High-strength ceramic glaze and preparation method thereof

Abstract

The invention discloses a high-strength ceramic glaze and a preparation method thereof, and relates to the technical field of ceramic glazes. The wollastonite / potassium feldspar composite material is prepared from the following raw materials in parts by mass: 70 to 84 parts of wollastonite, 122 to 146.4 parts of potassium feldspar, 18 to 21.6 parts of aluminum oxide, 8 to 10 parts of lithium carbonate, 15 to 18 parts of nano-zinc oxide, 24 to 28.8 parts of modified titanium dioxide and 45 to 54 parts of composite toughening agent. According to the invention, modified titanium dioxide formed by coating the surface of ytterbium-doped titanium dioxide with a hexagonal boron nitride layer is introduced; by introducing the composite toughening agent, the hardness, the wear resistance and the crack resistance of a glaze surface prepared from the glaze material are effectively improved by virtue of the introduction of the composite toughening agent which is prepared by carrying out ball-milling mixing on composite powder and silicon carbide whiskers, wherein the composite powder is prepared from barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride and tetrabutyl titanate through sol-gel, drying and presintering, and carrying out ball-milling mixing and argon atmosphere heat treatment on the composite powder and the silicon carbide whiskers; the stripping resistance and the self-cleaning capability are realized. Therefore, the method has a wider application prospect.

Description

TECHNICAL FIELD

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

[0002] Ceramics is a kind of solid material which is made of inorganic non-metallic minerals (such as clay, feldspar, quartz, etc.) or artificial synthetic compounds as raw materials, and is formed by molding and high-temperature firing. Ceramics can be divided into daily-use ceramics, building ceramics, industrial ceramics (engineering ceramics), and artistic ceramics (display ceramics) according to their uses. Among them, display ceramics focuses on artistic expression, with various shapes and fine crafts, and integrates sculpture, painting, and glaze techniques, such as ceramic ornaments, porcelain bottles, porcelain plates, ceramic sculptures, murals, and antique porcelain.

[0003] In actual application environment, ceramics still have problems such as scratches, dust accumulation, and cracking in long-term use, which make the surface rough and dull. In addition, when subjected to vibration, impact, or temperature change, the glaze layer may partially peel off from the surface of the body, exposing the underlying body. Therefore, the wear resistance, crack resistance, peeling resistance, and self-cleaning ability of the ceramic glaze made of the existing ceramic glaze still need to be improved. SUMMARY

[0004] The present application relates to the technical field of ceramic glaze, in particular to a high-strength ceramic glaze and a preparation method thereof. The present application relates to the technical field of ceramic glaze, in particular to a high-strength ceramic glaze and a preparation method thereof.

[0005] The present application relates to the technical field of ceramic glaze, in particular to a high-strength ceramic glaze and a preparation method thereof. A high-strength ceramic glaze, comprising the following raw materials by mass: 70-84 parts of wollastonite, 122-146.4 parts of potassium feldspar, 18-21.6 parts of aluminum oxide, 8-10 parts of lithium carbonate, 15-18 parts of nano-zinc oxide, 24-28.8 parts of modified titanium dioxide, and 45-54 parts of a composite toughening agent. The modified titanium dioxide is a powder formed by coating ytterbium-doped titanium dioxide with hexagonal boron nitride. The composite toughening agent is prepared by ball-milling and argon atmosphere heat treatment of a composite powder and silicon carbide whiskers. The composite powder is prepared by sol-gel and dry pre-burning of barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride, and tetrabutyl titanate.

[0006] Preferably, the preparation method of the modified titanium dioxide is as follows: A1: drop tetrabutyl titanate into anhydrous ethanol and stir for 10-20 min, then add ytterbium nitrate and stir for 30-50 min, then add deionized water and adjust pH to 2.5-3.0 with concentrated hydrochloric acid, stir for 30-50 min, then age at 78-80℃ for 12-15 h, then calcine at 500℃ for 2-2.5 h, grind and sieve through a 200 mesh sieve after cooling, to obtain pretreated titanium dioxide; A2: add boric acid to ammonia water and stir for 30-40 min, then add pretreated titanium dioxide and stir for 20-30 min, then ultrasonically disperse for 20-30 min, then heat at 160-165℃ in a closed container for 6-7 h, then centrifuge and wash the precipitate with deionized water until the pH of the supernatant is 7, then wash with anhydrous ethanol 2-4 times, then vacuum dry at 55-60℃ for 12-15 h, then grind and sieve through a 200-300 mesh sieve, to obtain modified titanium dioxide.

