Ceramic tile with granite texture and preparation method thereof

Abstract

The invention provides a ceramic tile with granite texture and a preparation method thereof.The preparation method comprises the four steps of blank preparation, glazing, ink jetting and firing, alumina-zirconia composite fibers subjected to surface modification treatment are prepared into glaze slip, the glaze slip is applied to a first blank body formed by pressing ceramic tile powder, and the first blank body is prepared into a ceramic tile body; after the printing ink is sprayed on a ceramic tile blank through an ink jet printer and sintered, the specific surface area of composite fibers is remarkably increased and the number of binding sites of the composite fibers is increased by utilizing the expansion rate difference of aluminum oxide and zirconium oxide, a three-dimensional connecting interface is formed between glaze and the blank during firing, and the binding sites in the glaze improve the anchoring strength of the printing ink; the bonding force of the ink and the glaze layer is remarkably enhanced, the wear resistance and mechanical performance of the large-grain pattern layer are improved, wear and scratches during use are reduced, the service life of the ceramic tile is prolonged, the use experience of a user is improved, and the ceramic tile has the advantages of being simple in preparation process, wide in application range and convenient to popularize and implement.

Description

Technical Field

[0001] The present application belongs to the technical field of ceramic tile production, and specifically relates to a ceramic tile with a granite texture and a preparation method thereof. Background Art

[0002] Ceramic inkjet printing technology plays an important role in architectural decoration. It can create a rich variety of patterns and textures on the surface of ceramic tiles, greatly enriching the decorative effects of ceramic tiles and meeting the market demand for personalized and diversified decoration. However, ceramic tiles produced using inkjet technology currently on the market still have some shortcomings, which limit their further development and application.

[0003] In existing technologies, after ink is printed on the ceramic tile base, the inkjet layer has poor wear resistance and is easily scratched and abraded during use, affecting the integrity and decorative effect of the pattern and shortening the product's lifespan. Furthermore, the insufficient hardness of the inkjet layer makes the ceramic tile surface susceptible to scratches and abrasion after external impact or long-term use, affecting its aesthetics and lifespan.

[0004] Furthermore, the bonding strength between the inkjet layer and the ceramic tile substrate may be insufficient, causing it to wear, scratch, or even peel or fall off during use, affecting the product's quality and lifespan. Furthermore, the inkjet layer has poor chemical resistance and is easily corroded by chemicals such as acids and alkalis, causing the pattern to fade or become damaged, affecting the decorative effect and lifespan of the ceramic tile.

[0005] Secondly, inkjet printing mainly forms two-dimensional patterns, lacking the delicate concave texture and matte texture of natural stone. It is difficult to create a three-dimensional texture effect on the surface of ceramic tiles that is similar to the real concave and convex feeling and microporous matte texture of natural marble. The decorative effect is not three-dimensional and realistic enough.

[0006] In summary, although the existing ceramic tile inkjet coating technology has met the market demand for ceramic tile decorative effects to a certain extent, it still has many shortcomings. Therefore, it is urgent to make improvements to meet the market demand for high-quality ceramic tiles. Summary of the Invention

[0007] In order to solve the technical problems in the prior art that the inkjet layer on the surface of marble-patterned ceramic tiles prepared by inkjet printing technology has poor wear resistance, wear and scratches occur during use, affecting the integrity and decorative effect of the pattern, the bonding ability of the ink to the ceramic tile surface is reduced, the overall mechanical properties of the ceramic tiles are poor, the service life is short, and the user experience is poor, this application proposes a ceramic tile with a granite texture.

[0008] In order to solve the technical problem raised in this application, this application also provides a method for preparing ceramic tiles with granite texture.

[0009] The present application adopts the following scheme, a method for preparing a ceramic tile with a granite texture, comprising the following steps:

[0010] Step 101: Pressing the prefabricated ceramic tile powder into a first embryonic body;

[0011] Step 102: Apply the prefabricated glaze slurry to the surface of the first embryonic body prepared in step 101 to obtain a second embryonic body;

[0012] Step 103: Spray the prefabricated ink onto the surface of the second embryonic body prepared in step 102 to obtain a third embryonic body;

[0013] Step 104. Transfer the third embryo body prepared in step 103 to a kiln and fire it at a firing temperature of 1200℃-1450℃, a heating rate of 20℃ / min, and a holding time of 20min. After the firing is completed, a finished ceramic tile with a granite texture is obtained.

[0014] In step 102, the glaze slurry is composed of the following components by weight: 15-18 parts of albite, 5-10 parts of potassium feldspar, 8-12 parts of alumina-zirconia composite fiber, 25-32 parts of waste clay bricks, and 12-18 parts of quartz;

[0015] Wherein, the alumina-zirconia composite fiber is surface-modified.

