[0051] Example 6: Application of a zirconium silicate composite ceramic glaze in the preparation of ceramic products, comprising the following steps: 1. The zirconium silicate composite ceramic glaze prepared in Example 3 was uniformly sprayed onto the body by spraying. The glaze layer thickness was 0.5 mm. After drying at 80°C for 30 min, it was fired. The firing regime was as follows: the temperature was increased from room temperature to 300°C at a heating rate of 3°C / min; then increased to 700°C at a heating rate of 2°C / min and held for 10 min; then increased to 900°C at a heating rate of 4°C / min and held for 15 min; then increased to 1150°C at a heating rate of 5°C / min; then increased to 1200°C at a heating rate of 2°C / min and held for 30 min; then cooled to 850°C at a cooling rate of 5°C / min; then cooled to 700°C at a cooling rate of 5°C / min and held at 500°C for 15 min. Finally, the ceramic was removed from the kiln and allowed to cool naturally to room temperature.

[0052] Comparative Example 1: A zirconium silicate composite ceramic glaze, which differs from Example 1 in that the zirconium silicate is not modified with hyperbranched polysiloxane, and includes the following components: by weight, 30 parts potassium feldspar, 20 parts quartz, 8 parts kaolinite, 10 parts calcite, 5 parts dolomite, 3 parts zinc oxide, 2 parts talc, 5 parts modified zirconium silicate, 2 parts spodumene, and 0.2 parts carboxymethyl cellulose.

[0053] The preparation method of the above-mentioned zirconium silicate composite ceramic glaze is as follows: 1. By weight, 0.6 parts tetraethyl silicate, 0.6 parts 1,2-bis(triethoxysilyl)ethane, and 0.8 parts cyclohexane were mixed and dissolved in 60 parts anhydrous ethanol. 0.64 parts hexadecyltrimethylammonium bromide were added and mixed thoroughly. Then, 100 parts water were added and stirred at 300 rpm for 60 min. Then, 1 part concentrated ammonia was added and the reaction was continued for 2.5 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min, washed three times with anhydrous ethanol, resuspended in hydrochloric acid-ethanol solution and refluxed for 12 h. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 min. The precipitate was washed twice with anhydrous ethanol and twice with deionized water, and then freeze-dried at -50℃ to obtain mesoporous silica microspheres. In the hydrochloric acid-ethanol solution, the volume ratio of hydrochloric acid to anhydrous ethanol was 1:9.

[0054] 2. Mesoporous silica microspheres were added to an ethanol-water solution at a mass ratio of 1:10. After ultrasonic dispersion at 300W for 10 min, the mixture was transferred to a high-speed homogenizer. The pH was adjusted to 4 using hydrochloric acid solution. γ-mercaptopropyltrimethoxysilane (KH590) was added dropwise and dispersed at 8000 rpm for 10 min. The mixture was then transferred to a four-necked flask and stirred at 60℃ and 400 rpm for 8 h. After the reaction was complete, the mixture was cooled, filtered, and ultrasonically washed three times with anhydrous ethanol. It was then vacuum dried at 80℃ to constant weight to obtain mercapto-modified mesoporous silica microspheres. The amount of silane coupling agent KH590 was 10 wt% of the mesoporous silica microspheres. The mass ratio of ethanol to water in the ethanol-water solution was 3:1.

[0055] 3. By weight, take 50 parts of zirconium silicate, 15 parts of mercapto-modified mesoporous silica microspheres, 2 parts of silane coupling agent KH560, and 1 part of anionic dispersant (BYK110), disperse them in ethylene glycol, add 0.5 parts of triethylamine, and use the suspension blending method to stir and react at 60℃ and 1000rpm for 2h. After the reaction is completed, filter the mixture, wash the product with anhydrous ethanol, and then vacuum dry it at 80℃ for 6h to obtain modified zirconium silicate.

[0056] 4. By weight, take 30 parts potassium feldspar, 20 parts quartz, 8 parts kaolin, 10 parts calcite, 5 parts dolomite, 3 parts zinc oxide, 2 parts talc, 5 parts modified zirconium silicate, 2 parts spodumene, and 0.2 parts carboxymethyl cellulose.

[0057] 5. Modified zirconium silicate is mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder; potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc are mixed, ball-milled, and passed through a 250-mesh sieve to obtain the basic glaze raw material; carboxymethyl cellulose is added to water, stirred and dissolved, then the basic glaze raw material is added, stirred at 1200 rpm for 30 min, then the mixed powder is added, and stirred at 300 rpm for 20 min to obtain zirconium silicate composite ceramic glaze; wherein, the mass ratio of the total mass of the basic glaze raw material and the mixed powder to the mass of water is 2:5.

