阅读说明：本技术 一种性能稳定的陶瓷釉料及其制备方法 (Ceramic glaze with stable performance and preparation method thereof ) 是由 涂祈林 于 2020-12-23 设计创作，主要内容包括：本发明涉及陶瓷釉料生产技术领域,提供了一种性能稳定的陶瓷釉料及其制备方法。其中陶瓷釉料包括：石英10～18份、左云土10～18份、熔块5～15份、改性纳米二氧化硅复合氧化石墨烯3～10份、硼酸3～10份、硅酸锆3～10份、方解石2～6份、钛酸锶2～6份、碳酸钡2～6份、磷酸二氢铵0.5～3份、氧化锌0.5～3份和含氟助剂0.5～3份；制备方法包括：S1、改性纳米二氧化硅复合氧化石墨烯的制备,S2、粉碎过筛,S3、浆料配制。本发明能够大幅提升釉料的硬度和耐磨性能,釉层结构致密且能填充陶瓷基体表面的气孔,改善了陶瓷产品的耐污耐寒性能,得到的釉面,品质高,性能稳定,使用寿命长。(The invention relates to the technical field of ceramic glaze production, and provides a ceramic glaze with stable performance and a preparation method thereof. Wherein the ceramic glaze comprises: 10-18 parts of quartz, 10-18 parts of Zuoyun soil, 5-15 parts of fusion cake, 3-10 parts of modified nano silicon dioxide composite graphene oxide, 3-10 parts of boric acid, 3-10 parts of zirconium silicate, 2-6 parts of calcite, 2-6 parts of strontium titanate, 2-6 parts of barium carbonate, 0.5-3 parts of ammonium dihydrogen phosphate, 0.5-3 parts of zinc oxide and 0.5-3 parts of fluorine-containing auxiliary agent; the preparation method comprises the following steps: s1, preparing modified nano silicon dioxide composite graphene oxide, S2, crushing and sieving, S3 and preparing slurry. The glaze disclosed by the invention can greatly improve the hardness and wear resistance of the glaze, the glaze layer has a compact structure and can fill pores on the surface of a ceramic substrate, the stain resistance and cold resistance of a ceramic product are improved, and the obtained glaze has high quality, stable performance and long service life.)

1. The ceramic glaze with stable performance is characterized by comprising the following raw materials in parts by weight: 10-18 parts of quartz, 10-18 parts of Zuoyun soil, 5-15 parts of fusion cake, 3-10 parts of modified nano silicon dioxide composite graphene oxide, 3-10 parts of boric acid, 3-10 parts of zirconium silicate, 2-6 parts of calcite, 2-6 parts of strontium titanate, 2-6 parts of barium carbonate, 0.5-3 parts of ammonium dihydrogen phosphate, 0.5-3 parts of zinc oxide and 0.5-3 parts of fluorine-containing auxiliary agent.

2. The ceramic glaze material with stable performance as claimed in claim 1, wherein the ceramic glaze material comprises the following raw materials in parts by weight: 12-15 parts of quartz, 15-18 parts of Zuoyun soil, 8-12 parts of fusion cake, 5-10 parts of modified nano silicon dioxide composite graphene oxide, 5-8 parts of boric acid, 5-8 parts of zirconium silicate, 3-5 parts of calcite, 3-5 parts of strontium titanate, 3-5 parts of barium carbonate, 1-2 parts of ammonium dihydrogen phosphate, 1-2 parts of zinc oxide and 1-2 parts of fluorine-containing auxiliary agent.

3. The stable ceramic glaze of claim 1 wherein the fluorine-containing adjuvant comprises hydroxyfluorosilicone oil and/or zinc hexafluorosilicate.