[0007] Preferably, the mass ratio of anhydrous ethanol, tetrabutyl titanate, ytterbium nitrate, and deionized water in A1 is 500-600:35-42:5.8-7.2:20-24.

[0008] Preferably, the mass ratio of ammonia water, boric acid, and pretreated titanium dioxide in A2 is 200-250:4-5:10-12.

[0009] Preferably, the mass fraction of ammonia water in A2 is 10%-12%.

[0010] Preferably, the preparation method of the composite toughening agent is as follows: B1: add barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride, and tetrabutyl titanate in sequence to ethylene glycol methyl ether and stir for 30-50 min, then add citric acid and stir for 1-1.5 h, then dry in stages, then pre-sinter after grinding, then grind and sieve through a 300-400 mesh sieve after cooling, to obtain a composite powder; B2: mix anhydrous ethanol, composite powder, silicon carbide whiskers, and polyvinyl alcohol, and ball mill with zirconium oxide grinding balls (ball to material ratio 3-5:1, grinding ball diameter 2 mm) at 200-250 r / min for 2-3 h, then vacuum filter and vacuum dry the precipitate at 55-60℃ for 8-10 h, then heat at 750-800℃ in an argon atmosphere for 1-1.5 h, then grind and sieve through a 300-400 mesh sieve after cooling, to obtain a composite toughening agent.

[0011] Preferably, the mass ratio of ethylene glycol methyl ether, barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride, tetrabutyl titanate, and citric acid in B1 is 500-600:22.2-26.6:3.5-4.2:3.2-3.8:30.6-36.7:46-55.2.

[0012] Preferably, the segment drying treatment in B1 is stirring for 2-3h at 78-80℃, and then drying for 12-14h at 118-122℃. The pre-burning treatment in B1 is pre-burning for 1.5-2h at 300-350℃, and then pre-burning for 2-2.5h at 750-800℃.

[0013] Preferably, the mass ratio of the anhydrous ethanol, the composite powder, the silicon carbide whisker and the polyvinyl alcohol in B2 is 500-600:70-84:30-36:5-6.

[0014] A preparation method of high-strength ceramic glaze, comprising the following steps: Wollastonite is ground to D50 of 3-5um, and then mixed with potassium feldspar, alumina, lithium carbonate, nano zinc oxide, modified titanium dioxide and composite toughening agent, and then melted at 1000-1200℃ for 1.5-2h, and finally quenched in cold water to cool down and ball milled to D90 of 8-10um to obtain high-strength ceramic glaze.

[0015] The beneficial effects of the present application are as follows: The present application provides a high-strength ceramic glaze and a preparation method thereof, which effectively improves the wear resistance, crack resistance, peeling resistance and self-cleaning ability of the ceramic glaze.

[0016] (1) The modified titanium dioxide in the application can improve the overall hardness of the glaze through the particle strengthening effect; the ytterbium ion doping can refine the titanium dioxide grains and increase the grain boundary density; the hexagonal boron nitride coating layer can inhibit the titanium dioxide agglomeration and avoid local hardness fluctuation. The titanium dioxide particles can directly resist plastic deformation and abrasive cutting in the friction process, reducing the loss of glaze material; the layered structure of hexagonal boron nitride has a low friction coefficient, which can reduce the friction resistance; the core-shell structure has good compatibility with the glaze glass phase, which can avoid particle shedding and improve wear resistance. The thermal expansion coefficient of the modified titanium dioxide is well matched with the glaze glass phase, which can reduce the thermal stress cracks in the sintering and cooling process, and the titanium dioxide particles can also hinder crack propagation; the flexible layered structure of hexagonal boron nitride can absorb crack tip energy, relieve stress concentration and reduce the risk of crack instability propagation. The hexagonal boron nitride layer may be combined with the silicate network in the glaze through boron-oxygen bonds, and the titanium dioxide core can be bonded with alumina in the matrix, strengthening the "matrix-glaze" interface transition zone; the nanoscale effect of the core-shell structure can reduce stress concentration at the interface and reduce the risk of interface peeling caused by thermal cycling or mechanical impact. Ytterbium ion-doped titanium dioxide can expand the light response range to the visible light region, enhance the photocatalytic activity, efficiently decompose the organic matter attached to the glaze, and form hydrophilic groups; the hydrophobicity of the hexagonal boron nitride coating layer can reduce the water film attachment, making it difficult for stains to infiltrate the glaze; both of them realize the dual self-cleaning function, and the hexagonal boron nitride can protect the titanium dioxide from the erosion of alkaline components in the glaze, prolonging the photocatalytic life.

