A truly wear-resistant ceramic tile and its preparation method

Abstract

The present invention discloses a true wear-resistant ceramic tile and a preparation method thereof, belonging to the technical field of ceramic tile preparation. The preparation method includes the following steps: The wear-resistant glaze slurry is applied to the surface of the ceramic blank by a glazing tool, and the glazing thickness is controlled to be 0.5 mm to 0.7 mm. Then, it is first dried at 130 °C to 150 °C for 30 min, and then calcined at 1180 °C to 1240 °C for 1.5 h to 2 h to obtain the ceramic tile. The present invention applies the wear-resistant glaze slurry prepared from an organosilicon-modified dispersant and a mixed mineral powder to the surface of the ceramic blank, achieving good hardness, wear resistance and low water absorption.

Description

Technical Field

[0001] The present invention belongs to the technical field of tile preparation, and particularly relates to a true wear-resistant ceramic tile and a preparation method thereof. Background Art

[0002] China is not only a large producer of tiles but also a large consumer of tiles. As a key building decoration material, tiles play an important role in the decoration of residential houses, office buildings and other architectural houses. Ceramic tiles are a kind of building material widely used in the decoration of walls and floors. It is mainly made of natural minerals such as clay, quartz, and feldspar, and is processed through processes such as forming and firing. Due to its beautiful appearance, durability, easy cleaning and other characteristics, ceramic tiles occupy an important position in modern architecture. The quality of the tile glaze directly affects the beauty and performance of the tile. For example, if there are fine cracks on the tile glaze, its waterproof performance will surely be affected. For most consumers, the quality of the tile glaze often becomes an important reference index for whether to purchase. Therefore, if there are problems with the tile glaze quality, it usually brings very adverse effects to the product. Among ceramic tile products, polished glazed tiles have the characteristics of a smooth and transparent surface and a background color with rich and diverse textures after a unique polishing process. However, the surface wear resistance of general polished glazed tiles is very low, and it is very easy to be damaged during the wear process, which will have an adverse impact on the brightness, color, and surface texture. And during transportation, the collision between tiles is also very easy to form scratches, causing transportation losses.

[0003] To solve the wear resistance problem of polished glazed tiles, improving the mechanical strength and wear resistance of the glaze has been the main research direction in recent years. Abrasive wear is one of the most common wear mechanisms on the surface of ceramic materials. It is mainly defined as a kind of wear caused by the migration of materials due to hard particles or hard protrusions, which refers to the phenomenon of surface material loss caused by the mutual friction between the object surface and hard particles or hard protrusions. Among them, pulling and cracking can strongly reduce mechanical properties, especially hardness and wear resistance, and will also cause deterioration of aesthetics, brightness and color, and material loss. In addition, the areas with cracks and material removal increase the surface roughness, which is convenient for the attachment of powder and other dirt and is difficult to clean.

[0004] Patent CN115745568A discloses a wear-resistant ceramic tile and a preparation method thereof. The invention improves the mechanical strength of the green body by adding raw materials such as strontium carbonate, cerium oxide and calcium phosphate to the green body; improves the hardness and wear resistance of the surface glaze by adding raw materials such as zirconium silicate and silicon nitride to the surface glaze layer; improves the wear resistance and anti-slip performance of the wear-resistant layer by adding raw materials such as zinc oxide whiskers, magnesium borate whiskers, aluminum nitride and titanium diboride to the wear-resistant layer, and appropriately proportions the green body, surface glaze and wear-resistant layer, so as to produce a synergistic effect, making the prepared ceramic tile have high surface wear strength and friction coefficient, and having good wear resistance and anti-slip performance.

[0005] Patent CN113999055A discloses an anti-fouling and wear-resistant ceramic tile and its preparation method. In this invention, wear-resistant particles are prepared by mixing oxides such as alumina, silica, calcium oxide, zirconium oxide, titanium oxide, and lanthanum oxide, and then an anti-fouling and wear-resistant ceramic tile is prepared.

[0006] The above improvement mainly prepares a glaze by adding wear-resistant inorganic oxides, then applies the glaze on the surface of the ceramic tile blank, and obtains a ceramic tile with good wear resistance after high-temperature firing. However, due to the large difference in the thermal expansion coefficients between different inorganic oxides, the glaze surface will crack and peel off, affecting the hardness performance of the ceramic tile.

