A high-temperature ceramic glaze with photocatalytic performance, its preparation method and application

Abstract

The present invention discloses a high-temperature ceramic glaze with photocatalytic performance, its preparation method and application. The raw material composition and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze: 75 - 95 parts, photocatalytic material: 5 - 25 parts; The high-temperature ceramic glaze of the present invention has an efficient photocatalytic effect, especially the photocatalytic activity after the glaze is fired at a high temperature (1250 - 1350 °C) can be realized, which helps to enhance the self-cleaning effect of ceramic products. It not only has a good photocatalytic effect under natural light conditions, but also has a good photocatalytic effect after high-temperature heat treatment, and is suitable for the production of high-temperature daily-use porcelain, electro-ceramics, etc.

Description

Technical Field

[0001] The present invention belongs to the technical field of new materials, relates to ceramic materials, and in particular to a high-temperature ceramic glaze with photocatalytic performance, a preparation method thereof, and applications thereof. Background Art

[0002] Since Fujishima, Honda, etc. discovered in the 1970s that TiO2 can dissociate water electrochemically, it has received extensive attention and applications due to its good photocatalytic decomposition efficiency for organic pollutants in the fields of sterilization, air purification, etc. The basic principle of photocatalysis mainly uses semiconductor oxide materials as catalysts. When semiconductor oxides are irradiated and activated by photons with energies greater than the energy band gap of their electron orbits, photogenerated electrons and photogenerated holes are generated. The electrons and holes are separated and migrate to different positions on the particle surface. The electrons react with O2 adsorbed on the surface of the semiconductor oxide photocatalyst to generate superoxide radicals [·O2 - , and the holes react with H2O to generate hydroxyl radicals [OH]. These radicals have extremely strong oxidizing properties and can oxidize and decompose most organic pollutants in nature.

[0003] With the rapid development of society and technology, the market has higher requirements for the performance of ceramic products. For example, the glaze on the surface of ceramic tableware in the field of daily-use ceramics for treating molds and bacteria, the photocatalytic degradation of formaldehyde in the indoor environment by floor tiles, and the photocatalytic degradation of stains on the surface of the glaze of high-voltage porcelain insulators in the field of high-voltage porcelain insulators to reduce their flashover effect, etc.

[0004] Patent publication document CN 114031295A discloses a photocatalytic ceramic glaze, a preparation method thereof, and applications thereof. The raw materials for preparing the photocatalytic ceramic glaze include 40-60 parts of a matrix material, 1-3 parts of a carbon material, 5-10 parts of a photocatalytic material, and 3-5 parts of an infrared conversion material. This material has the function of converting infrared light into ultraviolet light, so that the photocatalytic material can still achieve the photocatalytic function even when there is less visible light. However, its firing temperature range is only 1100-1200°C, and the sintering temperature cannot meet the requirements of high-temperature ceramic glazes at 1250-1350°C.

[0005] Patent publication CN 107651851 B discloses a photocatalytic glaze for humidity-regulating ceramic tiles and a preparation method thereof. The raw materials of the photocatalytic glaze for humidity-regulating ceramic tiles include 45-55 parts of low-temperature frit, 0.3-1.2 parts of anatase titanium dioxide, 0.5-2 parts of calcium carbonate, 0.5-2 parts of bentonite, 0.5-1.5 parts of dispersant, and 45-65 parts of water. The anatase titanium dioxide in the invention is a photocatalyst, which is directly added to the glaze components. It not only has good dispersion performance, but also can directly degrade the formaldehyde adsorbed by micropores under the action of natural light or lamp light after firing, so as to achieve the effect of removing formaldehyde in indoor air. At the same time, the nanoscale anatase titanium dioxide and the low-temperature frit are mixed and fired together under low-temperature conditions, which can further form a high-strength dense protective film on the surface of the humidity-regulating ceramic tiles. However, the glaze sintering temperature is only 780 °C, and the heat preservation time is only 0.5 h. This is because the anatase titanium dioxide with photocatalytic properties in the glaze is extremely easy to transform into rutile titanium dioxide with lower photocatalytic activity above 800 °C, thus reducing the photocatalytic activity of the glaze. Therefore, its limitations in use also cannot be adapted to the preparation of ceramic glazes at high temperatures of 1250-1350 °C.