[0017] (2) The silicon carbide whiskers and barium calcium zirconium titanium composite oxides in the composite toughening agent can hinder plastic deformation caused by external force through dispersion strengthening effect, reduce local stress concentration of the matrix, and significantly improve the hardness of the glaze; high-temperature argon atmosphere calcination can enhance the interface bonding between the toughening agent and the glaze matrix, further avoiding local softening caused by hard phase shedding. High-hardness silicon carbide whiskers and composite oxide powders can resist plowing and cutting effects in the wear process, reducing the direct loss of glaze material; the fibrous structure of the silicon carbide whiskers can form a "skeleton support" at the wear interface, delaying continuous wear in local areas, while the uniformly dispersed powders can reduce stress concentration during wear, avoiding local rapid failure. When the crack encounters the whisker, it will be forced to change the direction of propagation, significantly increasing the energy required for crack propagation; the whisker across the two ends of the crack can "hold" the two sides of the crack through its own strength, preventing the crack from further opening; the good compatibility of the composite powder with the glaze matrix can reduce interface defects and reduce the probability of crack initiation, further improving the crack resistance. The three-dimensional interlaced structure of the silicon carbide whisker can enhance the overall bonding strength of the glaze layer, reducing the delamination caused by internal stress; the composite powder can adjust the thermal expansion coefficient of the glaze layer, reducing the thermal stress difference between the glaze and the body, and reducing the interface peeling caused by temperature changes. The uniform dispersion of the composite toughening agent can make the glaze more dense, reducing pores and depressions and reducing the physical adsorption sites of stains.

[0018] Therefore, the high-strength ceramic glaze prepared by the application has excellent wear resistance, crack resistance, peeling resistance and self-cleaning ability, and has a more extensive application prospect. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only some of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0020] Embodiment 1: A preparation method of a high-strength ceramic glaze is as follows: S1: 35g of tetrabutyl titanate was added dropwise into 500g of anhydrous ethanol and stirred for 10min, then 5.8g of ytterbium nitrate was added and stirred for 30min, 20mL of deionized water was then added at a rate of 1mL / min and the pH was adjusted to 2.5 with concentrated hydrochloric acid, and after stirring for 30min, aging was first performed at 78℃ for 12h, and then calcination was performed at 500℃ for 2h, after cooling, grinding and sieving through a 200-mesh screen, pretreated titanium dioxide was obtained; S2: 4g of boric acid was added into 200g of 10% ammonia water and stirred for 30min, then 10g of the pretreated titanium dioxide was added and stirred for 20min, and then ultrasonic dispersion was performed for 20min, then closed heat preservation was performed at 160℃ for 6h, after cooling to room temperature, centrifugal separation was performed and the precipitate was washed with deionized water until the pH of the supernatant was 7, then the precipitate was washed twice with anhydrous ethanol, and finally vacuum drying was performed at 55℃ for 12h, after grinding and sieving through a 200-mesh screen, modified titanium dioxide was obtained; S3: 22.2g of barium nitrate, 3.5g of calcium nitrate tetrahydrate, 3.2g of zirconium oxychloride, 30.6g of tetrabutyl titanate were sequentially added into 500g of ethylene glycol methyl ether and stirred for 30min, then 46g of citric acid was added and stirred for 1h, then stirring was performed at 78℃ for 2h, and then drying was performed at 118℃ for 12h, after grinding, pre-sintering was first performed at 300℃ for 1.5h, and then pre-sintering was performed at 750℃ for 2h, after cooling, grinding and sieving through a 300-mesh screen, a composite powder was obtained; S4: 500g of anhydrous ethanol, 70g of the composite powder, 30g of silicon carbide whiskers and 5g of polyvinyl alcohol were mixed and ball-milled with zirconium oxide grinding balls (ball-to-material ratio 3:1, grinding ball diameter 2mm) at 200r / min for 2h, then vacuum filtration was performed and the precipitate was vacuum dried at 55℃ for 8h, then heat preservation was performed at 750℃ in an argon atmosphere for 1h, after cooling, grinding and sieving through a 300-mesh screen, a composite toughening agent was obtained; S5: 70 g of wollastonite was ground to a D50 of 3 μm, then mixed with 122 g of potassium feldspar, 18 g of alumina, 8 g of lithium carbonate, 15 g of nano-zinc oxide, 24 g of modified titanium dioxide, and 45 g of composite toughening agent, then melted at 1000 ℃ for 1.5 h, and finally quenched in cold water to cool down and ball milled to a D90 of 8 μm to obtain a high-strength ceramic glaze.