4. The stable ceramic glaze of claim 1 further comprising: one or more of nitrite, nitrate, carbonate and sulfate.

5. The preparation method of the ceramic glaze material with stable performance is characterized by comprising the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding the nano-silica, the silicon micropowder, the dispersing agent, the defoaming agent and the wetting agent into deionized water, and stirring and dispersing for a period of time to obtain nano-silica emulsion;

s12, preparing ethanol water solution of trimethylolpropane with the mass concentration of 10-20%, adding graphene oxide, a surfactant, a coupling agent and a modification treatment agent, and uniformly mixing to obtain mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, carrying out heating ultrasonic treatment or heating stirring treatment, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate and calcite according to the formula proportion, performing coarse grinding, sieving by a 100-200-mesh sieve, then performing fine grinding, and sieving by a 200-300-mesh sieve to obtain powder;

s3, slurry preparation: mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate, zinc oxide and a fluorine-containing auxiliary agent, adding water for wet ball milling, and sieving the obtained slurry with a 300-500-mesh sieve with 0.2-5 wt% of screen residue.

6. The method of claim 5, wherein the dispersant in step S11 is one or more of Disponer 929, EFKA SL 3034, Dow Corning 51;

the defoaming agent is one or more of Deform 6800, Efka SL 2038, SRE-CN and Dow Corning 65;

the wetting agent is one or more of alkyl sulfate, sulfonate and phosphate.

7. The method of claim 5, wherein the surfactant in step S12 is one or more of sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, and ammonium fatty alcohol polyoxyethylene ether sulfate;

the coupling agent is one or more of dodecyl silane, aminopropyl triethoxysilane and titanate coupling agent;

the modifying and treating agent is one or more of hexamethyl-dinitrogen silicane, dimethyl dichlorosilane and dimethyl silicone.

8. The method for preparing ceramic glaze with stable performance according to claim 5, wherein the conditions of the heating ultrasound in step S13 are as follows: the heating temperature is 50-90 ℃, and the ultrasonic frequency is 50-100 kHz; the heating and stirring conditions are as follows: the heating temperature is 50-90 ℃, and the stirring speed is 1000-1500 r/min.

9. The method for preparing a ceramic glaze material with stable performance according to claim 5, wherein the conditions of wet ball milling in step S3 are as follows: grinding balls: water in a weight ratio of 1: 0.8-1.5: ball milling is carried out for 8-15 h at 0.8-1.5.

10. The method of claim 5, wherein the sieved glaze slurry of step S3 contains particles of 5-20 μm or less in an amount of not less than 60%, and particles of 20-50 μm or less in an amount of not less than 80%.

Technical Field

The invention relates to the technical field of ceramic glaze production, in particular to a ceramic glaze with stable performance and a preparation method thereof.

Background

The glaze is a glassy thin layer covered on a ceramic body, but the composition of the glaze is more complex than that of glass, the property and microstructure of the glaze are different from those of the glass, for example, the high-temperature viscosity of the glaze is far greater than that of the glass, the composition and preparation process of the glaze are close to those of a blank but different from those of the glass, the glaze has the functions of improving the surface performance of the ceramic product, enabling the surface of the product to be smooth, impermeable to liquid and gas and not easy to stain, and can improve the mechanical strength, electrical property, chemical stability and thermal stability of the product, the glaze also has a decoration effect on the blank, can cover the poor color and the poor surface of the body, and a plurality of glazes such as color glaze, matt glaze, gold sand glaze, devitrified glaze and the like.

The traditional glaze is easy to generate bubbles and glaze in the using process, so that the surface of the ceramic product is not smooth enough, is easy to stain and is not easy to clean; the glaze material has low sintering hardness and is easy to scratch in the use process, so that the pollution resistance and the wear resistance of the glaze material are poor, and the performance is not stable enough.

Disclosure of Invention

The invention aims to overcome at least one of the defects of the prior art and provide a ceramic glaze with stable performance and a preparation method thereof, wherein the ceramic glaze can be uniformly glazed in the using process, no air bubble is generated, and the prepared ceramic product has good stain resistance and wear resistance. The purpose of the invention is realized based on the following technical scheme:

in one aspect, the invention provides a ceramic glaze with stable performance, which comprises the following raw materials in parts by weight: 10-18 parts of quartz, 10-18 parts of Zuoyun soil, 5-15 parts of fusion cake, 3-10 parts of modified nano silicon dioxide composite graphene oxide, 3-10 parts of boric acid, 3-10 parts of zirconium silicate, 2-6 parts of calcite, 2-6 parts of strontium titanate, 2-6 parts of barium carbonate, 0.5-3 parts of ammonium dihydrogen phosphate, 0.5-3 parts of zinc oxide and 0.5-3 parts of fluorine-containing auxiliary agent.

