Wear-resistant and cold and heat-resistant electric porcelain glaze and preparation method thereof

Abstract

The invention discloses a wear-resistant and cold and heat-resistant electric porcelain glaze and a preparation method thereof. The electric porcelain glaze is prepared by mixing raw materials such as potassium feldspar, hard kaolin, albite, calcined bauxite, calcined talc, limestone, bentonite, a coloring agent, a rodlike niobium pentoxide-spherical molybdenum trioxide compound, an antimony oxide carbon nitride composite material and the like. The electroceramic glaze is used for glazing the surface of an electroceramic product blank, so that the wear resistance and cold and heat resistance of an electroceramic product can be improved at the same time, and the application prospect is good.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of porcelain enamel, and particularly relates to a wear-resistant and heat-and-cold-resistant porcelain enamel and a preparation method thereof. Background Art

[0002] Porcelain is a functional ceramic material widely used in the power system, including various line insulators, insulators for power station electrical appliances, and other insulating components for isolating or supporting live bodies. Porcelain is usually made from natural minerals such as bauxite, kaolin, and feldspar through high-temperature firing.

[0003] Porcelain has excellent electrical properties, mechanical strength, and chemical stability. It is an important basic component in the power industry and plays a very important role in power transmission and distribution and the manufacture of high-voltage electrical equipment. It belongs to the basic industry of the national economy.

[0004] In order to make the surface of porcelain smooth, beautiful, and easy to clean, porcelain enamel is usually coated on the surface of the porcelain product blank to form an enamel layer. The enamel layer can also improve the mechanical properties, electrical properties, and environmental resistance of porcelain to a certain extent.

[0005] However, the working environment of porcelain is often relatively harsh. The improvement of the performance of porcelain by conventional porcelain enamel coating is limited. For example, in a harsh environment with sand and wind, ordinary porcelain enamel will be worn out in a short time. Once worn out, the porous porcelain blank will be directly exposed, seriously damaging the insulation of porcelain, increasing power transmission loss, and posing a danger of electric leakage. In addition, the outdoor environment temperature varies greatly, and both long-term high-temperature and low-temperature environments will affect porcelain enamel, and eventually the above situation will also occur. Therefore, through the technical improvement of porcelain enamel, improving the wear resistance and heat-and-cold resistance of porcelain is very important for power transmission safety.

[0006] Patent CN105924231B discloses a wear-resistant porcelain enamel and a preparation method thereof, which is prepared from porcelain enamel and inorganic wear-resistant particles with nano-submicron particle sizes. Among them, the inorganic wear-resistant particles with nano-submicron particle sizes are any one or more of alumina, zirconia, titanium diboride, silicon carbide, titanium carbide, and tungsten carbide in any ratio combination. This patented technology helps to improve the wear resistance of porcelain, but there is no obvious improvement in heat-and-cold resistance.

[0007] Currently, there is an urgent need for an electromagnetic enamel that can improve both wear resistance and heat-and-cold resistance. Summary of the Invention

[0008] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a wear-resistant and heat-and-cold-resistant porcelain enamel and a preparation method thereof, which can improve the wear resistance and heat-and-cold resistance of porcelain products at the same time.

[0009] To achieve the above object, the present invention adopts the following technical solutions:

[0010] A wear-resistant and heat and cold resistant porcelain glaze is made by mixing the following raw materials in parts by weight: 28 - 30 parts of potassium feldspar, 15 - 20 parts of hard kaolin, 10 - 12 parts of albite, 8 - 10 parts of calcined bauxite, 8 - 10 parts of calcined talc, 6 - 8 parts of limestone, 5 - 7 parts of bentonite, 5 - 7 parts of colorant, 4 - 5 parts of rod-shaped niobium pentoxide-spherical molybdenum trioxide complex, and 3 - 4 parts of antimony oxide-carbon nitride composite material.

[0011] Preferably, the colorant is selected from any one of iron oxide, copper oxide, manganese dioxide, cobalt oxide, vanadium pentoxide or titanium dioxide.

[0012] Preferably, the rod-shaped niobium pentoxide-spherical molybdenum trioxide complex is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop, stir evenly, then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer to a reaction kettle, heat at 180 - 200 °C for 20 - 22 hours, wash with absolute ethanol, dry in vacuum, and perform heat treatment at 420 - 450 °C for 2 - 3 hours to obtain it; wherein, the mass ratio of hydrogen peroxide, methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:5 - 6:3 - 4, the mass concentration of hydrogen peroxide is 25 - 30%, and the concentration of methanol solution of molybdenum acetylacetonate is 0.012 - 0.014 mol / L.

