Ceramic tile having a granite texture and method for manufacturing the same

Abstract

The application provides a ceramic tile with granite texture and a preparation method thereof, which comprises four steps of preparation, glazing, inkjet and sintering. The alumina-zirconia composite fiber subjected to surface modification treatment is made into glaze slurry, the glaze slurry is applied to a first body prepared by pressing ceramic tile powder, and the ink is sprayed on the ceramic tile body by an inkjet machine and sintered. After that, the specific surface area of the composite fiber is significantly increased by the difference in expansion rates of alumina and zirconia, the number of self-binding sites is increased, a three-dimensional connecting interface is formed between the glaze and the body during sintering, the binding sites in the glaze improve the anchoring strength of the ink, the binding force between the ink and the glaze layer is significantly enhanced, the wear resistance and mechanical properties of the big grain pattern layer are improved, the wear and scratches during use are reduced, the service life of the ceramic tile is prolonged, the use experience of the user is improved, and the method has the advantages of simple preparation process, wide application range and easy popularization and implementation.

Description

TECHNICAL FIELD

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

[0002] In the prior art, the ceramic inkjet printing technology plays an important role in the field of building decoration. Through the inkjet printing technology, rich patterns and textures can be formed on the surface of the ceramic tile, greatly enriching the decorative effect of the ceramic tile and meeting the market demand for personalized and diversified decoration. However, the ceramic tile prepared by the inkjet process on the market still has some deficiencies, which limits its further development and application.

[0003] In the prior art, after the ink is printed on the ceramic tile body, the wear resistance of the inkjet layer is poor, and wear and scratches are prone to occur during use, affecting the integrity of the pattern and the decorative effect and reducing the service life of the product. At the same time, the hardness of the inkjet layer is insufficient, so that the ceramic tile is prone to scratches and wear on the surface after being impacted by external force or being used for a long time, affecting its aesthetic appearance and service life.

[0004] Furthermore, the bonding force between the inkjet layer and the ceramic tile substrate may be insufficient, resulting in wear, scratches, even peeling and falling off of the inkjet layer during use, affecting the quality and service life of the product. In addition, the inkjet layer has poor chemical corrosion resistance and is easily eroded by acid, alkali and other chemicals, causing the pattern to fade or damage, affecting the decorative effect and service life of the ceramic tile.

[0005] Secondly, the inkjet printing mainly forms two-dimensional patterns, lacks the fine recessed texture and matte texture of natural stone, and is difficult to create a three-dimensional texture effect similar to the real concave-convex and microporous matte texture of natural marble on the surface of the ceramic tile, and the decorative effect is not stereoscopic and realistic enough.

[0006] In summary, although the existing ceramic tile inkjet layer technology meets the market demand for the decorative effect of ceramic tiles to some extent, there are still many deficiencies. Therefore, it is urgent to make improvements to meet the market demand for high-quality ceramic tiles. SUMMARY

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

[0008] In order to solve the technical problems proposed in the present application, the present application further provides a preparation method of a ceramic tile with granite texture.

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

[0010] Step 101. The pre-prepared ceramic tile powder is pressed into a first embryo;

[0011] Step 102. After the pre-prepared glaze slurry is applied to the surface of the first embryo prepared in step 101, a second embryo is obtained;

[0012] Step 103. After the pre-prepared ink is sprayed on the surface of the second embryo prepared in step 102, a third embryo is obtained;

[0013] Step 104. The third embryo prepared in step 103 is transferred to a kiln and fired at a firing temperature of 1200-1450°C, a heating rate of 20°C / min, and a holding time of 20 min. After firing, a finished product of a ceramic tile with granite texture is obtained.

[0014] In step 102, the glaze slurry consists of the following components by weight fraction: 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 brick, and 12-18 parts of quartz.

[0015] The alumina-zirconia composite fiber is subjected to surface modification treatment.

