Anti-pollution porcelain insulator glaze and preparation method thereof

Abstract

The present invention discloses a stain-resistant porcelain insulator glaze. The raw materials for the glaze include potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and a composite powder. Each raw material is sieved through a 1000-mesh sieve. The insulator glaze layer prepared by the method of the present invention exhibits excellent hydrophobicity and thermal stability, is resistant to surface contamination, and exhibits high resistance to pollution, reducing the risk of insulator breakdown during rainy weather. Furthermore, the high thermal stability enables the insulator to be used in areas with harsh climate conditions, broadening the application range of porcelain insulators.

Description

Technical Field

[0001] The present invention relates to the technical field of insulator materials, and in particular to an anti-fouling porcelain insulator glaze and a preparation method thereof. Background Art

[0002] Insulators are devices used between conductors at different electrical potentials, or between a conductor and the ground. They are primarily designed to withstand the stresses generated by voltage and mechanical components. Depending on their intended use, insulators can be divided into line insulators and power station insulators; and based on their material, they are further categorized as porcelain insulators, composite insulators, and glass insulators. Porcelain insulators are a traditional type of insulator, with a development history spanning over 100 years. However, the problem of flashover with porcelain insulators has long plagued the power and railway transportation industries, becoming a technological bottleneck in the development of power and electrified railways. Summary of the Invention

[0003] To this end, the present invention provides an anti-fouling porcelain insulator glaze, wherein the raw materials of the glaze include potassium feldspar powder, quartz stone powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite and composite powder, wherein each raw material is a sieved powder passing through a 1000-mesh sieve; and the composite powder is prepared by:

[0004] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, and the composite aqueous solution of zinc nitrate and cerium nitrate is stirred. Citric acid is added to the solution during the stirring process. After the addition is completed, the solution is stirred for 30 to 40 minutes. Then, glucose is added to the solution under stirring. After the addition is completed, the solution is stirred for more than 20 minutes. Then, hexadecyltrimethylammonium bromide is added to the solution. After the addition is completed, the solution is stirred for more than 20 minutes. Then, ammonia water is added dropwise to the solution under stirring. After the addition is completed, the reactor is sealed, heated to 150 to 160° C. and kept warm for more than 20 hours. After the insulation is completed, the reactor is air-cooled to room temperature. The reactor is opened, solid-liquid separation is carried out, the solid phase is washed with deionized water, dried at 100° C. for more than 1 hour, and then calcined at 500° C. for 3 to 4 hours. The solid phase powder I is obtained by air-cooling to room temperature.

[0005] (2) lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring. After the addition is completed, the solution is stirred for 3 to 4 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol. The powder is placed at 750±5°C and calcined for 2 to 3 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0006] (3) preparing an aqueous solution of calcium nitrate, dispersing the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, keeping the dispersion constant at 45±5°C in a water bath, stirring the dispersion after reaching the temperature, adding a phosphoric acid aqueous solution to the dispersion under stirring, adjusting the pH of the dispersion to 2.7 with dilute hydrochloric acid or sodium hydroxide solution after the addition is completed, and then stirring the dispersion for 10 to 15 minutes under the condition of keeping the temperature at 45±5°C, and then separating the solid and liquid, washing the solid phase with deionized water for more than 3 times, and drying at 100°C for more than 30 minutes to obtain a solid phase powder III;

[0007] (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the alcohol suspension is stirred under an ultrasonic environment. During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane is added to the alcohol suspension. After the addition is completed, the alcohol suspension is continued to be stirred under an ultrasonic environment for more than 20 minutes. The reaction kettle is sealed, heated to 120±3°C and kept warm for more than 6 hours, and then air-cooled to room temperature, solid-liquid separation is performed, the solid phase is washed with ethanol for more than 3 times, and dried at 80°C for more than 20 minutes to obtain the composite powder.

[0008] Furthermore, the raw materials of the glaze are calculated by weight as follows: 16 to 20 parts of potassium feldspar powder, 26 to 28 parts of quartz stone powder, 10 to 12 parts of calcium carbonate, 8 to 15 parts of boron trioxide, 1 to 2 parts of barium carbonate, 8 to 9 parts of zirconium silicate, 2 to 4 parts of calcium oxide, 2 to 4 parts of magnesium oxide, 3 to 6 parts of dolomite, and 13 to 15 parts of composite powder.

