Corrosion-resistant electric porcelain glaze and preparation method thereof

Abstract

The corrosion-resistant electroceramic glaze is prepared from the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talcum powder and sodium fluoride. The electric porcelain glaze prepared by the method has good corrosion resistance and wear resistance, the outdoor durability of electric porcelain is improved, and the maintenance cost is reduced.

Description

Technical Field

[0001] This invention relates to the field of electrical porcelain glaze technology, and in particular to a corrosion-resistant electrical porcelain glaze and its preparation method. Background Technology

[0002] Electrical ceramics, or simply electrical porcelain, refers to a type of ceramic electrical insulating material with excellent insulation and mechanical strength. Electrical porcelain is used for electrical insulation and mechanical fixation of electrical equipment or conductors at different potentials, playing a crucial role in power transmission and distribution systems. Because electrical porcelain is widely used as external insulation in high-voltage and ultra-high-voltage transmission lines and related electrical equipment, its electrical insulation and durability requirements are high. Outdoor electrical porcelain must withstand adverse environmental and atmospheric conditions, thus requiring specific performance characteristics such as corrosion resistance, anti-fouling properties, thermal stability, and resistance to environmental aging. The glaze on the surface of electrical porcelain not only enhances its appearance but also plays a decisive role in its electrical insulation, chemical stability, and mechanical strength. Summary of the Invention

[0003] Therefore, this invention provides a corrosion-resistant electrical porcelain glaze, the raw materials of which include: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; wherein the preparation method of the composite oxide powder is as follows: (1) Prepare an ethanol solution of tetrabutyl titanate in a reaction vessel; add triethanolamine to the ethanol solution of tetrabutyl titanate, stir and mix after adding, then add zinc acetate, cerium acetate, boric acid and deionized water, stir and mix after adding, then seal the reaction vessel, heat to above 130°C and keep warm, then separate the solid and liquid, calcine and decompose the solid phase to obtain an oxide powder matrix; (2) Dissolve zirconium dichloride octahydrate and aluminum chloride in deionized water to obtain an impregnation solution; immerse the oxide powder matrix in the impregnation solution, maintain pressure and stand under negative pressure, then separate the solid and liquid, dry the solid phase, immerse it in the impregnation solution again after drying, and place it under negative pressure and stand under negative pressure again, separate the solid and liquid, and dry the solid phase; the above immersion, negative pressure standing, solid-liquid separation, and drying constitute a set of impregnation processes; repeat the above impregnation processes more than 5 times; then calcine and decompose to obtain coated powder. (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane and an aqueous solution of 2-morpholinoethanesulfonic acid; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, heat and stir to perform surface modification, then separate the solid and liquid phases, wash the solid phase, and dry to obtain the dried solid phase; add N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine to the aqueous solution of 2-morpholinoethanesulfonic acid, adjust the pH to 5.5-6.5, stir to activate and obtain an activated solution, then add the dried solid phase to the activated solution, adjust the pH to weakly alkaline, stir the solution to react, separate the solid and liquid phases, wash the solid phase, and dry to obtain modified particles; add the modified particles to an aqueous solution of sodium hexametaphosphate, stir the solution for more than 30 minutes, separate the solid and liquid phases, wash the solid phase, and dry to obtain the composite oxide powder.

[0004] Furthermore, the raw materials, by weight, are as follows: 20 parts kaolin; 15-20 parts sodium feldspar; 14-18 parts quartz powder; 6-10 parts spodumene powder; 20-25 parts composite oxide powder; 2-5 parts barium carbonate powder; 2-4 parts talc powder; and 1-2 parts sodium fluoride. All raw materials are sieved powders after grinding and passing through a 200-250 mesh sieve.

[0005] Further, in step (1), the ethanol solution of tetrabutyl titanate has a mass percentage of 20% to 25% tetrabutyl titanate and is in ethanol as the solvent; the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of tetrabutyl titanate is ethanol solution of tetrabutyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 6 to 8g: 0.5 to 0.8g: 0.1 to 0.3g: 8 to 10mL.

[0006] Furthermore, in step (1), the temperature is kept at 130°C or above for more than 5 hours; the calcination temperature is 500-550°C and the calcination time is 1-2 hours.

[0007] Further, in step (2), the concentration of zirconium dichloride in the impregnation solution is 30-40 g / L, the concentration of aluminum chloride is 22-26 g / L, and the solvent is water; the negative pressure environment is below 0.01 standard atmospheres, and the pressure holding time is more than 10 min.