[0007] Therefore, it is of great significance to develop a new method to improve the surface wear resistance of ceramic tiles. Summary of the Invention

[0008] In view of the deficiencies of the prior art, the present invention applies the prepared wear-resistant glaze slurry on the surface of the ceramic blank, and then obtains a ceramic tile with good wear resistance after high-temperature calcination, thereby solving the technical problems raised in the background art. Specifically, the technical solution of the present invention includes the following:

[0009] A truly wear-resistant ceramic tile, which is composed of a ceramic blank and a wear-resistant glaze slurry.

[0010] Furthermore, the preparation method of the ceramic blank includes the steps of:

[0011] Quartz, kaolin, glass powder, ceramic waste, and plagioclase are mixed and crushed according to the weight ratio of 1-2:19-25:11-14:17-20:3-6 to obtain a crushed material. The crushed material, water, and grinding beads are mixed and wet-ground according to the weight ratio of 1:1:2 to obtain a blank slurry;

[0012] The blank slurry and the binder are mixed and atomized granulated according to the weight ratio of 10:0.2-0.3 to obtain blank powder. After the blank powder is pressed into shape, it is dried to obtain a ceramic blank.

[0013] Furthermore, the binder includes polyvinyl alcohol.

[0014] Furthermore, the preparation method of the wear-resistant glaze slurry includes the following steps:

[0015] White corundum, mullite, glass fiber, zirconium silicate, and wollastonite are mixed and crushed according to the weight ratio of 15-18:8-11:1-4:2-3:6-12 to obtain a crushed ore material. The crushed ore material and grinding beads are mixed and dry-ground according to the weight ratio of 1:2.5 and sieved to obtain a mixed mineral powder;

[0016] Weigh 5 - 8 parts by weight of the mixed mineral powder, 0.08 - 0.1 parts by weight of the organosilicon - modified dispersant, and 2 - 4 parts by weight of water. Mix and stir them according to the weight ratio of 5 - 8:0.08 - 0.1:2 - 4, and then age to obtain the wear - resistant glaze slurry.

[0017] Furthermore, the preparation method of the organosilicon - modified dispersant includes the following steps:

[0018] Mix and stir the silane coupling agent, ethanol - aqueous solution, and dispersant according to the weight ratio of 1:95 - 100:10 - 12 to obtain a mixed solution. After adjusting the pH of the mixed solution to 6.0 - 6.5, carry out a heat - preservation reaction to obtain the organosilicon - modified dispersant.

[0019] Furthermore, the silane coupling agent includes γ - aminopropyltrimethoxysilane or γ - aminopropyltriethoxysilane.

[0020] Furthermore, the ethanol - aqueous solution is composed of anhydrous ethanol and deionized water mixed according to the weight ratio of 1:7 - 9.

[0021] Furthermore, the dispersant includes sodium lignosulfonate.

[0022] Furthermore, the conditions of the heat - preservation reaction include a reaction temperature of 30°C - 40°C and a reaction time of 4h - 6h.

[0023] A preparation method of a true wear - resistant ceramic tile, the preparation method includes the following steps:

[0024] Apply the wear - resistant glaze slurry on the surface of the ceramic body with a glazing tool, control the glazing thickness to be 0.5mm - 0.7mm, then first carry out a drying treatment at 130°C - 150°C for 30min, and then calcine at 1180°C - 1240°C for 1.5h - 2h to obtain the ceramic tile.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] The present invention uses white fused alumina, mullite, glass fiber, zirconium silicate and wollastonite as raw materials for preparing wear-resistant glaze slurry. The thermal expansion coefficients of white fused alumina, mullite, glass fiber, zirconium silicate and wollastonite are relatively low, which can reduce the adverse effects of cracking caused by expansion during high-temperature calcination. Then, they are mixed, ground and sieved to obtain mixed mineral powder with a certain particle size. The reduction of particle size helps to reduce the formation of pores during high-temperature calcination, preventing the increase of water absorption caused by excessive pores and affecting the hardness of ceramic tiles. However, it is found in the experiment that the hardness of the ceramic tiles finally prepared by simply mixing after grinding is relatively poor. By adding an organosilicon-modified dispersant, the finer mixed mineral powder can be evenly dispersed when preparing the wear-resistant glaze slurry, reducing agglomeration. The organosilicon-modified dispersant can not only disperse the mixed mineral powder and reduce the use of water, reducing the adverse effects of glaze surface cracking caused by the formation of pores during high-temperature calcination, but also complex the metal ions in the inorganic mineral materials through the carboxyl groups in its structure, further increasing the surface hardness of the ceramic tiles. And compared with ordinary sodium lignosulfonate, the organosilicon-modified dispersant can resist the rapid decomposition of sodium lignosulfonate due to the high temperature in the heating stage, thus losing its function of improving the glaze surface performance of the ceramic tiles. Detailed implementation mode

[0027] The technical solutions of the present invention will be clearly and completely described below through the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present invention.