[0016] In some feasible embodiments, the firing temperature in step 104 is 1200° C.-1450° C., the heating rate is 20° C. / min, and the holding time is 20 min.

[0017] In some feasible embodiments, the waste clay bricks are composed of the following components by weight:

[0018] Al2O3 13.12wt%-13.61wt%, Fe2O3 5.12wt%-5.77wt%, MgO2 2.11wt%-2.35wt%, Na2O1.55wt%-1.60wt%, K2O 2.12wt%-2.33wt%, TiO2 0.51wt%-0.65wt%, SiO2 balance, loss on ignition 2.3%.

[0019] In some feasible embodiments, the method for preparing the alumina-zirconia composite fiber comprises the following steps:

[0020] Step 201. Ethyl acetoacetate and isopropyl alcohol are sequentially added to a magnetic stirring kettle and stirred at room temperature at 800-1200 rpm until uniformly mixed. Zirconium oxychloride is then added and stirred at room temperature at 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system becomes uniformly milky white, thereby obtaining reaction solution A.

[0021] Step 202. To the reaction solution A prepared in step 201, aluminum tert-butoxide and N,N-dimethylformamide were added in sequence, and the mixture was stirred at room temperature, in a water bath at 33°C, and at 1000 rpm until the liquid system became transparent, thereby obtaining reaction solution B.

[0022] Step 203. Add polyvinyl pyrrolidone to the reaction solution B prepared in step 201, and stir at room temperature and 500 rpm for 5 h-10 h to obtain spinning solution C;

[0023] Step 204. Transfer the spinning solution C prepared in step 203 to an electrospinning device, and spin it under the conditions of a spinning voltage of 13.5 kV and a spinning distance of 15 cm. After the spinning is completed, alumina-zirconia composite fibers are obtained.

[0024] In some feasible embodiments, in step 201, the mass ratio of ethyl acetoacetate, isopropyl alcohol and zirconium oxychloride is (1.2-1.7): (8.9-9.5): (0.1-0.3);

[0025] (11.3-14.7): (92-100): 1;

[0026] In step 202, the mass ratio of reaction solution A, aluminum tert-butoxide, and N,N-dimethylformamide is 1:(0.13-0.17):(0.11-0.13);

[0027] In step 203 , the mass ratio of reaction solution B to polyvinyl pyrrolidone is 1:(0.17-0.21).

[0028] In some feasible embodiments, the cross-sectional diameter of the alumina-zirconia composite fiber is 1160 nm-1274 nm, and the aspect ratio is (11.5-14.8):1.

[0029] In some feasible embodiments, in step 102, the surface modification treatment of the alumina-zirconia composite fiber includes the following steps:

[0030] Alumina-zirconia composite fiber, butyl orthosilicate, distilled water and anhydrous ethanol were added to a reactor in sequence, and ultrasonic treatment was carried out in a water bath at 40°C and an ultrasonic frequency of 20kHz-25kHz. During the ultrasonic treatment, 1.5mol / L nitric acid solution was added dropwise to the reaction system. After ultrasonic treatment for 20min-30min, the reaction system was filtered and dried in sequence to obtain surface-modified alumina-zirconia composite fiber.

[0031] In some feasible embodiments, in step 102, the method for preparing the glaze slurry includes the following steps:

[0032] After adding the components of the glaze slurry into the ball mill in a predetermined proportion, 0.3 wt % of carboxymethyl cellulose was added to the ball mill as a suspending agent, and the glaze slurry was obtained after ball milling for 40-60 minutes.

[0033] During the ball milling process, the mass ratio of glaze, suspending agent, grinding balls and water in the ball mill is 1: (1.25-1.5): (10-15): (3-5).

[0034] In some feasible embodiments, in step 101, the ceramic tile powder is composed of the following components, by weight: 15-18 parts of talc, 3-8 parts of nano-calcium carbonate, 12-15 parts of quartz, 10-12 parts of potassium feldspar, and 5-10 parts of kaolin.

[0035] In actual implementation, the median size of the nano calcium carbonate is 53.8 μm.

[0036] In some feasible embodiments, in step 101, the method for preparing ceramic tile powder includes the following steps:

[0037] The components of the ceramic tile powder are sequentially added into the grinder according to a preset ratio. After ball milling, the first powder is obtained. The first powder is sequentially sieved through a 50-mesh sieve, sealed and aged to obtain the ceramic tile powder.

[0038] During the aging process, the mass ratio of water to the first powder is (0.04-0.06):1;

[0039] In step 101, the method for preparing the first embryo body includes the following steps:

[0040] The ceramic tile powder is pressed into a preset mold under a pressure of 5MPa-10MPa, and then dried and demolded to obtain a first embryonic body;

[0041] The thickness of the first embryonic body is 3mm-8mm.