[0013] Further preferably, the process conditions for stirring evenly are: stirring at 300 - 400 r / min for 30 - 40 minutes; the process conditions for ultrasonic oscillation treatment are: ultrasonic oscillation at 500 - 600 W for 50 - 60 minutes; the process conditions for vacuum drying are: vacuum drying at 60 - 70 °C for 10 - 12 hours.

[0014] Further preferably, the rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse metal niobium powder in distilled water with a mass 30 - 40 times that of it, transfer to a reaction kettle, age at 200 - 220 °C for 6 - 7 days, filter to obtain the solid, wash 2 - 3 times with an ethanol aqueous solution with a volume concentration of 60 - 65%, and dry at 60 - 65 °C for 1 - 2 hours to obtain it.

[0015] Even more preferably, the process conditions for stirring and dispersing are: stirring at 800 - 1000 r / min for 30 - 40 minutes.

[0016] Preferably, in parts by weight, the antimony oxide-carbon nitride composite material is prepared by the following method: First, dissolve 1 part of antimony trichloride in 8 - 10 parts of water, then add 5 - 7 parts of urea, stir evenly, dry, calcine at 600 - 650 °C for 3 - 5 hours, and grind for 30 - 40 minutes to obtain it.

[0017] The preparation method of the above-mentioned wear-resistant and heat and cold resistant porcelain glaze is as follows:

[0018] (1) First, mix all the raw materials in the formula amount evenly to obtain a mixed material; then transfer the mixed material to a ball mill, add ball material and water, and conduct the first wet ball milling. After the ball material separation, obtain the ball milled material. The ball milling conditions are: ball milling at 600 - 700 rpm for 30 - 40 minutes, ball milling at 150 - 200 rpm for 100 - 120 minutes, and ball milling at 350 - 400 rpm for 50 - 60 minutes;

[0019] (2) Then, conduct microwave irradiation treatment on the ball milled material, and then heat it to 1600 - 1700 °C, keep it warm for 50 - 60 minutes, perform water quenching, crush it to obtain the crushed material, add ball material and water, conduct the second wet ball milling, separate the ball material, and dry it to obtain the described porcelain glaze; the ball milling conditions are: ball milling at 500 - 600 rpm for 80 - 100 minutes.

[0020] Preferably, in step (1), the mass ratio of the mixed material, ball material and water is 1:3 - 4:0.7 - 0.9, and the ball material is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls.

[0021] Preferably, in step (2), the process conditions of the microwave irradiation treatment are: microwave irradiation at 500 - 600 W for 1 - 2 minutes, stop for 1 minute, and cycle like this until the cumulative microwave irradiation time is 12 - 15 minutes.

[0022] Preferably, in step (2), crush it to a particle size of less than 1 mm.

[0023] Preferably, in step (2), the mass ratio of the crushed material, ball material and water is 1:2.2 - 2.5:0.7 - 0.9, and the ball material is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention provides a wear-resistant and heat and cold resistant porcelain glaze, which is made by mixing raw materials such as potassium feldspar, hard kaolin, sodium feldspar, calcined bauxite, calcined talc, limestone, bentonite, colorant, rod-shaped niobium pentoxide - spherical molybdenum trioxide composite, antimony oxide carbon nitride composite material, etc. Using this porcelain glaze to glaze the surface of the porcelain product body can improve the wear resistance and heat and cold resistance of the porcelain product at the same time, and has good application prospects.

[0026] The present invention introduces a rod-shaped niobium pentoxide-spherical molybdenum trioxide composite and an antimony oxide-carbon nitride composite into the raw materials. The synergistic effect of the two helps to improve the wear resistance and resistance to heat and cold of the porcelain. The rod-shaped niobium pentoxide-spherical molybdenum trioxide composite and the antimony oxide-carbon nitride composite enable the porcelain glaze to form a cross structure microscopically, which has a buffering effect and helps to further improve the wear resistance and resistance to heat and cold.