[0006] Patent publication CN 108911512 A discloses a formula and a preparation method of a photocatalytic glaze capable of precipitating anatase crystals. The raw materials of the photocatalytic glaze capable of precipitating anatase crystals include 10-12 parts of TiO2, 48-50 parts of SiO2, 2-4 parts of Al2O3, 16-18 parts of B2O3, 7.5-9 parts of Na2O, 6-7.5 parts of K2O, 1-3 parts of MgO, 1-3 parts of P2O5, and 1 part of fluorine (F). The mixture is loaded into a corundum crucible and placed in a muffle furnace, heated to 1300-1500 °C, and kept warm to form high-temperature glass, which is then poured into water for quenching; the cooled glass balls are ground, sieved, and dried to obtain a frit glaze. During use, the glaze is heated to 1180 °C and kept warm for 20 min, then cooled with air for 2.5 min and kept warm at 750 °C for 20 min, and anatase crystals with photocatalytic activity and trace rutile are precipitated on the glaze surface. However, limited by the bandgap problem of TiO2, the bandgap of anatase crystals is 3.2 eV, and theoretically only ultraviolet light (below 387.5 nm) can be utilized in photoelectric conversion.

[0007] Therefore, it is necessary to provide a ceramic glaze that can have photocatalytic activity in a higher light wavelength band under natural light conditions after being fired at a high temperature of ceramics (1250-1350 °C).

[0008] Through retrieval, no patent publication related to this invention patent application was found. Summary of the Invention

[0009] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a high-temperature ceramic glaze with photocatalytic performance, its preparation method and application.

[0010] The technical solution adopted by the present invention to solve its technical problems is as follows:

[0011] A high-temperature ceramic glaze with photocatalytic performance, the raw material composition and weight parts thereof include: matrix glaze: 75-95 parts, photocatalytic material: 5-25 parts.

[0012] Further, the matrix glaze includes potassium feldspar, quartz, kaolin, talc and alumina;

[0013] Or, the photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate.

[0014] Further, the composition and weight parts of the matrix glaze include:

[0015]

[0016] Or, the volume ratio of the triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water is 15:34:50:2 (i.e., the final ratio: 15:34:50:2); the molar ratio of the zinc acetate to the tetrabutyl titanate is 5:1-9:1.

[0017] Further, the particle sizes of the potassium feldspar, quartz, kaolin, talc and alumina are all 300 mesh.

[0018] Further, the preparation method of the matrix glaze includes the following steps:

[0019] Mix potassium feldspar, quartz, kaolin, talc and alumina, and ball mill for 1-2 h to obtain the matrix glaze;

[0020] Or, the preparation method of the photocatalytic material includes the following steps:

[0021] Mix triethanolamine, tetrabutyl titanate and absolute ethanol and stir for 1-2 h, add deionized water, stir for 1-2 h, add zinc acetate, and continue to stir for 1-2 h to mix evenly to obtain a titanium-zinc mixed slurry; heat the stirred titanium-zinc mixed slurry at 140-150 °C for 12-14 h, and then calcine at 1250-1350 °C for 1-2 h to obtain a titanium-zinc-oxygen photocatalytic material.

[0022] The preparation method of the high-temperature ceramic glaze with photocatalytic performance as described above includes the following steps:

[0023] Mix the matrix glaze with the photocatalytic material. The solid component: water: balls are wet ball-milled at a weight ratio of 1:1:3 for 10 - 12 h, dried, and sieved through a sieve mesh to obtain a high-temperature ceramic glaze with photocatalytic properties.

[0024] Further, after drying, sieve through a 325-mesh sieve.

[0025] Application of the high-temperature ceramic glaze with photocatalytic properties as described above in the sintering preparation of high-temperature ceramics.

[0026] A method for sintering and preparing high-temperature ceramics using the high-temperature ceramic glaze with photocatalytic properties as described above, the method comprising the following steps:

[0027] Spray the high-temperature ceramic glaze with photocatalytic properties on the surface of the ceramic blank and sinter it into a ceramic;

[0028] Among them, the sintering conditions are: heating from room temperature to 300 °C for 1 - 1.5 h; heating from 300 °C to 600 °C for 1 - 1.5 h; heating from 600 °C to 900 °C for 1 - 1.5 h; heating from 900 °C to 1250 - 1350 °C for 2 - 2.5 h; after the heating is completed, keep warm for 1 - 2 h.

[0029] Application of the high-temperature ceramic glaze with photocatalytic properties as described above in the preparation of high-temperature daily-use ceramics and / or electrical ceramics.