[0008] Furthermore, the calcination decomposition temperature in step (2) is 500-550℃, and the calcination time is 2-3h.

[0009] Further, in step (3), the ethanol solution of γ-aminopropyltriethoxysilane contains 2% to 3% γ-aminopropyltriethoxysilane by mass, and the solvent is ethanol; the mass ratio of the coating powder added to the ethanol solution of γ-aminopropyltriethoxysilane is 1:30 to 50; the heating temperature for surface modification by heating and stirring is 40±5℃, and the mixture is kept warm and stirred for 5 to 8 hours after reaching the set temperature.

[0010] Further, in step (3), the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution of 2-morpholinoethanesulfonic acid is 40 mmol / L, and the solvent is water; the ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine added to the aqueous solution of 2-morpholinoethanesulfonic acid is N-hydroxysuccinimide: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride: arginine: aqueous solution of 2-morpholinoethanesulfonic acid = 0.2g: 0.2g: 0.1~0.3g: 100mL; the ratio of the dried solid phase added to the activation solution is dried solid phase: activation solution = 1g: 50~200mL; the pH is adjusted to 7.5~8, and then the solution is stirred for more than 8 hours.

[0011] Further, in step (3), the concentration of sodium hexametaphosphate in the aqueous solution of sodium hexametaphosphate is 40-50 g / L, and the solvent is water; the ratio of the modified particles added to the aqueous solution of sodium hexametaphosphate is modified particles: aqueous solution of sodium hexametaphosphate = 1 g: 30-100 mL.

[0012] This invention also discloses a method for applying the above-mentioned corrosion-resistant electrical porcelain glaze, comprising: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry; Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, dry it, and then fire it to obtain the corrosion-resistant porcelain glaze.

[0013] Furthermore, in step one, the mixed raw materials are added to deionized water to adjust the slurry to 40 Baume degrees.

[0014] Further, in step two, the drying temperature is 120-150℃ and the drying time is 1-2 hours; the firing process is as follows: first, the temperature is raised to 600-650℃ at 10-15℃ / min and held for 30-50 minutes, then the temperature is raised to 800-850℃ at 5℃ / min and held for 30-50 minutes, then the temperature is raised to 1250℃ at 2℃ / min and held for 60-90 minutes, after which the temperature is lowered to 650-700℃ at 2℃ / min, and then the cooling rate is adjusted to 5℃ / min to cool down to room temperature.

[0015] The beneficial effects of this invention are as follows: the electrical porcelain glaze prepared by the method of this invention has good corrosion resistance and wear resistance, improving the durability of the electrical porcelain outdoors and reducing maintenance costs. The introduction of the composite oxide powder can significantly improve the corrosion resistance and wear resistance of the glaze layer. This may be because: this invention first prepares titanium composite oxide particles doped with rare earth cerium, zinc, and boron via a hydrothermal method, significantly increasing the specific surface area of ​​the particles and providing conditions for subsequent modification. Simultaneously, the addition of cerium is beneficial to the sintering of the glaze, promoting its densification, reducing porosity, reducing the penetration of corrosive media, and improving corrosion resistance. Furthermore, the added boron forms a eutectic glass phase with silicon in the raw materials during sintering, which further promotes the densification of the ceramic material. The subsequent coating of zirconium oxide-alumina composite layer significantly promotes the formation of the liquid phase during ceramic sintering, increasing the density of the two-phase interface region and improving corrosion resistance. Finally, through silanization and modification, guanidinium groups of arginine are introduced. Sodium hexametaphosphate ions ionized in water have 6 negatively charged oxygen atoms. These negatively charged oxygen atoms can interact strongly with the guanidinium groups, forming a coating layer on the surface of the composite oxide powder, reducing its surface energy, thereby effectively preventing particle agglomeration, improving the dispersion of particles in the glaze, making the glaze layer more uniform, reducing the possibility of local defects, and improving the overall performance of the glaze layer. Detailed Implementation

[0016] The present invention will be further described below with reference to the embodiments.