[0058] Comparative Example 2: A zirconium silicate composite ceramic glaze, which differs from Example 1 in that it does not coat hyperbranched polysiloxane-grafted zirconium silicate with mercaptoized mesoporous silica microspheres, and includes the following components: by weight, 30 parts potassium feldspar, 20 parts quartz, 8 parts kaolin, 10 parts calcite, 5 parts dolomite, 3 parts zinc oxide, 2 parts talc, 5 parts modified zirconium silicate, 2 parts spodumene, and 0.2 parts carboxymethyl cellulose.

[0059] The preparation method of the above-mentioned zirconium silicate composite ceramic glaze is as follows: 1. Under a nitrogen atmosphere, silane coupling agent KH560 and diethylene glycol were added to a four-necked round-bottom flask equipped with a thermometer, mechanical stirrer and distillation apparatus at a molar ratio of 1:1.8. The mixture was heated to 120°C and gradually increased to 150°C at a heating rate of 1°C / min. The mixture was then kept at 150°C for 30 min and then heated to 160°C to continue the reaction for 1 h. After the reaction was completed, a pale yellow transparent liquid hyperbranched polysiloxane was obtained in the round-bottom flask.

[0060] 2. Disperse zirconium silicate powder in 1 mol / L dilute hydrochloric acid at a mass ratio of 1:5. Stir at 400 rpm and 60°C for 2 hours. Then, filter to separate the solid and liquid phases. Wash with deionized water until neutral and dry at 80°C for 4 hours to obtain activated zirconium silicate.

[0061] 3. Toluene and anhydrous ethanol were mixed at a mass ratio of 1:5 and added to a three-necked flask equipped with a mechanical stirrer, thermometer, water separator, and reflux condenser. 100 parts by weight of activated zirconium silicate were slowly added to the solvent and stirred at 400 rpm until homogeneous. 5 parts of hyperbranched polysiloxane were added, and the mixture was ultrasonically dispersed at 600 W for 30 min. Finally, 0.05 parts of p-toluenesulfonic acid and 0.5 parts of deionized water were added. A water separator and reflux apparatus was set up, and the reaction was carried out at 500 rpm and 85℃ in an oil bath for 8 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a suspension. The mass ratio of activated zirconium silicate to solvent was 1:3.

[0062] 4. Centrifuge the suspension at 8000 rpm for 10 min, separate and discard the supernatant, wash 3 times with toluene and 2 times with anhydrous ethanol, and then dry under vacuum at 60℃ and 0.15 MPa for 4 h to obtain modified zirconium silicate.

[0063] 5. By weight, take 30 parts potassium feldspar, 20 parts quartz, 8 parts kaolin, 10 parts calcite, 5 parts dolomite, 3 parts zinc oxide, 2 parts talc, 5 parts modified zirconium silicate, 2 parts spodumene, and 0.2 parts carboxymethyl cellulose.

[0064] 6. Modified zirconium silicate is mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder; potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc are mixed, ball-milled, and passed through a 250-mesh sieve to obtain the basic glaze raw material; carboxymethyl cellulose is added to water, stirred and dissolved, then the basic glaze raw material is added, stirred at 1200 rpm for 30 min, then the mixed powder is added, and stirred at 300 rpm for 20 min to obtain zirconium silicate composite ceramic glaze; wherein, the mass ratio of the total mass of the basic glaze raw material and the mixed powder to the mass of water is 2:5.

[0065] Comparative Example 3: Application of a zirconium silicate composite ceramic glaze in the preparation of ceramic products, comprising the following steps: 1. The zirconium silicate composite ceramic glaze prepared in Comparative Example 1 was uniformly sprayed onto the body by spraying. The glaze layer thickness was 0.3 mm. After drying at 80℃ for 30 min, it was fired. The firing regime was as follows: heating from room temperature to 300℃ at a heating rate of 3℃ / min; then heating to 600℃ at a heating rate of 2℃ / min and holding for 10 min; then heating to 800℃ at a heating rate of 4℃ / min and holding for 15 min; then heating to 1050℃ at a heating rate of 5℃ / min; then heating to 1200℃ at a heating rate of 2℃ / min and holding for 20 min; then cooling to 800℃ at a cooling rate of 5℃ / min; then cooling to 700℃ at a cooling rate of 5℃ / min and holding at 500℃ for 15 min; finally, it was removed from the kiln and allowed to cool naturally to room temperature.