Preferably, the feed comprises the following raw materials in parts by weight: 12-15 parts of quartz, 15-18 parts of Zuoyun soil, 8-12 parts of fusion cake, 5-10 parts of modified nano silicon dioxide composite graphene oxide, 5-8 parts of boric acid, 5-8 parts of zirconium silicate, 3-5 parts of calcite, 3-5 parts of strontium titanate, 3-5 parts of barium carbonate, 1-2 parts of ammonium dihydrogen phosphate, 1-2 parts of zinc oxide and 1-2 parts of fluorine-containing auxiliary agent.

Preferably, the fluorine-containing auxiliary agent comprises hydroxyfluorosilicone oil and/or zinc hexafluorosilicate.

Preferably, the method further comprises the following steps: one or more of nitrite, nitrate, carbonate and sulfate can improve the freeze-thaw resistance of the glaze.

In another aspect of the present invention, a method for preparing a ceramic glaze with stable performance is provided, which comprises the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding the nano-silica, the silicon micropowder, the dispersing agent, the defoaming agent and the wetting agent into deionized water, and stirring and dispersing for a period of time to obtain nano-silica emulsion;

s12, preparing ethanol water solution of trimethylolpropane with the mass concentration of 10-20%, adding graphene oxide, a surfactant, a coupling agent and a modification treatment agent, and uniformly mixing to obtain mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, carrying out heating ultrasonic treatment or heating stirring treatment, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate and calcite according to the formula proportion, performing coarse grinding, sieving by a 100-200-mesh sieve, then performing fine grinding, and sieving by a 200-300-mesh sieve to obtain powder;

s3, slurry preparation: and mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate and zinc oxide, adding water for wet ball milling, and sieving the obtained slurry with a 300-500-mesh sieve with the residue of the sieve being 0.2-5 wt%.

Preferably, the dispersant in step S11 is one or more of dispower 929, EFKA SL 3034, Dow Corning 51;

preferably, the defoaming agent is one or more of Deform 6800, Efka SL 2038, SRE-CN and Dow Corning 65;

preferably, the wetting agent is one or more of alkyl sulfate, sulfonate and phosphate.

Preferably, in step S12, the surfactant is one or more of sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate and ammonium fatty alcohol polyoxyethylene ether sulfate;

preferably, the coupling agent is one or more of a dodecylsilane, aminopropyltriethoxysilane and titanate coupling agent;

preferably, the modifying treatment agent is one or more of hexamethyldisilazane, dimethyldichlorosilane, and dimethylsilicone.

Preferably, the conditions of the heating ultrasound in step S13 are: the heating temperature is 50-90 ℃, and the ultrasonic frequency is 50-100 kHz; the heating and stirring conditions are as follows: the heating temperature is 50-90 ℃, and the stirring speed is 1000-1500 r/min.

Preferably, the wet ball milling conditions in step S3 are the total raw materials: grinding balls: water in a weight ratio of 1: 0.8-1.5: ball milling for 8-15 h at 0.8-1.5;

preferably, the sieved glaze slurry in the step S3 has a content of particles with a size of 5-20 μm or less not less than 60%, and a content of particles with a size of 20-50 μm or less not less than 80%.

The invention can obtain the following beneficial effects:

1. the modified nano-silica composite graphene oxide and the fluorine-containing auxiliary agent in the invention have synergistic effect to enhance the hydrophobicity and weather resistance of the glaze, greatly improve the anti-pollution capability to inorganic substances such as water drops, dust and the like, and simultaneously improve the dispersion uniformity and functional stability of the ceramic glaze. The modified nano-silica composite graphene oxide, the Zuoyun soil, the zirconium silicate and the strontium titanate increase the hardness and the wear resistance of the glaze, the nano-silica and the silicon micro powder are modified and then are filled and grafted on the graphene oxide, the obtained material is high in surface activity and structural strength, and the hardness and the wear resistance of the glaze can be greatly improved. And the melting temperature of the strontium titanate and the silicon simple substance is very high, and the strontium titanate and the silicon simple substance are dispersed in the original ceramic matrix layer as dispersed phases to fill gaps in the ceramic matrix, so that the pollution resistance and the aging resistance of the ceramic product are improved. In addition, the modified nano silicon dioxide composite graphene oxide is matched with ammonium dihydrogen phosphate and zinc oxide, so that the antibacterial property is better, and the use quality of the glaze is improved.