[0009] Furthermore, in the step (1), in the composite aqueous solution of zinc nitrate and cerium nitrate, the concentration of zinc nitrate is 3-4 g / L, the concentration of cerium nitrate is 1-3 g / L, and the solvent is water; the amount of citric acid, glucose, hexadecyltrimethylammonium bromide, and ammonia water added to the composite aqueous solution of zinc nitrate and cerium nitrate is citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 2-3 g: 6-8 g: 3-5 g: 20-30 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%.

[0010] Furthermore, in step (2), the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 16-18 g: 1-2 g: 6-9 mL: 500 mL, and the solid-liquid mass ratio of the solid phase powder I added to the mixed liquid is solid / liquid = 1:30.

[0011] Furthermore, in step (3), the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 18-20 g / L, and the solvent is water; the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid = 1:30.

[0012] Furthermore, in step (3), the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and the volume ratio of the added phosphoric acid aqueous solution to the calcium nitrate aqueous solution is phosphoric acid aqueous solution: calcium nitrate aqueous solution = 1:8; the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water.

[0013] Furthermore, in the step (4), the volume ratio of ammonia water added dropwise to the ethanol aqueous solution is ammonia water: ethanol aqueous solution = 1:25-30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added to the alcohol suspension is 1H,1H,2H,2H-perfluorodecyltriethoxysilane: alcohol suspension = 1-2:100.

[0014] Furthermore, the ultrasonic power is 30-40 kW and the frequency is 20 kHz.

[0015] The technical mechanism of the present invention lies in the following: by adding the composite powder described herein to the glaze components, the zinc-cerium composite oxide in the composite powder maintains a certain high-temperature viscosity and surface tension in the glaze melt during sintering, resulting in a denser glaze layer, significantly reducing surface pits and internal microcracks, and increasing the glaze's strength and corrosion resistance. Furthermore, the lithium-gallium composite modification hinders the formation of a glass network in the glaze layer, lowering the melting temperature and inhibiting the formation of large particles, which promotes grain refinement and uniformity. The formation of a calcium-phosphorus coating promotes the formation of a microcrystalline structure during sintering of the zirconium silicate component, thereby improving the mechanical properties of the glaze. Furthermore, treatment with 1H,1H,2H,2H-perfluorodecyltriethoxysilane prevents particle agglomeration during sintering. The resulting glaze layer, formed after sintering using this raw material formula, exhibits excellent anti-fouling properties, preventing rainwater from depositing on the surface and reducing the risk of flashover on insulators.

[0016] The present invention has the following beneficial effects: the insulator glaze layer prepared by the method has excellent hydrophobicity and thermal stability, making it less susceptible to accumulation of dirty water on the surface and highly resistant to contamination, thereby reducing the risk of insulator breakdown during rainy weather. Furthermore, the high thermal stability enables the insulator to be used in areas with harsh climate conditions, broadening the application range of porcelain insulators. DETAILED DESCRIPTION

[0017] The present invention will be further described below with reference to the embodiments.

[0018] Example 1

[0019] A stain-resistant porcelain insulator glaze, the raw materials of which include potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and composite powder, all of which are sieved powders through a 1000-mesh sieve. The raw materials of the glaze are calculated by weight as follows: 16 parts potassium feldspar powder, 26 parts quartz powder, 10 parts calcium carbonate, 8 parts boron trioxide, 1 part barium carbonate, 8 parts zirconium silicate, 2 parts calcium oxide, 2 parts magnesium oxide, 3 parts dolomite, and 13 parts composite powder. The composite powder is prepared by:

[0020] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 3 g / L and the concentration of cerium nitrate is 1 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, and citric acid is added to the solution during the stirring process, and the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, and the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, and the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, and the citric acid and glucose are added to the solution. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 2 g: 6 g: 3 g: 20 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0021] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 16 g: 1 g: 6 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, and the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0022] (3) Prepare an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 18 g / L, and the solvent is water; disperse the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid=1:30; keep the dispersion in a water bath at a constant temperature of 45±5°C, stir the dispersion after reaching the temperature, add phosphoric acid aqueous solution to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and add the phosphoric acid aqueous solution to the dispersion. The volume ratio of the phosphoric acid aqueous solution to the calcium nitrate aqueous solution is 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, followed by solid-liquid separation, and the solid phase is washed three times with deionized water and dried at 100°C for 30 minutes to obtain solid phase powder III;

[0023] (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz) During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 1:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reaction kettle was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was carried out, the solid phase was washed with ethanol 3 times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0024] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After glazing, heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of this embodiment.