[0030] The advantages and positive effects achieved by the present invention are:

[0031] 1. The present invention uses a sol-hydrothermal process to prepare a titanium-zinc-oxygen material with photocatalytic activity. This process enables the titanium-zinc-oxygen material to achieve atomic-level mixing. After firing at 1250 - 1350 °C, a ZnO-Zn2TiO4 heterojunction is formed. Since both ZnO and Zn2TiO4 have semiconductor characteristics, the coupling mechanism of ZnO and Zn2TiO4 semiconductors can promote the separation of photo-generated charges, reduce the electron-hole recombination, and thus enhance the photocatalytic activity of the material.

[0032] 2. The titanium-zinc-oxygen photocatalytic material prepared by the present invention is fired at a high temperature of 1250 - 1350 °C and has good high-temperature stability. At the same time, since the main substance of the titanium-zinc-oxygen photocatalytic material after firing at 1250 - 1350 °C is the ZnO-Zn2TiO4 complex, ZnO can be well fused with the vitrified glaze under high-temperature conditions and can prevent the vitrified glaze from corroding the Zn2TiO4 substance, so that the glaze still has good photocatalytic activity after high-temperature firing.

[0033] 3. The titanium-zinc-oxide photocatalytic material prepared by the present invention is incorporated into the base glaze. After firing at a high temperature of 1250-1350°C, it is found by solid ultraviolet detection that the absorption wave number of the glaze doped with the titanium-zinc-oxide photocatalytic material redshifts into the visible light range; at the same time, through experimental verification, the glaze doped with the titanium-zinc-oxide photocatalytic material has photocatalytic activity under sunlight irradiation after being fired at a high temperature. The photocatalytic glaze prepared by the present invention can be applied to the production of high-temperature daily-use ceramics and electroceramics, which helps to improve the self-cleaning effect of ceramic products. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 XRD patterns of the matrix glaze (a-glaze) and the ceramic glaze with photocatalytic performance (b-ZTO-glaze) in Example 2 of the present invention after heat treatment at 1300°C;

[0035] Figure 2 Solid ultraviolet-visible absorption spectra of the matrix glaze (a-glaze) and the ceramic glaze with photocatalytic performance (b-ZTO-glaze) in Example 2 of the present invention after heat treatment at 1300°C. DETAILED DESCRIPTION OF THE INVENTION

[0036] The following further illustrates the present invention in conjunction with embodiments. The following embodiments are narrative and not restrictive, and the protection scope of the present invention cannot be limited by the following embodiments.

[0037] All kinds of experimental operations involved in the specific embodiments are conventional techniques in the art. For the parts not specifically annotated in this article, those of ordinary skill in the art can refer to various common reference books, scientific and technological literatures or relevant specifications, manuals, etc. before the filing date of the present invention application for implementation.

[0038] A high-temperature ceramic glaze with photocatalytic performance, the raw material composition and weight parts thereof include: matrix glaze: 75-95 parts, photocatalytic material: 5-25 parts.

[0039] Preferably, the matrix glaze includes potassium feldspar, quartz, kaolin, talc and alumina;

[0040] Alternatively, the photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate.

[0041] Preferably, the composition and weight parts of the matrix glaze include:

[0042]

[0043] Alternatively, the volume ratio of triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water is 15:34:50:2; the molar ratio of zinc acetate to tetrabutyl titanate is 5:1-9:1.

[0044] Preferably, the particle sizes of the potassium feldspar, quartz, kaolin, talc and alumina are all 300 mesh.

[0045] Preferably, the preparation method of the matrix glaze comprises the following steps:

[0046] Mix the potassium feldspar, quartz, kaolin, talc and alumina, and ball mill for 1 - 2 h to obtain the matrix glaze;

[0047] Alternatively, the preparation method of the photocatalytic material comprises the following steps:

[0048] Mix and stir triethanolamine, tetrabutyl titanate and absolute ethanol for 1 - 2 h, add deionized water, stir for 1 - 2 h, add zinc acetate, and continue to stir for 1 - 2 h to mix evenly to obtain a titanium-zinc mixed slurry; heat the stirred titanium-zinc mixed slurry at 140 - 150 °C for 12 - 14 h, and then calcine at 1250 - 1350 °C for 1 - 2 h to obtain a titanium-zinc-oxygen photocatalytic material.

[0049] The preparation method of the high-temperature ceramic glaze with photocatalytic performance as described above comprises the following steps:

[0050] Mix the matrix glaze and the photocatalytic material, and perform wet ball milling with a weight ratio of solid components: water: balls of 1:1:3 for 10 - 12 h, dry and screen through a screen mesh to obtain a high-temperature ceramic glaze with photocatalytic performance.

[0051] Preferably, after drying, screen through a 325-mesh screen.

[0052] The application of the high-temperature ceramic glaze with photocatalytic performance as described above in the sintering preparation of high-temperature ceramics.