[0027] In the preparation, first, the raw materials in the formula amount are mixed evenly to obtain a mixture; then the mixture is transferred to a ball mill, ball materials and water are added, and the first wet ball milling is carried out. After the ball materials are separated, a ball-milled material is obtained; then the ball-milled material is subjected to microwave irradiation treatment, heated, water-quenched, and pulverized to obtain a pulverized material. Ball materials and water are added, and the second wet ball milling is carried out. After the ball materials are separated, it is dried. On the basis of the above formula, the present invention first realizes the full mixing of the raw materials through the first wet ball milling. The microwave irradiation and heat treatment promote the compounding of the raw materials. Then, through the second wet ball milling, the particle size of the glaze is further reduced, the uniformity of the glaze is improved, and a better protective effect is formed after glazing, further improving the wear resistance and resistance to heat and cold of the porcelain products. Specific Embodiments

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] Unless otherwise specified, all products in the present invention are purchased through market channels.

[0030] Example 1

[0031] A wear-resistant and heat-and-cold-resistant porcelain glaze is made by mixing the following raw materials: 2.8 kg of potassium feldspar, 1.5 kg of hard kaolin, 1 kg of albite, 0.8 kg of calcined bauxite, 0.8 kg of calcined talc, 0.6 kg of limestone, 0.5 kg of bentonite, 0.5 kg of a colorant (vanadium pentoxide), 0.4 kg of a rod-shaped niobium pentoxide-spherical molybdenum trioxide composite, and 0.3 kg of an antimony oxide-carbon nitride composite.

[0032] The rod-shaped niobium pentoxide-spherical molybdenum trioxide composite is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop, stir evenly, then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer it to a reaction kettle, heat at 180 °C for 20 hours, wash with absolute ethanol, dry in vacuum, and heat-treat at 420 °C for 2 hours to obtain it; wherein, the mass ratio of hydrogen peroxide, the methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:5:3, the mass concentration of hydrogen peroxide is 25%, and the concentration of the methanol solution of molybdenum acetylacetonate is 0.012 mol / L. The process conditions for stirring evenly are: stirring at 300 r / min for 30 minutes; the process conditions for ultrasonic oscillation treatment are: ultrasonic oscillation at 500 W for 50 minutes; the process conditions for vacuum drying are: vacuum drying at 60 °C for 10 hours.

[0033] The rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse the metal niobium powder in distilled water with a mass 30 times that of it, transfer it to a reaction kettle, age at 200 °C for 6 days, filter to obtain the solid, wash it twice with an ethanol aqueous solution with a volume concentration of 60%, and dry at 60 °C for 1 hour to obtain it. The process conditions for stirring and dispersing are: stirring at 800 r / min for 30 minutes.

[0034] The antimony oxide-carbon nitride composite is prepared by the following method: First, dissolve 1 kg of antimony trichloride in 8 kg of water, then add 5 kg of urea, stir evenly, dry, calcine at 600 °C for 3 hours, and grind for 30 minutes to obtain it.

[0035] The preparation method of the aforementioned wear-resistant and heat / cold-resistant porcelain glaze is as follows:

[0036] (1) First, mix the raw materials in the formula amounts evenly to obtain a mixture; then transfer the mixture to a ball mill, add grinding media and water, and perform the first wet ball milling. After separating the grinding media, obtain the ball-milled material; the ball milling conditions are: ball milling at 600 rpm for 30 minutes, at 150 rpm for 100 minutes, and at 350 rpm for 50 minutes; the mass ratio of the mixture, grinding media, and water is 1:3:0.7, and the grinding media is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls;

[0037] (2) Then, perform microwave irradiation treatment on the ball-milled material, then heat it to 1600 °C, keep it warm for 50 minutes, quench it in water, crush it to obtain a crushed material (with a particle size of less than 1 mm), add grinding media and water, perform the second wet ball milling, separate the grinding media, and dry to obtain the porcelain glaze; the ball milling conditions are: ball milling at 500 rpm for 80 minutes;

[0038] The process conditions for microwave irradiation treatment are: microwave irradiation at 500 W for 1 minute, stop for 1 minute, and so on in cycles until the cumulative microwave irradiation time is 12 minutes;

[0039] The mass ratio of the crushed material, ball material, and water is 1:2.2:0.7, and the ball material is obtained by mixing equal amounts of 80mm large grinding balls, 65mm medium grinding balls, and 30mm small grinding balls.