[0025] Example 2

[0026] A stain-resistant porcelain insulator glaze, the raw materials of which include potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and composite powder, all of which are sieved powders through a 1000-mesh sieve. The raw materials of the glaze are calculated by weight as follows: 18 parts potassium feldspar powder, 27 parts quartz powder, 11 parts calcium carbonate, 10 parts boron trioxide, 1 part barium carbonate, 8 parts zirconium silicate, 3 parts calcium oxide, 3 parts magnesium oxide, 4 parts dolomite, and 14 parts composite powder. The composite powder is prepared by:

[0027] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 3 g / L and the concentration of cerium nitrate is 2 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, citric acid is added to the solution during the stirring process, the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, the citric acid and glucose are added to the solution, and the solution is stirred for 20 minutes after the addition is completed. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 2 g: 7 g: 4 g: 24 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0028] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 17 g: 1 g: 7 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0029] (3) Prepare an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 19 g / L and the solvent is water; disperse the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid=1:30; keep the dispersion in a water bath at a constant temperature of 45±5°C, stir the dispersion after reaching the temperature, add phosphoric acid aqueous solution to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and add the phosphoric acid aqueous solution to the dispersion. The volume ratio of the phosphoric acid aqueous solution to the calcium nitrate aqueous solution is 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, followed by solid-liquid separation, and the solid phase is washed three times with deionized water and dried at 100°C for 30 minutes to obtain solid phase powder III;

[0030] (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz) During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 1:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reaction kettle was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was carried out, the solid phase was washed with ethanol 3 times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0031] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After glazing, heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of this embodiment.

[0032] Example 3

[0033] A stain-resistant porcelain insulator glaze, the raw materials of which include potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and composite powder, all of which are sieved powders through a 1000-mesh sieve. The raw materials of the glaze are calculated by weight as follows: 18 parts potassium feldspar powder, 27 parts quartz powder, 11 parts calcium carbonate, 12 parts boron trioxide, 2 parts barium carbonate, 9 parts zirconium silicate, 3 parts calcium oxide, 3 parts magnesium oxide, 5 parts dolomite, and 14 parts composite powder. The composite powder is prepared by:

[0034] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 4 g / L and the concentration of cerium nitrate is 2 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, and citric acid is added to the solution during the stirring process, and the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, and the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, and the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, and the citric acid and glucose are added to the solution. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 3 g: 7 g: 4 g: 28 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0035] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 17 g: 2 g: 8 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0036] (3) Prepare an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 19 g / L and the solvent is water; disperse the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid=1:30; keep the dispersion in a water bath at a constant temperature of 45±5°C, stir the dispersion after reaching the temperature, add phosphoric acid aqueous solution to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and add the phosphoric acid aqueous solution to the dispersion. The volume ratio of the phosphoric acid aqueous solution to the calcium nitrate aqueous solution is 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, followed by solid-liquid separation, and the solid phase is washed three times with deionized water and dried at 100°C for 30 minutes to obtain solid phase powder III;

[0037] (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz) During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 2:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reactor was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was carried out, the solid phase was washed with ethanol three times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0038] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After glazing, heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of this embodiment.

[0039] Example 4

[0040] A stain-resistant porcelain insulator glaze, the raw materials of which include potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and composite powder, all of which are sieved powders through a 1000-mesh sieve. The raw materials of the glaze are calculated by weight as follows: 20 parts potassium feldspar powder, 28 parts quartz powder, 12 parts calcium carbonate, 15 parts boron trioxide, 2 parts barium carbonate, 9 parts zirconium silicate, 4 parts calcium oxide, 4 parts magnesium oxide, 6 parts dolomite, and 15 parts composite powder. The composite powder is prepared by:

[0041] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 4 g / L and the concentration of cerium nitrate is 3 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, citric acid is added to the solution during the stirring process, the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, the citric acid and glucose are added to the solution, and the solution is stirred for 20 minutes after the addition is completed. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 3 g: 8 g: 5 g: 30 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0042] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 18 g: 2 g: 9 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0043] (3) Prepare an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 20 g / L and the solvent is water; disperse the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid=1:30; keep the dispersion in a water bath at a constant temperature of 45±5°C, stir the dispersion after reaching the temperature, add phosphoric acid aqueous solution to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and add the phosphoric acid aqueous solution to the dispersion. The volume ratio of the phosphoric acid aqueous solution to the calcium nitrate aqueous solution is 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, followed by solid-liquid separation, and the solid phase is washed three times with deionized water and dried at 100°C for 30 minutes to obtain solid phase powder III;

[0044] (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz) During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 2:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reactor was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was carried out, the solid phase was washed with ethanol three times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0045] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After glazing, heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of this embodiment.