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

[0017] In some feasible embodiments, the waste clay brick consists of the following components by weight fraction:

[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 preparation method of the alumina-zirconia composite fiber comprises the following steps:

[0020] Step 201. Ethyl acetoacetate and isopropanol are sequentially added into a magnetic stirring kettle, after stirring uniformly at room temperature and 800 rpm-1200 rpm, zirconium oxychloride is added into the kettle, and stirring is carried out at room temperature and 1300 rpm until the zirconium oxychloride is uniformly dispersed, and the liquid system is uniformly milky white, to obtain reaction liquid A;

[0021] Step 202. Tert-butyl alcohol aluminum and N,N-dimethylformamide are sequentially added into the reaction liquid A prepared in step 201, and stirring is carried out at room temperature, in a water bath at 33℃, and 1000 rpm until the liquid system is transparent, to obtain reaction liquid B;

[0022] Step 203. Polyvinylpyrrolidone is added into the reaction liquid B prepared in step 201, and stirring is carried out at room temperature and 500 rpm for 5h-10h, to obtain a spinning liquid C;

[0023] Step 204. The spinning liquid C prepared in step 203 is transferred into an electrospinning device, and spinning is carried out under the conditions of a spinning voltage of 13.5kV and a spinning distance of 15cm, to obtain an aluminum oxide-zirconium oxide composite fiber.

[0024] In some possible embodiments, in step 201, the mass ratio of ethyl acetoacetate, isopropanol 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 liquid A, tert-butyl alcohol aluminum and N,N-dimethylformamide is 1:(0.13-0.17):(0.11-0.13);

[0027] In step 203, the mass ratio of reaction liquid B and polyvinylpyrrolidone is 1:(0.17-0.21).

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

[0029] In some possible embodiments, in step 102, the surface modification treatment of the aluminum oxide-zirconium oxide composite fiber includes the following steps:

[0030] The alumina-zirconia composite fiber, tetraethyl orthosilicate, distilled water and anhydrous ethanol are sequentially added into a reaction kettle, and are ultrasonically treated under the condition of a water bath at 40 DEG C and an ultrasonic frequency of 20 kHz-25 kHz; during the ultrasonic treatment, 1.5 mol / L nitric acid solution is added dropwise into the reaction system; after the ultrasonic treatment for 20 min-30 min, the reaction system is sequentially filtered and dried to obtain the surface-modified alumina-zirconia composite fiber.

[0031] In some possible embodiments, in step 102, the preparation method of the glaze slurry comprises the following steps:

[0032] After the components of the glaze slurry are sequentially added into a ball mill according to the preset proportions, 0.3 wt% of carboxymethyl cellulose is added into the ball mill as a suspending agent; after ball milling for 40 min-60 min, the glaze slurry is obtained.

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

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

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

[0036] In some possible embodiments, in step 101, the preparation method of the ceramic tile powder comprises the following steps:

[0037] The components of the ceramic tile powder are sequentially added into a grinding mill according to the preset proportions; after the ball milling is completed, a first powder is obtained; the first powder is sequentially sieved through a 50-mesh screen and sealed for aging to obtain the ceramic tile powder.

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

[0039] In step 101, the preparation method of the first body comprises the following steps:

[0040] The ceramic tile powder is pressed in a preset mold under the condition of 5 MPa-10 MPa, and then sequentially dried and demolded to obtain the first body.

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

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

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

[0044] The present application provides a ceramic tile with granite texture and a preparation method thereof, which comprises four steps of blank preparation, glazing, inkjet and sintering. The alumina-zirconia composite fiber subjected to surface modification treatment is made into glaze slurry, and the glaze slurry is applied to the first blank body prepared by pressing ceramic tile powder. The ink is sprayed on the tile blank body by an inkjet machine and sintered. By utilizing the difference in expansion rates of alumina and zirconia, the specific surface area of the composite fiber is significantly increased, and the number of self-binding sites is significantly increased. During sintering, a three-dimensional connecting interface is formed between the glaze and the blank body. The binding sites in the glaze improve the anchoring strength of the ink, significantly enhance the bonding force of the ink and the surface of the ceramic tile, improve the wear resistance and mechanical properties of the granite pattern layer on the surface of the ceramic tile, reduce wear and scratches during use, prolong the service life of the ceramic tile, improve the user experience, and have the advantages of simple preparation process, high mass production feasibility, wide application range, and easy popularization and implementation. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 is a trend graph of the breaking strength of the ceramic tile in Example 2 and Comparative Examples 3-6 of the present application with the diameter of the alumina-zirconia composite fiber;