[0053] The method for sintering and preparing high-temperature ceramics by using the high-temperature ceramic glaze with photocatalytic performance as described above, the method comprises the following steps:

[0054] Spray the high-temperature ceramic glaze with photocatalytic performance on the surface of the ceramic green body, and sinter to form ceramics;

[0055] Among them, the sintering conditions are: raise the temperature from room temperature to 300 °C for 1 - 1.5 h; raise the temperature from 300 °C to 600 °C for 1 - 1.5 h; raise the temperature from 600 °C to 900 °C for 1 - 1.5 h; raise the temperature from 900 °C to 1250 - 1350 °C for 2 - 2.5 h; keep the temperature for 1 - 2 h after the temperature raising is completed.

[0056] The application of the high-temperature ceramic glaze with photocatalytic performance as described above in the preparation of high-temperature daily-use ceramics and / or electrical ceramics.

[0057] Specifically, the relevant preparation and detection are as follows:

[0058] Example 1:

[0059] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0060] The raw material components and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze and photocatalytic material;

[0061] Among them, the composition components and weight parts of the matrix glaze include: 33 parts of potassium feldspar, 26 parts of quartz, 25 parts of kaolin, 10 parts of talc, 6 parts of alumina. The particle size of the selected raw materials is 300 mesh, and the above materials are ball-milled and mixed for 2 h.

[0062] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate. Triethanolamine, tetrabutyl titanate and absolute ethanol are mixed and stirred for 1 h according to a volume ratio of 15:34:50. Deionized water is added according to a volume ratio of tetrabutyl titanate, absolute ethanol and deionized water of 34:50:2, and mixed and stirred for 1 h. Then, zinc acetate is added according to a molar ratio of zinc acetate to tetrabutyl titanate of 9:1, and mixed and stirred for 2 h. After the stirred titanium-zinc mixed slurry is placed in a reaction kettle and heated at 140 °C for 14 h, the mixture is poured into an alumina crucible and calcined at 1350 °C for 1 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0063] The matrix glaze and the photocatalytic material are mixed according to a weight ratio of 75:25, and the solid component: water: ball is wet ball-milled for 12 h according to a weight ratio of 1:1:3, dried and sieved through a 325-mesh sieve to obtain the high-temperature ceramic glaze with photocatalytic performance.

[0064] The method for sintering and preparing high-temperature ceramics using the above ceramic glaze includes the following steps:

[0065] The ceramic glaze is sprayed on the surface of the ceramic blank and sintered into ceramics;

[0066] The sintering process of the photocatalytic performance ceramic glaze is: room temperature to 300 °C, 1 h; 300 to 600 °C, 1 h; 600 to 900 °C, 1.5 h; 900 to 1350 °C, 2.5 h; 1350 °C for heat preservation for 1.5 h.

[0067] Example 2:

[0068] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0069] The raw material components and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze and photocatalytic material;

[0070] Among them, the composition components and weight parts of the matrix glaze include: 34 parts of potassium feldspar, 27 parts of quartz, 24 parts of kaolin, 11 parts of talc, and 4 parts of alumina. The particle size of the selected raw materials is 300 mesh, and the above materials are ball-milled and mixed for 1.5 h.

[0071] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water, and zinc acetate. Triethanolamine, tetrabutyl titanate, and absolute ethanol are mixed and stirred for 1.5 h according to a volume ratio of 15:34:50. Deionized water is added according to a volume ratio of tetrabutyl titanate, absolute ethanol, and deionized water of 34:50:2, and the mixture is stirred for 1 h. Then, zinc acetate is added according to a molar ratio of zinc acetate to tetrabutyl titanate of 8:1, and the mixture is stirred for 1.5 h. The stirred titanium-zinc mixed slurry is poured into a reaction kettle and heated at 145 °C for 13 h, and then the mixture is poured into an alumina crucible and calcined at 1300 °C for 2 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0072] The matrix glaze and the photocatalytic material are mixed according to a weight ratio of 80:20. The solid component: water: balls are wet ball-milled for 10 h according to a weight ratio of 1:1:3, dried, and passed through a 325-mesh sieve to obtain the prepared ceramic glaze with photocatalytic performance.

[0073] A method for sintering and preparing high-temperature ceramics using the above ceramic glaze includes the following steps:

[0074] The ceramic glaze is sprayed on the surface of the ceramic blank and sintered into ceramics;

[0075] The sintering process of the photocatalytic performance ceramic glaze is: room temperature to 300 °C, 1.5 h; 300 to 600 °C, 1.5 h; 600 to 900 °C, 1.5 h; 900 to 1300 °C, 2 h; 1300 °C for heat preservation for 1.5 h.