[0017] Example 1 A corrosion-resistant electrical porcelain glaze, comprising the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials, by weight, are: 20 parts kaolin; 15 parts albite; 14 parts quartz powder; 6 parts spodumene powder; 20 parts composite oxide powder; 2 parts barium carbonate powder; 2 parts talc powder; and 1 part sodium fluoride; all raw materials are ground powders that have passed through a 200-mesh sieve; wherein the composite oxide powder is prepared by: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 20%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate, boric acid and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 6g: 0.5g: 0.1g: 8mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 500℃ and the calcination time is 2 h; obtain an oxide powder matrix; (2) Zirconium dichloride octahydrate and aluminum chloride are dissolved in deionized water to obtain an impregnation solution; the concentration of zirconium dichloride in the impregnation solution is 30 g / L, the concentration of aluminum chloride is 22 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain the coated powder; the calcination decomposition temperature is 500℃, and the calcination time is 3 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 2%, and the solvent is ethanol; prepare an aqueous solution of 2-morpholinoethanesulfonic acid, wherein the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is coated powder: γ-aminopropyltriethoxysilane. The ethanol solution was prepared at a ratio of 1:30. The surface was modified by heating to 40°C and stirring for 5 hours. After modification, the solid and liquid phases were separated. The solid phase was washed three times with ethanol and dried at 100°C for 1 hour to obtain the dried solid phase. N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine were added to the aqueous solution of 2-morpholinoethanesulfonic acid. The ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine in the aqueous solution of 2-morpholinoethanesulfonic acid was N-hydroxysuccinimide:1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. An aqueous solution of (aminopropyl)-3-ethylcarbodiimide hydrochloride:arginine:2-morpholinoethanesulfonic acid was prepared in a ratio of 0.2 g:0.2 g:0.1 g:100 mL. The pH was adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution, and the mixture was stirred for 30 min to obtain an activated solution. The dried solid phase was then added to the activated solution in a ratio of 1 g of dried solid phase to 50 mL of activated solution. The pH was then adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution. The pH was adjusted to 7.5, and the solution was stirred for 8 hours to allow the reaction to proceed. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain modified particles. The modified particles were then added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 40 g / L and the solvent was water. The ratio of modified particles to sodium hexametaphosphate aqueous solution was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid phases were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0018] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 60 minutes. After the holding period, lower the temperature to 650℃ at 2℃ / min, and then adjust the cooling rate to 5℃ / min to cool to room temperature; obtain the corrosion-resistant porcelain glaze with a glaze layer thickness of 0.5mm.

[0019] Example 2 A corrosion-resistant electrical porcelain glaze comprises the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials are distributed in the following weight proportions: 20 parts kaolin; 15 parts albite; 16 parts quartz powder; 8 parts spodumene powder; 20 parts composite oxide powder; 3 parts barium carbonate powder; 3 parts talc powder; and 1 part sodium fluoride; all raw materials are ground powders that have passed through a 200-mesh sieve; the composite oxide powder is prepared by the following method: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 20%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate, boric acid and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 7g: 0.6g: 0.2g: 9mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 500℃ and the calcination time is 2 h; obtain an oxide powder matrix; (2) Zirconium dichloride octahydrate and aluminum chloride are dissolved in deionized water to obtain an impregnation solution; the concentration of zirconium dichloride in the impregnation solution is 35 g / L, the concentration of aluminum chloride is 24 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain the coated powder; the calcination decomposition temperature is 500℃, and the calcination time is 3 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 2%, and the solvent is ethanol; prepare an aqueous solution of 2-morpholinoethanesulfonic acid, wherein the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is coated powder: γ-aminopropyltriethoxysilane. The ethanol solution was prepared at a ratio of 1:30. The surface was modified by heating to 40°C and stirring for 5 hours. After modification, the solid and liquid phases were separated. The solid phase was washed three times with ethanol and dried at 100°C for 1 hour to obtain the dried solid phase. N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine were added to the aqueous solution of 2-morpholinoethanesulfonic acid. The ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine in the aqueous solution of 2-morpholinoethanesulfonic acid was N-hydroxysuccinimide:1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. An aqueous solution of (aminopropyl)-3-ethylcarbodiimide hydrochloride:arginine:2-morpholinoethanesulfonic acid was prepared in a ratio of 0.2 g:0.2 g:0.2 g:100 mL. The pH was adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution, and the mixture was stirred for 30 min to obtain an activated solution. The dried solid phase was then added to the activated solution in a ratio of 1 g of dried solid phase to 50 mL of activated solution. The pH was then adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution. The pH was adjusted to 7.5, and the solution was stirred for 8 hours to allow the reaction to proceed. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain modified particles. The modified particles were then added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 45 g / L and the solvent was water. The ratio of modified particles to sodium hexametaphosphate aqueous solution was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid phases were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0020] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 70 minutes. After the holding period, lower the temperature to 650℃ at 2℃ / min, and then adjust the cooling rate to 5℃ / min to cool to room temperature; obtain the corrosion-resistant porcelain glaze with a glaze layer thickness of 0.5mm.