[0046] Figure 2 is a trend graph of the wear amount of the ceramic tile in Example 2 and Comparative Examples 3-6 of the present application with the diameter of the alumina-zirconia composite fiber;

[0047] Figure 3 is a trend graph of the breaking modulus of the ceramic tile in Example 2 and Comparative Examples 3-6 of the present application with the diameter of the alumina-zirconia composite fiber;

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

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

[0050] Figure 6 is a trend graph of the breaking modulus of the ceramic tile in Example 2 and Comparative Examples 7-10 of the present application with the particle size of the nano calcium carbonate;

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

[0052] Figure 8 is a SEM scanning diagram of the sintered alumina-zirconia composite fiber in Embodiment 2 of the present application. DETAILED DESCRIPTION

[0053] In combination Figures 1-8 The technical solutions proposed in the present application are further described with reference to the accompanying drawings. Embodiment 1

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

[0055] Step 201. Ethyl acetoacetate and isopropyl alcohol are sequentially added into a magnetic stirring kettle, and after being uniformly stirred at room temperature and 800 rpm, zirconium oxychloride is added into the kettle, and after being uniformly stirred at room temperature and 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system is uniformly milky white, a reaction liquid A is obtained;

[0056] In the formula, the mass ratio of ethyl acetoacetate, isopropyl alcohol and zirconium oxychloride is 1.2:8.9:0.1.

[0057] Step 202. Tert-butyl alcohol aluminum and N,N-dimethylformamide are sequentially added into the reaction liquid A prepared in step 201, and after being stirred at room temperature, in a water bath at 33℃ and at 1000 rpm until the liquid system is transparent, a reaction liquid B is obtained;

[0058] In the formula, the mass ratio of the reaction liquid A, tert-butyl alcohol aluminum and N,N-dimethylformamide is 1:0.13:0.11.

[0059] Step 203. Polyvinylpyrrolidone is added into the reaction liquid B prepared in step 201, and after being stirred at room temperature and at 500 rpm for 5-10 hours, a spinning liquid C is obtained;

[0060] In the formula, the mass ratio of the reaction liquid B and polyvinylpyrrolidone is 1:0.17.

[0061] Step 204. The spinning liquid C prepared in step 203 is transferred into an electrostatic spinning device, and after being spun under the conditions of a spinning voltage of 13.5 kV and a spinning distance of 15 cm, an alumina-zirconia composite fiber is obtained.

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

[0063] The alumina-zirconia composite fiber, tetraorthosilicate, distilled water and anhydrous ethanol are sequentially added into a reaction kettle, and ultrasonic treatment is carried out under the condition of a water bath at 40℃ and an ultrasonic frequency of 20 kHz; during the ultrasonic treatment, 1.5 mol / L nitric acid solution is added drop by drop into the reaction system; after 20-30 min of ultrasonic treatment, the surface-modified alumina-zirconia composite fiber is obtained after the reaction system is sequentially filtered and dried.

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

[0065] (3) The preparation method of the glaze slurry comprises the following steps:

[0066] According to the component table shown in Table 1, the components of the glaze slurry are sequentially added into a ball mill at a preset ratio, then 0.3 wt% of carboxymethyl cellulose is added into the ball mill as a suspending agent, and the ball milling is carried out for 40 min, so that the glaze slurry is obtained.

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

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

[0069] According to the component table shown in Table 1, the components of the ceramic brick powder are sequentially added into a grinding machine at a preset ratio, and after the ball milling is completed, the first powder is obtained; the first powder is sequentially sieved through a 50-mesh screen and sealed and aged, so that the ceramic brick powder is obtained.

[0070] (5) The preparation method of the ceramic brick with granite texture comprises the following steps:

[0071] Step 101. The ceramic brick powder is pressed in a preset mold under the condition of 5 MPa, and then sequentially dried and demolded, so that the first body with a thickness of 5 mm is obtained.

[0072] Step 102. The prepared glaze slurry is applied to the surface of the first body prepared in step 101 by the dipping glazing method, and then naturally dried, so that the second body is obtained.

[0073] Step 103. The prepared ink is sprayed on the surface of the second body prepared in step 102, so that the third body is obtained.