[0040] Example 2

[0041] A wear-resistant and heat / cold-resistant electroceramic glaze is made by mixing the following raw materials: 3 kg of potassium feldspar, 2 kg of hard kaolin, 1.2 kg of sodium feldspar, 1 kg of calcined bauxite, 1 kg of calcined talc, 0.8 kg of limestone, 0.7 kg of bentonite, 0.7 kg of a colorant (vanadium pentoxide), 0.5 kg of a rod-shaped niobium pentoxide-spherical molybdenum trioxide composite, and 0.4 kg of an antimony oxide-carbon nitride composite.

[0042] The rod-shaped niobium pentoxide-spherical molybdenum trioxide composite is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop, stir evenly, then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer to a reaction kettle, heat at 200 °C for 22 hours, wash with absolute ethanol, dry in vacuum, and perform heat treatment at 450 °C for 3 hours to obtain it; among them, the mass ratio of hydrogen peroxide, the methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:6:4, the mass concentration of hydrogen peroxide is 30%, and the concentration of the methanol solution of molybdenum acetylacetonate is 0.014 mol / L. The process conditions for stirring evenly are: stirring at 400 r / min for 40 minutes; the process conditions for ultrasonic oscillation treatment are: ultrasonic oscillation at 600 W for 60 minutes; the process conditions for vacuum drying are: vacuum drying at 70 °C for 12 hours.

[0043] The rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse metal niobium powder in distilled water with 40 times its mass, transfer to a reaction kettle, age at 220 °C for 7 days, filter to obtain the solid, wash 3 times with an ethanol aqueous solution with a volume concentration of 65%, and dry at 65 °C for 2 hours to obtain it. The process conditions for stirring and dispersing are: stirring at 1000 r / min for 40 minutes.

[0044] The antimony oxide-carbon nitride composite is prepared by the following method: First, dissolve 1 kg of antimony trichloride in 10 kg of water, then add 7 kg of urea, stir evenly, dry, calcine at 650 °C for 5 hours, and grind for 40 minutes to obtain it.

[0045] The preparation method of the aforementioned wear-resistant and heat / cold-resistant electroceramic glaze is as follows:

[0046] (1) First, mix all the raw materials in the formula amounts evenly to obtain a mixed material; then transfer the mixed material to a ball mill, add grinding balls and water, and conduct the first wet ball milling. After the grinding balls are separated, a ball-milled material is obtained. The ball milling conditions are: ball milling at 700 rpm for 40 minutes, at 200 rpm for 120 minutes, and at 400 rpm for 60 minutes; the mass ratio of the mixed material, grinding balls, and water is 1:4:0.9. The grinding balls are obtained by mixing equal quantities of 80-mm large grinding balls, 65-mm medium grinding balls, and 30-mm small grinding balls.

[0047] (2) Then, conduct microwave irradiation treatment on the ball-milled material, and then heat it to 1700 °C, hold it for 60 minutes, perform water quenching, and pulverize it to obtain a pulverized material (with a particle size of less than 1 mm). Add grinding balls and water, conduct the second wet ball milling, separate the grinding balls, and dry it to obtain the electroceramic glaze. The ball milling conditions are: ball milling at 600 rpm for 100 minutes.

[0048] The process conditions for the microwave irradiation treatment are: irradiate with 600 W of microwave for 2 minutes, stop for 1 minute, and repeat this cycle until the cumulative microwave irradiation time reaches 15 minutes.

[0049] The mass ratio of the pulverized material, grinding balls, and water is 1:2.5:0.9. The grinding balls are obtained by mixing equal quantities of 80-mm large grinding balls, 65-mm medium grinding balls, and 30-mm small grinding balls.

[0050] Example 3

[0051] A wear-resistant and heat / cold-resistant electroceramic glaze is made by mixing the following raw materials: 2.8 kg of potassium feldspar, 2 kg of hard kaolin, 1 kg of albite, 1 kg of calcined bauxite, 0.8 kg of calcined talc, 0.8 kg of limestone, 0.5 kg of bentonite, 0.7 kg of a colorant (vanadium pentoxide), 0.4 kg of a rod-shaped niobium pentoxide-spherical molybdenum trioxide composite, and 0.4 kg of an antimony oxide-carbon nitride composite.