[0042] In order to solve the technical problem raised in the present application, the present application also provides a ceramic tile with a granite texture, which is prepared by the above-mentioned method for preparing a ceramic tile with a granite texture.

[0043] Compared with the prior art, this application has the following beneficial effects:

[0044] The present application provides a ceramic tile with a granite texture and a preparation method thereof, which includes four steps: embryo preparation, glazing, inkjet printing and firing. The method comprises the following steps: preparing a glaze slurry from a surface-modified alumina-zirconia composite fiber, applying the glaze slurry to a first embryo body pressed from ceramic tile powder, spraying ink on the ceramic tile embryo body through an inkjet machine and sintering. The difference in expansion coefficients of alumina and zirconia is utilized to significantly increase the specific surface area of ​​the composite fiber and significantly increase the number of its own binding sites. During firing, a three-dimensional connection interface is formed between the glaze and the embryo body. The binding sites in the glaze improve the anchoring strength of the ink, significantly enhance the bonding force between the ink and the surface of the ceramic tile, improve the wear resistance and mechanical properties of the marble pattern layer on the surface of the ceramic tile, reduce wear and scratches during use, extend the service life of the ceramic tile, and improve the user experience. The method has the advantages of simple preparation process, high mass production feasibility, wide application range, and easy promotion and implementation. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is a trend chart showing the variation of the breaking strength of ceramic tiles with the diameter of alumina-zirconia composite fibers in Example 2 and Comparative Examples 3-6 of the present application;

[0046] Figure 2 This is a trend chart showing the change in ceramic tile wear versus alumina-zirconia composite fiber diameter in Example 2 and Comparative Examples 3-6 of the present application;

[0047] Figure 3 This is a trend chart showing the change in modulus of rupture of ceramic tiles with the diameter of alumina-zirconia composite fibers in Example 2 and Comparative Examples 3-6 of the present application;

[0048] Figure 4 This is a trend chart showing the change in the breaking strength of ceramic tiles with the particle size of nano-calcium carbonate in Example 2 and Comparative Examples 7-10 of the present application;

[0049] Figure 5 This is a trend chart showing the variation of ceramic tile wear with nano-calcium carbonate particle size in Example 2 and Comparative Examples 7-10 of the present application;

[0050] Figure 6 This is a trend diagram of the fracture coefficient of ceramic tiles in Example 2 and Comparative Examples 7-10 of the present application as a function of the particle size of nano-calcium carbonate;

[0051] Figure 7is a SEM scan of the alumina-zirconia composite fiber prepared in Example 2 of the present application;

[0052] Figure 8 This is a SEM scan of the sintered alumina-zirconia composite fiber in Example 2 of the present application. DETAILED DESCRIPTION

[0053] Combine Figure 1-8 The following content further illustrates the technical solution proposed in this application. Example 1

[0054] (1) The preparation method of alumina-zirconia composite fiber includes the following steps:

[0055] Step 201. Ethyl acetoacetate and isopropyl alcohol are sequentially added to a magnetic stirring kettle and stirred at room temperature and 800 rpm until uniformly mixed. Zirconium oxychloride is then added and stirred at room temperature and 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system becomes uniformly milky white, thereby obtaining reaction solution A.

[0056] The mass ratio of ethyl acetoacetate, isopropyl alcohol and zirconium oxychloride is 1.2:8.9:0.1;

[0057] Step 202. To the reaction solution A prepared in step 201, aluminum tert-butoxide and N,N-dimethylformamide were added in sequence, and the mixture was stirred at room temperature, in a water bath at 33°C, and at 1000 rpm until the liquid system became transparent, thereby obtaining reaction solution B.

[0058] The mass ratio of reaction solution A, aluminum tert-butoxide, and N,N-dimethylformamide is 1:0.13:0.11;

[0059] Step 203. Add polyvinyl pyrrolidone to the reaction solution B prepared in step 201, and stir at room temperature and 500 rpm for 5 h-10 h to obtain spinning solution C;

[0060] Among them, the mass ratio of reaction solution B to polyvinyl pyrrolidone is 1:0.17;

[0061] Step 204. Transfer the spinning solution C prepared in step 203 to an electrospinning device, and spin it under the conditions of a spinning voltage of 13.5 kV and a spinning distance of 15 cm. After the spinning is completed, alumina-zirconia composite fibers are obtained.

[0062] (2) The surface modification treatment of alumina-zirconia composite fibers includes the following steps:

[0063] Alumina-zirconia composite fiber, butyl orthosilicate, distilled water and anhydrous ethanol were sequentially added to a reactor, and ultrasonic treatment was performed in a water bath at 40° C. and an ultrasonic frequency of 20 kHz. During the ultrasonic treatment, 1.5 mol / L nitric acid solution was added dropwise to the reaction system. After ultrasonic treatment for 20 min to 30 min, the reaction system was filtered and dried to obtain surface-modified alumina-zirconia composite fiber.