[0028] Unless otherwise specified, the raw materials and reagents used in the present invention below are all commercially available products, or can be prepared by known methods.

[0029] The ceramic waste comes from Shandong Hemusen New Materials Co., Ltd.

[0030] Preparation example 1:

[0031] The preparation method of the ceramic green body specifically includes the following process:

[0032] Weigh 1 part by weight of quartz, 19 parts by weight of kaolin, 11 parts by weight of glass powder, 17 parts by weight of ceramic waste and 3 parts by weight of plagioclase, mix them in a crusher for crushing treatment, add the crushed material obtained by sieving through a 50-mesh sieve and water to a ball mill together, and control the weight ratio of the crushed material: water: grinding beads to be 1:1:2. Wet grind for 10 min to obtain the green body slurry. Weigh 10 parts by weight of the green body slurry and 0.2 parts by weight of polyvinyl alcohol, mix and stir, and then atomize and granulate to obtain the green body powder. The green body powder is sent to a press for molding, and then dried at 55 °C for 5 h to obtain the ceramic green body.

[0033] Preparation Example 2:

[0034] A method for preparing a ceramic green body, specifically including the following process:

[0035] Weigh 1 part by weight of quartz, 21 parts by weight of kaolin, 12 parts by weight of glass powder, 18 parts by weight of ceramic waste, and 4 parts by weight of plagioclase, mix them in a crusher for crushing treatment, add the crushed material obtained by passing through a 50-mesh sieve after the crushing treatment and water together into a ball mill, control the weight ratio of the crushed material: water: grinding beads to be 1:1:2, and wet-mill for 10 min to obtain a green body slurry. Weigh 10 parts by weight of the green body slurry and 0.2 part by weight of polyvinyl alcohol, mix and stir them, then atomize and granulate to obtain a green body powder. The green body powder is sent to a press for molding, and then dried at 55 °C for 5 h to obtain a ceramic green body.

[0036] Preparation Example 3:

[0037] A method for preparing a ceramic green body, specifically including the following process:

[0038] Weigh 2 parts by weight of quartz, 23 parts by weight of kaolin, 13 parts by weight of glass powder, 19 parts by weight of ceramic waste, and 5 parts by weight of plagioclase, mix them in a crusher for crushing treatment, add the crushed material obtained by passing through a 50-mesh sieve after the crushing treatment and water together into a ball mill, control the weight ratio of the crushed material: water: grinding beads to be 1:1:2, and wet-mill for 10 min to obtain a green body slurry. Weigh 10 parts by weight of the green body slurry and 0.3 part by weight of polyvinyl alcohol, mix and stir them, then atomize and granulate to obtain a green body powder. The green body powder is sent to a press for molding, and then dried at 55 °C for 5 h to obtain a ceramic green body.

[0039] Preparation Example 4:

[0040] A method for preparing a ceramic green body, specifically including the following process:

[0041] Weigh 2 parts by weight of quartz, 25 parts by weight of kaolin, 14 parts by weight of glass powder, 20 parts by weight of ceramic waste, and 6 parts by weight of plagioclase, mix them in a crusher for crushing treatment, add the crushed material obtained by passing through a 50-mesh sieve after the crushing treatment and water together into a ball mill, control the weight ratio of the crushed material: water: grinding beads to be 1:1:2, and wet-mill for 10 min to obtain a green body slurry. Weigh 10 parts by weight of the green body slurry and 0.3 part by weight of polyvinyl alcohol, mix and stir them, then atomize and granulate to obtain a green body powder. The green body powder is sent to a press for molding, and then dried at 55 °C for 5 h to obtain a ceramic green body.

[0042] Preparation Example 5:

[0043] A method for preparing a ceramic green body, specifically including the following process:

[0044] Weigh 5 parts by weight of quartz, 25 parts by weight of kaolin, 14 parts by weight of glass powder, 20 parts by weight of ceramic waste, and 6 parts by weight of plagioclase, mix them in a crusher for crushing treatment. Add the crushed material obtained by passing through a 50-mesh sieve after the crushing treatment and water together into a ball mill. Control the weight ratio of the crushed material: water: grinding beads to be 1:1:2, and mix and wet grind for 10 min to obtain a green body slurry. Weigh 10 parts by weight of the green body slurry and 0.3 parts by weight of polyvinyl alcohol, mix and stir, and then atomize and granulate to obtain a green body powder. Feed the green body powder into a press for molding, and then dry at 55 °C for 5 h to obtain a ceramic green body.