[0021] Example 3 A corrosion-resistant electrical porcelain glaze, comprising the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials, by weight, are: 20 parts kaolin; 20 parts albite; 16 parts quartz powder; 8 parts spodumene powder; 25 parts composite oxide powder; 4 parts barium carbonate powder; 3 parts talc powder; and 2 parts sodium fluoride; all raw materials are ground powders that have passed through a 200-mesh sieve; wherein the composite oxide powder is prepared by: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 25%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate, boric acid and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 7g: 0.7g: 0.2g: 9mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 550℃ and the calcination time is 1 h; obtain an oxide powder matrix; (2) Zirconium dichloride octahydrate and aluminum chloride are dissolved in deionized water to obtain an impregnation solution; the concentration of zirconium dichloride in the impregnation solution is 35 g / L, the concentration of aluminum chloride is 24 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain coated powder; the calcination decomposition temperature is 550℃, and the calcination time is 2 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3%, and the solvent is ethanol; prepare an aqueous solution of 2-morpholinoethanesulfonic acid, wherein the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is coated powder: γ-aminopropyltriethoxysilane. The ethanol solution was prepared at a ratio of 1:30. The surface was modified by heating to 40°C and stirring for 5 hours. After modification, the solid and liquid phases were separated. The solid phase was washed three times with ethanol and dried at 100°C for 1 hour to obtain the dried solid phase. N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine were added to the aqueous solution of 2-morpholinoethanesulfonic acid. The ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine in the aqueous solution of 2-morpholinoethanesulfonic acid was N-hydroxysuccinimide:1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. An aqueous solution of (aminopropyl)-3-ethylcarbodiimide hydrochloride:arginine:2-morpholinoethanesulfonic acid was prepared in a ratio of 0.2 g:0.2 g:0.2 g:100 mL. The pH was adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution, and the mixture was stirred for 30 min to obtain an activated solution. The dried solid phase was then added to the activated solution in a ratio of 1 g of dried solid phase to 50 mL of activated solution. The pH was then adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution. The pH was adjusted to 7.5, and the solution was stirred for 8 hours to allow the reaction to proceed. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain modified particles. The modified particles were then added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 45 g / L and the solvent was water. The ratio of modified particles to sodium hexametaphosphate aqueous solution was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid phases were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0022] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 80 minutes. After the holding period, lower the temperature to 650℃ at 2℃ / min, and then adjust the cooling rate to 5℃ / min to cool to room temperature; obtain the corrosion-resistant porcelain glaze with a glaze layer thickness of 0.5mm.

[0023] Example 4 A corrosion-resistant electrical porcelain glaze, comprising the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials, by weight, are: 20 parts kaolin; 20 parts albite; 18 parts quartz powder; 10 parts spodumene powder; 25 parts composite oxide powder; 5 parts barium carbonate powder; 4 parts talc powder; and 2 parts sodium fluoride; all raw materials are ground powders that have passed through a 200-mesh sieve; wherein the composite oxide powder is prepared by: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 25%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate, boric acid and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 8g: 0.8g: 0.3g: 10mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 550℃ and the calcination time is 1 h; obtain an oxide powder matrix; (2) Zirconium dichloride octahydrate and aluminum chloride are dissolved in deionized water to obtain an impregnation solution; the concentration of zirconium dichloride in the impregnation solution is 40 g / L, the concentration of aluminum chloride is 26 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain the coated powder; the calcination decomposition temperature is 550℃, and the calcination time is 2 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3%, and the solvent is ethanol; prepare an aqueous solution of 2-morpholinoethanesulfonic acid, wherein the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is coated powder: γ-aminopropyltriethoxysilane. The ethanol solution was prepared at a ratio of 1:30. The surface was modified by heating to 40°C and stirring for 5 hours. After modification, the solid and liquid phases were separated. The solid phase was washed three times with ethanol and dried at 100°C for 1 hour to obtain the dried solid phase. N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine were added to the aqueous solution of 2-morpholinoethanesulfonic acid. The ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine in the aqueous solution of 2-morpholinoethanesulfonic acid was N-hydroxysuccinimide:1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. An aqueous solution of (aminopropyl)-3-ethylcarbodiimide hydrochloride:arginine:2-morpholinoethanesulfonic acid was prepared in a ratio of 0.2 g:0.2 g:0.3 g:100 mL. The pH was adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution, and the mixture was stirred for 30 min to obtain an activated solution. The dried solid phase was then added to the activated solution in a ratio of 1 g of dried solid phase to 50 mL of activated solution. The pH was then adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution. The pH was adjusted to 7.5, and the solution was stirred for 8 hours to allow the reaction to proceed. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain modified particles. The modified particles were then added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 50 g / L and the solvent was water. The ratio of modified particles to sodium hexametaphosphate aqueous solution was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid phases were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0024] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 90 minutes. After the holding period, lower the temperature to 650℃ at 2℃ / min, and then adjust the cooling rate to 5℃ / min to cool to room temperature; obtain the corrosion-resistant porcelain glaze with a glaze layer thickness of 0.5mm.