[0064] The mass ratio of alumina-zirconia composite fiber, butyl orthosilicate, distilled water, anhydrous ethanol and nitric acid solution is 1:5.6:8.2:3.5:0.6.

[0065] (3) The method for preparing the glaze slurry comprises the following steps:

[0066] According to the component table shown in Table 1, the components of the glaze slurry were added to the ball mill in a predetermined proportion, and then 0.3 wt % of carboxymethyl cellulose was added to the ball mill as a suspending agent. After ball milling for 40 minutes, the glaze slurry was obtained.

[0067] During the ball milling process, the mass ratio of glaze, suspending agent, grinding balls and water in the ball mill is 1:1.25:10:3.

[0068] (4) The preparation method of ceramic tile powder includes the following steps:

[0069] According to the component table shown in Table 1, the components of the ceramic tile powder are added into the grinder in sequence according to the preset proportions. After ball milling, the first powder is obtained. The first powder is sieved through a 50-mesh sieve, sealed and aged to obtain the ceramic tile powder.

[0070] (5) The method for preparing a ceramic tile having a granite texture comprises the following steps:

[0071] Step 101: Ceramic tile powder is pressed into a predetermined mold under a pressure of 5 MPa, and then dried and demolded to obtain a first embryonic body with a thickness of 5 mm.

[0072] Step 102: Apply the prefabricated glaze slurry to the surface of the first embryo body prepared in step 101 by dipping, and naturally dry to obtain a second embryo body;

[0073] Step 103: Spray the prefabricated ink onto the surface of the second embryonic body prepared in step 102 to obtain a third embryonic body;

[0074] Step 104. Transfer the third embryo body prepared in step 103 to a kiln and fire it at a firing temperature of 1200°C, a heating rate of 20°C / min, and a holding time of 20 minutes. After the firing is completed, a finished ceramic tile with a granite texture is obtained. Example 2

[0075] (1) The preparation method of alumina-zirconia composite fiber includes the following steps:

[0076] Step 201. Ethyl acetoacetate and isopropyl alcohol are sequentially added to a magnetic stirring kettle and stirred at room temperature and 1000 rpm until uniformly mixed. Zirconium oxychloride is then added and stirred at room temperature and 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system becomes uniformly milky white, thereby obtaining reaction solution A.

[0077] The mass ratio of ethyl acetoacetate, isopropyl alcohol and zirconium oxychloride is 1.5:9:0.2;

[0078] Step 202. To the reaction solution A prepared in step 201, aluminum tert-butoxide and N,N-dimethylformamide were added in sequence, and the mixture was stirred at room temperature, in a water bath at 33°C, and at 1000 rpm until the liquid system became transparent, thereby obtaining reaction solution B.

[0079] The mass ratio of reaction solution A, aluminum tert-butoxide, and N,N-dimethylformamide is 1:0.15:0.12;

[0080] Step 203. Add polyvinyl pyrrolidone to the reaction solution B prepared in step 201, and stir at room temperature and 500 rpm for 5 h-10 h to obtain spinning solution C;

[0081] Among them, the mass ratio of reaction solution B to polyvinyl pyrrolidone is 1:0.19;

[0082] Step 204. Transfer the spinning solution C prepared in step 203 to an electrospinning device, and spin it under the conditions of a spinning voltage of 13.5 kV and a spinning distance of 15 cm. After the spinning is completed, alumina-zirconia composite fibers are obtained.

[0083] (2) The surface modification treatment of alumina-zirconia composite fibers includes the following steps:

[0084] Alumina-zirconia composite fiber, butyl orthosilicate, distilled water, and anhydrous ethanol were sequentially added to a reactor and ultrasonically treated in a water bath at 40°C and an ultrasonic frequency of 22 kHz. During the ultrasonic treatment, 1.5 mol / L nitric acid solution was added dropwise to the reaction system. After ultrasonic treatment for 25 minutes, the reaction system was filtered and dried to obtain surface-modified alumina-zirconia composite fiber.

[0085] The mass ratio of alumina-zirconia composite fiber, butyl orthosilicate, distilled water, anhydrous ethanol and nitric acid solution is 1:5.6:8.2:3.5:0.6.

[0086] (3) The method for preparing the glaze slurry comprises the following steps:

[0087] According to the component table shown in Table 1, the components of the glaze slurry were added to the ball mill in a preset proportion, and then 0.3 wt% of carboxymethyl cellulose was added to the ball mill as a suspending agent. After ball milling for 50 minutes, the glaze slurry was obtained;

[0088] During the ball milling process, the mass ratio of glaze, suspending agent, grinding balls and water in the ball mill is 1:1.3:12:4.