[0045] Preparation Example 6:

[0046] A method for preparing a ceramic green body specifically includes the following process:

[0047] Weigh 2 parts by weight of quartz, 25 parts by weight of kaolin, 14 parts by weight of glass powder, 20 parts by weight of ceramic waste, and 6 parts by weight of plagioclase, mix them in a crusher for crushing treatment. Add the crushed material obtained by passing through a 50-mesh sieve after the crushing treatment and water together into a ball mill. Control the weight ratio of the crushed material: water: grinding beads to be 1:1:2, and mix and wet grind for 10 min to obtain a green body slurry. Weigh 10 parts by weight of the green body slurry and 0.5 parts by weight of polyvinyl alcohol, mix and stir, and then atomize and granulate to obtain a green body powder. Feed the green body powder into a press for molding, and then dry at 55 °C for 5 h to obtain a ceramic green body.

[0048] Preparation Example 7:

[0049] A method for preparing an organosilicon-modified dispersant specifically includes the following process:

[0050] Disperse 1 part by weight of γ-aminopropyltrimethoxysilane in 95 parts by weight of an ethanol-water solution (obtained by mixing and stirring 1 part by weight of absolute ethanol and 7 parts by weight of deionized water), then add 10 parts by weight of a lignosulfonate dispersant and mix and stir to obtain a mixed solution. Adjust the pH value of the mixed solution to 6.0 with dilute hydrochloric acid, and then place it in a water bath at 30 °C and stir and react at a speed of 200 r / min for 4 h. After the reaction is completed, pour the reaction solution into a dialysis bag with a cut-off molecular weight of 500 Da and perform dialysis treatment with distilled water for 60 h to obtain an organosilicon-modified dispersant.

[0051] Preparation Example 8:

[0052] A method for preparing an organosilicon-modified dispersant specifically includes the following process:

[0053] Disperse 1 part by weight of γ-aminopropyltrimethoxysilane in 96 parts by weight of an ethanol-water solution (obtained by mixing 1 part by weight of absolute ethanol and 8 parts by weight of deionized water and stirring), then add 11 parts by weight of sodium lignosulfonate dispersant and mix and stir to obtain a mixed solution. Adjust the pH value of the mixed solution to 6.0 with dilute hydrochloric acid, and then place it in a water bath at 35°C and stir and react at a speed of 200 r / min for 5 h. After the reaction is completed, pour the reaction solution into a dialysis bag with a molecular weight cut-off of 500 Da and dialyze it with distilled water for 60 h to obtain an organosilicon-modified dispersant.

[0054] Preparation Example 9:

[0055] A method for preparing an organosilicon-modified dispersant specifically includes the following process:

[0056] Disperse 1 part by weight of γ-aminopropyltriethoxysilane in 98 parts by weight of an ethanol-water solution (obtained by mixing 1 part by weight of absolute ethanol and 9 parts by weight of deionized water and stirring), then add 11 parts by weight of sodium lignosulfonate dispersant and mix and stir to obtain a mixed solution. Adjust the pH value of the mixed solution to 6.5 with dilute hydrochloric acid, and then place it in a water bath at 35°C and stir and react at a speed of 200 r / min for 5 h. After the reaction is completed, pour the reaction solution into a dialysis bag with a molecular weight cut-off of 500 Da and dialyze it with distilled water for 60 h to obtain an organosilicon-modified dispersant.

[0057] Preparation Example 10:

[0058] A method for preparing an organosilicon-modified dispersant specifically includes the following process:

[0059] Disperse 1 part by weight of γ-aminopropyltriethoxysilane in 100 parts by weight of an ethanol-water solution (obtained by mixing 1 part by weight of absolute ethanol and 9 parts by weight of deionized water and stirring), then add 12 parts by weight of sodium lignosulfonate dispersant and mix and stir to obtain a mixed solution. Adjust the pH value of the mixed solution to 6.5 with dilute hydrochloric acid, and then place it in a water bath at 40°C and stir and react at a speed of 200 r / min for 6 h. After the reaction is completed, pour the reaction solution into a dialysis bag with a molecular weight cut-off of 500 Da and dialyze it with distilled water for 60 h to obtain an organosilicon-modified dispersant.