[0076] Example 3:

[0077] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0078] The raw material composition components and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze and photocatalytic material;

[0079] Among them, the composition components and weight parts of the matrix glaze include: 35 parts of potassium feldspar, 28 parts of quartz, 23 parts of kaolin, 9 parts of talc, and 5 parts of alumina. The particle size of the selected raw materials is 300 mesh, and the above materials are ball-milled and mixed for 1 h.

[0080] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate. Triethanolamine, tetrabutyl titanate and absolute ethanol are mixed and stirred for 1.5 h according to a volume ratio of 15:34:50. Deionized water is added according to a volume ratio of tetrabutyl titanate, absolute ethanol and deionized water of 34:50:2, and the mixture is stirred for 2 h. Then, zinc acetate is added according to a molar ratio of zinc acetate to tetrabutyl titanate of 7:1, and the mixture is stirred for 1.5 h. The stirred titanium-zinc mixed slurry is placed in a reaction kettle and heated at 150 °C for 12 h, and then the mixture is poured into an alumina crucible and calcined at 1280 °C for 1.5 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0081] The matrix glaze and the photocatalytic material are mixed according to a weight ratio of 85:15. The solid components: water: balls are wet ball-milled for 11 h according to a weight ratio of 1:1:3, dried and sieved through a 325-mesh sieve to obtain the prepared ceramic glaze with photocatalytic performance.

[0082] A method for sintering a high-temperature ceramic using the above ceramic glaze includes the following steps:

[0083] The ceramic glaze is sprayed on the surface of the ceramic green body and sintered into a ceramic;

[0084] The sintering process of the ceramic glaze with photocatalytic performance is: room temperature to 300 °C, 1.5 h; 300 to 600 °C, 1.5 h; 600 to 900 °C, 1.5 h; 900 to 1280 °C, 2 h; keep warm at 1280 °C for 1.5 h.

[0085] Example 4:

[0086] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0087] The raw material composition and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze and photocatalytic material;

[0088] Among them, the composition and weight parts of the matrix glaze include: 36 parts of potassium feldspar, 29 parts of quartz, 22 parts of kaolin, 10 parts of talc, 3 parts of alumina. The selected raw material particle size is 300 mesh, and the above materials are ball-milled and mixed for 1.5 h.

[0089] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate. Triethanolamine, tetrabutyl titanate and absolute ethanol are mixed and stirred for 1 h at a volume ratio of 15:34:50. Deionized water is added according to the volume ratio of tetrabutyl titanate, absolute ethanol and deionized water being 34:50:2, and the mixture is stirred for 2 h. Then zinc acetate is added at a molar ratio of zinc acetate to tetrabutyl titanate of 6:1, and the mixture is stirred for 2 h. The stirred titanium-zinc mixed slurry is placed in a reaction kettle and heated at 140 °C for 14 h, and then the mixture is poured into an alumina crucible and calcined at 1280 °C for 1.5 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0090] The matrix glaze and the photocatalytic material are mixed at a weight ratio of 90:10, and the solid component: water: balls are wet ball-milled at a weight ratio of 1:1:3 for 11 h, dried and sieved through a 325-mesh sieve to obtain the prepared ceramic glaze with photocatalytic properties.

[0091] The method for sintering high-temperature ceramics using the above ceramic glaze includes the following steps:

[0092] The ceramic glaze is sprayed on the surface of the ceramic blank and sintered into ceramics;

[0093] The sintering process of the photocatalytic performance ceramic glaze is: room temperature to 300 °C, 1.5 h; 300 to 600 °C, 1.5 h; 600 to 900 °C, 1.5 h; 900 to 1280 °C, 2 h; 1280 °C for heat preservation for 2 h.

[0094] Example 5:

[0095] A high-temperature ceramic glaze with photocatalytic properties and its preparation method are as follows:

[0096] The raw material composition and weight parts of the high-temperature ceramic glaze with photocatalytic properties include: matrix glaze and photocatalytic material;

[0097] Among them, the composition and weight parts of the matrix glaze include: 37 parts of potassium feldspar, 30 parts of quartz, 21 parts of kaolin, 8 parts of talc, 4 parts of alumina. The particle size of the selected raw materials is 300 mesh, and the above materials are ball-milled and mixed for 1.5 h.