[0074] Step 104. The third body prepared in step 103 is transferred to a kiln and fired at a firing temperature of 1200℃, a heating rate of 20℃ / min and a holding time of 20 min, so that the finished product of the ceramic brick with granite texture is obtained. Example 2

[0075] (1) The preparation method of the aluminum oxide-zirconium oxide composite fiber comprises the following steps:

[0076] Step 201. Ethyl acetoacetate and isopropanol are sequentially added to a magnetic stirring kettle, and after being uniformly stirred at room temperature and 1000 rpm, zirconium oxychloride is added thereto, and after being uniformly stirred at room temperature and 1300 rpm until the zirconium oxychloride is uniformly dispersed and the liquid system is uniformly milky white, a reaction liquid A is obtained;

[0077] The mass ratio of ethyl acetoacetate, isopropanol and zirconium oxychloride is 1.5:9:0.2.

[0078] Step 202. Tert-butyl alcohol aluminum and N,N-dimethylformamide are sequentially added to the reaction liquid A prepared in step 201, and after being stirred at room temperature, in a water bath at 33°C and at 1000 rpm until the liquid system is transparent, a reaction liquid B is obtained.

[0079] The mass ratio of the reaction liquid A, tert-butyl alcohol aluminum and N,N-dimethylformamide is 1:0.15:0.12.

[0080] Step 203. Polyvinylpyrrolidone is added to the reaction liquid B prepared in step 201, and after being stirred at room temperature and at 500 rpm for 5-10 hours, a spinning liquid C is obtained.

[0081] The mass ratio of the reaction liquid B and polyvinylpyrrolidone is 1:0.19.

[0082] Step 204. The spinning liquid C prepared in step 203 is transferred to an electrospinning device, and spinning is performed under the conditions of a spinning voltage of 13.5 kV and a spinning distance of 15 cm, and after the spinning is completed, an aluminum oxide-zirconium oxide composite fiber is obtained.

[0083] (2) The surface modification treatment of the aluminum oxide-zirconium oxide composite fiber comprises the following steps:

[0084] Aluminum oxide-zirconium oxide composite fiber, butyl orthosilicate, distilled water and anhydrous ethanol are sequentially added to a reaction kettle, and under the conditions of a water bath at 40°C and an ultrasonic frequency of 22 kHz, ultrasonic treatment is performed, during which 1.5 mol / L nitric acid solution is added dropwise to the reaction system, and after ultrasonic treatment for 25 minutes, the reaction system is sequentially filtered and dried to obtain surface-modified aluminum oxide-zirconium oxide composite fiber.

[0085] The mass ratio of the aluminum oxide-zirconium oxide 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 preparation method of the glaze slurry comprises the following steps:

[0087] The components of the glaze slurry are added into a ball mill in the proportions shown in Table 1, then 0.3wt% of carboxymethyl cellulose is added into the ball mill as a suspending agent, and the ball milling is carried out for 50 minutes to obtain the glaze slurry.

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

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

[0090] The components of the ceramic tile powder are added into a ball mill in the proportions shown in Table 1, and after the ball milling is completed, the first powder is obtained, and the first powder is sieved through a 50 mesh screen and sealed and aged to obtain the ceramic tile powder.

[0091] (5) The preparation method of the ceramic tile with granite texture comprises the following steps:

[0092] Step 101. The ceramic tile powder is pressed in a predetermined mold under the condition of 5MPa, and then dried and demolded to obtain a first body with a thickness of 5mm;

[0093] Step 102. The prepared glaze slurry is applied to the surface of the first body prepared in step 101 by dipping, and then naturally dried to obtain a second body;

[0094] Step 103. The prepared ink is sprayed on the surface of the second body prepared in step 102 to obtain a third body;

[0095] Step 104. The third body prepared in step 103 is transferred to a kiln and fired at a firing temperature of 1300℃, a heating rate of 20℃ / min and a holding time of 20min, and after the firing is completed, a finished product of the ceramic tile with granite texture is obtained. Example 3

[0096] (1) The preparation method of the aluminum oxide-zirconium oxide composite fiber comprises the following steps:

[0097] Step 201. Ethyl acetoacetate and isopropyl alcohol are added into a magnetic stirring kettle in sequence, and after being stirred uniformly at room temperature and 1200rpm, zirconium oxychloride is added into the kettle, and stirred at room temperature and 1300rpm until the zirconium oxychloride is uniformly dispersed and the liquid system is uniformly milky white to obtain a reaction liquid A;

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

[0099] Step 202. Add aluminum tert-butoxide and N,N-dimethylformamide into the reaction liquid A prepared in step 201 in sequence, and stir at room temperature, in a water bath at 33℃, and at 1000 rpm until the liquid system is transparent, to obtain reaction liquid B;

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

[0101] Step 203. Add polyvinylpyrrolidone into the reaction liquid B prepared in step 201, and stir at room temperature and at 500 rpm for 10 h, to obtain the spinning liquid C;

[0102] The mass ratio of the reaction liquid B and polyvinylpyrrolidone is 1:0.21.

