Ceramic glaze with high gloss and high whiteness and preparation method thereof

Abstract

The application relates to the technical field of ceramics, and discloses a high-gloss high-whiteness ceramic glaze and a preparation method thereof.The high-gloss high-whiteness ceramic glaze comprises, in terms of weight fractions, 35-40 parts of calcite, 38-45 parts of wollastonite, 0.6-1.4 parts of potassium feldspar, 0.3-0.8 parts of calcined kaolin, 0.6-1.3 parts of clay, 1.2-2.8 parts of calcined zinc oxide, 4-16 parts of high-dispersibility zirconium silicate powder and the like; the phytic acid-based polyethylene glycol contains hydroxyl groups and a large number of sodium phosphate groups, can improve the interaction between polyethylene glycol molecular chains and the surface of zirconium silicate powder, effectively realizes surface modification and modification of the zirconium silicate powder, is favorable for overcoming the agglomeration of the zirconium silicate, and can be uniformly dispersed in a ceramic glaze matrix, and the gloss and whiteness of the glaze surface of the glaze are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, specifically to a high-gloss, high-whiteness ceramic glaze and its preparation method. Background Technology

[0002] Glazes can protect ceramic bodies, improve durability, enhance whiteness and gloss, and provide decorative effects, thus improving aesthetics. Glazes have diverse compositions, and different components can play unique roles. Zirconium silicate, for example, can act as an opacifier, causing the glaze layer to milky whiten, covering the original color of the body, and forming a white glaze surface, which helps improve the whiteness and gloss of the ceramic body.

[0003] Improving the dispersibility of zirconium silicate in glazes can better leverage its role as an opacifier. Common dispersants for zirconium silicate include polyethylene glycol, sodium polyacrylate, and sodium hexametaphosphate. Patent CN120157345A discloses a method for preparing antibacterial glazes using zirconium silicate. Modified acrylic acid and polyethylene glycol are used as a composite dispersant for zirconium silicate, which can make the glaze denser and improve its self-cleaning properties. However, this patent does not improve the whiteness, gloss, or other properties of the glaze. Summary of the Invention

[0004] (I) Technical problem to be solved: In view of the shortcomings of the prior art, the present invention provides a ceramic glaze with high gloss and high whiteness and its preparation method, which solves the problem that the poor dispersibility of zirconium silicate in the glaze affects the whiteness and gloss of the glaze surface.

[0005] (II) To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a high-gloss, high-whiteness ceramic glaze and its preparation method: (1) Add an aqueous solution of polyethylene glycol diglycidyl ether and phytic acid to water, stir to react, add sodium hydroxide aqueous solution dropwise, heat to evaporate until precipitate is formed, cool in an ice-water bath, filter, and dry to obtain phytic acid-based polyethylene glycol. The reaction formula is as follows: .

[0006] (2) Add zirconium silicate, phytic acid-based polyethylene glycol and water into a ball mill jar, ball mill, filter, wash with water and dry to obtain highly dispersible zirconium silicate powder.

[0007] (3) Add water, calcite, wollastonite, potassium feldspar, calcined kaolin, quartz powder, frit, clay, calcined talc powder, calcined zinc oxide, and highly dispersible zirconium silicate powder to the ball mill jar, ball mill, sieve, spray the glaze onto the ceramic substrate, dry it, place it in a tunnel kiln for firing, cool it, and obtain a high-gloss, high-whiteness ceramic glaze.

[0008] Furthermore, by weight, (1) contains 100 parts of polyethylene glycol diglycidyl ether and 132-145 parts of phytic acid.

[0009] Furthermore, in (1), the temperature during the stirring reaction is 65-80℃ and the reaction time is 2-5h.

[0010] Furthermore, in (1), sodium hydroxide aqueous solution is added dropwise to adjust the pH to 7-8.

[0011] Furthermore, by weight, (2) contains 100 parts of zirconium silicate and 0.8-4 parts of phytic acid-based polyethylene glycol.

[0012] Furthermore, in (2), the ball milling speed is 150-300 r / min and the ball milling time is 0.5-3 h.

[0013] Furthermore, by weight, (3) the amount of Chinese calcite is 35-40 parts, wollastonite is 38-45 parts, potassium feldspar is 0.6-1.4 parts, calcined kaolin is 0.3-0.8 parts, quartz powder is 0.1-0.7 parts, frit is 0.2-0.6 parts, clay is 0.6-1.3 parts, calcined talc is 0.5-1.4 parts, calcined zinc oxide is 1.2-2.8 parts, and highly dispersible zirconium silicate powder is 4-16 parts.

[0014] Furthermore, in the preparation method of medium-high gloss and high whiteness ceramic glaze (3), the ball milling speed is 60-100 r / min and the ball milling time is 10-18 h.