[0098] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate. Triethanolamine, tetrabutyl titanate and absolute ethanol are mixed and stirred for 2 h at a volume ratio of 15:34:50. Deionized water is added according to the volume ratio of tetrabutyl titanate, absolute ethanol and deionized water being 34:50:2, and the mixture is stirred for 2 h. Then zinc acetate is added at a molar ratio of zinc acetate to tetrabutyl titanate of 5:1, and the mixture is stirred for 1 h. The stirred titanium-zinc mixed slurry is placed in a reaction kettle and heated at 140 °C for 14 h, and then the mixture is poured into an alumina crucible and calcined at 1260 °C for 2 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0099] Mix the matrix glaze and the photocatalytic material in a weight ratio of 86:14. For wet ball milling, the weight ratio of solid components: water: balls is 1:1:3, and ball mill for 11 h, then dry and sieve through a 325-mesh sieve to obtain the ceramic glaze with photocatalytic performance.

[0100] A method for sintering high-temperature ceramics using the above ceramic glaze includes the following steps:

[0101] Spray the ceramic glaze on the surface of the ceramic body and sinter it into ceramics.

[0102] The sintering process of the photocatalytic performance ceramic glaze is as follows: at room temperature to 300 °C for 1.5 h; 300 to 600 °C for 1.5 h; 600 to 900 °C for 1.5 h; 900 to 1260 °C for 2 h; keep the temperature at 1260 °C for 1 h.

[0103] Example 6:

[0104] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0105] The raw material composition and weight parts of the high-temperature ceramic glaze with photocatalytic performance include matrix glaze and photocatalytic material.

[0106] Among them, the composition and weight parts of the matrix glaze include 38 parts of potassium feldspar, 30 parts of quartz, 20 parts of kaolin, 8 parts of talc, and 4 parts of alumina. The particle size of the selected raw materials is 300 mesh, and ball mill and mix the above materials for 1 h.

[0107] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water, and zinc acetate. Mix triethanolamine, tetrabutyl titanate, and absolute ethanol in a volume ratio of 15:34:50 and stir for 1 h. Add deionized water according to the volume ratio of tetrabutyl titanate, absolute ethanol, and deionized water of 34:50:2, and mix and stir for 2 h. Then add zinc acetate according to the molar ratio of zinc acetate to tetrabutyl titanate of 9:1, and mix and stir for 2 h. Place the stirred titanium-zinc mixed slurry in a reaction kettle, heat it at 150 °C for 12 h, then pour the mixture into an alumina crucible and calcine it at 1250 °C for 1.5 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0108] Mix the matrix glaze and the photocatalytic material in a weight ratio of 95:5. For wet ball milling, the weight ratio of solid components: water: balls is 1:1:3, and ball mill for 11 h, then dry and sieve through a 325-mesh sieve to obtain the ceramic glaze with photocatalytic performance.

[0109] A method for sintering high-temperature ceramics using the above ceramic glaze includes the following steps:

[0110] Spray the ceramic glaze on the surface of the ceramic body and sinter it into ceramics.

[0111] The sintering process of the photocatalytic performance ceramic glaze is as follows: from room temperature to 300 °C for 1.5 h; from 300 to 600 °C for 1.5 h; from 600 to 900 °C for 1.5 h; from 900 to 1250 °C for 2.5 h; keep the temperature at 1250 °C for 2 h.

[0112] Comparative Example 1:

[0113] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0114] The raw material composition and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze and photocatalytic material;

[0115] Among them, the composition and weight parts of the matrix glaze include: 34 parts of potassium feldspar, 27 parts of quartz, 24 parts of kaolin, 11 parts of talc, 4 parts of alumina. The particle size of the selected raw materials is 300 mesh, and the above materials are ball-milled and mixed for 1.5 h.

[0116] The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate. Triethanolamine, tetrabutyl titanate and absolute ethanol are mixed and stirred for 1.5 h according to a volume ratio of 15:34:50. Deionized water is added according to a volume ratio of tetrabutyl titanate, absolute ethanol and deionized water of 34:50:2, and mixed and stirred for 1 h. Then zinc acetate is added according to a molar ratio of zinc acetate to tetrabutyl titanate of 1:1, and mixed and stirred for 1.5 h. The stirred titanium-zinc mixed slurry is poured into a reaction kettle and heated at 145 °C for 13 h, and then the mixture is poured into an alumina crucible and calcined at 1300 °C for 2 h to obtain the titanium-zinc-oxygen photocatalytic material.

[0117] The matrix glaze and the photocatalytic material are mixed according to a weight ratio of 80:20, and the solid component: water: ball is wet ball-milled for 10 h according to a weight ratio of 1:1:3, dried and sieved through a 325-mesh sieve to obtain the prepared ceramic glaze with photocatalytic performance.