[0052] The rod-shaped niobium pentoxide-spherical molybdenum trioxide composite is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop, stir evenly, then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer it to a reaction kettle, heat it at 180 °C for 22 hours, wash it with absolute ethanol, conduct vacuum drying, and perform heat treatment at 420 °C for 3 hours to obtain it. Among them, the mass ratio of hydrogen peroxide, the methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:5:4. The mass concentration of hydrogen peroxide is 25%, and the concentration of the methanol solution of molybdenum acetylacetonate is 0.014 mol / L. The process conditions for stirring evenly are: stir at 300 r / min for 40 minutes; the process conditions for ultrasonic oscillation treatment are: ultrasonic oscillation at 500 W for 60 minutes; the process conditions for vacuum drying are: vacuum dry at 60 °C for 12 hours.

[0053] Rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse metallic niobium powder in distilled water with a mass 30 times that of the metallic niobium powder, transfer it to a reaction kettle, age it at 220 °C for 6 days, filter to obtain the solid, wash it twice with an ethanol aqueous solution with a volume concentration of 65%, and dry it at 65 °C for 1 hour to obtain the product. The process conditions for stirring and dispersing are: Stir at 1000 r / min for 30 minutes.

[0054] Antimony oxide carbon nitride composite material is prepared by the following method: First, dissolve 1 kg of antimony trichloride in 10 kg of water, then add 5 kg of urea, stir evenly, dry it, calcine it at 650 °C for 3 hours, and grind it for 40 minutes to obtain the product.

[0055] The preparation method of the aforementioned wear-resistant and heat / cold-resistant porcelain glaze is as follows:

[0056] (1) First, mix the raw materials in the formula amounts evenly to obtain a mixture; then transfer the mixture to a ball mill, add grinding media and water, and conduct the first wet ball milling. After separating the grinding media, obtain the ball-milled material. The ball milling conditions are: Ball mill at 600 rpm for 40 minutes, 150 rpm for 120 minutes, and 350 rpm for 60 minutes; the mass ratio of the mixture, grinding media, and water is 1:3:0.9. The grinding media is obtained by mixing large grinding balls with a diameter of 80 mm, medium grinding balls with a diameter of 65 mm, and small grinding balls with a diameter of 30 mm in equal amounts.

[0057] (2) Then, perform microwave irradiation treatment on the ball-milled material, then heat it to 1600 °C, hold the temperature for 60 minutes, quench it with water, crush it to obtain a crushed material (with a particle size of less than 1 mm), add grinding media and water, conduct the second wet ball milling, separate the grinding media, and dry it to obtain the porcelain glaze; the ball milling conditions are: Ball mill at 500 rpm for 100 minutes.

[0058] The process conditions for microwave irradiation treatment are: Microwave irradiate at 500 W for 2 minutes, stop for 1 minute, and repeat this cycle until the cumulative microwave irradiation time reaches 12 minutes;

[0059] The mass ratio of the crushed material, grinding media, and water is 1:2.5:0.7. The grinding media is obtained by mixing large grinding balls with a diameter of 80 mm, medium grinding balls with a diameter of 65 mm, and small grinding balls with a diameter of 30 mm in equal amounts.

[0060] Example 4

[0061] A wear-resistant and heat / cold-resistant porcelain glaze is made by mixing the following raw materials: 2.9 kg of potassium feldspar, 1.8 kg of hard kaolin, 1.1 kg of albite, 0.9 kg of calcined bauxite, 0.9 kg of calcined talc, 0.7 kg of limestone, 0.6 kg of bentonite, 0.6 kg of coloring agent (vanadium pentoxide), 0.45 kg of rod-shaped niobium pentoxide-spherical molybdenum trioxide composite, and 0.35 kg of antimony oxide carbon nitride composite material.

[0062] The rod-shaped niobium pentoxide-spherical molybdenum trioxide composite is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop, stir evenly, then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer it to a reaction kettle, heat at 190 °C for 21 hours, wash with absolute ethanol, dry in vacuum, and perform heat treatment at 430 °C for 2.5 hours to obtain it; among them, the mass ratio of hydrogen peroxide, the methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:5.5:3.5, the mass concentration of hydrogen peroxide is 27%, and the concentration of the methanol solution of molybdenum acetylacetonate is 0.013 mol / L. The process conditions for stirring evenly are: stir at 400 r / min for 35 minutes; the process conditions for ultrasonic oscillation treatment are: ultrasonic oscillation at 600 W for 55 minutes; the process conditions for vacuum drying are: vacuum drying at 65 °C for 11 hours.