[0015] Furthermore, during firing (3), the temperature is increased to 1180-1250℃ at a rate of 2-4℃ / min, and held for 30-40min.

[0016] (III) The beneficial technical effects of adopting the above technical solution are as follows: Phytic acid-based polyethylene glycol (PEG) reacts with the double-terminal epoxy groups of polyethylene glycol diglycidyl ether to obtain phytic acid-based PEG. This PEG is then used as a dispersant for ball milling modification of zirconium silicate. Finally, it is mixed with calcite, wollastonite, zinc oxide, etc., sprayed with glaze, and fired to obtain a high-gloss, high-whiteness ceramic glaze. Phytic acid-based PEG contains hydroxyl groups and a large number of sodium phosphate groups, which can enhance the interaction between the PEG molecular chains and the surface of zirconium silicate powder. This effectively modifies and modifies the surface of zirconium silicate powder, helps overcome zirconium silicate agglomeration, and ensures uniform dispersion in the ceramic glaze matrix, thus acting as a better opacifier and significantly improving the gloss and whiteness of the glaze surface. It can be applied to ceramic sanitary ware products, etc. Detailed Implementation

[0017] The technical solution of the present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following embodiments.

[0018] Example 1: (1) Add 2g of polyethylene glycol diglycidyl ether (molecular weight about 1000, the same below) and 5mL of aqueous solution containing 2.72g of phytic acid to 20mL of water, heat to 65℃, stir for 5h, add sodium hydroxide aqueous solution to adjust pH to 7, heat to evaporate until precipitate is formed, cool in ice water bath, filter, dry to obtain phytic acid-based polyethylene glycol.

[0019] (2) Add 100g zirconium silicate, 0.8g phytic acid-based polyethylene glycol and 150mL water to a ball mill jar, mill at 200r / min for 0.5h, filter, wash with water, and dry to obtain highly dispersible zirconium silicate powder.

[0020] (3) Add 600mL of water, 380g of calcite, 440g of wollastonite, 9g of potassium feldspar, 3g of calcined kaolin, 4g of quartz powder, 6g of frit, 12g of clay, 5g of calcined talc, 26g of calcined zinc oxide, and 120g of highly dispersible zirconium silicate powder to a ball mill jar. The ball mill is run at 80r / min for 10h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the glaze is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The temperature is then maintained for 40min and cooled to obtain a ceramic glaze with high gloss and high whiteness.

[0021] Comparative Example 1: (1) 100g of zirconium silicate and 150mL of water were added to a ball mill jar, the speed was 200r / min, the ball mill was 0.5h, filtered and dried to obtain zirconium silicate powder.

[0022] (2) Add 600mL of water, 380g of calcite, 440g of wollastonite, 9g of potassium feldspar, 3g of calcined kaolin, 4g of quartz powder, 6g of frit, 12g of clay, 5g of calcined talc, 26g of calcined zinc oxide, and 120g of zirconium silicate to a ball mill jar. The ball mill is run at 80r / min for 10h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the substrate is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The substrate is then held at this temperature for 40min and cooled to obtain the ceramic glaze.

[0023] Comparative Example 2: (1) 100g zirconium silicate, 0.8g polyethylene glycol 1000 and 150mL water were added to a ball mill jar, the speed was 200r / min, the ball mill was 0.5h, filtered and washed with water, and dried to obtain zirconium silicate powder.

[0024] (2) Add 600mL of water, 380g of calcite, 440g of wollastonite, 9g of potassium feldspar, 3g of calcined kaolin, 4g of quartz powder, 6g of frit, 12g of clay, 5g of calcined talc, 26g of calcined zinc oxide, and 120g of zirconium silicate powder to a ball mill jar. The ball mill is run at 80r / min for 10h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the substrate is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The substrate is then held at this temperature for 40min and cooled to obtain the ceramic glaze.

[0025] Comparative Example 3: (1) 100g zirconium silicate, 1.12g sodium phytate and 150mL water were added to a ball mill jar, the speed was 200r / min, the ball mill was 0.5h, filtered, washed with water and dried to obtain zirconium silicate powder.

[0026] (2) Add 600mL of water, 380g of calcite, 440g of wollastonite, 9g of potassium feldspar, 3g of calcined kaolin, 4g of quartz powder, 6g of frit, 12g of clay, 5g of calcined talc, 26g of calcined zinc oxide, and 120g of zirconium silicate powder to a ball mill jar. The ball mill is run at 80r / min for 10h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the substrate is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The substrate is then held at this temperature for 40min and cooled to obtain the ceramic glaze.

[0027] Comparative Example 4: (1) 2g of polyethylene glycol 1000 and 5mL of aqueous solution containing 2.72g of phytic acid were stirred and mixed. Sodium hydroxide aqueous solution was added dropwise to adjust the pH to 7. The mixture was dried to remove water and obtained sodium phytate-polyethylene glycol mixture.

