High-strength wear-resistant ceramic glaze and preparation method thereof

Abstract

The invention relates to the technical field of ceramic glazes, and discloses a high-strength wear-resistant ceramic glaze and a preparation method thereof, 3-chloro-2-chloromethyl propylene and diethyl iminodiacetate are subjected to nucleophilic substitution, the obtained product is hydrolyzed under an acidic condition, and 2-(N, N '-dimethylene carboxyl) aminomethyl-allyl diacetic acid is obtained. And carrying out addition reaction on the poly (ethylene glycol) methacrylate and sodium vinyl sulfonate to obtain the dispersing agent. The preparation method comprises the following steps: adding a dispersing agent into a preparation process of a zirconium silicate precursor, drying to obtain dispersing agent modified zirconium silicate superfine powder, mixing with potassium feldspar, albite, high-purity quartz, calcined kaolin, aluminum oxide, calcium carbonate and zinc oxide, carrying out ball milling, and sieving to remove iron, so as to prepare the high-strength wear-resistant ceramic glaze, so that the wear resistance, high strength and corrosion resistance of the ceramic glaze are improved, and the service life of the ceramic glaze is prolonged. Therefore, the wear resistance, high strength and corrosion resistance of the ceramic product are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic glaze, in particular to a high-strength and wear-resistant ceramic glaze and a preparation method thereof. BACKGROUND

[0002] Ceramic materials have the characteristics of acid and alkali corrosion resistance, high thermal stability, environmental protection and beauty, and are excellent materials indispensable in various fields. However, in the application process in daily use, building and other aspects, due to the insufficient strength and wear resistance of the glaze surface, it is easy to crack or produce scratches, which shortens the service life of the ceramic product. Although the existing technology adds modified components to the ceramic glaze to make the ceramic have certain mechanical properties, wear resistance and other properties, the hardness and wear resistance of the ceramic glaze surface still need to be further improved. Zirconium silicate has the effect of improving the hardness and whitening of the ceramic glaze, and the wear resistance, hydrolysis resistance and chemical corrosion resistance of ultra-fine zirconium silicate are higher, but the surface energy is high and the characteristics of easy agglomeration will affect its performance.

[0003] Surface modification can improve the dispersibility and stability of zirconium silicate. For example, patent CN104609868B “A dispersing agent for wet grinding of zirconium silicate-based composite ceramic raw materials and a preparation method thereof” discloses a dispersing agent for wet grinding of zirconium silicate prepared from water-soluble allyl polymer, sodium hexametaphosphate, sodium pyrophosphate and the like. The dispersing agent has strong dispersing effect, can effectively reduce the viscosity of zirconium silicate-based composite ceramic slurry and improve its rheological property. However, the phosphorus-containing compound can cause secondary pollution to the environment, and the adsorption of the allyl polymer dispersing agent on the particle surface and the wetting ability are still poor, resulting in low efficiency of wet ultra-fine grinding particles. Therefore, the dispersibility and stability of zirconium silicate ultra-fine powder can be improved by using hydrogen bond effect, electrostatic effect and steric hindrance effect. SUMMARY

[0004] (1) Technical problems solved

[0005] In view of the deficiencies of the prior art, the present application provides a high-strength and wear-resistant ceramic glaze and a preparation method thereof.

[0006] (2) Technical solutions

[0007] A high-strength and wear-resistant ceramic glaze, the high-strength and wear-resistant ceramic glaze comprises 30-40 parts by weight of potassium feldspar, 20-30 parts by weight of sodium feldspar, 5-15 parts by weight of high-purity quartz, 2-10 parts by weight of calcined kaolin, 3-8 parts by weight of alumina, 3-8 parts by weight of dispersant modified zirconium silicate ultra-fine powder, 10-16 parts by weight of calcium carbonate and 1-4 parts by weight of zinc oxide.