[0021] Example 2: A high-strength ceramic glaze was prepared as follows: S1: 38.5 g of tetrabutyl titanate was added dropwise to 550 g of anhydrous ethanol and stirred for 15 min, then 6.5 g of ytterbium nitrate was added and stirred for 40 min, then 22 mL of deionized water was added at a rate of 1 mL / min and the pH was adjusted to 2.7 with concentrated hydrochloric acid, and stirred for 40 min, then aged at 79 ℃ for 14 h, and then calcined at 500 ℃ for 2.2 h, cooled, ground, and sieved through a 200 mesh screen to obtain pretreated titanium dioxide; S2: 4.5 g of boric acid was added to 225 g of 11% ammonia water and stirred for 35 min, then 11 g of pretreated titanium dioxide was added and stirred for 25 min, then ultrasonically dispersed for 25 min, then sealed and incubated at 163 ℃ for 6.7 h, then centrifuged and washed the precipitate with deionized water until the supernatant pH was 7, then washed with anhydrous ethanol three times, and finally vacuum dried at 58 ℃ for 13 h, ground, and sieved through a 250 mesh screen to obtain modified titanium dioxide; S3: 24.4 g of barium nitrate, 3.8 g of calcium nitrate tetrahydrate, 3.5 g of zirconium oxychloride, and 33.7 g of tetrabutyl titanate were added to 550 g of ethylene glycol methyl ether and stirred for 40 min, then 50.6 g of citric acid was added and stirred for 1.2 h, then stirred at 79 ℃ for 2.5 h, then dried at 120 ℃ for 13 h, then pre-fired at 330 ℃ for 1.8 h, then pre-fired at 780 ℃ for 2.2 h, cooled, ground, and sieved through a 350 mesh screen to obtain a composite powder; S4: 550 g of anhydrous ethanol, 77 g of the composite powder, 33 g of silicon carbide whiskers, and 5.5 g of polyvinyl alcohol were mixed and ball milled with zirconium oxide grinding balls (ball-to-material ratio of 4:1, grinding ball diameter of 2 mm) at 230 r / min for 2.5 h, then vacuum filtered and the precipitate was vacuum dried at 58 ℃ for 9 h, then incubated at 780 ℃ in an argon atmosphere for 1.3 h, cooled, ground, and sieved through a 350 mesh screen to obtain a composite toughening agent; S5: 77 g of wollastonite was ground to a D50 of 4 μm, then mixed with 134.2 g of potassium feldspar, 19.8 g of alumina, 9 g of lithium carbonate, 16.5 g of nano-zinc oxide, 26.4 g of modified titanium dioxide, and 49.5 g of composite toughening agent, then melted at 1100 ℃ for 1.8 h, and finally quenched in cold water to cool down and ball milled to a D90 of 9 μm to obtain a high-strength ceramic glaze.