[0025] Comparative Example 1 A comparative electric porcelain glaze comprises the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials are present in the following weight parts: kaolin 20 parts; albite 20 parts; quartz powder 16 parts; spodumene powder 8 parts; composite oxide powder 25 parts; barium carbonate powder 4 parts; talc powder 3 parts; and sodium fluoride 2 parts; all raw materials are ground powders that have passed through a 200-mesh sieve; wherein the composite oxide powder is prepared by: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 25%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: deionized water = 10g: 7g: 0.7g: 9mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 550℃ and the calcination time is 1 h; obtain an oxide powder matrix; (2) Zirconium dichloride octahydrate and aluminum chloride are dissolved in deionized water to obtain an impregnation solution; the concentration of zirconium dichloride in the impregnation solution is 35 g / L, the concentration of aluminum chloride is 24 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain coated powder; the calcination decomposition temperature is 550℃, and the calcination time is 2 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3%, and the solvent is ethanol; prepare an aqueous solution of 2-morpholinoethanesulfonic acid, wherein the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is coated powder: γ-aminopropyltriethoxysilane. The ethanol solution was prepared at a ratio of 1:30. The surface was modified by heating to 40°C and stirring for 5 hours. After modification, the solid and liquid phases were separated. The solid phase was washed three times with ethanol and dried at 100°C for 1 hour to obtain the dried solid phase. N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine were added to the aqueous solution of 2-morpholinoethanesulfonic acid. The ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine in the aqueous solution of 2-morpholinoethanesulfonic acid was N-hydroxysuccinimide:1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. An aqueous solution of (aminopropyl)-3-ethylcarbodiimide hydrochloride:arginine:2-morpholinoethanesulfonic acid was prepared in a ratio of 0.2 g:0.2 g:0.2 g:100 mL. The pH was adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution, and the mixture was stirred for 30 min to obtain an activated solution. The dried solid phase was then added to the activated solution in a ratio of 1 g of dried solid phase to 50 mL of activated solution. The pH was then adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution. The pH was adjusted to 7.5, and the solution was stirred for 8 hours to allow the reaction to proceed. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain modified particles. The modified particles were then added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 45 g / L and the solvent was water. The ratio of modified particles to sodium hexametaphosphate aqueous solution was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid phases were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0026] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 80 minutes, after which the temperature is lowered to 650℃ at 2℃ / min, and then the cooling rate is adjusted to 5℃ / min to cool to room temperature; the porcelain glaze described in this comparative example is obtained, with a glaze layer thickness of 0.5mm.