[0089] (4) The preparation method of ceramic tile powder includes the following steps:

[0090] According to the component table shown in Table 1, the components of the ceramic tile powder are added into the grinder in sequence according to the preset proportions. After ball milling, the first powder is obtained. The first powder is sieved through a 50-mesh sieve, sealed and aged to obtain the ceramic tile powder.

[0091] (5) The method for preparing a ceramic tile having a granite texture comprises the following steps:

[0092] Step 101: Ceramic tile powder is pressed into a predetermined mold under a pressure of 5 MPa, and then dried and demolded to obtain a first embryonic body with a thickness of 5 mm.

[0093] Step 102: Apply the prefabricated glaze slurry to the surface of the first embryo body prepared in step 101 by dipping, and naturally dry to obtain a second embryo body;

[0094] Step 103: Spray the prefabricated ink onto the surface of the second embryonic body prepared in step 102 to obtain a third embryonic body;

[0095] Step 104. Transfer the third embryo body prepared in step 103 to a kiln and fire it at a firing temperature of 1300°C, a heating rate of 20°C / min, and a holding time of 20 minutes. After the firing is completed, a finished ceramic tile with a granite texture is obtained. Example 3

[0096] (1) The preparation method of alumina-zirconia composite fiber includes the following steps:

[0097] Step 201. Ethyl acetoacetate and isopropyl alcohol are sequentially added to a magnetic stirring kettle and stirred at room temperature and 1200 rpm until uniformly mixed. Zirconium oxychloride is then added and stirred at room temperature and 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system becomes uniformly milky white, thereby obtaining reaction solution A.

[0098] The mass ratio of ethyl acetoacetate, isopropyl alcohol and zirconium oxychloride is 1.7:9.5:0.3;

[0099] Step 202. To the reaction solution A prepared in step 201, aluminum tert-butoxide and N,N-dimethylformamide were added in sequence, and the mixture was stirred at room temperature, in a water bath at 33°C, and at 1000 rpm until the liquid system became transparent, thereby obtaining reaction solution B.

[0100] The mass ratio of reaction solution A, aluminum tert-butoxide, and N,N-dimethylformamide is 1:0.17:0.13;

[0101] Step 203. Add polyvinyl pyrrolidone to the reaction solution B prepared in step 201, and stir at room temperature and 500 rpm for 10 hours to obtain spinning solution C;

[0102] The mass ratio of reaction solution B to polyvinyl pyrrolidone is 1:0.21;

[0103] Step 204. Transfer the spinning solution C prepared in step 203 to an electrospinning device, and spin it under the conditions of a spinning voltage of 13.5 kV and a spinning distance of 15 cm. After the spinning is completed, alumina-zirconia composite fibers are obtained.

[0104] (2) The surface modification treatment of alumina-zirconia composite fibers includes the following steps:

[0105] Alumina-zirconia composite fiber, butyl orthosilicate, distilled water, and anhydrous ethanol were sequentially added to a reactor and ultrasonically treated in a water bath at 40°C and an ultrasonic frequency of 25 kHz. During the ultrasonic treatment, 1.5 mol / L nitric acid solution was added dropwise to the reaction system. After ultrasonic treatment for 30 minutes, the reaction system was filtered and dried to obtain surface-modified alumina-zirconia composite fiber.

[0106] The mass ratio of alumina-zirconia composite fiber, butyl orthosilicate, distilled water, anhydrous ethanol and nitric acid solution is 1:5.6:8.2:3.5:0.6.

[0107] (3) The method for preparing the glaze slurry comprises the following steps:

[0108] After adding the components of the glaze slurry into the ball mill in a predetermined proportion, 0.3 wt % of carboxymethyl cellulose was added into the ball mill as a suspending agent, and the glaze slurry was obtained after ball milling for 60 minutes;

[0109] During the ball milling process, the mass ratio of glaze, suspending agent, grinding balls and water in the ball mill is 1:1.5:15:5.

[0110] (4) The preparation method of ceramic tile powder includes the following steps:

[0111] The components of the ceramic tile powder are added into the grinder in sequence according to a preset ratio. After ball milling, the first powder is obtained. The first powder is sieved through a 50-mesh sieve in sequence, sealed and aged to obtain the ceramic tile powder.

[0112] (5) The method for preparing a ceramic tile having a granite texture comprises the following steps:

[0113] Step 101: Ceramic tile powder is pressed into a predetermined mold under a pressure of 5 MPa, and then dried and demolded to obtain a first embryonic body with a thickness of 5 mm.

[0114] Step 102: Apply the prefabricated glaze slurry to the surface of the first embryo body prepared in step 101 by dipping, and naturally dry to obtain a second embryo body;

[0115] Step 103: Spray the prefabricated ink onto the surface of the second embryonic body prepared in step 102 to obtain a third embryonic body;

[0116] Step 104. Transfer the third embryo body prepared in step 103 to a kiln and fire it at a firing temperature of 1200℃-1450℃, a heating rate of 20℃ / min, and a holding time of 20min. After the firing is completed, a finished ceramic tile with a granite texture is obtained.