2. According to the invention, the amount of aluminum oxide is increased by introducing the Zuoyun soil into the glaze, and the ultrahigh-hardness glaze vitreous body which is rich in fine crystals, low in pore content and compact in network structure is formed through high-temperature treatment, so that the anti-scratch capability is strong, the hardness of the glaze is high, and the glaze of a ceramic product can withstand invasion of metal and wind sand without scratches. The boric acid and the ammonium dihydrogen phosphate in the glaze of the invention are used as cosolvents to improve the fluidity of the glaze slurry, further improve the use quality of the glaze, and ensure that the use mode of the glaze is not limited and the glaze can be sprayed, showered and coated, and the like.

3. According to the invention, the raw materials in the insulator formula are mixed and ball-milled in batches, the raw materials are modified to obtain powder with smaller granularity, and other raw materials are added for ball milling and mixing, so that the uniform dispersion of the raw materials is facilitated, and the functional glaze slip is obtained. The preparation process is simple and can be applied to industrial production.

4. The glaze surface obtained by the method has the advantages of high quality, stable performance and long service life. The glaze layer has compact structure and can fill pores on the surface of the ceramic substrate, effectively prevent water adsorbed on the surface of the ceramic product from permeating inwards, greatly reduce the damage effect of water freezing volume expansion on the material and improve the stain-resistant cold-resistant performance of the ceramic product.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

a ceramic glaze with stable performance comprises the following raw materials in parts by weight: 18 parts of quartz, 10 parts of Zuoyun soil, 5 parts of frit, 3 parts of modified nano silicon dioxide composite graphene oxide, 3 parts of boric acid, 10 parts of zirconium silicate, 6 parts of calcite, 2 parts of strontium titanate, 2 parts of barium carbonate, 0.5 part of ammonium dihydrogen phosphate, 0.5 part of zinc oxide and 0.5 part of zinc hexafluorosilicate.

A preparation method of ceramic glaze with stable performance comprises the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding 1 part of nano silicon dioxide, 1 part of silicon powder, a dispersing agent Disponer 929, a defoaming agent Deform 6800 and a wetting agent sodium alkyl sulfate into deionized water, stirring and dispersing for 60min, and preparing nano silicon dioxide emulsion with the mass concentration of 2.25%;

s12, preparing an ethanol water solution of trimethylolpropane with the mass concentration of 10% (mass ratio ethanol: water is 4: 1), adding 25 parts of graphene oxide, a surfactant sodium dodecyl sulfate, a coupling agent dodecyl silane and a modification treatment agent hexamethyl-dinitrogen silane, and uniformly mixing to obtain a mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, heating and ultrasonically treating at 50 ℃, stirring at the speed of 1000r/min for 90min, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate and calcite according to the formula proportion, performing coarse grinding, sieving by a 100-mesh sieve, then performing fine grinding, and sieving by a 200-mesh sieve to obtain powder;

s3, slurry preparation: mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate and zinc oxide, adding water for wet ball milling, wherein the conditions of the wet ball milling are as follows: grinding balls: water in a weight ratio of 1: 0.8: 1.5 ball milling for 15 h; the obtained slurry is sieved by a 300-mesh sieve, the residue on the sieve is 4.5 wt%, the content of particles with the particle size of less than 5-20 mu m in the sieved glaze slurry is not less than 60%, and the content of particles with the particle size of less than 20-50 mu m in the sieved glaze slurry is not less than 80%.

Example 2:

a ceramic glaze with stable performance comprises the following raw materials in parts by weight: 18 parts of quartz, 10 parts of Zuoyun soil, 15 parts of clinker, 10 parts of modified nano silicon dioxide composite graphene oxide, 10 parts of boric acid, 3 parts of zirconium silicate, 2 parts of calcite, 2 parts of strontium titanate, 6 parts of barium carbonate, 3 parts of ammonium dihydrogen phosphate, 3 parts of zinc oxide, 3 parts of zinc hexafluorosilicate and 0.1 part of sodium nitrite.