[0008] Preferably, the preparation method of the high-strength wear-resistant ceramic glaze comprises the following steps: mixing potash feldspar, soda feldspar, high-purity quartz, calcined kaolin, alumina, dispersant modified zirconium silicate superfine powder, calcium carbonate and zinc oxide, ball milling, screening and removing iron to obtain the high-strength wear-resistant ceramic glaze.

[0009] Preferably, the preparation method of the dispersant modified zirconium silicate superfine powder comprises the following steps:

[0010] (1) 3-chloro-2-chloromethyl acrylate and triethylamine are dissolved in tetrahydrofuran, and diethyl imino diacetate is added dropwise under the condition of nitrogen atmosphere and-15℃ to-5℃, then the reaction is stirred at 18-25℃ for 12-36h, after the reaction is completed, the filter residue is discarded by suction filtration and rotary evaporation, then the obtained product is dissolved in dichloromethane, impurities are extracted with deionized water for 2-3 times, the water phase is discarded and the organic phase is dried with anhydrous calcium chloride, then the mixture is obtained by filtering after 6-14h, then dilute hydrochloric acid is added, the reaction is stirred at 18-25℃ for 12-36h, after the reaction is completed, the pH of the product is adjusted to 4.4-5.6 with sodium hydroxide, then rotary evaporation and filtration are performed to remove the filter residue, and 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid is obtained.

[0011] (2) Poly(ethylene glycol) methacrylate is dissolved in deionized water, and 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid aqueous solution, sodium vinyl sulfonate aqueous solution and ammonium persulfate aqueous solution are added dropwise under the condition of nitrogen atmosphere and 70-90℃, and the reaction is carried out for 10-20h to obtain a dispersant.

[0012] (3) Ethyl orthosilicate and lithium fluoride are stirred uniformly, then anhydrous zirconium tetrachloride is added, then the temperature is increased to 60-70℃ and the stirring is continued, then the dispersant is added after the stirring is uniform, the oil bath is heated to 105-115℃ to reflux for 12-36h, the product is dried, and then the temperature is kept at 650-750℃ for 20-40min to obtain dispersant modified zirconium silicate superfine powder.

[0013] Preferably, the mass ratio of 3-chloro-2-chloromethyl acrylate, triethylamine and diethyl imino diacetate in (1) is 1.5-2.5:3.5-4.5:7-8.

[0014] Preferably, the mass fraction of dilute hydrochloric acid in (1) is 5%-12%, and the mass fraction of sodium hydroxide is 2%-7%.

[0015] Preferably, the mass ratio of poly(ethylene glycol) methacrylate, 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid, sodium vinyl sulfonate and ammonium persulfate in (2) is 4-5:15-25:16-28:1-2.

[0016] Preferably, the mass ratio of tetraethyl orthosilicate, lithium fluoride, anhydrous zirconium tetrachloride and dispersant in (3) is 17-24:0.3-1.2:16-24:0.8-1.5.

[0017] (III) Beneficial technical effects

[0018] 3-chloro-2-chloromethyl acrylate and diethyl iminodiacetate undergo nucleophilic substitution reaction under the action of basic catalyst triethylamine to obtain a tetraacetate structure containing a double bond, and then the ester group is hydrolyzed under acidic conditions to obtain 2-(N,N'-dimethylene carboxyl) aminomethyl-propyl diacetic acid. The compound undergoes addition reaction with poly(ethylene glycol) methacrylate and sodium vinyl sulfonate under the action of ammonium persulfate initiator to obtain a dispersant.

[0019] The dispersant is added to the preparation process of zirconium silicate precursor, and after drying, a dispersant modified zirconium silicate ultrafine powder is obtained. The carboxyl and sulfonic acid groups in the dispersant have a strong ability to reduce the interfacial tension and adsorb on the surface of the particles, which increases the effective radius of the particles, thereby enhancing the repulsive force between the particles. The hydroxyl groups in the dispersant can form hydrogen bonds with the surface of the particles, which also have a strong adsorption ability. The dispersant is an organic polymer, which is adsorbed on the surface of zirconium silicate due to electrostatic interaction and hydrogen bonding, and the main chain forms a spatial network structure, forming effective steric hindrance. Therefore, under the dual effects of steric stabilization mechanism and electrostatic stabilization mechanism, the zirconium silicate ultrafine powder can be effectively dispersed.