[0118] The method for sintering and preparing high-temperature ceramics using the above ceramic glaze includes the following steps:

[0119] Spray the ceramic glaze on the surface of the ceramic blank and sinter it into ceramics;

[0120] The sintering process of the photocatalytic performance ceramic glaze is from room temperature to 300 °C for 1.5 h; from 300 to 600 °C for 1.5 h; from 600 to 900 °C for 1.5 h; from 900 to 1300 °C for 2 h; keep the temperature at 1300 °C for 1.5 h.

[0121] Comparative Example 2:

[0122] A high-temperature ceramic glaze with photocatalytic performance and its preparation method are as follows:

[0123] The raw material composition and weight parts of the high-temperature ceramic glaze with photocatalytic performance include: matrix glaze and photocatalytic material;

[0124] Among them, the composition and weight parts of the matrix glaze include: 34 parts of potassium feldspar, 27 parts of quartz, 24 parts of kaolin, 11 parts of talc, 4 parts of alumina. The particle size of the selected raw materials is 300 mesh. The above materials are ball-milled and mixed for 1.5 h.

[0125] The photocatalytic material includes commercially available zinc oxide (300 mesh) and nano-titanium dioxide (photocatalyst powder). They are stirred and mixed for 1 h according to the molar ratio of zinc oxide to titanium dioxide of 8:1.

[0126] Mix the matrix glaze and the photocatalytic material according to a weight ratio of 80:20. The solid component: water: ball is wet ball-milled for 10 h according to a weight ratio of 1:1:3, dried and sieved through a 325-mesh sieve to obtain the prepared ceramic glaze with photocatalytic performance.

[0127] The method for sintering and preparing high-temperature ceramics using the above ceramic glaze includes the following steps:

[0128] Spray the ceramic glaze on the surface of the ceramic blank and sinter it into ceramics;

[0129] The sintering process of the photocatalytic performance ceramic glaze is: room temperature to 300 °C for 1.5 h; 300 to 600 °C for 1.5 h; 600 to 900 °C for 1.5 h; 900 to 1300 °C for 2 h; keep warm at 1300 °C for 1 h.

[0130] Spray the photocatalytic glazes prepared in the examples and comparative examples on the surfaces of ceramic blanks of the same size, and sinter them into ceramic samples through the corresponding sintering processes of each example.

[0131] Measure the same volume of 12 mg / L methylene blue as the photocatalytic degradation target. Place the ceramic samples of the prepared photocatalytic glaze into it, and place them under natural light irradiation conditions indoors. Calculate the degradation rate by measuring the absorbance of the methylene blue solution within the same time.

[0132] The degradation data of methylene blue by each example under the same conditions are shown in Table 1.

[0133] Table 1 Degradation data of methylene blue by each example under the same conditions

[0134]

[0135] Analysis of the experimental results of the present invention shows that: in the embodiments of the present invention, as the molar ratio of zinc acetate to tetrabutyl titanate increases, the photocatalytic degradation ability of the prepared photocatalytic glaze on methylene blue is enhanced. This is because in the high-temperature firing system of the glaze, the photocatalytic substances need to retain high photocatalytic activity. The semiconductor heterojunction ZnO-Zn2TiO4 has good high-temperature stability. At the same time, a part of ZnO can be well fused with the vitrified glaze under high-temperature conditions and can prevent the vitrified glaze from corroding Zn2TiO4 substances, so that the glaze still has good photocatalytic activity after high-temperature firing. Therefore, as the molar ratio of zinc acetate to tetrabutyl titanate increases, the photocatalytic degradation ability of the prepared photocatalytic glaze on methylene blue is enhanced. Therefore, compared with Comparative Example 1 (the molar ratio of zinc acetate to tetrabutyl titanate is 1:1), the photocatalytic glazes prepared in Examples 1-6 have a higher photocatalytic degradation effect on methylene blue. At the same time, it can also be seen that there is a synergistic effect between 33-38 parts by weight of potassium feldspar, 26-30 parts by weight of quartz, 20-25 parts by weight of kaolin, 8-11 parts by weight of talc, 3-6 parts by weight of alumina in the matrix glaze and triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water with a volume ratio of 15:34:50:2 for the photocatalytic material, and zinc acetate and tetrabutyl titanate with a molar ratio of 5:1-9:1, which can synergistically improve the photocatalytic degradation effect of the prepared photocatalytic glaze on methylene blue. Comparative Example 2 selects a method of mixing commercially available zinc oxide (300 mesh) and nano-titanium dioxide (photocatalyst powder) with the glaze. Although this process has a simple preparation process, since zinc oxide and nano-titanium dioxide are mixed by a separate solid-phase mixing process instead of the solvothermal mixing process that can achieve the mixing of zinc and titanium atoms at the atomic level as in the embodiments of the present invention, a better ZnO-Zn2TiO4 heterojunction substance with high-temperature stable photocatalytic activity cannot be formed. At the same time, during the firing process of the glaze, nano-titanium dioxide (photocatalyst powder) affects its photocatalytic activity due to crystal structure transformation or melting reaction with the glaze at high temperature. At the same time, from the reaction data of Example 1, it can be seen that temperature also has an important influence on photocatalytic performance. The higher the temperature, the more the glass phase of the glaze increases, the stronger the melting ability of the glaze on ZnO, the amount of the semiconductor heterojunction ZnO-Zn2TiO4 decreases, and at the same time, the erosion ability of the glaze glass phase on Zn2TiO4 also increases. Therefore, the higher the temperature, the lower the photocatalytic activity of the glaze. At the same time, it is further seen that there is a synergistic effect between the matrix glaze and the photocatalytic material in the present invention, which can synergistically improve the photocatalytic degradation effect of the prepared photocatalytic glaze.