A preparation method of ceramic glaze with stable performance comprises the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding 5 parts of nano silicon dioxide, 1 part of silicon powder, an EFKA SL 3034 dispersant, an Efka SL 2038 defoamer and sodium sulfonate wetting agent into deionized water, stirring and dispersing for 60min, and preparing nano silicon dioxide emulsion with the mass concentration of 2.5%;

s12, preparing an ethanol water solution of trimethylolpropane with the mass concentration of 20% (mass ratio ethanol: water is 4: 1), adding 30 parts of graphene oxide, ammonium dodecyl sulfate serving as a surfactant, aminopropyltriethoxysilane serving as a coupling agent and dimethyldichlorosilane serving as a modification treatment agent, and uniformly mixing to obtain a mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, heating and ultrasonically treating at 90 ℃, stirring at 1500r/min for 30min, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate, calcite and sodium nitrite according to the formula proportion, carrying out coarse grinding, sieving by a 200-mesh sieve, then carrying out fine grinding, and sieving by a 300-mesh sieve to obtain powder;

s3, slurry preparation: mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate, zinc oxide and zinc hexafluorosilicate, adding water for wet ball milling, wherein the conditions of the wet ball milling are as follows: grinding balls: water in a weight ratio of 1: 1.5: 0.8 ball milling 8; sieving the obtained slurry with a 500-mesh sieve to obtain 0.2 wt% of sieved residual, wherein the content of particles with the particle size of less than 5-20 mu m in the sieved glaze slurry is not less than 70%, and the content of particles with the particle size of less than 20-50 mu m in the sieved glaze slurry is not less than 80%.

Example 3:

a ceramic glaze with stable performance comprises the following raw materials in parts by weight: 12 parts of quartz, 17 parts of Zuoyun soil, 10 parts of fusion cake, 8 parts of modified nano silicon dioxide composite graphene oxide, 6 parts of boric acid, 5 parts of zirconium silicate, 4 parts of calcite, 4 parts of strontium titanate, 3 parts of barium carbonate, 1 part of ammonium dihydrogen phosphate, 2 parts of zinc oxide, 2 parts of hydroxy fluorosilicone oil, 0.5 part of sodium nitrite and 0.5 part of sodium nitrate.

A preparation method of ceramic glaze with stable performance comprises the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding 3 parts of nano silicon dioxide, 2 parts of silicon powder, a dispersing agent Dow Corning 51, a defoaming agent SRE-CN and a wetting agent alkyl sulfate into deionized water, stirring and dispersing for 60min, and preparing nano silicon dioxide emulsion with the mass concentration of 2.0%;

s12, preparing 15% trimethylolpropane ethanol water solution (mass ratio ethanol: water is 4: 1), adding 20 parts of graphene oxide, a surfactant sodium dodecyl sulfate, a coupling agent titanate coupling agent and a modification treatment agent dimethyl silicone, and uniformly mixing to obtain a mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, heating and ultrasonically treating for 30min at 75 ℃ and an ultrasonic frequency of 80kHz, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate, calcite, sodium nitrite and sodium nitrate according to the formula proportion, coarsely grinding, sieving by a 200-mesh sieve, finely grinding, and sieving by a 300-mesh sieve to obtain powder;

s3, slurry preparation: mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate, zinc oxide and hydroxyl fluorosilicone oil, adding water for wet ball milling, wherein the conditions of the wet ball milling are as follows: grinding balls: water in a weight ratio of 1: 1.2: 1, ball milling for 10 hours; sieving the obtained slurry with a 500-mesh sieve to obtain 0.5 wt% of sieved residual, wherein the content of particles with the particle size of less than 5-20 mu m in the sieved glaze slurry is not less than 70%, and the content of particles with the particle size of less than 20-50 mu m in the sieved glaze slurry is not less than 85%.