[0066] Comparative Example 4: Application of a zirconium silicate composite ceramic glaze in the preparation of ceramic products, comprising the following steps: 1. The zirconium silicate composite ceramic glaze prepared in Comparative Example 2 was uniformly sprayed onto the body by spraying. The glaze layer thickness was 0.3 mm. After drying at 80℃ for 30 min, it was fired. The firing regime was as follows: heating from room temperature to 300℃ at a heating rate of 3℃ / min; then heating to 600℃ at a heating rate of 2℃ / min and holding for 10 min; then heating to 800℃ at a heating rate of 4℃ / min and holding for 15 min; then heating to 1050℃ at a heating rate of 5℃ / min; then heating to 1200℃ at a heating rate of 2℃ / min and holding for 20 min; then cooling to 800℃ at a cooling rate of 5℃ / min; then cooling to 700℃ at a cooling rate of 5℃ / min and holding at 500℃ for 15 min; finally, it was removed from the kiln and allowed to cool naturally to room temperature.

[0067] The high-temperature viscosity of the zirconium silicate composite ceramic glazes obtained in Examples 1-3 and Comparative Examples 1 and 2 was determined: Cylindrical samples of the same mass of glaze were prepared and adhered to the flat surface of a fired rectangular ceramic slab. The slab with the glaze sample was placed on a refractory base with an inclination angle of 20° and fired in a kiln with the product. When firing to the high-temperature stage, the cylindrical glaze sample melted into a glassy melt. As the temperature increased, the viscosity of the glaze gradually decreased, and the molten glaze flowed to the remaining surface and sides of the ceramic slab. After firing, the maximum length and width of the glaze flow were measured using calipers. The sum of these two measurements in millimeters represents the flowability of the glaze at high temperature, thus characterizing the viscosity of the glaze at high temperature. The test results are shown in Table 1. Table 1 High-temperature viscosity test of zirconium silicate composite ceramic glaze

[0068] According to experiments, a high-temperature fluidity of 50–70 mm ensures a normal glaze surface appearance. If it is below 50 mm, due to the higher viscosity, the glaze layer has poor fluidity, often resulting in ripples, glaze build-up, or glaze streaks on the surface, and poor gloss. If it is above 70 mm, the glaze surface often exhibits over-firing characteristics, as some components of the glaze evaporate or are easily absorbed by the body, causing it to thin. Sometimes, the glaze layer becomes opaque or even dull and lacks luster. Adjusting the high-temperature fluidity of the glaze to 55–65 mm results in the smoothest and most lustrous glaze surface.

[0069] As shown in Table 1, the zirconium silicate composite ceramic glazes obtained in Examples 1-3 have a flowability between 58 and 66 mm and a suitable viscosity. However, in Comparative Example 1, the lack of hyperbranched polysiloxane grafting resulted in a lack of physical barriers on the surface of the zirconium silicate particles after the mesoporous silica melted, making them prone to high-temperature agglomeration and forming local enrichment areas. These areas exhibited different melting behaviors and surface tensions compared to the surrounding glazes, leading to a decrease in the flowability of the glaze. In Comparative Example 2, the lack of synergistic effect between the mesoporous silica microspheres and the hyperbranched polysiloxane resulted in excessively high local zirconium ion concentrations during the glaze melting process, causing a decrease in the flowability of the glaze.

[0070] The whiteness of the ceramic samples prepared in Examples 4-6 and Comparative Examples 3-4 was tested, and the glaze quality of the samples was observed. The whiteness was tested using a digital whiteness meter, and the test results are shown in Table 2.

[0071] Table 2 Performance Tests of Ceramic Samples Prepared with Zirconium Silicate Composite Ceramic Glaze

[0072] As shown in Table 2, the whiteness of the ceramic samples obtained in Examples 4-6 and Comparative Examples 3 and 4 did not differ significantly, proving that the modification of zirconium silicate did not affect the whiteness of the ceramic samples; however, the visual effect of the glaze in Examples 4-6 was far superior to that in Comparative Examples 3 and 4. As shown in Table 1, the fluidity of the zirconium silicate composite ceramic glaze obtained in Examples 1-3 was higher than that in Comparative Examples 3 and 4, and the high-temperature viscosity of the glaze prepared using modified zirconium silicate was lower than that of the glaze obtained in Comparative Examples 1 and 2. The visual effect of the ceramic samples obtained in Examples 4-6 was also superior to that in Comparative Examples 3 and 4.

[0073] The surface pore distribution and microstructure of ceramic product samples obtained in Example 6 and Comparative Examples 3 and 4 were observed, and the results are as follows: Figures 2-4 As shown in the figure, the ceramic products obtained in Comparative Examples 3 and 4 have significantly more pores than those in Example 6, and the pore diameter is also significantly larger. The glaze surface made from the zirconium silicate composite ceramic glaze obtained by this technical solution has less noticeable defects such as pinholes and spots, which is beneficial to improving the glaze surface's stain resistance and ease of cleaning.