[0022] Example 3: A method for preparing a high-strength ceramic glaze is as follows: S1: 42 g of tetrabutyl titanate was added dropwise to 600 g of anhydrous ethanol and stirred for 20 min, then 7.2 g of ytterbium nitrate was added and stirred for 50 min, then 24 mL of deionized water was added at a rate of 1 mL / min and the pH was adjusted to 3.0 with concentrated hydrochloric acid, and after stirring for 50 min, it was aged at 80°C for 15 h, then calcined at 500°C for 2.5 h, cooled and ground through a 200 mesh screen to obtain pretreated titanium dioxide; S2: 5 g of boric acid was added to 250 g of 12% ammonia water and stirred for 40 min, then 12 g of pretreated titanium dioxide was added and stirred for 30 min, then ultrasonic dispersion was performed for 30 min, then it was sealed and incubated at 165°C for 7 h, after cooling to room temperature, it was centrifuged and the precipitate was washed with deionized water until the pH of the supernatant was 7, then it was washed with anhydrous ethanol 4 times, and finally it was vacuum dried at 60°C for 15 h, ground and passed through a 300 mesh screen to obtain modified titanium dioxide; S3: 26.6 g of barium nitrate, 4.2 g of calcium nitrate tetrahydrate, 3.8 g of zirconium oxychloride, 36.7 g of tetrabutyl titanate were added in sequence to 600 g of ethylene glycol methyl ether and stirred for 50 min, then 55.2 g of citric acid was added and stirred for 1.5 h, then it was stirred at 80°C for 3 h, then dried at 122°C for 14 h, then ground and pre-fired at 350°C for 2 h, then pre-fired at 800°C for 2.5 h, then cooled and ground through a 400 mesh screen to obtain a composite powder; S4: 600 g of anhydrous ethanol, 84 g of the composite powder, 36 g of silicon carbide whiskers, and 6 g of polyvinyl alcohol were mixed and ball milled with zirconium oxide grinding balls (ball to material ratio of 5:1, grinding ball diameter of 2 mm) at 250 r / min for 3 h, then vacuum filtered and the precipitate was vacuum dried at 60°C for 10 h, then incubated at 800°C in an argon atmosphere for 1.5 h, then cooled and ground through a 400 mesh screen to obtain a composite toughening agent; S5: 84 g of wollastonite was ground to a D50 of 5 μm, then mixed with 146.4 g of potassium feldspar, 21.6 g of alumina, 10 g of lithium carbonate, 18 g of nano-zinc oxide, 28.8 g of modified titanium dioxide, and 54 g of the composite toughening agent, then melted at 1200°C for 2 h, and finally quenched in cold water to cool and ball milled to a D90 of 10 μm to obtain a high-strength ceramic glaze.

[0023] Comparative Example 1: This comparative example is compared with Example 1 only by replacing the "pretreated titanium dioxide" added in the preparation process of S2 with "nano-titanium dioxide", and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, a high-strength ceramic glaze is obtained.

[0024] Comparative Example 2: The comparative example is compared with example 1 only by replacing the “modified titanium dioxide” added in the preparation process of S5 with the “pretreated titanium dioxide” prepared in S1, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, high-strength ceramic glaze is obtained.

[0025] Comparative example 3: The comparative example is compared with example 1 only by not adding “modified titanium dioxide” in the preparation process of S5, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, high-strength ceramic glaze is obtained. Comparative example 4: The comparative example is compared with example 1 only by replacing the “composite toughening agent” added in the preparation process of S5 with the “composite powder” prepared in S3, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, high-strength ceramic glaze is obtained.

[0026] Comparative example 5: The comparative example is compared with example 1 only by not adding “composite toughening agent” in the preparation process of S5, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, high-strength ceramic glaze is obtained.

[0027] Performance detection: Mix the body powder with deionized water to make a plastic body (water content about 15%-20%), then dry-press into a mold, press in a press machine at a pressure of 10-30MPa, and pre-dry at 60℃ for 2h after holding for 30s, then dry at 110℃ for 6-12h, to obtain a green body; Mix the high-strength ceramic glaze and deionized water at a mass ratio of 1:0.6, then ball mill with zirconium oxide balls (ball to material ratio 3:1) for 30min, then remove impurities through a 200 mesh sieve, to obtain a glaze slurry; Spray the glaze slurry evenly on the surface of the body with an airbrush, control the thickness to be 0.3mm after multiple spraying, then place it in a well-ventilated place for 4h, then first heat to 300℃ at a rate of 5℃ / min, then heat to 900℃ at a rate of 10℃ / min and keep for 2h, finally heat to 1200℃ at a rate of 4℃ / min and keep for 3h, then cool to 600℃ at a rate of 5℃ / min and cool in the furnace, to obtain a ceramic test piece.