Example 4:

a ceramic glaze with stable performance comprises the following raw materials in parts by weight: 15 parts of quartz, 16 parts of Zuoyun soil, 12 parts of fusion cake, 6 parts of modified nano silicon dioxide composite graphene oxide, 5 parts of boric acid, 6 parts of zirconium silicate, 3 parts of calcite, 3 parts of strontium titanate, 5 parts of barium carbonate, 2 parts of ammonium dihydrogen phosphate, 1 part of zinc oxide, 1 part of hydroxy fluorosilicone oil, 1 part of sodium carbonate and 1 part of sodium sulfate.

A preparation method of ceramic glaze with stable performance comprises the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding 2 parts of nano silicon dioxide, 3 parts of silicon powder, a dispersing agent Disponer 929, EFKA SL 3034, a defoaming agent Dow Corning 65, a wetting agent alkyl sulfate and triethyl phosphate into deionized water, stirring and dispersing for 60min, and preparing nano silicon dioxide emulsion with the mass concentration of 2.25%;

s12, preparing 15% trimethylolpropane ethanol water solution (mass ratio ethanol: water is 4: 1), adding 15 parts of graphene oxide, surfactant lauryl sodium sulfate, fatty alcohol polyoxyethylene ether ammonium sulfate, coupling agent dodecylsilane, titanate coupling agent, modification treatment agent hexamethyl-dinitrogen silane and dimethyl silicone, and uniformly mixing to obtain a mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, heating and ultrasonically treating for 20min at the heating temperature of 80 ℃ and the ultrasonic frequency of 50kHz, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate, calcite, sodium carbonate and sodium sulfate according to the formula proportion, coarsely grinding, sieving by a 150-mesh sieve, finely grinding, and sieving by a 250-mesh sieve to obtain powder;

s3, slurry preparation: mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate, zinc oxide and hydroxyl fluorosilicone oil, adding water for wet ball milling, wherein the conditions of the wet ball milling are as follows: grinding balls: water in a weight ratio of 1: 1: 1, ball milling for 12 h; the obtained slurry is sieved by a 400-mesh sieve, the residue on the sieve is 1 wt%, the content of particles with the particle size of less than 5-20 mu m in the sieved glaze slurry is not less than 65%, and the content of particles with the particle size of less than 20-50 mu m in the sieved glaze slurry is not less than 80%.

Example 5:

a ceramic glaze with stable performance comprises the following raw materials in parts by weight: 12-15 parts of quartz, 15-18 parts of Zuoyun soil, 8-12 parts of fusion cake, 5-10 parts of modified nano silicon dioxide composite graphene oxide, 5-8 parts of boric acid, 5-8 parts of zirconium silicate, 3-5 parts of calcite, 3-5 parts of strontium titanate, 3-5 parts of barium carbonate, 1-2 parts of ammonium dihydrogen phosphate, 1-2 parts of zinc oxide, 1-2 parts of hydroxyl fluorosilicone oil and 0.1-1 part of sodium sulfate.

A preparation method of ceramic glaze with stable performance comprises the following steps:

s1, preparing the modified nano silicon dioxide composite graphene oxide:

s11, adding 2.5 parts of nano silicon dioxide, 2 parts of silicon powder, a dispersing agent Dow Corning 51, a defoaming agent Dow Corning 65 and a wetting agent sodium alkyl sulfate into deionized water, stirring and dispersing for 60min, and preparing nano silicon dioxide emulsion with the mass concentration of 2.0%;

s12, preparing 15% trimethylolpropane ethanol water solution (mass ratio ethanol: water is 4: 1), adding 25 parts of graphene oxide, surfactant fatty alcohol-polyoxyethylene ether sodium sulfate, coupling agent aminopropyl triethoxysilane and modification treatment agent dimethyldichlorosilane, and uniformly mixing to obtain a mixed solution;

s13, adding the nano silicon dioxide emulsion into the mixed solution, heating and ultrasonically treating for 45min at the temperature of 70 ℃ and the ultrasonic frequency of 90kHz, separating to obtain a solid product, and drying to obtain the nano silicon dioxide emulsion;

s2, crushing and sieving: adding quartz, levant soil, clinker, modified nano silicon dioxide composite graphene oxide, boric acid, zirconium silicate, calcite and sodium sulfate according to the formula proportion, performing coarse grinding, sieving by a 200-mesh sieve, then performing fine grinding, and sieving by a 300-mesh sieve to obtain powder;