[0136] Although the embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art can understand that: without departing from the spirit and scope of the present invention and the appended claims, various substitutions, changes and modifications are possible. Therefore, the scope of the present invention is not limited to the content disclosed in the embodiments.

Claims

1. A high-temperature ceramic glaze with photocatalytic performance, characterized in that: Its raw material composition and weight parts include: matrix glaze: 75-95 parts, photocatalytic material: 5-25 parts; The matrix glaze includes potassium feldspar, quartz, kaolin, talc and alumina; The photocatalytic material includes triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water and zinc acetate; The composition and weight parts of the matrix glaze include: Potassium feldspar 33-38 parts; Quartz 26-30 parts; Kaolin 20-25 parts; Talc 8-11 parts; Alumina 3-6 parts; The volume ratio of the triethanolamine, tetrabutyl titanate, absolute ethanol, deionized water is 15:34:50:2; the molar ratio of zinc acetate to tetrabutyl titanate is 5:1-9:1; The preparation method of the matrix glaze includes the following steps: Mix potassium feldspar, quartz, kaolin, talc and alumina, and ball mill for 1-2 h to obtain the matrix glaze; The preparation method of the photocatalytic material includes the following steps: Mix triethanolamine, tetrabutyl titanate and absolute ethanol and stir for 1-2 h, add deionized water, stir for 1-2 h, add zinc acetate, and continue to stir for 1-2 h to mix evenly to obtain a titanium-zinc mixed slurry; heat the stirred titanium-zinc mixed slurry at 140-150 °C for 12-14 h, and then calcine at 1250-1350 °C for 1-2 h to obtain a titanium-zinc-oxygen photocatalytic material; The method for sintering a high-temperature ceramic by using the high-temperature ceramic glaze with photocatalytic performance, the method includes the following steps: Spray the high-temperature ceramic glaze with photocatalytic performance on the surface of the ceramic blank, and sinter to make a ceramic; Among them, the sintering conditions are: heat from room temperature to 300 °C, 1-1.5 h; heat from 300 °C to 600 °C, 1-1.5 h; heat from 600 °C to 900 °C, 1-1.5 h; heat from 900 °C to 1250-1350 °C, 2-2.5 h; keep warm for 1-2 h after the heating is over.

2. The photocatalytic high-temperature ceramic glaze according to claim 1, characterized in that: The particle sizes of the potassium feldspar, quartz, kaolin, talc and alumina are all 300 mesh.

3. The preparation method of the high-temperature ceramic glaze with photocatalytic performance according to claim 1 or 2, characterized in that: Include the following steps: Mix the matrix glaze and the photocatalytic material, and wet ball mill the solid component: water: ball at a weight ratio of 1:1:3 for 10-12 h, dry and screen to obtain a high-temperature ceramic glaze with photocatalytic performance.

4. The preparation method according to claim 3, characterized in that: Sieve through a 325-mesh sieve after drying.

5. The application of the high-temperature ceramic glaze with photocatalytic performance as claimed in claim 1 or 2 in sintering and preparing high-temperature ceramics.

6. The application of the high-temperature ceramic glaze with photocatalytic performance as claimed in claim 1 or 2 in preparing high-temperature daily-use ceramics and / or electrical ceramics.

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