[0028] Hardness determination: According to the standard GB / T 3810.7-2016, the Vickers hardness (HV) of the ceramic test piece made of high-strength ceramic glaze prepared in examples 1-3 and comparative examples 1-5 is determined, and the determination results are shown in Table 1. Abrasion resistance determination: The abrasion loss (mg) of the ceramic test piece prepared from the high-strength ceramic glaze prepared in the application examples 1-3 and the comparative examples 1-5 after 5000 revolutions of the abrasion test was determined according to the GB / T 35160.4-2017 standard, and the determination results are shown in Table 1. The determination of the crack resistance: The determination of the crack resistance: The determination of the crack resistance: The anti-peeling impact energy (J) of the ceramic test piece prepared from the high-strength ceramic glaze prepared in the application examples 1-3 and the comparative examples 1-5 was determined according to the ASTM C368-88 standard, and the determination results are shown in Table 1. The determination of the crack resistance: The water contact angle (°) of the ceramic test piece prepared from the high-strength ceramic glaze prepared in the application examples 1-3 and the comparative examples 1-5 was determined, and the determination results are shown in Table 1. The oil stain degradation rate (%) of the ceramic test piece prepared from the high-strength ceramic glaze prepared in the application examples 1-3 and the comparative examples 1-5 under ultraviolet light for 4h was determined by measuring the change in absorbance, and the determination results are shown in Table 1.

[0029] Table 1: Performance test results of the application examples 1-3 and the comparative examples 1-5

[0030] Data analysis: As can be seen from Table 1, the high-strength ceramic glaze prepared in the application examples has excellent hardness, wear resistance, crack resistance, anti-peeling property and self-cleaning ability.

[0031] In the above-mentioned preparation process of the modified titanium dioxide, the pre-processed titanium dioxide is replaced by nano-titanium dioxide in Comparative Example 1; the modified titanium dioxide used in the preparation process of the glaze is replaced by pre-processed titanium dioxide in Comparative Example 2; and no modified titanium dioxide is added in the preparation process of the glaze in Comparative Example 3. It can be seen from the determination results that the hardness, wear resistance, anti-chipping property and self-cleaning ability of Comparative Examples 1 and 2 are all decreased to different extents as compared with the embodiment, and the hardness, wear resistance, anti-chipping property and self-cleaning ability of Comparative Example 3 are all decreased to a greater extent as compared with Comparative Examples 1 and 2, and even cracks appear on the glaze surface during the anti-cracking determination. This shows that the pre-processed titanium dioxide prepared according to the embodiment can more effectively improve the hardness, wear resistance, anti-chipping property and self-cleaning ability of the glaze as compared with nano-titanium dioxide, and the modification of the pre-processed titanium dioxide can improve the performance of the glaze, and the pre-processing and modification can have a synergistic effect, and more greatly improve the hardness, wear resistance, anti-chipping property and self-cleaning ability of the glaze. In Comparative Example 4, the composite toughening agent used in the preparation process of the glaze is replaced by the composite powder; and in Comparative Example 5, no composite toughening agent is added in the preparation process of the glaze. It can be seen from the determination results that the hardness, wear resistance, anti-chipping property, anti-cracking property and self-cleaning ability of Comparative Example 4 are all decreased as compared with the embodiment, and the hardness, wear resistance, anti-chipping property, anti-cracking property and self-cleaning ability of Comparative Example 5 are all decreased to a greater extent as compared with Comparative Example 4. This shows that the composite powder prepared according to the embodiment can effectively improve the performance of the glaze, and the composite powder obtained by co-processing of the silicon carbide whiskers can more effectively improve the hardness, wear resistance, anti-chipping property, anti-cracking property and self-cleaning ability of the glaze.

[0032] The above describes one embodiment of the present application in detail, but the above description is only a preferred embodiment of the present application and cannot be considered as limiting the scope of the present application. Any equivalent changes and improvements made according to the scope of the present application should still fall within the scope of the present application.