[0063] The rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse metal niobium powder in distilled water with a mass 35 times that of it, transfer it to a reaction kettle, age at 210 °C for 6 days, filter to obtain the solid, wash it 2 times with an ethanol aqueous solution with a volume concentration of 62%, and dry at 62 °C for 1-2 hours to obtain it. The process conditions for stirring and dispersing are: stir at 900 r / min for 35 minutes.

[0064] The antimony oxide-carbon nitride composite is prepared by the following method: First, dissolve 1 kg of antimony trichloride in 9 kg of water, then add 6 kg of urea, stir evenly, dry, calcine at 620 °C for 4 hours, and grind for 35 minutes to obtain it.

[0065] The preparation method of the aforementioned wear-resistant and heat and cold-resistant porcelain glaze is as follows:

[0066] (1) First, mix the raw materials in the formula amounts evenly to obtain a mixture; then transfer the mixture to a ball mill, add grinding media and water, and perform the first wet ball milling. After separating the grinding media, obtain the ball-milled material; the ball milling conditions are: ball mill at 700 rpm for 35 minutes, ball mill at 180 rpm for 110 minutes, and ball mill at 350 rpm for 55 minutes; the mass ratio of the mixture, grinding media, and water is 1:3.5:0.8, and the grinding media is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls;

[0067] (2) Then, perform microwave irradiation treatment on the ball-milled material, then heat it to 1650 °C, keep it warm for 55 minutes, perform water quenching, crush it to obtain a crushed material (with a particle size of less than 1 mm), add grinding media and water, perform the second wet ball milling, separate the grinding media, and dry to obtain the porcelain glaze; the ball milling conditions are: ball mill at 600 rpm for 90 minutes;

[0068] The process conditions for microwave irradiation treatment are as follows: microwave irradiation at 600W for 1 minute, then stop for 1 minute, and repeat this cycle until the cumulative microwave irradiation time reaches 14 minutes;

[0069] The mass ratio of the crushed material, ball material, and water is 1:2.4:0.8. The ball material is obtained by mixing equal amounts of 80mm large grinding balls, 65mm medium grinding balls, and 30mm small grinding balls.

[0070] Comparative Example 1

[0071] Omit the rod-shaped niobium pentoxide-spherical molybdenum trioxide composite. The rest is the same as in Example 1.

[0072] Comparative Example 2

[0073] Omit the antimony oxide-carbon nitride composite. The rest is the same as in Example 1.

[0074] Comparative Example 3

[0075] An electroceramic glaze is made by mixing the following raw materials: 2.8 kg of potassium feldspar, 1.5 kg of hard kaolin, 1 kg of sodium feldspar, 0.8 kg of calcined bauxite, 0.8 kg of calcined talc, 0.6 kg of limestone, 0.5 kg of bentonite, 0.5 kg of coloring agent (vanadium pentoxide), 0.4 kg of rod-shaped niobium pentoxide-spherical molybdenum trioxide composite, and 0.3 kg of antimony oxide-carbon nitride composite.

[0076] The rod-shaped niobium pentoxide-spherical molybdenum trioxide composite is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop and stir evenly. Then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer to a reaction kettle, heat at 180°C for 20 hours, wash with absolute ethanol, and dry under vacuum. Heat-treat at 420°C for 2 hours to obtain it; among them, the mass ratio of hydrogen peroxide, the methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:5:3, the mass concentration of hydrogen peroxide is 25%, and the concentration of the methanol solution of molybdenum acetylacetonate is 0.012 mol / L. The process conditions for stirring evenly are: stir at 300 r / min for 30 minutes; the process conditions for ultrasonic oscillation treatment are: ultrasonic oscillation at 500W for 50 minutes; the process conditions for vacuum drying are: vacuum drying at 60°C for 10 hours.

[0077] The rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse metal niobium powder in distilled water with 30 times its mass, transfer to a reaction kettle, age at 200°C for 6 days, filter to obtain the solid, wash 2 times with an ethanol aqueous solution with a volume concentration of 60%, and dry at 60°C for 1 hour to obtain it. The process conditions for stirring and dispersing are: stir at 800 r / min for 30 minutes.