[0020] Since zirconium silicate itself has the property of enhancing wear resistance, and ultrafine zirconium silicate has higher wear resistance, hydrolysis resistance and chemical corrosion resistance, the dispersant modified zirconium silicate ultrafine powder is mixed with potassium feldspar, sodium feldspar, high-purity quartz, calcined kaolin, alumina, calcium carbonate and zinc oxide, ball milled, screened and iron removed, so that high-strength wear-resistant ceramic glaze can be prepared, which improves the wear resistance, high strength and corrosion resistance of the ceramic glaze, thereby improving the wear resistance, high strength and corrosion resistance of the ceramic products, and has excellent application prospect in the field of ceramics. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a synthesis route of the dispersant.

[0022] Figure 2 is a viscosity test diagram of the zirconium silicate ultrafine powder. DETAILED DESCRIPTION

[0023] Example 1

[0024] (1) 5.9 g of 3-chloro-2-chloromethyl acrylate and 12.2 g of triethylamine were dissolved in tetrahydrofuran, 22.7 g of diethyl iminodiacetate was added dropwise under a nitrogen atmosphere at -10°C, and then the reaction was stirred at 20°C for 24 hours. After the reaction was completed, the filtrate was obtained by suction filtration, and then the filtrate was distilled under reduced pressure. The obtained product was dissolved in dichloromethane, and then the product was extracted with deionized water twice. The water phase was discarded, and then the organic phase was dried with anhydrous calcium chloride. After 10 hours, the mixture was filtered, and then 7 wt.% dilute hydrochloric acid was added. The reaction was stirred at 20°C for 24 hours. After the reaction was completed, the pH of the product was adjusted to 5 with 5 wt.% sodium hydroxide. The product was distilled under reduced pressure, and then the filtrate was filtered to obtain 2-(N,N'-dimethylene carboxyl) aminomethyl-acrylic diacetic acid.

[0025] (2) 2 g of poly(ethylene glycol) methacrylate was dissolved in deionized water, and then 7.5 g of 2-(N,N'-dimethylene carboxyl) aminomethyl-acrylic diacetic acid aqueous solution, 8 g of sodium vinyl sulfonate aqueous solution, and 0.5 g of ammonium persulfate aqueous solution were added dropwise under a nitrogen atmosphere at 70°C. The reaction was performed for 10 hours to obtain a dispersant.

[0026] (3) 10 g of tetraethyl orthosilicate and 0.35 g of lithium fluoride were stirred to be uniform, and then 10 g of anhydrous zirconium tetrachloride was added. The mixture was heated to 65°C, and then the stirring was continued. After the mixture was stirred to be uniform, 0.65 g of the dispersant was added. The oil bath was heated to 110°C to reflux for 24 hours. The product was dried, and then the dried product was maintained at 700°C for 30 minutes to obtain a dispersant-modified zirconium silicate ultrafine powder.

[0027] (4) 45 g of potassium feldspar, 30 g of sodium feldspar, 7.5 g of high-purity quartz, 3 g of calcined kaolin, 4.5 g of alumina, 4.5 g of the dispersant-modified zirconium silicate ultrafine powder, 15 g of calcium carbonate, and 1.5 g of zinc oxide were mixed and ball-milled. The mixture was sieved to remove iron to obtain a high-strength and wear-resistant ceramic glaze.

[0028] Example 2

[0029] (1) 7.5 g of 3-chloro-2-chloromethyl acrylate and 13.5 g of triethylamine were dissolved in tetrahydrofuran, 24 g of diethyl iminodiacetate was added dropwise under a nitrogen atmosphere at -5°C, and then the reaction was stirred at 25°C for 36 hours. After the reaction was completed, the filtrate was obtained by suction filtration, and then the filtrate was distilled under reduced pressure. The obtained product was dissolved in dichloromethane, and then the product was extracted with deionized water three times. The water phase was discarded, and then the organic phase was dried with anhydrous calcium chloride. After 14 hours, the mixture was filtered, and then 12 wt.% dilute hydrochloric acid was added. The reaction was stirred at 25°C for 36 hours. After the reaction was completed, the pH of the product was adjusted to 5.6 with 7 wt.% sodium hydroxide. The product was distilled under reduced pressure, and then the filtrate was filtered to obtain 2-(N,N'-dimethylene carboxyl) aminomethyl-acrylic diacetic acid.