Claims

1. A high-strength ceramic glaze, characterized in that, The raw materials include the following parts by weight: 70-84 parts wollastonite, 122-146.4 parts potassium feldspar, 18-21.6 parts alumina, 8-10 parts lithium carbonate, 15-18 parts nano zinc oxide, 24-28.8 parts modified titanium dioxide, and 45-54 parts composite toughening agent. The modified titanium dioxide is a powder formed by coating ytterbium-doped titanium dioxide with hexagonal boron nitride; The composite toughening agent is prepared by ball milling and mixing composite powder with silicon carbide whiskers and heat treatment in an argon atmosphere; the composite powder is prepared by sol-geling and drying pre-calcination of barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride and tetrabutyl titanate.

2. The high-strength ceramic glaze according to claim 1, characterized in that, The modified titanium dioxide is prepared as follows: A1: Add tetrabutyl titanate dropwise to anhydrous ethanol and stir well. Then add ytterbium nitrate and stir for 30-50 min. Then add deionized water and adjust the pH to 2.5-3.

0. Stir for 30-50 min and then age at 78-80℃ for 12-15 h. Then calcine at 500℃ for 2-2.5 h. After cooling, grind and sieve to obtain pretreated titanium dioxide. A2: Add boric acid to ammonia water and stir well. Then add pretreated titanium dioxide and stir for 20-30 minutes. Then disperse it ultrasonically for 20-30 minutes. Then keep it sealed at 160-165℃ for 6-7 hours. After cooling, centrifuge and wash the precipitate. Finally, vacuum dry, grind and sieve to obtain modified titanium dioxide.

3. The high-strength ceramic glaze according to claim 2, characterized in that, The mass ratio of anhydrous ethanol, tetrabutyl titanate, ytterbium nitrate, and deionized water in A1 is 500-600:35-42:5.8-7.2:20-24.

4. The high-strength ceramic glaze according to claim 2, characterized in that, The mass ratio of ammonia, boric acid, and pretreated titanium dioxide in A2 is 200-250:4-5:10-12.

5. The high-strength ceramic glaze according to claim 2, characterized in that, The mass fraction of ammonia in A2 is 10%-12%.

6. The high-strength ceramic glaze according to claim 1, characterized in that, The preparation method of the composite toughening agent is as follows: B1: Add barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride, and tetrabutyl titanate to ethylene glycol methyl ether and stir for 30-50 min. Then add citric acid and stir for 1-1.5 h. Then dry in stages, grind and pre-calcine, cool and grind and sieve to obtain composite powder. B2: Mix anhydrous ethanol, composite powder, silicon carbide whiskers, and polyvinyl alcohol and ball mill them with zirconia milling balls for 2-3 hours. Then, vacuum filter the mixture and vacuum dry the precipitate. Then, keep it at 750-800℃ in an argon atmosphere for 1-1.5 hours. After cooling, grind and sieve to obtain the composite toughening agent.

7. The high-strength ceramic glaze according to claim 6, characterized in that, The mass ratio of ethylene glycol methyl ether, barium nitrate, calcium nitrate tetrahydrate, zirconium oxychloride, tetrabutyl titanate, and citric acid in B1 is 500-600: 22.2-26.6: 3.5-4.2: 3.2-3.8: 30.6-36.7: 46-55.

2.

8. The high-strength ceramic glaze according to claim 6, characterized in that, The segmented drying process described in B1 is as follows: first, stir at 78-80℃ for 2-3 hours, then dry at 118-122℃ for 12-14 hours; The pre-firing treatment described in B1 is as follows: first pre-firing at 300-350℃ for 1.5-2 hours, and then pre-firing at 750-800℃ for 2-2.5 hours.

9. The high-strength ceramic glaze according to claim 6, characterized in that, The mass ratio of anhydrous ethanol, composite powder, silicon carbide whiskers, and polyvinyl alcohol described in B2 is 500-600:70-84:30-36:5-6.

10. A method for preparing a high-strength ceramic glaze according to any one of claims 1-9, characterized in that, Includes the following steps: After grinding wollastonite, it is mixed with potassium feldspar, alumina, lithium carbonate, nano zinc oxide, modified titanium dioxide, and composite toughening agent. Then, it is melted at 1000-1200℃ for 1.5-2 hours, and finally quenched in cold water to cool and ball-milled to obtain high-strength ceramic glaze.

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