s3, slurry preparation: mixing the obtained powder with strontium titanate, barium carbonate, ammonium dihydrogen phosphate, zinc oxide and hydroxyl fluorosilicone oil, adding water for wet ball milling, wherein the conditions of the wet ball milling are as follows: grinding balls: water in a weight ratio of 1: 0.8: 1.2 ball milling for 12 h; sieving the obtained slurry with a 500-mesh sieve to obtain 0.5 wt% of sieved residual, wherein the content of particles with the particle size of less than 5-20 mu m in the sieved glaze slurry is not less than 70%, and the content of particles with the particle size of less than 20-50 mu m in the sieved glaze slurry is not less than 85%.

Comparative example 1:

the modified nano silicon dioxide composite graphene oxide is not added, the proportion of the other raw materials is increased in an equal ratio, and the rest is the same as that of the embodiment 3.

Comparative example 2:

the modified nano silicon dioxide composite graphene oxide and the fluorine-containing auxiliary agent are not added, the proportion of the other raw materials is increased in an equal ratio, and the rest is the same as that in the embodiment 3.

Comparative example 3:

the modified nano silicon dioxide composite graphene oxide and the Zuoyun soil are not added, the proportion of the other raw materials is increased in an equal ratio, and the rest raw materials are the same as those in the embodiment 3.

Comparative example 4:

the modified nano-silica composite graphene oxide, the Zuoyun soil, the zirconium silicate and the strontium titanate are not added, the proportion of the other raw materials is increased in an equal ratio, and the rest raw materials are the same as those in the embodiment 3.

The examples 1 to 5 and comparative examples 1 to 4 were subjected to the moisture absorption expansion coefficient, abrasion resistance rating, and hardness rating tests.

Coating the prepared glaze on the same ceramic blank (the ceramic blank is a cuboid sample with the length, width and height of 6cm multiplied by 2cm multiplied by 1.5 cm), then carrying out firing treatment, controlling the firing temperature to be 1050 ℃, and carrying out performance detection on the prepared ceramic finished product by completely using the same processing treatment methods except different types of the glaze; the hygroscopical expansion rate is characterized in that a container filled with distilled water is heated and boiled, a corresponding ceramic finished product is put into boiling water (the ceramic finished product is kept not to be in contact with the wall of the container and the bottom of the container), the ceramic finished product is continuously boiled for 24 hours, then the ceramic finished product is taken out and naturally cooled to room temperature, the length of the ceramic finished product is measured, and the hygroscopical expansion rate is represented by the length change rate of the ceramic finished product before and after boiling; the abrasion resistance grade is tested according to GB/T4100-2006; the hardness scale was tested using a Mohs hardness tester.

TABLE 1

	Coefficient of hygroexpansion	Wear rating	Mohs hardness
				Example 1	0.022％	Grade 5	Grade 9
Example 2	0.020％	Grade 5	Grade 9
				Example 3	0.016％	Grade 5	Grade 9
Example 4	0.021％	Grade 5	Grade 9
				Example 5	0.019％	Grade 5	Grade 9
Comparative example 1	0.034％	4 stage	Stage 8
				Comparative example 2	0.058％	4 stage	Stage 8
Comparative example 3	0.042％	Grade 3	7-8 stages
				Comparative example 4	0.049％	Grade 3	7.5 grade

As can be seen from the data in Table 1, compared with comparative examples 1-4, the glaze material obtained in the embodiment of the invention has excellent hardness and wear resistance, is not easy to stain, has high quality, stable performance and long service life. The modified nano silicon dioxide composite graphene oxide, the Zuoyun soil, the zirconium silicate and the strontium titanate (compared with comparative examples 1, 3 and 4) can obviously enhance the hardness and the wear resistance of the ceramic glaze; the moisture absorption expansion rate of the embodiment of the invention is between 0.016 and 0.022 percent, which shows that the modified nano silicon dioxide composite graphene oxide and the fluorine-containing additive (compared with comparative examples 1 and 2) can obviously enhance the stain resistance of the ceramic glaze.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.