[0046] Comparative Example 1

[0047] A comparative porcelain insulator glaze, comprising raw materials including potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and a composite powder, wherein each raw material is a sieved powder passing through a 1000-mesh sieve. The raw materials of the glaze are, by weight, 18 parts potassium feldspar powder, 27 parts quartz powder, 11 parts calcium carbonate, 12 parts boron trioxide, 2 parts barium carbonate, 9 parts zirconium silicate, 3 parts calcium oxide, 3 parts magnesium oxide, 5 parts dolomite, and 14 parts composite powder. The composite powder is prepared by:

[0048] (1) A zinc nitrate aqueous solution is prepared in a reactor, wherein the concentration of zinc nitrate in the zinc nitrate aqueous solution is 4 g / L and the solvent is water; the zinc nitrate aqueous solution is stirred, citric acid is added to the solution during the stirring process, the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, the citric acid, glucose, hexadecyltrimethylammonium bromide are added to the solution, the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, The ratio of ammonium bromide and ammonia water to the zinc nitrate aqueous solution is 3 g citric acid: glucose: cetyltrimethylammonium bromide: ammonia water: zinc nitrate aqueous solution = 3 g: 7 g: 4 g: 28 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and kept warm for 20 hours, air-cooled to room temperature after the end of the heat preservation, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0049] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 17 g: 2 g: 8 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0050] (3) Prepare an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 19 g / L and the solvent is water; disperse the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid=1:30; keep the dispersion in a water bath at a constant temperature of 45±5°C, stir the dispersion after reaching the temperature, add phosphoric acid aqueous solution to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and add the phosphoric acid aqueous solution to the dispersion. The volume ratio of the phosphoric acid aqueous solution to the calcium nitrate aqueous solution is 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, followed by solid-liquid separation, and the solid phase is washed three times with deionized water and dried at 100°C for 30 minutes to obtain solid phase powder III;

[0051] (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz) During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 2:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reactor was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was carried out, the solid phase was washed with ethanol three times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0052] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After spraying the glaze, it was heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of the comparative example.

[0053] Comparative Example 2

[0054] A comparative porcelain insulator glaze, comprising raw materials including potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and a composite powder, wherein each raw material is a sieved powder passing through a 1000-mesh sieve. The raw materials of the glaze are, by weight, 18 parts potassium feldspar powder, 27 parts quartz powder, 11 parts calcium carbonate, 12 parts boron trioxide, 2 parts barium carbonate, 9 parts zirconium silicate, 3 parts calcium oxide, 3 parts magnesium oxide, 5 parts dolomite, and 14 parts composite powder. The composite powder is prepared by:

[0055] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 4 g / L and the concentration of cerium nitrate is 2 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, and citric acid is added to the solution during the stirring process, and the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, and the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, and the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, and the citric acid and glucose are added to the solution. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 3 g: 7 g: 4 g: 28 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0056] (2) preparing an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 19 g / L and the solvent is water; dispersing the solid phase powder I in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder I dispersed in the aqueous solution of calcium nitrate is solid / liquid=1:30; the dispersion is kept at a constant temperature of 45±5°C in a water bath, and the dispersion is stirred after reaching the temperature, and phosphoric acid aqueous solution is added to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and the volume of the phosphoric acid aqueous solution added is equal to that of the dispersion. The volume ratio of the calcium nitrate aqueous solution is phosphoric acid aqueous solution: calcium nitrate aqueous solution = 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, followed by solid-liquid separation, and the solid phase is washed three times with deionized water and dried at 100°C for 30 minutes to obtain solid phase powder III of this comparative example;

[0057] (3) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz) During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 2:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reactor was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was carried out, the solid phase was washed with ethanol three times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0058] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After spraying the glaze, it was heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of the comparative example.