[0074] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A zirconium silicate composite ceramic glaze, characterized in that, By weight, it includes the following components: 30-40 parts potassium feldspar, 20-25 parts quartz, 8-12 parts kaolin, 10-12 parts calcite, 5-8 parts dolomite, 3-5 parts zinc oxide, 2-4 parts talc, 5-8 parts modified zirconium silicate, 2-4 parts spodumene, and 0.2-0.3 parts carboxymethyl cellulose. The method for preparing the modified zirconium silicate includes the following steps: dispersing hyperbranched polysiloxane-grafted zirconium silicate, mercaptoized mesoporous silica microspheres, silane coupling agent KH560, and anionic dispersant in ethylene glycol, adding triethylamine, and reacting by suspension blending at high speed at 60~100℃ for 2~4h. After the reaction is completed, the modified zirconium silicate is obtained by filtration, washing, and vacuum drying.

2. The zirconium silicate composite ceramic glaze according to claim 1, characterized in that, By weight, it includes: 50-60 parts of hyperbranched polysiloxane-grafted zirconium silicate, 15-20 parts of mercapto-modified mesoporous silica microspheres, 2-3 parts of silane coupling agent KH560, 1-2 parts of anionic dispersant and 0.5-1 parts of triethylamine.

3. The zirconium silicate composite ceramic glaze according to claim 1, characterized in that, The preparation method of hyperbranched polysiloxane-grafted zirconium silicate includes the following steps: toluene and anhydrous ethanol are mixed at a mass ratio of 1:5 as solvents, activated zirconium silicate is slowly added to the solvent, and after stirring evenly, hyperbranched polysiloxane is added. After ultrasonic dispersion and mixing evenly, p-toluenesulfonic acid and deionized water are added. The mixture is refluxed for 8 hours in an oil bath at 85-90°C with stirring. After high-speed centrifugation and filtration, the mixture is washed successively with toluene and anhydrous ethanol, and then vacuum dried at 60°C to obtain hyperbranched polysiloxane-grafted zirconium silicate.

4. The zirconium silicate composite ceramic glaze according to claim 3, characterized in that, By weight, it includes 100-120 parts activated zirconium silicate, 5-8 parts hyperbranched polysiloxane, 0.05-0.1 parts p-toluenesulfonic acid and 0.5-1 parts deionized water.

5. The zirconium silicate composite ceramic glaze according to claim 4, characterized in that, The preparation method of the hyperbranched polysiloxane includes the following steps: Under a nitrogen atmosphere, silane coupling agent KH560 is mixed with diethylene glycol at a molar ratio of 1:1.8~2, heated to 120°C, and then the mixture is gradually heated from 120°C to 150°C at a heating rate of 1°C / min, and kept at 150°C for 30 min. Then, it is heated to 160°C and the reaction continues for 1 h. After the reaction is completed, hyperbranched polysiloxane is obtained.

6. The zirconium silicate composite ceramic glaze according to claim 4, characterized in that, The method for preparing activated zirconium silicate includes the following steps: dispersing zirconium silicate powder in 1-2 mol / L dilute hydrochloric acid at a mass ratio of 1:5, stirring and reacting at 400 rpm and 60-80℃ for 2-4 hours, filtering, washing with deionized water until neutral, and drying to obtain activated zirconium silicate.

7. The zirconium silicate composite ceramic glaze according to claim 2, characterized in that, The preparation method of the mercapto-modified mesoporous silica microspheres includes the following steps: adding mesoporous silica microspheres to an ethanol-water solution at a mass ratio of 1:10~15, dispersing by ultrasonication at 300W, adjusting the pH to 4~5, adding silane coupling agent KH590 dropwise, dispersing at high speed for 10 min, stirring and reacting at 60~80℃ for 8~10 h, after the reaction is complete, cooling, filtering, ultrasonically washing three times with anhydrous ethanol, and vacuum drying at 80℃ to constant weight to obtain mercapto-modified mesoporous silica microspheres; the amount of silane coupling agent KH590 used is 10~15wt% of the mesoporous silica microspheres; in the ethanol-water solution, the mass ratio of ethanol to water is 3:

1.

8. The method for preparing the zirconium silicate composite ceramic glaze according to claim 1, characterized in that, Includes the following steps: Modified zirconium silicate was mixed with spodumene, ball-milled, and passed through a 250-mesh sieve to obtain a mixed powder; potassium feldspar, quartz, kaolin, calcite, dolomite, zinc oxide, and talc were mixed, ball-milled, and passed through a 250-mesh sieve to obtain the basic glaze raw material. Carboxymethyl cellulose was added to water and stirred until dissolved. Then, the base glaze raw material was added and stirred at high speed for 30 minutes. Finally, the mixed powder was added and stirred at low speed for 20 minutes to obtain zirconium silicate composite ceramic glaze. The mass ratio of the base glaze raw material and the mixed powder to the water was 2:

5.

9. The application of the zirconium silicate composite ceramic glaze according to claim 1 in the preparation of ceramic products.

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