[0117] Comparative Example 1

[0118] The difference between Comparative Example 1 and Example 2 is that the alumina-zirconia composite fiber is removed from the glaze slurry and is supplemented with an equal amount of waste clay bricks, while the other components and processes remain unchanged.

[0119] Comparative Example 2

[0120] The difference between Comparative Example 2 and Example 2 is that the surface treatment process of the alumina-zirconia composite fiber in the glaze slurry is eliminated, and the processes of other components remain unchanged.

[0121] Comparative Examples 3-6

[0122] The difference between Comparative Examples 3-6 and Example 2 is that, on the basis of Example 2, by adjusting the spinning parameters of the electrospinning equipment in step 204, the alumina-zirconia composite fiber with a cross-sectional diameter of 1200 nm in Example 2 is replaced by alumina-zirconia composite fibers with equal cross-sectional diameters of 800 nm, 1000 nm, 1100 nm, and 1300 nm, respectively, and the processes of other components remain unchanged.

[0123] Comparative Examples 7-10

[0124] The difference between Comparative Examples 3-6 and Example 2 is that, on the basis of Example 2, the nano-calcium carbonate with a median particle size of 53.8 μm in Example 2 is replaced by equal amounts of nano-calcium carbonate with a median particle size of 40 μm, 45 μm, 50 μm, and 60 μm, respectively, and the other components and processes remain unchanged.

[0125] Comparative Example 11

[0126] The difference between Comparative Example 11 and Example 2 is that, based on Example 2, the nano-calcium carbonate with a median particle size of 53.8 μm in Example 2 is removed and supplemented with an equal amount of talc, and the other components and processes remain unchanged.

[0127] Table 1 Components of Examples 1-3 and Comparative Examples 1-10

[0128]

[0129] Table 1

[0130]

[0131] Table 1

[0132]

[0133] The finished ceramic tiles (length: 10 cm, width: 10 cm, thickness: 5 mm) prepared in Examples 1-3 and Comparative Examples 1-11 were subjected to the following experiments:

[0134] Test 1: Measure the surface wear resistance of finished ceramic tiles according to GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of surface wear resistance of glazed tiles";

[0135] Test 2: Referring to GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of surface wear resistance of glazed tiles", we further tested the surface wear of the finished ceramic tiles and quantitatively analyzed their surface wear resistance.

[0136] Test 3: Measure the surface crack resistance of finished ceramic tiles according to GB / T 3810.11-2016 "Test methods for ceramic tiles - Part 11: Determination of glaze crack resistance of glazed tiles";

[0137] Test 4: Referring to the relevant standards of JC / T 908-2013 "Artificial Stone", the mechanical impact and scratch resistance of the finished ceramic tile surface were measured.

[0138] Test 5: Measure the modulus of rupture of finished ceramic tiles according to GB / T 3810.4-2016 "Test methods for ceramic tiles - Part 4: Determination of modulus of rupture and breaking strength";

[0139] Test 6: Measure the destructive strength of finished ceramic tiles according to GB / T 3810.4-2016 “Test methods for ceramic tiles - Part 4: Determination of modulus of rupture and destructive strength”.

[0140] The test results are shown in Table 2 below

[0141] Table 2 Test results of Examples 1-3 and Comparisons 1-10

[0142]

[0143] From Table 2 and Figure 1-8 It can be seen that by using alumina-zirconia composite fibers as glaze slurry, a three-dimensional network structure can be introduced into the glaze slurry. During the sintering process, Figure 7-8 As shown, the zirconia crystals in the alumina-zirconia composite fibers undergo a tetragonal-to-monoclinic phase transition and undergo volume expansion. On the one hand, the resulting protrusions fill the large-diameter micropores in the glaze layer; on the other hand, the branches of the composite fibers embed into the small-diameter micropores in the glaze layer, significantly increasing the topological complexity of the micropores on the glaze surface. After ink is sprayed onto the glaze layer, it penetrates into the highly disordered microporous structure, significantly increasing the ink's anchoring depth and, in turn, improving the wear resistance of the ink on the ceramic tile surface. This makes the ceramic tile less susceptible to wear and scratches during actual use, effectively maintaining the integrity of the pattern and the decorative effect.

[0144] Specifically, if Figure 8 As shown in the figure, during the sintering process of alumina-zirconia composite fibers, the expansion rate of zirconia is higher than that of alumina due to the difference in thermal expansion coefficients between the alumina and zirconia phases. The tetragonal to monoclinic phase transition of zirconia causes microscale undulations on the surface of the composite fibers, which are evenly distributed within the glaze layer and form a continuous skeleton.