[0060] Preparation Example 11:

[0061] A method for preparing an organosilicon-modified dispersant specifically includes the following process:

[0062] Disperse 1 part by weight of vinyltriethoxysilane in 100 parts by weight of an ethanol - aqueous solution (obtained by mixing and stirring 1 part by weight of absolute ethanol and 9 parts by weight of deionized water), then add 12 parts by weight of sodium lignosulfonate dispersant and mix and stir to obtain a mixed solution. Adjust the pH value of the mixed solution to 6.5 with dilute hydrochloric acid, and then place it in a water bath at 40 °C and stir - react at a speed of 200 r / min for 6 h. After the reaction is completed, pour the reaction solution into a dialysis bag with a cut - off molecular weight of 500 Da and dialyze it with distilled water for 60 h to obtain an organosilicon - modified dispersant.

[0063] Preparation Example 12:

[0064] A preparation method of an organosilicon - modified dispersant specifically includes the following process:

[0065] Disperse 1 part by weight of γ - aminopropyltriethoxysilane in 100 parts by weight of an ethanol - aqueous solution (obtained by mixing and stirring 1 part by weight of absolute ethanol and 9 parts by weight of deionized water), then add 12 parts by weight of sulfonated melamine - formaldehyde dispersant and mix and stir to obtain a mixed solution. Adjust the pH value of the mixed solution to 6.5 with dilute hydrochloric acid, and then place it in a water bath at 40 °C and stir - react at a speed of 200 r / min for 6 h. After the reaction is completed, pour the reaction solution into a dialysis bag with a cut - off molecular weight of 500 Da and dialyze it with distilled water for 60 h to obtain an organosilicon - modified dispersant.

[0066] Preparation Example 13:

[0067] A preparation method of wear - resistant glaze slurry specifically includes the following process:

[0068] Weigh 15 parts by weight of white corundum, 8 parts by weight of mullite, 1 part by weight of glass fiber, 2 parts by weight of zirconium silicate and 6 parts by weight of wollastonite, mix them in a crusher for crushing treatment, add the crushed ore obtained after the crushing treatment to a ball mill, control the weight - part ratio of the crushed ore to the grinding beads to be 1:2.5, mix and dry - grind at a speed of 400 r / min for 80 min, and after the dry - grinding is completed, pass through a 500 - mesh sieve to obtain a mixed mineral powder. Weigh 5 parts by weight of the mixed mineral powder, 0.08 part by weight of the organosilicon - modified dispersant obtained in Preparation Example 7 and 2 parts by weight of water, mix and stir for 1 h, and then age for 2 days to obtain the wear - resistant glaze slurry.

[0069] Preparation Example 14:

[0070] A preparation method of wear - resistant glaze slurry specifically includes the following process:

[0071] Weigh 16 parts by weight of white fused alumina, 9 parts by weight of mullite, 2 parts by weight of glass fiber, 2 parts by weight of zirconium silicate and 8 parts by weight of wollastonite, mix them and conduct crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill. Control the weight ratio of the crushed ore to the grinding beads to 1:2.5, and mix and dry grind at a speed of 400 r / min for 85 min. After the dry grinding is completed, pass through a 500-mesh sieve to obtain a mixed mineral powder. Weigh 6 parts by weight of the mixed mineral powder, 0.09 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 8 and 3 parts by weight of water, mix and stir for 1 h, and then age for 2 days to obtain a wear-resistant glaze slurry.

[0072] Preparation Example 15:

[0073] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0074] Weigh 17 parts by weight of white fused alumina, 10 parts by weight of mullite, 3 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 10 parts by weight of wollastonite, mix them and conduct crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill. Control the weight ratio of the crushed ore to the grinding beads to 1:2.5, and mix and dry grind at a speed of 400 r / min for 85 min. After the dry grinding is completed, pass through a 500-mesh sieve to obtain a mixed mineral powder. Weigh 7 parts by weight of the mixed mineral powder, 0.1 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 9 and 3 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0075] Preparation Example 16:

[0076] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0077] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and conduct crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill. Control the weight ratio of the crushed ore to the grinding beads to 1:2.5, and mix and dry grind at a speed of 400 r / min for 90 min. After the dry grinding is completed, pass through a 500-mesh sieve to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder, 0.1 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 10 and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0078] Preparation Example 17:

[0079] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0080] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and conduct crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill, control the weight ratio of the crushed ore to the grinding beads to 1:2.5, mix and dry grind at a speed of 400 r / min for 90 min, and pass through a 500-mesh sieve after the dry grinding to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder, 0.1 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 11 and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0081] Preparation Example 18:

[0082] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0083] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and conduct crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill, control the weight ratio of the crushed ore to the grinding beads to 1:2.5, mix and dry grind at a speed of 400 r / min for 90 min, and pass through a 500-mesh sieve after the dry grinding to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder, 0.1 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 12 and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0084] Preparation Example 19:

[0085] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0086] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and conduct crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill, control the weight ratio of the crushed ore to the grinding beads to 1:2.5, mix and dry grind at a speed of 400 r / min for 10 min to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder, 0.1 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 10 and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0087] Preparation Example 20:

[0088] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0089] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and carry out crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill, and control the weight ratio of the crushed ore to the grinding beads to 1:2.5. Mix and dry grind at a speed of 400 r / min for 90 min. After the dry grinding is completed, pass through a 500-mesh sieve to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder, 0.1 part by weight of sodium lignosulfonate and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0090] Preparation Example 21:

[0091] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0092] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and carry out crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill, and control the weight ratio of the crushed ore to the grinding beads to 1:2.5. Mix and dry grind for 90 min. After the dry grinding is completed, pass through a 500-mesh sieve to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder, 0.5 part by weight of the organosilicon-modified dispersant obtained in Preparation Example 10 and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry.

[0093] Preparation Example 22:

[0094] A method for preparing a wear-resistant glaze slurry, specifically including the following process:

[0095] Weigh 18 parts by weight of white fused alumina, 11 parts by weight of mullite, 4 parts by weight of glass fiber, 3 parts by weight of zirconium silicate and 12 parts by weight of wollastonite, mix them and carry out crushing treatment in a crusher. Add the crushed ore obtained after the crushing treatment to a ball mill, and control the weight ratio of the crushed ore to the grinding beads to 1:2.5. Mix and dry grind at a speed of 400 r / min for 90 min. After the dry grinding is completed, pass through a 500-mesh sieve to obtain a mixed mineral powder. Weigh 8 parts by weight of the mixed mineral powder and 4 parts by weight of water, mix and stir for 2 h, and then age for 3 days to obtain a wear-resistant glaze slurry. Example 1

[0096] A method for preparing a true wear-resistant ceramic tile, specifically including the following process:

[0097] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 13 onto the surface of the ceramic green body obtained in Preparation Example 1, control the glazing thickness to be 0.5 mm, then place the glazed ceramic green body in a temperature environment of 130 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1180 °C at a heating rate of 20 °C / min for calcination for 1.5 h, and then naturally cool to obtain a ceramic tile. Example 2

[0098] A method for preparing a true wear-resistant ceramic tile specifically includes the following process:

[0099] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 14 onto the surface of the ceramic green body obtained in Preparation Example 2, control the glazing thickness to be 0.6 mm, then place the glazed ceramic green body in a temperature environment of 140 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1200 °C at a heating rate of 20 °C / min for calcination for 1.5 h, and then naturally cool to obtain a ceramic tile. Example 3

[0100] A method for preparing a true wear-resistant ceramic tile specifically includes the following process:

[0101] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 15 onto the surface of the ceramic green body obtained in Preparation Example 3, control the glazing thickness to be 0.6 mm, then place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1220 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool to obtain a ceramic tile. Example 4

[0102] A method for preparing a true wear-resistant ceramic tile specifically includes the following process:

[0103] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 16 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm, then place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool to obtain a ceramic tile.

[0104] Comparative Example 1:

[0105] A method for preparing a true wear-resistant ceramic tile specifically includes the following process:

[0106] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 16 onto the surface of the ceramic green body obtained in Preparation Example 5, control the glazing thickness to be 0.7 mm, then place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0107] Comparative Example 2:

[0108] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0109] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 16 onto the surface of the ceramic green body obtained in Preparation Example 6, control the glazing thickness to be 0.7 mm, then place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0110] Comparative Example 3:

[0111] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0112] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 17 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm, then place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0113] Comparative Example 4:

[0114] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0115] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 18 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm, then place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min, and then put it into a muffle furnace and heat it up to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0116] Comparative Example 5:

[0117] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0118] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 19 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm. Then, place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min. Next, put it into a muffle furnace and heat it to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0119] Comparative Example 6:

[0120] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0121] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 20 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm. Then, place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min. Next, put it into a muffle furnace and heat it to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0122] Comparative Example 7:

[0123] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0124] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 21 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm. Then, place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min. Next, put it into a muffle furnace and heat it to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0125] Comparative Example 8:

[0126] A preparation method of a true wear-resistant ceramic tile specifically includes the following process:

[0127] Use a glazing tool to apply the wear-resistant glaze slurry obtained in Preparation Example 22 onto the surface of the ceramic green body obtained in Preparation Example 4, control the glazing thickness to be 0.7 mm. Then, place the glazed ceramic green body in a temperature environment of 150 °C for drying treatment for 30 min. Next, put it into a muffle furnace and heat it to 1240 °C at a heating rate of 20 °C / min for calcination for 2 h, and then naturally cool it to obtain a ceramic tile.