[0103] Step 204. Transfer the spinning liquid C prepared in step 203 to an electrostatic spinning device, and spin at a spinning voltage of 13.5 kV and a spinning distance of 15 cm, to obtain the aluminum oxide-zirconium oxide composite fiber.

[0104] (2) The surface modification treatment of the aluminum oxide-zirconium oxide composite fiber includes the following steps:

[0105] Add the aluminum oxide-zirconium oxide composite fiber, tetra-n-butyl orthosilicate, distilled water, and anhydrous ethanol into a reaction kettle in sequence, and ultrasonically treat at a water bath temperature of 40℃ and an ultrasonic frequency of 25 kHz, drop 1.5 mol / L nitric acid solution into the reaction system drop by drop during the ultrasonic treatment, and after ultrasonic treatment for 30 min, filter and dry the reaction system in sequence, to obtain the surface-modified aluminum oxide-zirconium oxide composite fiber.

[0106] The mass ratio of the aluminum oxide-zirconium oxide composite fiber, tetra-n-butyl orthosilicate, distilled water, anhydrous ethanol, and nitric acid solution is 1:5.6:8.2:3.5:0.6.

[0107] (3) The preparation method of the glaze slurry includes the following steps:

[0108] After the components of the glaze slurry are added into a ball mill in a preset ratio, 0.3 wt% of carboxymethyl cellulose is added into the ball mill as a suspending agent, and after ball milling for 60 min, the glaze slurry is obtained.

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

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

[0111] The ceramic tile powder is obtained by adding each component of the ceramic tile powder into a grinding machine in a preset proportion, and the first powder is obtained after ball milling is completed.

[0112] (5) A method for preparing a ceramic tile with granite texture includes the following steps:

[0113] Step 101. The ceramic tile powder is pressed in a preset mold under the condition of 5 MPa, and then the first body with a thickness of 5 mm is obtained after drying and demolding.

[0114] Step 102. The prepared glaze slurry is applied to the surface of the first body prepared in step 101 by the glazing method, and the second body is obtained after natural drying.

[0115] Step 103. The prepared ink is sprayed on the surface of the second body prepared in step 102, and the third body is obtained.

[0116] Step 104. The third body prepared in step 103 is transferred to a kiln and fired at a firing temperature of 1200-1450°C, a heating rate of 20°C / min, and a holding time of 20 min. After firing, the finished product of the ceramic tile with granite texture is obtained.

[0117] Comparative Example 1

[0118] Comparative Example 1 and Example 2 differ in that the alumina-zirconia composite fiber in the glaze slurry is removed and an equal amount of waste clay brick is added, and the rest of the components remain unchanged.

[0119] Comparative Example 2

[0120] Comparative Example 2 and Example 2 differ in that the surface treatment process of the alumina-zirconia composite fiber in the glaze slurry is removed, and the rest of the components remain unchanged.

[0121] Comparative Examples 3-6

[0122] Comparative Examples 3-6 and Example 2 differ in that on the basis of Example 2, the spinning parameters of the electrospinning equipment in step 204 are adjusted, the alumina-zirconia composite fiber with a cross-sectional diameter of 1200 nm in Example 2 is replaced by an equal amount of alumina-zirconia composite fiber with a cross-sectional diameter of 800 nm, 1000 nm, 1100 nm, and 1300 nm, respectively, and the rest of the components remain unchanged.

[0123] Comparative Examples 7-10

[0124] Comparative Example 3-6 is different from Example 2 in 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 with an equal amount of nano calcium carbonate with a median particle size of 40 μm, 45 μm, 50 μm, or 60 μm, and the rest of the components and processes remain unchanged.