[0078] The antimony oxide-carbon nitride composite material is prepared by the following method: First, dissolve 1 kg of antimony trichloride in 8 kg of water, then add 5 kg of urea, stir evenly, dry, calcine at 600 °C for 3 hours, and grind for 30 minutes to obtain the product.

[0079] The preparation method of the aforementioned electroceramic glaze is as follows:

[0080] (1) First, mix the raw materials in the formula amounts evenly to obtain a mixture; then transfer the mixture to a ball mill, add grinding media and water, and conduct the first wet ball milling. After separating the grinding media, obtain the ball-milled material. The ball milling conditions are: ball milling at 350 rpm for 180 minutes; the mass ratio of the mixture, grinding media and water is 1:3:0.7, and the grinding media is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls.

[0081] (2) Then, perform microwave irradiation treatment on the ball-milled material, then heat to 1600 °C, hold for 50 minutes, quench in water, crush to obtain a crushed material (particle size below 1 mm), add grinding media and water, conduct the second wet ball milling, separate the grinding media, and dry to obtain the electroceramic glaze. The ball milling conditions are: ball milling at 500 rpm for 80 minutes.

[0082] The process conditions for the microwave irradiation treatment are: microwave irradiation at 500 W for 1 minute, stop for 1 minute, and cycle like this until the cumulative microwave irradiation time is 12 minutes.

[0083] The mass ratio of the crushed material, grinding media and water is 1:2.2:0.7, and the grinding media is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls.

[0084] Test examples

[0085] Add water with a mass 0.6 times that of the electroceramic glazes obtained in Examples 1 to 4 and Comparative Examples 1 to 3 respectively, stir at 150 r / min for 30 minutes to obtain a glaze slurry. Use the spraying method to evenly spray the glaze slurry on the surface of the electroceramic product blank (100 mm × 100 mm × 10 mm), dry at 60 °C for 5 hours, and sinter at 1250 °C for 2 hours to obtain an electroceramic product (the glaze layer thickness is 0.5 mm). Examine the abrasion resistance and heat and cold resistance of the electroceramic products. The specific methods are as follows:

[0086] 1. Abrasion resistance: Refer to GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of surface abrasion resistance of glazed tiles", grind at 600 revolutions, measure the mass loss of each specimen, and calculate the average wear value.

[0087] 2. Resistance to heat and cold: Place the porcelain insulators in a low-temperature (-60°C) environment and keep them warm for 1 hour. After taking them out, let them warm up to room temperature (25°C) naturally, and observe whether there are any changes in the glaze surface. Place the porcelain insulators in a high-temperature (1500°C) environment and keep them warm for 1 hour. After taking them out, let them cool down to room temperature naturally, and observe whether there are any changes in the glaze surface.

[0088] The results are shown in Table 1.

[0089] Table 1. Investigation of wear resistance and resistance to heat and cold

[0090]

[0091] As can be seen from Table 1, the porcelain glaze materials obtained in Examples 1 to 3 have excellent wear resistance and resistance to heat and cold.

[0092] In Comparative Example 1, the rod-shaped niobium pentoxide-spherical molybdenum trioxide composite is omitted. In Comparative Example 2, the antimony oxide-carbon nitride composite material is omitted. In Comparative Example 3, the first wet ball milling is carried out by one-time ball milling, and the wear resistance and resistance to heat and cold are significantly deteriorated. This shows that the rod-shaped niobium pentoxide-spherical molybdenum trioxide composite and the antimony oxide-carbon nitride composite material act synergistically to improve the wear resistance and resistance to heat and cold of the product, and the wet ball milling conditions promote the full and uniform mixing of raw materials, which is also beneficial to the further improvement of wear resistance and resistance to heat and cold.

[0093] The present invention uses the above-mentioned examples to illustrate the technical concept of the present invention. However, the present invention is not limited to the above-mentioned examples, that is, it does not mean that the present invention must rely on the above-mentioned examples to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of individual raw materials of the products of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A wear-resistant and heat / cold-resistant porcelain enamel glaze, characterized in that, It is made by mixing the following raw materials in parts by weight: 28 - 30 parts of potassium feldspar, 15 - 20 parts of hard kaolin, 10 - 12 parts of albite, 8 - 10 parts of calcined bauxite, 8 - 10 parts of calcined talc, 6 - 8 parts of limestone, 5 - 7 parts of bentonite, 5 - 7 parts of colorant, 4 - 5 parts of rod-shaped niobium pentoxide - spherical molybdenum trioxide composite, and 3 - 4 parts of antimony oxide carbon nitride composite material.