[0059] Comparative Example 3

[0060] A comparative porcelain insulator glaze, comprising raw materials including potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and a composite powder, wherein each raw material is a sieved powder passing through a 1000-mesh sieve. The raw materials of the glaze are, by weight, 18 parts potassium feldspar powder, 27 parts quartz powder, 11 parts calcium carbonate, 12 parts boron trioxide, 2 parts barium carbonate, 9 parts zirconium silicate, 3 parts calcium oxide, 3 parts magnesium oxide, 5 parts dolomite, and 14 parts composite powder. The composite powder is prepared by:

[0061] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 4 g / L and the concentration of cerium nitrate is 2 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, and citric acid is added to the solution during the stirring process, and the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, and the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, and the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, and the citric acid and glucose are added to the solution. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 3 g: 7 g: 4 g: 28 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0062] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 17 g: 2 g: 8 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0063] (3) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and the volume ratio of the ammonia water to the ethanol aqueous solution is ammonia water:ethanol aqueous solution = 1:30, wherein the mass percentage of the solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; then the solid phase powder II is dispersed in the alcohol solution to form an alcohol suspension, and the solid-liquid mass ratio of the solid phase powder II dispersed in the alcohol solution is solid / liquid = 1:50; the alcohol suspension is stirred under an ultrasonic environment (ultrasonic power 30 kW, frequency 20 kHz), During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added to the alcohol suspension, and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane to the alcohol suspension was 1H,1H,2H,2H-perfluorodecyltriethoxysilane:alcohol suspension = 2:100; after the addition was completed, the alcohol suspension was continued to be stirred under an ultrasonic environment for 20 minutes, the reaction kettle was sealed, heated to 120±3°C and kept warm for 6 hours, and then air-cooled to room temperature, solid-liquid separation was performed, the solid phase was washed with ethanol 3 times, and dried at 80°C for 20 minutes to obtain the composite powder.

[0064] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After spraying the glaze, it was heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of the comparative example.

[0065] Comparative Example 4

[0066] A comparative porcelain insulator glaze, comprising raw materials including potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite, and a composite powder, wherein each raw material is a sieved powder passing through a 1000-mesh sieve. The raw materials of the glaze are, by weight, 18 parts potassium feldspar powder, 27 parts quartz powder, 11 parts calcium carbonate, 12 parts boron trioxide, 2 parts barium carbonate, 9 parts zirconium silicate, 3 parts calcium oxide, 3 parts magnesium oxide, 5 parts dolomite, and 14 parts composite powder. The composite powder is prepared by:

[0067] (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, wherein the concentration of zinc nitrate is 4 g / L and the concentration of cerium nitrate is 2 g / L, and the solvent is water; the composite aqueous solution of zinc nitrate and cerium nitrate is stirred, and citric acid is added to the solution during the stirring process, and the solution is stirred for 30 minutes after the addition is completed, and then glucose is added to the solution under stirring, and the solution is stirred for 20 minutes after the addition is completed, and then hexadecyltrimethylammonium bromide is added to the solution, and the solution is stirred for 20 minutes after the addition is completed, and then ammonia water is added dropwise to the solution under stirring, and the citric acid and glucose are added to the solution. The added amounts of sugar, hexadecyltrimethylammonium bromide, and ammonia water and the composite aqueous solution of zinc nitrate and cerium nitrate are in the following ratio: citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 3 g: 7 g: 4 g: 28 mL: 200 mL; the mass percentage of the solute in the ammonia water is 20%; after the dropwise addition is completed, the reactor is sealed, heated to 150° C. and held for 20 hours, air-cooled to room temperature after the holding period, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed three times with deionized water, dried at 100° C. for 1 hour, then calcined at 500° C. for 3 hours, and air-cooled to room temperature to obtain solid phase powder I;

[0068] (2) Lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, wherein the mixing ratio of lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 17 g: 2 g: 8 mL: 500 mL, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring, and the solid-liquid mass ratio of the solid phase powder I added to the mixed solution is solid / liquid = 1:30; after the addition is completed, the solution is stirred for 3 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol, the powder is placed at 750±5°C and calcined for 2 hours, and then air-cooled to room temperature to obtain solid phase powder II;

[0069] (3) Prepare an aqueous solution of calcium nitrate, wherein the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 19 g / L and the solvent is water; disperse the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, wherein the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid = 1:30; keep the dispersion in a water bath at a constant temperature of 45±5°C, stir the dispersion after reaching the temperature, and add a phosphoric acid aqueous solution to the dispersion under stirring, wherein the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and the volume of the phosphoric acid aqueous solution added is equal to that of the nitric acid. The volume ratio of the calcium aqueous solution is phosphoric acid aqueous solution: calcium nitrate aqueous solution = 1:8; after the addition is completed, the pH of the dispersion is adjusted to 2.7 with dilute hydrochloric acid or sodium hydroxide solution, the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water; then, the dispersion is stirred at 45±5°C for 10 minutes, and then solid-liquid separation is performed, the solid phase is washed three times with deionized water, and dried at 100°C for 30 minutes to obtain solid phase powder III, which is used as the composite powder of this comparative example.