[0027] Comparative Example 2 A comparative electric porcelain glaze comprises the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials are present in the following weight parts: kaolin 20 parts; albite 20 parts; quartz powder 16 parts; spodumene powder 8 parts; composite oxide powder 25 parts; barium carbonate powder 4 parts; talc powder 3 parts; and sodium fluoride 2 parts; all raw materials are ground powders that have passed through a 200-mesh sieve; wherein the composite oxide powder is prepared by: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 25%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate, boric acid and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 7g: 0.7g: 0.2g: 9mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 550℃ and the calcination time is 1 h; obtain an oxide powder matrix; (2) Aluminum chloride is dissolved in deionized water to obtain an impregnation solution; the concentration of aluminum chloride in the impregnation solution is 24 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain the coated powder; the calcination decomposition temperature is 550℃, and the calcination time is 2 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3%, and the solvent is ethanol; prepare an aqueous solution of 2-morpholinoethanesulfonic acid, wherein the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is coated powder: γ-aminopropyltriethoxysilane. The ethanol solution was prepared at a ratio of 1:30. The surface was modified by heating to 40°C and stirring for 5 hours. After modification, the solid and liquid phases were separated. The solid phase was washed three times with ethanol and dried at 100°C for 1 hour to obtain the dried solid phase. N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine were added to the aqueous solution of 2-morpholinoethanesulfonic acid. The ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine in the aqueous solution of 2-morpholinoethanesulfonic acid was N-hydroxysuccinimide:1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. An aqueous solution of (aminopropyl)-3-ethylcarbodiimide hydrochloride:arginine:2-morpholinoethanesulfonic acid was prepared in a ratio of 0.2 g:0.2 g:0.2 g:100 mL. The pH was adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution, and the mixture was stirred for 30 min to obtain an activated solution. The dried solid phase was then added to the activated solution in a ratio of 1 g of dried solid phase to 50 mL of activated solution. The pH was then adjusted to 5.5 with 0.5 mol / L hydrochloric acid or 0.5 mol / L sodium hydroxide solution. The pH was adjusted to 7.5, and the solution was stirred for 8 hours to allow the reaction to proceed. After stirring, the solid and liquid phases were separated. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain modified particles. The modified particles were then added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 45 g / L and the solvent was water. The ratio of modified particles to sodium hexametaphosphate aqueous solution was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid phases were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0028] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 80 minutes, after which the temperature is lowered to 650℃ at 2℃ / min, and then the cooling rate is adjusted to 5℃ / min to cool to room temperature; the porcelain glaze described in this comparative example is obtained, with a glaze layer thickness of 0.5mm.

[0029] Comparative Example 3 A comparative electric porcelain glaze comprises the following raw materials: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; the raw materials are present in the following weight parts: kaolin 20 parts; albite 20 parts; quartz powder 16 parts; spodumene powder 8 parts; composite oxide powder 25 parts; barium carbonate powder 4 parts; talc powder 3 parts; and sodium fluoride 2 parts; all raw materials are ground powders that have passed through a 200-mesh sieve; wherein the composite oxide powder is prepared by: (1) Prepare an ethanol solution of n-butyl titanate in a reaction vessel; the mass percentage of n-butyl titanate in the ethanol solution of n-butyl titanate is 25%, and the solvent is ethanol; add triethanolamine to the ethanol solution of n-butyl titanate, stir for 10 min after addition to mix evenly, then add zinc acetate, cerium acetate, boric acid and deionized water, the ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of n-butyl titanate is ethanol solution of n-butyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 7g: 0.7g: 0.2g: 9mL; after the addition is completed, stir for 1 h to mix evenly, then seal the reaction vessel, heat to 130℃ and keep warm for 5 h, then separate the solid and liquid, calcine the solid phase to decompose, the calcination temperature is 550℃ and the calcination time is 1 h; obtain an oxide powder matrix; (2) Zirconium dichloride octahydrate and aluminum chloride are dissolved in deionized water to obtain an impregnation solution; the concentration of zirconium dichloride in the impregnation solution is 35 g / L, the concentration of aluminum chloride is 24 g / L, and the solvent is water; the oxide powder matrix is ​​immersed in the impregnation solution (the solid-liquid mass ratio is solid:liquid = 1:30) and stirred for 5 min, held under negative pressure at 0.01 standard atmospheres for 10 min, then the solid and liquid are separated, the solid phase is dried at 120℃ for 10 min, and after drying, it is immersed in the above impregnation solution again and stirred for 5 min, and then placed under negative pressure at 0.01 standard atmospheres for 10 min, the solid and liquid are separated, and the solid phase is dried at 120℃ for 10 min; the above immersion, negative pressure holding, solid-liquid separation, and drying constitute one set of impregnation steps; the above impregnation steps are repeated 5 times; then calcination decomposition is performed to obtain coated powder; the calcination decomposition temperature is 550℃, and the calcination time is 2 h; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3%, and the solvent is ethanol; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass ratio of the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane is 1:30; heat to 40°C and stir for 5 hours to perform surface modification, and then the solid-liquid mixture is obtained. The solid phase was separated, washed three times with ethanol, and dried at 100°C for 1 hour to obtain the dried solid phase. The dried solid phase was added to an aqueous solution of sodium hexametaphosphate, wherein the concentration of sodium hexametaphosphate in the aqueous solution was 45 g / L, and the solvent was water. The ratio of the dried solid phase to the aqueous solution of sodium hexametaphosphate was 1 g: 30 mL. The solution was stirred for 30 minutes, and then the solid and liquid were separated again. The solid phase was washed three times with deionized water and dried at 100°C for 2 hours to obtain the composite oxide powder.