[0030] (2) Dissolve 2.5 g of poly(ethylene glycol) methacrylate in deionized water, and under a nitrogen atmosphere, 90°C, simultaneously add 12.5 g of 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid aqueous solution, 14 g of sodium vinyl sulfonate aqueous solution and 1 g of ammonium persulfate aqueous solution dropwise, and react for 20 h to obtain a dispersant.

[0031] (3) Stir 8.5 g of tetraethyl orthosilicate and 0.6 g of lithium fluoride uniformly, then add 8 g of anhydrous zirconium tetrachloride, and continue to stir while heating to 70°C. After stirring uniformly, add 0.4 g of dispersant, and heat to 115°C in an oil bath to reflux for 12 h. After drying the product, heat to 750°C for 20 min to obtain dispersant modified zirconium silicate ultrafine powder.

[0032] (4) Mix 60 g of potassium feldspar, 45 g of sodium feldspar, 22.5 g of high-purity quartz, 15 g of calcined kaolin, 12 g of alumina, 12 g of dispersant modified zirconium silicate ultrafine powder, 24 g of calcium carbonate, and 6 g of zinc oxide after ball milling, and sieve to remove iron to obtain high-strength wear-resistant ceramic glaze.

[0033] Example 3

[0034] (1) Dissolve 4.5 g of 3-chloro-2-chloromethyl acrylate and 10.5 g of triethylamine in tetrahydrofuran, and under a nitrogen atmosphere, -15°C, add 21 g of diethyl iminodiacetate dropwise, then stir at 18°C for 12 h. After the reaction is complete, filter and discard the residue, and then rotary evaporate. Dissolve the obtained product in dichloromethane, extract the impurities with deionized water twice, discard the water phase, and dry the organic phase with anhydrous calcium chloride. After 6 h, filter the mixture, then add 5 wt.% dilute hydrochloric acid, and stir at 18°C for 12 h. After the reaction is complete, adjust the pH of the product to 4.4 with 2 wt.% sodium hydroxide, and then rotary evaporate and filter to remove the residue to obtain 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid.

[0035] (2) Dissolve 2.3 g of poly(ethylene glycol) methacrylate in deionized water, and under a nitrogen atmosphere, 80°C, simultaneously add 10 g of 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid aqueous solution, 11 g of sodium vinyl sulfonate aqueous solution and 0.75 g of ammonium persulfate aqueous solution dropwise, and react for 15 h to obtain a dispersant.

[0036] (3) Stir 8.5 g of tetraethyl orthosilicate and 0.15 g of lithium fluoride uniformly, then add 8 g of anhydrous zirconium tetrachloride, and continue to stir while heating to 60°C. After stirring uniformly, add 0.4 g of dispersant, and heat to 105°C in an oil bath to reflux for 12 h. After drying the product, heat to 650°C for 20 min to obtain dispersant modified zirconium silicate ultrafine powder.

[0037] (4) 52 g of potassium feldspar, 38 g of sodium feldspar, 16 g of high-purity quartz, 9 g of calcined kaolin, 6.5 g of alumina, 9 g of dispersant modified zirconium silicate superfine powder, 20 g of calcium carbonate, and 4.5 g of zinc oxide are mixed and ball milled, and then sieved to remove iron to obtain a high-strength wear-resistant ceramic glaze.