[0128] Use a micro-Vickers hardness tester to test the Vickers hardness of the ceramic tiles obtained in Examples 1 to 4 and Comparative Examples 1 to 8, and the results are shown in Table 1 below.

[0129]

[0130] According to "GB / T 3810.7-2016 Test methods for ceramic tiles - Part 7: Determination of resistance to abrasion of glazed tiles", the abrasion resistance of the ceramic tiles obtained in Examples 1 to 4 and Comparative Examples 1 to 8 was tested. The size was 100 mm × 100 mm. The results are shown in Table 2 below.

[0131]

[0132] According to "GB / T 3810.7-2016 Test methods for ceramic tiles - Part 3: Determination of water absorption, apparent porosity, apparent relative density and bulk density", the water absorption of the ceramic tiles obtained in Examples 1 to 4 and Comparative Examples 1 to 8 was determined. The results are shown in Table 3 below.

[0133]

[0134] From the results of Tables 1 to 3 above, the following conclusions can be drawn:

[0135] (1) It can be found from Examples 1 to 4 that the wear-resistant glaze slurry prepared by the present invention from the organosilicon-modified dispersant and the mixed mineral powder was applied to the surface of the ceramic body, achieving good hardness, abrasion resistance and low water absorption.

[0136] (2) It can be found from Comparative Example 1 that the abrasion resistance and hardness of the prepared ceramic tiles are poor, and the water absorption is high. This may be because although quartz has good hardness and wear resistance, adding too much in this system may lead to a large difference in the thermal expansion coefficient between quartz itself and the materials in the wear-resistant glaze slurry, resulting in a large difference in the shrinkage degree, which may cause the wear-resistant glaze slurry to be subjected to excessive tensile stress, leading to cracking and fragmentation of the glaze layer. Moreover, the structure of quartz itself is relatively loose, which is easy to increase micropores, and then may lead to poor denseness, resulting in an increase in water absorption. The increase in water absorption is easy to cause the deformation of the ceramic tile, further affecting the hardness and abrasion resistance.

[0137] (3) It can be found from Comparative Example 2 that the abrasion resistance and hardness of the prepared ceramic tiles are poor, and the water absorption is high. This may be because although the binder can be decomposed and removed by high-temperature calcination, in the initial stage of mixing and preparation, excessive binder may hinder the combination between mineral particles, resulting in uneven mixing and bonding, and may instead make the internal structure of the green body loose and the pores increase, thus deteriorating the performance of the finally calcined ceramic tile.

[0138] (4) It can be found from Comparative Example 3 that the hardness and wear resistance of the prepared ceramic tiles are reduced, and the water absorption rate is increased. This may be because although vinyl triethoxysilane can be hydrolyzed in an acidic environment to produce silanol groups and then cross-linked with the hydroxyl groups on sodium lignin sulfonate, due to the presence of unsaturated double bonds, the introduction of hydrophobic groups may affect the dispersion of finer mixed mineral powders, which may cause local aggregation and reduce the fluidity of the wear-resistant glaze slurry, resulting in poor performance of the ceramic tiles.

[0139] (5) It can be found from Comparative Example 4 that the hardness and wear resistance of the prepared ceramic tiles are reduced, and the water absorption rate is increased. This may be because the sulfonated melamine formaldehyde is difficult to be modified with the silane coupling agent through the condensation cross-linking of silanol and hydroxyl groups. As a result, although the sulfonated melamine formaldehyde can be dispersed and mixed with mineral powders to prepare wear-resistant glaze slurry, it is not resistant to high temperatures and is prone to decompose too quickly in the high temperature stage, which affects the performance of the ceramic tiles finally calcined.

[0140] (6) It can be found from Comparative Example 5 that the hardness and wear resistance of the prepared ceramic tiles are reduced, while the water absorption rate is increased. This may be due to the short dry grinding time, which leads to the mixed mineral powder having a large particle size. A large particle size will easily lead to more gaps during mixed calcination. The increase in gaps will easily increase the water absorption rate of the ceramic tiles, thereby affecting the hardness and wear resistance.