[0070] The raw materials of the above glaze were mixed evenly to form a mixture, and the mixture was wet ball milled. The ball milling process was as follows: the mass ratio of material to ball to water was material: ball: water = 1:2.2:0.7; the ball milling time was 10 hours, and the planetary ball mill speed was 100 r / min. After ball milling, a slurry was obtained, and the specific gravity of the slurry was adjusted to 1.75 g / cm 3 , and then sprayed on the surface of the insulator blank with a glaze thickness of 0.8 mm. After spraying the glaze, it was heated to 400°C and kept warm for 3 hours, and then heated to 1210±5°C and sintered for 16 hours to obtain an insulator with a glaze layer of the comparative example.

[0071] Example 5

[0072] The water droplet contact angle and thermal stability of the glazes obtained in the above examples and comparative examples were tested. Thermal stability was assessed by cyclically heating and cooling at 5-100°C. The samples were first placed at 5°C for 30 minutes, then at room temperature for 1 minute, then at 100°C for 30 minutes, and then at room temperature for 1 minute. This constituted a single cycle. A total of 40 cycles were repeated, and the glazes were observed for cracks. The results are shown in Table 1.

[0073] Table 1

[0074]

[0075] As shown in Table 1, the insulator glaze layer prepared by the method of the present invention exhibits excellent hydrophobicity and thermal stability. It resists the accumulation of dirty water on the surface, exhibits high pollution resistance, and reduces the risk of insulator breakdown during rainy weather. Furthermore, this high thermal stability enables the insulator to be used in areas with harsh climate conditions, broadening the application range of porcelain insulators.

[0076] The technical solutions provided by the present invention are described in detail above. For those skilled in the art, according to the ideas of the embodiments of the present invention, there may be changes in the specific implementation methods and application scopes. In summary, the contents of this specification should not be understood as limiting the present invention.

Claims

1. A stain-resistant porcelain insulator glaze, characterized in that: The raw materials of the glaze include potassium feldspar powder, quartz powder, calcium carbonate, boron trioxide, barium carbonate, zirconium silicate, calcium oxide, magnesium oxide, dolomite and composite powder, and each raw material is a sieved powder passing through a 1000-mesh sieve; the preparation method of the composite powder is as follows: (1) A composite aqueous solution of zinc nitrate and cerium nitrate is prepared in a reactor, and the composite aqueous solution of zinc nitrate and cerium nitrate is stirred. Citric acid is added to the solution during the stirring process, and the solution is stirred for 30 to 40 minutes after the addition is completed. Then, glucose is added to the solution under stirring, and the solution is stirred for more than 20 minutes after the addition is completed. Hexadecyltrimethylammonium bromide is added to the solution, and the solution is stirred for more than 20 minutes after the addition is completed. Then, ammonia water is added dropwise to the solution under stirring, and after the addition is completed, the reactor is sealed, heated to 150 to 160° C. and kept warm for more than 20 hours. After the insulation is completed, the reactor is air-cooled to room temperature, the reactor is opened, solid-liquid separation is carried out, the solid phase is washed with deionized water, dried at 100° C. for more than 1 hour, and then calcined at 500° C. for 3 to 4 hours, and air-cooled to room temperature to obtain solid phase powder I; (2) lithium nitrate, gallium nitrate, phosphoric acid and ethanol are mixed to form a mixed solution, the mixed solution is stirred, and then the solid phase powder I is added to the mixed solution under stirring. After the addition is completed, the solution is stirred for 3 to 4 hours, and then heated to 80±5°C and kept warm to evaporate the ethanol. The powder is placed at 750±5°C and calcined for 2 to 3 hours, and then air-cooled to room temperature to obtain solid phase powder II; (3) preparing an aqueous solution of calcium nitrate, dispersing the solid phase powder II in the aqueous solution of calcium nitrate to form a dispersion, keeping the dispersion constant at 45±5°C in a water bath, stirring the dispersion after reaching the temperature, adding a phosphoric acid aqueous solution to the dispersion under stirring, adjusting the pH of the dispersion to 2.7 with dilute hydrochloric acid or sodium hydroxide solution after the addition is completed, and then stirring the dispersion for 10 to 15 minutes under the condition of keeping the temperature at 45±5°C, and then separating the solid and liquid, washing the solid phase with deionized water for more than 3 times, and drying at 100°C for more than 30 minutes to obtain a solid phase powder III; (4) In a reaction kettle, ammonia water is added dropwise to an ethanol aqueous solution to form an alcohol solution, and then the solid phase powder III is dispersed in the alcohol solution to form an alcohol suspension, and the alcohol suspension is stirred under an ultrasonic environment. During the stirring process, 1H,1H,2H,2H-perfluorodecyltriethoxysilane is added to the alcohol suspension. After the addition is completed, the alcohol suspension is continued to be stirred under an ultrasonic environment for more than 20 minutes, the reaction kettle is sealed, heated to 120±3°C and kept warm for more than 6 hours, and then air-cooled to room temperature, solid-liquid separation is performed, the solid phase is washed with ethanol for more than 3 times, and dried at 80°C for more than 20 minutes to obtain the composite powder.

2. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: The raw materials of the glaze are as follows by weight: 16 to 20 parts of potassium feldspar powder, 26 to 28 parts of quartz stone powder, 10 to 12 parts of calcium carbonate, 8 to 15 parts of boron trioxide, 1 to 2 parts of barium carbonate, 8 to 9 parts of zirconium silicate, 2 to 4 parts of calcium oxide, 2 to 4 parts of magnesium oxide, 3 to 6 parts of dolomite, and 13 to 15 parts of composite powder.

3. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: In the step (1), in the composite aqueous solution of zinc nitrate and cerium nitrate, the concentration of zinc nitrate is 3-4 g / L, the concentration of cerium nitrate is 1-3 g / L, and the solvent is water; the amount of citric acid, glucose, hexadecyltrimethylammonium bromide, and ammonia water added to the composite aqueous solution of zinc nitrate and cerium nitrate is in the ratio of citric acid: glucose: hexadecyltrimethylammonium bromide: ammonia water: composite aqueous solution of zinc nitrate and cerium nitrate = 2-3 g: 6-8 g: 3-5 g: 20-30 mL: 200 mL; and the mass percentage of the solute in the ammonia water is 20%.

4. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: In the step (2), the mixing ratio of the lithium nitrate, gallium nitrate, phosphoric acid and ethanol is lithium nitrate: gallium nitrate: phosphoric acid: ethanol = 16-18 g: 1-2 g: 6-9 mL: 500 mL, and the solid phase powder I is added to the mixed solution at a solid / liquid mass ratio of solid / liquid = 1:

30.

5. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: In the step (3), the concentration of calcium nitrate in the aqueous solution of calcium nitrate is 18-20 g / L, and the solvent is water; the solid-liquid mass ratio of the solid phase powder II dispersed in the aqueous solution of calcium nitrate is solid / liquid = 1:

30.

6. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: In the step (3), the concentration of phosphoric acid in the phosphoric acid aqueous solution is 150 mL / L, and the volume ratio of the added phosphoric acid aqueous solution to the calcium nitrate aqueous solution is phosphoric acid aqueous solution:calcium nitrate aqueous solution = 1:8; the mass percentage of the solute in the dilute hydrochloric acid is 10%, and the solvent is water; the mass percentage of the solute in the sodium hydroxide solution is 10%, and the solvent is water.

7. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: In the step (4), the volume ratio of ammonia water to ethanol aqueous solution is ammonia water: ethanol aqueous solution = 1:25-30, wherein the mass percentage of solute in the ammonia water is 25%, and the volume percentage of ethanol in the ethanol aqueous solution is 75%; the solid-liquid mass ratio of the solid phase powder III dispersed in the alcohol solution is solid / liquid = 1:50; and the volume ratio of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added to the alcohol suspension is 1H,1H,2H,2H-perfluorodecyltriethoxysilane: alcohol suspension = 1-2:

100.

8. The anti-fouling porcelain insulator glaze according to claim 1, characterized in that: The ultrasonic power is 30-40 kW and the frequency is 20 kHz.

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