[0038] Example 4

[0039] (1) 7.5 g of 3-chloro-2-chloromethyl acrylate and 10.5 g of triethylamine are dissolved in tetrahydrofuran, 21 g of diethyl iminodiacetate is added dropwise under a nitrogen atmosphere at -5°C, and then the reaction is stirred at 25°C for 12 h. After the reaction is completed, the filtrate is removed by suction filtration, and then rotary evaporation is performed. The obtained product is dissolved in dichloromethane, and impurities are extracted with deionized water three times. The water phase is discarded, and the organic phase is dried with anhydrous calcium chloride. After 6 h, the mixture is filtered, 12 wt.% dilute hydrochloric acid is added, and the reaction is stirred at 18°C for 36 h. After the reaction is completed, the pH of the product is adjusted to 5.6 with 2 wt.% sodium hydroxide. Rotary evaporation is performed again, and the filtrate is removed by filtration to obtain 2-(N,N'-dimethylene carboxyl) aminomethyl-propyl diacetic acid.

[0040] (2) 2 g of poly(ethylene glycol) methacrylate is dissolved in deionized water, and 7.5 g of 2-(N,N'-dimethylene carboxyl) aminomethyl-propyl diacetic acid aqueous solution, 14 g of sodium vinyl sulfonate aqueous solution, and 0.5 g of ammonium persulfate aqueous solution are added dropwise simultaneously under a nitrogen atmosphere at 90°C, and the reaction is performed for 20 h to obtain a dispersant.

[0041] (3) 12 g of tetraethyl orthosilicate and 0.6 g of lithium fluoride are stirred uniformly, and then 12 g of anhydrous zirconium tetrachloride is added. The temperature is increased to 70°C, and the stirring is continued. After the stirring is uniform, 0.75 g of the dispersant is added, and the oil bath is heated to 115°C to reflux for 36 h. The product is dried, and then heat treatment is performed at 750°C for 40 min to obtain dispersant modified zirconium silicate superfine powder.

[0042] (4) 60 g of potassium feldspar, 30 g of sodium feldspar, 22.5 g of high-purity quartz, 3 g of calcined kaolin, 12 g of alumina, 4.5 g of dispersant modified zirconium silicate superfine powder, 24 g of calcium carbonate, and 1.5 g of zinc oxide are mixed and ball milled, and then sieved to remove iron to obtain a high-strength wear-resistant ceramic glaze.

[0043] Comparative Example 1

[0044] 52 g of potassium feldspar, 38 g of sodium feldspar, 16 g of high-purity quartz, 9 g of calcined kaolin, 6.5 g of alumina, 9 g of zirconium silicate superfine powder, 20 g of calcium carbonate, and 4.5 g of zinc oxide are mixed and ball milled, and then sieved to remove iron to obtain a high-strength wear-resistant ceramic glaze.

[0045] The viscosity of the zirconium silicate superfine powder is measured by using an NDJ-5S type rotary viscometer.

[0046] like Figure 2 As shown, the viscosity of the zirconium silicate ultrafine powder in the example decreased significantly to 10 mPa·s after modification with a dispersant. 1 The viscosity of the unmodified zirconium silicate ultrafine powder in the comparative example was as high as 60 mPa·s. 1 The above demonstrates that the dispersant prepared by this invention has excellent performance.

[0047] High-strength and wear-resistant ceramic glaze is applied to the ceramic body, dried, and fired. After cooling, the ceramic glaze is obtained. The breaking strength and modulus of rupture of the ceramic glaze are tested according to GB / T3810.4-2016, and the wear resistance of the ceramic glaze is tested according to GB / T3810.7-2016.

[0048] Breaking strength (N) Breaking modulus (MPa) Wear resistance Example 1 2503 44.2 4th grade Example 2 2491 45.5 5th grade Example 3 2514 46.8 5th grade Example 4 2539 45.2 4th grade Comparative Example 1 1768 32.9 3rd grade

[0049] According to the table, the ceramic glaze prepared by firing the high-strength and wear-resistant ceramic glaze in the examples has a breaking strength of 2491-2539 N, a rupture modulus of 44.2-46.8 MPa, and a wear resistance of level 4-5, which is far superior to the ceramic glaze prepared by firing the ceramic glaze in the comparative examples. Therefore, the high-strength and wear-resistant ceramic glaze prepared by this invention has significantly improved both its strength and wear resistance.