[0145] More specifically, the zirconia crystals raised on the surface of the alumina-zirconia composite fiber can fill the large-diameter micropores in the glaze layer, and the branches of the alumina-zirconia composite fiber can mechanically engage with the small-diameter micropores in the glaze layer, which can effectively squeeze the crack tips of the glaze layer, increase the diffusion resistance of cracks inside the glaze layer, and form a three-dimensional mesh connection interface between the body and the glaze layer, thereby improving the bonding performance of the body and the glaze layer, avoiding stratification of the glaze layer and the body, and thus significantly improving the crack resistance of the glaze layer, the overall destructive strength of the ceramic tile and the modulus of rupture.

[0146] By modifying the surface of the alumina-zirconia composite fiber, on the one hand, nitric acid solution is used to etch nanopores on the surface of the alumina-zirconia composite fiber to increase the binding sites on the surface of the alumina-zirconia composite fiber. On the other hand, a surface modifier is used to modify it to effectively improve its interface performance, facilitate its excessive aggregation in the subsequent glaze slurry preparation process, and improve the uniformity of the distribution of the three-dimensional network structure.

[0147] In Example 1, the alumina-zirconia composite fibers were removed from the glaze slurry. This significantly reduced the complexity of the pore structure within the glaze layer, exposing the porous matrix after wear. This reduced ink anchoring depth, significantly degraded wear resistance, and easily caused scratches on the surface pattern. Furthermore, the absence of the zirconia phase (its phase transition and volume effects) in the glaze layer exacerbated stress concentration within the glaze layer, significantly reducing crack resistance. Furthermore, the lack of a three-dimensional network mechanical interlocking between the glaze layer and the base significantly degraded the overall mechanical properties of the ceramic tile.

[0148] In Comparative Example 2, the alumina-zirconia composite fibers were not surface-modified. During the glaze slurry preparation process, the degree of composite fiber agglomeration increased, and the number of effective binding sites on the fiber surface decreased. After sintering, the continuity of the fiber skeleton within the glaze layer decreased, the distribution uniformity of the three-dimensional network structure decreased, and the complexity of the void structure varied across the surface of the ceramic tile, resulting in cracks and scratches in localized areas and reduced overall mechanical properties of the ceramic tile.

[0149] In Comparative Example 11, after the glaze slurry is applied to the surface of the ceramic tile body, the alumina-zirconia composite fibers in the glaze layer branch and anchor into the surface of the ceramic tile body. Nano-calcium carbonate (CaCO3) particles on the surface of the body react with the surface of the modified composite fibers to form Si-O-Ca interfacial chemical bonds, thereby significantly improving the interfacial bonding between the glaze layer and the body layer, preventing the glaze layer from delaminating and the ink from peeling off along with the glaze layer. After the nano-calcium carbonate in the ceramic tile body is removed, the connection structure between the body and the glaze layer, composed of a three-dimensional network and chemical bonding, is significantly reduced, and the overall performance of the ceramic tile is reduced.

[0150] In Comparative Examples 3-6, when the diameter of the alumina-zirconia composite fiber is too small (800nm), even after surface modification, it is still easy to agglomerate during the glaze slurry preparation process. After sintering, the local stress concentration of the glaze layer is obvious, which is easy to cause microcracks, and the overall performance of the ceramic tile is reduced. When the diameter of the composite fiber is too large (1300nm), the matching degree between its diameter and the micropore size of the glaze layer is reduced, the continuity of the skeleton in the glaze layer is reduced, and it may even block part of the microporous channels of the glaze layer, resulting in reduced ink permeability and easy scratching of the surface pattern of the ceramic tile. In addition, when the number density of the composite fiber is insufficient, its restraining effect on the crack tip of the glaze layer is weakened during sintering, and new microcracks may even be generated due to local excessive extrusion, and the overall performance of the ceramic tile is reduced. In summary, the optimal value of the diameter of the alumina-zirconia composite fiber is 1200nm.

[0151] In Comparative Examples 7-10, the nano-calcium carbonate particles are too small (40 μm) and are prone to agglomeration during the ceramic powder preparation process. This reduces the melting uniformity of the embryo during the subsequent firing process, easily forming crack sources inside the ceramic tile, and reducing the overall performance of the ceramic tile.

[0152] If the particle size of nano-calcium carbonate is too large (60μm), unmelted particles will easily remain in the subsequent embryo during the firing process, which will easily form crack sources inside the ceramic tile and reduce the overall performance of the ceramic tile. That is, the optimal particle size of nano-calcium carbonate is 53.8μm.