2. A wear-resistant and heat and cold resistant porcelain enamel glaze according to claim 1, characterized in that The colorant is selected from any one of iron oxide, copper oxide, manganese dioxide, cobalt oxide, vanadium pentoxide or titanium dioxide.

3. An abrasion-resistant and heat / cold-resistant porcelain enamel glaze according to claim 1, characterized in that, The rod-shaped niobium pentoxide - spherical molybdenum trioxide composite is prepared by the following method: First, drop hydrogen peroxide into the methanol solution of molybdenum acetylacetonate drop by drop, stir evenly, then add rod-shaped niobium pentoxide, perform ultrasonic oscillation treatment, transfer to a reaction kettle, heat at 180 - 200 °C for 20 - 22 hours, wash with absolute ethanol, dry in vacuum, and perform heat treatment at 420 - 450 °C for 2 - 3 hours to obtain it; among them, the mass ratio of hydrogen peroxide, the methanol solution of molybdenum acetylacetonate, and rod-shaped niobium pentoxide is 1:5 - 6:3 - 4, the mass concentration of hydrogen peroxide is 25 - 30%, and the concentration of the methanol solution of molybdenum acetylacetonate is 0.012 - 0.014 mol / L.

4. A wear-resistant and heat / cold-resistant porcelain enamel according to claim 3, characterized in that, The rod-shaped niobium pentoxide is prepared by the following method: Stir and disperse metal niobium powder in distilled water with a mass 30 - 40 times that of it, transfer to a reaction kettle, age at 200 - 220 °C for 6 - 7 days, filter to obtain the solid, wash 2 - 3 times with an ethanol aqueous solution with a volume concentration of 60 - 65%, and dry at 60 - 65 °C for 1 - 2 hours to obtain it.

5. A wear-resistant and heat / cold-resistant porcelain enamel according to claim 1, characterized in that, In parts by weight, the antimony oxide carbon nitride composite material is prepared by the following method: First, dissolve 1 part of antimony trichloride in 8 - 10 parts of water, then add 5 - 7 parts of urea, stir evenly, dry, calcine at 600 - 650 °C for 3 - 5 hours, and grind for 30 - 40 minutes to obtain it.

6. The preparation method of an electroceramic glaze that is wear-resistant, resistant to heat and cold according to any one of claims 1 to 5, characterized in that, The specific steps are as follows: (1) First, mix the raw materials in the formula amount evenly to obtain a mixture; then transfer the mixture to a ball mill, add grinding media and water, and perform the first wet ball milling. After separating the grinding media, obtain the ball-milled material; the ball milling conditions are: ball milling at 600 - 700 rpm for 30 - 40 minutes, ball milling at 150 - 200 rpm for 100 - 120 minutes, and ball milling at 350 - 400 rpm for 50 - 60 minutes. (2) Then perform microwave irradiation treatment on the ball-milled material, then heat to 1600 - 1700 °C, keep warm for 50 - 60 minutes, perform water quenching, crush to obtain the crushed material, add grinding media and water, perform the second wet ball milling, separate the grinding media, and dry to obtain the electroceramic glaze; the ball milling conditions are: ball milling at 500 - 600 rpm for 80 - 100 minutes.

7. The preparation method according to claim 6, characterized in that, In step (1), the mass ratio of the mixture, grinding media and water is 1:3 - 4:0.7 - 0.9, and the grinding media is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls.

8. The preparation method according to claim 6, characterized in that, In step (2), the process conditions for microwave irradiation treatment are as follows: microwave irradiation at 500 - 600 W for 1 - 2 minutes, then stopping for 1 minute, and repeating this cycle until the cumulative microwave irradiation time reaches 12 - 15 minutes.

9. The preparation method according to claim 6, characterized in that, In step (2), it is crushed to a particle size of less than 1 mm.

10. The preparation method according to claim 6, characterized in that, In step (2), the mass ratio of the crushed material, the ball material, and water is 1:2.2 - 2.5:0.7 - 0.9, and the ball material is obtained by mixing equal amounts of 80 mm large grinding balls, 65 mm medium grinding balls, and 30 mm small grinding balls.

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