Claims

1. A high-strength wear-resistant ceramic glaze, characterized by: The high-strength wear-resistant ceramic glaze comprises 30-40 parts by weight of potassium feldspar, 20-30 parts by weight of sodium feldspar, 5-15 parts by weight of high-purity quartz, 2-10 parts by weight of calcined kaolin, 3-8 parts by weight of alumina, 3-8 parts by weight of dispersant modified zirconium silicate superfine powder, 10-16 parts by weight of calcium carbonate, and 1-4 parts by weight of zinc oxide.

2. A method of preparing a high-strength wear-resistant ceramic glaze as claimed in claim 1, characterized in that: The preparation method of the high-strength wear-resistant ceramic glaze comprises the following steps: mixing potassium feldspar, sodium feldspar, high-purity quartz, calcined kaolin, alumina, dispersant modified zirconium silicate superfine powder, calcium carbonate, and zinc oxide, ball milling, screening and removing iron to obtain the high-strength wear-resistant ceramic glaze.

3. The method for preparing high-strength and wear-resistant ceramic glaze according to claim 2, characterized in that: The preparation method of the dispersant modified zirconium silicate superfine powder comprises the following steps: (1) dissolving 3-chloro-2-chloromethyl propylene and triethylamine in tetrahydrofuran, adding diethyl imino diacetate dropwise under the condition of nitrogen atmosphere and at-15℃ to-5℃, then stirring and reacting for 12-36 hours at 18-25℃, after the reaction is completed, filtering and discarding the residue, then rotary evaporating, dissolving the obtained product in dichloromethane, extracting impurities with deionized water for 2-3 times, discarding the water phase, drying the organic phase with anhydrous calcium chloride, filtering the mixture after 6-14 hours, then adding dilute hydrochloric acid, stirring and reacting for 12-36 hours at 18-25℃, adjusting the pH of the product to 4.4-5.6 with sodium hydroxide, then rotary evaporating and filtering to remove the residue, and obtaining 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid; (2) dissolving poly(ethylene glycol) methacrylate in deionized water, adding 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid aqueous solution, sodium vinyl sulfonate aqueous solution and ammonium persulfate aqueous solution dropwise under the condition of nitrogen atmosphere and at 70-90℃, and reacting for 10-20 hours to obtain a dispersant; (3) stirring tetraethyl orthosilicate and lithium fluoride uniformly, then adding anhydrous zirconium tetrachloride, then heating to 60-70℃ and continuing to stir, then adding the dispersant, heating to 105-115℃ in an oil bath and refluxing for 12-36 hours, drying the product, and then heating to 650-750℃ for 20-40 minutes to obtain the dispersant modified zirconium silicate superfine powder.

4. The method for preparing the high-strength and wear-resistant ceramic glaze according to claim 3, characterized in that: The mass ratio of 3-chloro-2-chloromethyl propylene, triethylamine and diethyl imino diacetate in (1) is 1.5-2.5:3.5-4.5:7-8.

5. The method for preparing the high-strength and wear-resistant ceramic glaze according to claim 3, characterized in that: The mass fraction of dilute hydrochloric acid in (1) is 5%-12%, and the mass fraction of sodium hydroxide is 2%-7%.

6. The method for preparing the high-strength and wear-resistant ceramic glaze according to claim 3, characterized in that: The mass ratio of poly(ethylene glycol) methacrylate, 2-(N,N'-dimethylene carboxyl) aminomethyl-propylene diacetic acid, sodium vinyl sulfonate and ammonium persulfate in (2) is 4-5:15-25:16-28:1-2.

7. The method of making a high strength wear resistant ceramic glaze of claim 3, wherein: The mass ratio of tetraethyl orthosilicate, lithium fluoride, anhydrous zirconium tetrachloride and the dispersant in (3) is 17-24:0.3-1.2:16-24:0.8-1.5.

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