[0153] The embodiments provided by the present invention are described in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only intended to help understand the method and core concept of the present invention. It should be noted that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a ceramic tile with a granite texture, characterized in that: The following steps are involved: Step 101: Pressing the prefabricated ceramic tile powder into a first embryonic body; Step 102: Apply the prefabricated glaze slurry to the surface of the first embryonic body prepared in step 101 to obtain a second embryonic body; Step 103: Spray the prefabricated ink onto the surface of the second embryonic body prepared in step 102 to obtain a third embryonic body; Step 104: The third embryonic body prepared in step 103 is transferred to a kiln for firing. After firing, a finished ceramic tile with a granite texture is obtained. In step 102, the glaze slurry is composed of the following components by weight: 15-18 parts of albite, 5-10 parts of potassium feldspar, 8-12 parts of alumina-zirconia composite fiber, 25-32 parts of waste clay bricks, and 12-18 parts of quartz; Wherein, the alumina-zirconia composite fiber is surface-modified.

2. The method for preparing a ceramic tile with a granite texture according to claim 1, characterized in that: The preparation method of the alumina-zirconia composite fiber comprises the following steps: Step 201. Ethyl acetoacetate and isopropyl alcohol are sequentially added to a magnetic stirring kettle and stirred at room temperature at 800-1200 rpm until uniformly mixed. Zirconium oxychloride is then added and stirred at room temperature at 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system becomes uniformly milky white, thereby obtaining reaction solution A. Step 202. To the reaction solution A prepared in step 201, aluminum tert-butoxide and N,N-dimethylformamide were added in sequence, and the mixture was stirred at room temperature, in a water bath at 33°C, and at 1000 rpm until the liquid system became transparent, thereby obtaining reaction solution B. Step 203. Add polyvinyl pyrrolidone to the reaction solution B prepared in step 201, and stir at room temperature and 500 rpm for 5 h-10 h to obtain spinning solution C; Step 204: The spinning solution C prepared in step 203 is transferred to an electrospinning device for spinning, and the alumina-zirconia composite fiber is obtained after drying.

3. The method for preparing a ceramic tile with a granite texture according to claim 2, characterized in that: In step 201, the mass ratio of ethyl acetoacetate, isopropyl alcohol, and zirconium oxychloride is (1.2-1.7): (8.9-9.5): (0.1-0.3); In step 202, the mass ratio of reaction solution A, aluminum tert-butoxide, and N,N-dimethylformamide is 1:(0.13-0.17):(0.11-0.13); In step 203 , the mass ratio of reaction solution B to polyvinyl pyrrolidone is 1:(0.17-0.21).

4. The method for preparing a ceramic tile with a granite texture according to claim 2, wherein: The cross-sectional diameter of the alumina-zirconia composite fiber is 1160 nm-1274 nm, and the aspect ratio is (11.5-14.8):

1.

5. The method for preparing a ceramic tile with a granite texture according to claim 2, characterized in that: In step 102, the surface modification treatment of the alumina-zirconia composite fiber includes the following steps: Alumina-zirconia composite fiber, butyl orthosilicate, distilled water and anhydrous ethanol were added to a reactor in sequence, and ultrasonic treatment was carried out in a water bath at 40°C and an ultrasonic frequency of 20kHz-25kHz. During the ultrasonic treatment, 1.5mol / L nitric acid solution was added dropwise to the reaction system. After ultrasonic treatment for 20min-30min, the reaction system was filtered and dried in sequence to obtain surface-modified alumina-zirconia composite fiber.

6. The method for preparing a ceramic tile with a granite texture according to claim 2, characterized in that: In step 102, the method for preparing the glaze slurry includes the following steps: After adding the components of the glaze slurry into the ball mill in a predetermined proportion, 0.3 wt % of carboxymethyl cellulose was added to the ball mill as a suspending agent, and the glaze slurry was obtained after ball milling for 40-60 minutes. During the ball milling process, the mass ratio of glaze, suspending agent, grinding balls and water in the ball mill is 1: (1.25-1.5): (10-15): (3-5).

7. The method for preparing a ceramic tile with a granite texture according to claim 2, characterized in that: In step 101, the ceramic tile powder is composed of the following components in parts by weight: 15-18 parts of talc, 3-8 parts of nano-calcium carbonate, 12-15 parts of quartz, 10-12 parts of potassium feldspar, and 5-10 parts of kaolin.

8. The method for preparing a ceramic tile with a granite texture according to claim 2, characterized in that: In step 101, the method for preparing ceramic tile powder includes the following steps: The components of the ceramic tile powder are added into the grinder in sequence according to a preset ratio. After ball milling, the first powder is obtained. The first powder is sieved through a 50-mesh sieve in sequence, sealed and aged to obtain the ceramic tile powder.

9. A ceramic tile with a granite texture, characterized in that: The ceramic tile is prepared by the method for preparing a ceramic tile with a granite texture according to any one of claims 1 to 8.

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