[0030] The above-mentioned glazing method for corrosion-resistant electrical porcelain glaze includes: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at 150℃ for 1 hour; then fire it. The firing process is as follows: first, raise the temperature to 600℃ at 10℃ / min and hold for 30 minutes, then raise the temperature to 800℃ at 5℃ / min and hold for 40 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 80 minutes, after which the temperature is lowered to 650℃ at 2℃ / min, and then the cooling rate is adjusted to 5℃ / min to cool to room temperature; the porcelain glaze described in this comparative example is obtained, with a glaze layer thickness of 0.5mm.

[0031] Example 5 The corrosion resistance of the electrical porcelain glazes prepared by the methods described in the above embodiments and comparative examples was tested according to standard GB / T3810.13-2016. A 100 g / L citric acid solution and a 30 g / L potassium hydroxide solution were used for immersion in the glazes for 24 hours, and the changes on the surface of the glazes were observed. The wear resistance of the electrical porcelain glazes prepared by the methods described in the above embodiments and comparative examples was tested according to standard GB / T3810.7-2016. The results are shown in Table 1.

[0032] Table 1 As shown in Table 1, the electrical porcelain glaze prepared by the method of the present invention has good corrosion resistance and wear resistance, improving the durability of the electrical porcelain outdoors and reducing maintenance costs. Comparing Example 3 and the comparative examples, it can be seen that the introduction of the composite oxide powder can significantly improve the corrosion resistance and wear resistance of the glaze layer. This may be because: the present invention first prepares titanium composite oxide particles doped with rare earth cerium, zinc, and boron using a hydrothermal method, significantly increasing the specific surface area of ​​the particles and providing conditions for subsequent modification. Simultaneously, the addition of cerium is beneficial to the sintering of the glaze, promoting its densification, reducing porosity, reducing the penetration of corrosive media, and improving corrosion resistance. Furthermore, the added boron forms a eutectic glass phase with silicon in the raw materials during sintering, which further promotes the densification of the ceramic material during sintering. The subsequent coating of zirconium oxide-alumina composite layer significantly promotes the formation of the liquid phase during ceramic sintering, increasing the density of the two-phase interface region and improving corrosion resistance. Finally, through silanization and modification, guanidinium groups of arginine are introduced. Sodium hexametaphosphate ions ionized in water have 6 negatively charged oxygen atoms. These negatively charged oxygen atoms can interact strongly with the guanidinium groups, forming a coating layer on the surface of the composite oxide powder, reducing its surface energy, thereby effectively preventing particle agglomeration, improving the dispersion of particles in the glaze, making the glaze layer more uniform, reducing the possibility of local defects, and improving the overall performance of the glaze layer.

[0033] The technical solutions provided by the present invention have been described in detail above. For those skilled in the art, there will be changes in specific implementation methods and application scope based on the ideas of the embodiments of the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A corrosion-resistant electrical porcelain glaze, characterized in that, The raw materials include: kaolin, albite, quartz powder, spodumene powder, composite oxide powder, barium carbonate powder, talc powder, and sodium fluoride; wherein the preparation method of the composite oxide powder is as follows: (1) Prepare an ethanol solution of tetrabutyl titanate in a reaction vessel; add triethanolamine to the ethanol solution of tetrabutyl titanate, stir and mix after adding, then add zinc acetate, cerium acetate, boric acid and deionized water, stir and mix after adding, then seal the reaction vessel, heat to above 130°C and keep warm, then separate the solid and liquid, calcine and decompose the solid phase to obtain an oxide powder matrix; (2) Dissolve zirconium dichloride octahydrate and aluminum chloride in deionized water to obtain an impregnation solution; immerse the oxide powder matrix in the impregnation solution, maintain pressure and stand under negative pressure, then separate the solid and liquid, dry the solid phase, immerse it in the impregnation solution again after drying, and place it under negative pressure and stand under negative pressure again, separate the solid and liquid, and dry the solid phase; the above immersion, negative pressure standing, solid-liquid separation, and drying constitute a set of impregnation processes; repeat the above impregnation processes more than 5 times; then calcine and decompose to obtain coated powder. (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane and an aqueous solution of 2-morpholinoethanesulfonic acid; add the coated powder to the ethanol solution of γ-aminopropyltriethoxysilane, heat and stir to perform surface modification, then separate the solid and liquid phases, wash the solid phase, and dry to obtain the dried solid phase; add N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine to the aqueous solution of 2-morpholinoethanesulfonic acid, adjust the pH to 5.5-6.5, stir to activate and obtain an activated solution, then add the dried solid phase to the activated solution, adjust the pH to weakly alkaline, stir the solution to react, separate the solid and liquid phases, wash the solid phase, and dry to obtain modified particles; add the modified particles to an aqueous solution of sodium hexametaphosphate, stir the solution for more than 30 minutes, separate the solid and liquid phases, wash the solid phase, and dry to obtain the composite oxide powder.

2. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, The raw materials described herein are in the following proportions by weight: 20 parts kaolin; 15-20 parts sodium feldspar; 14-18 parts quartz powder; 6-10 parts spodumene powder; 20-25 parts composite oxide powder; 2-5 parts barium carbonate powder; 2-4 parts talc powder; and 1-2 parts sodium fluoride. All raw materials are ground powders that have passed through a 200-250 mesh sieve.

3. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, In step (1), the ethanol solution of tetrabutyl titanate has a mass percentage of 20% to 25% and is in ethanol. The ratio of triethanolamine, zinc acetate, cerium acetate, boric acid and deionized water added to the ethanol solution of tetrabutyl titanate is ethanol solution of tetrabutyl titanate: triethanolamine: zinc acetate: cerium acetate: boric acid: deionized water = 10g: 6 to 8g: 0.5 to 0.8g: 0.1 to 0.3g: 8 to 10mL.

4. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, In step (1), the temperature is kept at 130°C or above for more than 5 hours; the calcination temperature is 500-550°C and the calcination time is 1-2 hours.

5. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, In step (2), the concentration of zirconium dichloride in the impregnation solution is 30-40 g / L, the concentration of aluminum chloride is 22-26 g / L, and the solvent is water; the negative pressure environment is below 0.01 standard atmospheres, and the pressure holding time is more than 10 min.

6. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, The calcination decomposition temperature in step (2) is 500-550℃, and the calcination time is 2-3h.

7. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, In step (3), the ethanol solution of γ-aminopropyltriethoxysilane contains 2% to 3% γ-aminopropyltriethoxysilane by mass, and ethanol is used as the solvent. The mass ratio of the coating powder added to the ethanol solution of γ-aminopropyltriethoxysilane is 1:30 to 50. The heating temperature for surface modification by heating and stirring is 40±5℃, and the mixture is kept warm and stirred for 5 to 8 hours after reaching the set temperature.

8. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, In step (3), the concentration of 2-morpholinoethanesulfonic acid in the aqueous solution is 40 mmol / L, and the solvent is water; the ratio of N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and arginine added to the aqueous solution of 2-morpholinoethanesulfonic acid is N-hydroxysuccinimide: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride: arginine: aqueous solution of 2-morpholinoethanesulfonic acid = 0.2g: 0.2g: 0.1~0.3g: 100mL; the ratio of the dried solid phase added to the activation solution is dried solid phase: activation solution = 1g: 50~200mL; the pH is adjusted to 7.5~8, and then the solution is stirred for more than 8 hours.

9. The corrosion-resistant electrical porcelain glaze according to claim 1, characterized in that, In step (3), the concentration of sodium hexametaphosphate in the aqueous solution is 40-50 g / L, and the solvent is water; the ratio of the modified particles added to the aqueous solution of sodium hexametaphosphate is modified particles: aqueous solution of sodium hexametaphosphate = 1 g: 30-100 mL.

10. A method for applying a corrosion-resistant electrical porcelain glaze as described in any one of claims 1 to 9, characterized in that, include: Step 1: Weigh each raw material according to the stated weight proportions, mix each raw material evenly to obtain a mixed raw material, and add the mixed raw material to deionized water to prepare a slurry with a Baume degree of 40. Step 2: Wipe the surface of the porcelain blank to be glazed clean, then spray the slurry onto the surface of the porcelain blank, and dry it at a temperature of 120-150℃ for 1-2 hours; then fire it. The firing process is as follows: first, raise the temperature to 600-650℃ at 10-15℃ / min and hold for 30-50 minutes, then raise the temperature to 800-850℃ at 5℃ / min and hold for 30-50 minutes, then raise the temperature to 1250℃ at 2℃ / min and hold for 60-90 minutes. After the holding period, lower the temperature to 650-700℃ at 2℃ / min, and then adjust the cooling rate to 5℃ / min to cool to room temperature. The corrosion-resistant electrical porcelain glaze is obtained.

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