[0028] (2) Add 100g zirconium silicate, 0.8g sodium phytate-polyethylene glycol mixture and 150mL water into a ball mill jar, mill at 200r / min for 0.5h, filter, wash with water, and dry to obtain zirconium silicate powder.

[0029] (3) Add 600mL of water, 380g of calcite, 440g of wollastonite, 9g of potassium feldspar, 3g of calcined kaolin, 4g of quartz powder, 6g of frit, 12g of clay, 5g of calcined talc, 26g of calcined zinc oxide, and 120g of zirconium silicate powder to a ball mill jar. The ball mill is run at 80r / min for 10h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the substrate is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The substrate is then held at this temperature for 40min and cooled to obtain a ceramic glaze with high gloss and high whiteness.

[0030] Comparative Example 5: (1) 100g zirconium silicate, 0.8g sodium hexametaphosphate and 150mL water were added to a ball mill jar, the speed was 200r / min, the ball mill was 0.5h, filtered and washed with water, and dried to obtain zirconium silicate powder.

[0031] (2) Add 600mL of water, 380g of calcite, 440g of wollastonite, 9g of potassium feldspar, 3g of calcined kaolin, 4g of quartz powder, 6g of frit, 12g of clay, 5g of calcined talc, 26g of calcined zinc oxide, and 120g of zirconium silicate powder to a ball mill jar. The ball mill is run at 80r / min for 10h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the substrate is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The substrate is then held at this temperature for 40min and cooled to obtain the ceramic glaze.

[0032] Example 2: (1) Add 2g of polyethylene glycol diglycidyl ether and 6mL of aqueous solution containing 2.9g of phytic acid to 30mL of water, heat to 75°C, stir for 2h, add sodium hydroxide aqueous solution to adjust pH to 8, heat to evaporate until precipitate is formed, cool in ice water bath, filter, dry to obtain phytic acid-based polyethylene glycol.

[0033] (2) Add 100g zirconium silicate, 1.5g phytic acid-based polyethylene glycol and 150mL water to a ball mill jar, mill at 300r / min for 0.5h, filter, wash with water, and dry to obtain highly dispersible zirconium silicate powder.

[0034] (3) Add 650mL of water, 350g of calcite, 450g of wollastonite, 6g of potassium feldspar, 6g of calcined kaolin, 1g of quartz powder, 6g of frit, 8g of clay, 12g of calcined talc, 17g of calcined zinc oxide, and 40g of highly dispersible zirconium silicate powder to a ball mill jar. The ball mill is run at 60r / min for 18h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the glaze is placed in a tunnel kiln and heated to 1250℃ at a heating rate of 4℃ / min. The temperature is then maintained for 40min and the glaze is cooled to obtain a ceramic glaze with high gloss and high whiteness.

[0035] Example 3: (1) Add 2g of polyethylene glycol diglycidyl ether and 5mL of aqueous solution containing 2.64g of phytic acid to 20mL of water, heat to 80℃, stir for 2h, add sodium hydroxide aqueous solution to adjust pH to 7, heat to evaporate until precipitate is formed, cool in ice water bath, filter, dry to obtain phytic acid-based polyethylene glycol.

[0036] (2) Add 100g zirconium silicate, 3g phytic acid-based polyethylene glycol and 150mL water to a ball mill jar, mill at 200r / min for 2h, filter, wash with water and dry to obtain highly dispersed zirconium silicate powder.

[0037] (3) Add 700mL of water, 360g of calcite, 410g of wollastonite, 14g of potassium feldspar, 4g of calcined kaolin, 7g of quartz powder, 2g of frit, 6g of clay, 14g of calcined talc, 12g of calcined zinc oxide, and 160g of highly dispersible zirconium silicate powder to a ball mill jar. The ball mill is run at 100r / min for 12h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the glaze is placed in a tunnel kiln and heated to 1180℃ at a heating rate of 2℃ / min. The temperature is then maintained for 40min and cooled to obtain a ceramic glaze with high gloss and high whiteness.

[0038] Example 4: (1) Add 2g of polyethylene glycol diglycidyl ether and 6mL of aqueous solution containing 2.9g of phytic acid to 30mL of water, heat to 70℃, stir for 3h, add sodium hydroxide aqueous solution to adjust pH to 7, heat to evaporate until precipitate is formed, cool in ice water bath, filter, dry to obtain phytic acid-based polyethylene glycol.

[0039] (2) Add 100g zirconium silicate, 4g phytic acid-based polyethylene glycol and 150mL water to a ball mill jar, mill at 150r / min for 3h, filter, wash with water and dry to obtain highly dispersible zirconium silicate powder.