[0141] (7) It can be found from Comparative Example 6 that the hardness and wear resistance of the prepared ceramic tiles are reduced, and the water absorption rate is increased. This may be because although the unmodified sodium lignin sulfonate can disperse the mixed mineral powder with a finer particle size, it has poor high temperature resistance and may easily cause the sodium lignin sulfonate to decompose too quickly during high-temperature calcination, thereby affecting the stable formation of wear-resistant glaze slurry on the surface of the ceramic body, and ultimately causing the performance of the ceramic tiles to deteriorate.

[0142] (8) It can be found from Comparative Example 7 that the hardness and wear resistance of the prepared ceramic tiles are reduced, while the water absorption rate is increased. This may be because although the organosilicon-modified dispersant helps to disperse the mixed mineral powder with a finer particle size, excessive use may lead to an increase in the repulsive force between the particles, hindering the fusion of the particles during the sintering process and reducing the grain boundary bonding strength. In addition, it is easy to decompose at high temperatures to produce excessive gas, forming pores, reducing the density of the tile, and thus affecting the stable formation of wear-resistant glaze slurry on the surface of the ceramic body, ultimately causing the performance of the ceramic tile to deteriorate.

[0143] (9) It can be found from Comparative Example 8 that the hardness and wear resistance of the prepared ceramic tiles are reduced, and the water absorption rate is increased. This may be because the particle size of the mixed mineral powder is relatively fine, and it may be difficult to achieve effective dispersion by simply adding water and mixing. It is easy to agglomerate, which in turn deteriorates the performance of the ceramic tiles.

[0144] The above-described embodiments have elaborated in detail the technical solutions and beneficial effects of the present invention. It should be understood that the above is only specific embodiments of the present invention and is not used to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A true wear-resistant ceramic tile, characterized in that, The ceramic tile is composed of a ceramic body and a wear-resistant glaze slurry; The preparation method of the wear-resistant glaze slurry comprises the following steps: White fused alumina, mullite, glass fiber, zirconium silicate and wollastonite are mixed and crushed according to the weight ratio of 15-18:8-11:1-4:2-3:6-12 to obtain crushed ore materials. The crushed ore materials and grinding beads are mixed and dry-ground according to the weight ratio of 1:2.5 and then sieved to obtain mixed mineral powder; Weigh 5-8 parts by weight of the mixed mineral powder, 0.08-0.1 part by weight of the organosilicon-modified dispersant and 2-4 parts by weight of water, and mix and stir according to the weight ratio of 5-8:0.08-0.1:2-4, and then age to obtain the wear-resistant glaze slurry; The preparation method of the organosilicon-modified dispersant comprises the following steps: A silane coupling agent, an ethanol-aqueous solution and a dispersant are mixed and stirred according to the weight ratio of 1:95-100:10-12 to obtain a mixed solution. After adjusting the pH of the mixed solution to 6.0-6.5, it is subjected to a heat preservation reaction to obtain the organosilicon-modified dispersant; The silane coupling agent is γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane; The dispersant is sodium lignosulfonate.

2. The true wear-resistant ceramic tile according to claim 1, characterized in that, The preparation method of the ceramic body comprises the steps: Quartz, kaolin, glass powder, ceramic waste and plagioclase are mixed and crushed according to the weight ratio of 1-2:19-25:11-14:17-21:3-6 to obtain crushed materials. The crushed materials, water and grinding beads are mixed and wet-ground according to the weight ratio of 1:1:2 to obtain a body slurry; The body slurry and a binder are mixed and atomized granulated according to the weight ratio of 10:0.2-0.3 to obtain body powder. After the body powder is pressed into shape, it is dried to obtain a ceramic body.

3. The true wear-resistant ceramic tile according to claim 1, characterized in that, The ethanol-aqueous solution is composed of absolute ethanol and deionized water mixed according to the weight ratio of 1:7-9.

4. The true wear-resistant ceramic tile according to claim 1, wherein The conditions of the heat preservation reaction include a reaction temperature of 30°C-40°C and a reaction time of 4h-6h.

5. A preparation method of a true wear-resistant ceramic tile as described in any one of claims 1 to 4, characterized in that, The preparation method comprises the following steps: The wear-resistant glaze slurry is applied to the surface of the ceramic body by a glazing tool, and the glazing thickness is controlled to be 0.5mm-0.7mm. Then, it is first dried at 130°C-150°C for 30min, and then calcined at 1180°C-1240°C for 1.5h-2h to obtain the ceramic tile.

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