[0040] (3) Add 580mL of water, 400g of calcite, 380g of wollastonite, 11g of potassium feldspar, 8g of calcined kaolin, 5g of quartz powder, 3g of frit, 13g of clay, 7g of calcined talc, 28g of calcined zinc oxide, and 80g of highly dispersible zirconium silicate powder to a ball mill jar. The ball mill is run at 60r / min for 18h. The mixture is then sieved through a 200-mesh sieve. The glaze is sprayed onto the ceramic substrate. After drying, the substrate is placed in a tunnel kiln and heated to 1200℃ at a heating rate of 2℃ / min. The substrate is then held at this temperature for 30min and cooled to obtain a ceramic glaze with high gloss and high whiteness.

[0041] The gloss of ceramic glazes shall be tested according to GB / T 11420-2024, and the whiteness shall be tested according to QB / T 1503-2011.

[0042] Table 1 Performance Tests Compared with Comparative Example 1, Example 1 uses phytic acid-based polyethylene glycol as a dispersant, which contains hydroxyl groups and a large number of sodium phosphate groups. This can improve the interaction between the polyethylene glycol molecular chains and the surface of zirconium silicate powder, effectively achieving surface modification and alteration of zirconium silicate powder. This helps to overcome the agglomeration of zirconium silicate and disperse it uniformly in the ceramic glaze matrix, significantly improving the gloss and whiteness of the glaze.

[0043] Comparative Example 2 used conventional polyethylene glycol as a dispersant, Comparative Example 3 used sodium phytate as a dispersant, Comparative Example 4 used a mixture of sodium phytate and polyethylene glycol as a dispersant, and Comparative Example 5 used sodium hexametaphosphate as a dispersant. The dispersion modification effect on zirconium silicate was not good, and the gloss and whiteness of the glazes of the four examples were low.

[0044] Finally, it should be noted that the above embodiments are merely illustrative of several implementations of the present invention and are not intended to limit the scope of the invention. For those skilled in the art, any modifications, equivalent substitutions, or improvements made without departing from the concept of the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A high-gloss, high-whiteness ceramic glaze, characterized in that, The raw materials of the ceramic glaze, by weight, are: 35-40 parts calcite, 38-45 parts wollastonite, 0.6-1.4 parts potassium feldspar, 0.3-0.8 parts calcined kaolin, 0.1-0.7 parts quartz powder, 0.2-0.6 parts frit, 0.6-1.3 parts clay, 0.5-1.4 parts calcined talc, 1.2-2.8 parts calcined zinc oxide, and 4-16 parts highly dispersed zirconium silicate powder; The highly dispersed zirconium silicate powder is prepared by the following method: zirconium silicate, phytic acid-based polyethylene glycol, and water are added to a ball mill jar, ball milled, filtered, washed, and dried to obtain highly dispersed zirconium silicate powder; The amount of zirconium silicate is 100 parts by weight, and the amount of phytic acid-based polyethylene glycol is 0.8-4 parts. The preparation method of the phytic acid-based polyethylene glycol is as follows: add polyethylene glycol diglycidyl ether and an aqueous solution of phytic acid to water, stir and react, add sodium hydroxide aqueous solution dropwise, heat and evaporate, cool in an ice-water bath, filter, and dry to obtain phytic acid-based polyethylene glycol; the pH is adjusted to 7-8 by adding sodium hydroxide aqueous solution dropwise.

2. The high-gloss, high-whiteness ceramic glaze according to claim 1, characterized in that, The ball milling speed is 150-300 r / min, and the ball milling time is 0.5-3 h.

3. The high-gloss, high-whiteness ceramic glaze according to claim 1, characterized in that, The amount of polyethylene glycol diglycidyl ether is 100 parts by weight, and the amount of phytic acid is 132-145 parts.

4. The high-gloss, high-whiteness ceramic glaze according to claim 1, characterized in that, The stirring reaction is carried out at a temperature of 65-80℃ for 2-5 hours.

5. A method for preparing a high-gloss, high-whiteness ceramic glaze as described in any one of claims 1-4, characterized in that, The preparation method is as follows: water, calcite, wollastonite, potassium feldspar, calcined kaolin, quartz powder, frit, clay, calcined talc powder, calcined zinc oxide, and highly dispersible zirconium silicate powder are added to a ball mill jar, ball milled, sieved, the glaze is sprayed onto the ceramic substrate, dried, and then fired in a tunnel kiln and cooled to obtain a high-gloss, high-whiteness ceramic glaze.

6. The method for preparing a high-gloss, high-whiteness ceramic glaze according to claim 5, characterized in that, In the preparation method of the high-gloss and high-whiteness ceramic glaze, the ball milling speed is 60-100 r / min and the ball milling time is 10-18 h.

7. The method for preparing a high-gloss, high-whiteness ceramic glaze according to claim 6, characterized in that, The firing process involves heating at a rate of 2-4℃ / min to 1180-1250℃ and holding at that temperature for 30-40 minutes.

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