[0125] Comparative Example 11

[0126] Comparative Example 11 is different from Example 2 in that, on the basis of Example 2, the nano calcium carbonate with a median particle size of 53.8 μm in Example 2 is removed and an equal amount of talc is added, and the rest of the components and processes remain unchanged.

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

[0128]

[0129] Continued Table 1

[0130]

[0131] Continued Table 1

[0132]

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

[0134] Test 1: The surface wear resistance of the ceramic tile finished products is measured according to GB / T 3810.7-2016 “Ceramic Tiles-Determination of Abrasion Resistance of Glazed Tiles” respectively;

[0135] Test 2: The surface wear resistance of the ceramic tile finished products is further tested according to GB / T 3810.7-2016 “Ceramic Tiles-Determination of Abrasion Resistance of Glazed Tiles” respectively, and the surface wear resistance of the ceramic tile finished products is quantitatively analyzed;

[0136] Test 3: The surface crack resistance of the ceramic tile finished products is measured according to GB / T 3810.11-2016 “Ceramic Tiles-Determination of Glaze Crack Resistance of Glazed Tiles” respectively;

[0137] Test 4: The surface mechanical impact and scratch resistance of the ceramic tile finished products is measured according to JC / T 908-2013 “Artificial Stone” related standards respectively.

[0138] Test 5: The fracture modulus of the ceramic tile finished products is measured according to GB / T 3810.4-2016 “Ceramic Tiles-Determination of Fracture Modulus and Breaking Strength” respectively.

[0139] Test 6: The breaking strength of the ceramic tile product was measured according to GB / T 3810.4-2016 "Ceramic tiles-Determination of breaking strength and modulus of rupture".

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

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

[0142]

[0143] As shown in Table 2 and Figures 1-8 It can be seen that by using the alumina-zirconia composite fiber as the glaze slurry, a three-dimensional network structure can be introduced into the glaze slurry. During the sintering process, as shown in Figures 7-8 , the zirconia crystals in the alumina-zirconia composite fiber undergo a phase transition from tetragonal to monoclinic and expand in volume. On the one hand, the protrusions generated by the expansion can fill the large-pore micropores in the glaze layer; on the other hand, the branches of the composite fiber can be embedded in the small-pore micropores in the glaze layer, thereby significantly increasing the topological complexity of the micropore structure on the surface of the glaze layer. After the ink is sprayed on the glaze layer, it penetrates into the micropore structure with high disorder, significantly improving the anchoring depth of the ink, and thus improving the wear resistance of the ink on the surface of the ceramic tile. The ceramic tile is not prone to wear and tear during actual use, effectively ensuring the integrity of the pattern and the decorative effect.

[0144] Specifically, as shown in Figure 8 , during the sintering process, due to the difference in the thermal expansion coefficients of the alumina phase and the zirconia phase, the expansion rate of the zirconia is higher than that of the alumina. The phase transition of the zirconia from tetragonal to monoclinic causes the formation of micro-scale undulations on the surface of the composite fiber, which are uniformly distributed and form a continuous skeleton in the glaze layer.

[0145] More specifically, the zirconia crystals protruding from the surface of the alumina-zirconia composite fiber can fill the large-pore micropores in the glaze layer, and the branches of the alumina-zirconia composite fiber can mechanically engage the small-pore micropores in the glaze layer, effectively extruding the crack tips in the glaze layer, improving the crack diffusion resistance in the glaze layer, forming a three-dimensional network interfacial connection between the body and the glaze layer, improving the bonding performance of the body and the glaze layer, avoiding delamination of the glaze layer and the body, and thus significantly improving the crack resistance of the glaze layer, the breaking strength of the ceramic tile as a whole, and the modulus of rupture.

[0146] By surface modification treatment of the surface of the alumina-zirconia composite fiber, on the one hand, the alumina-zirconia composite fiber surface is etched with a nitric acid solution to form nano micropores, increasing the bonding sites on the surface of the alumina-zirconia composite fiber, on the other hand, the surface modifier is used for modification, which effectively improves the interface performance, and facilitates the excessive agglomeration in the subsequent glaze preparation process, and improves the uniformity of the three-dimensional network structure distribution.

[0147] In proportion 1, the alumina-zirconia composite fiber is removed from the glaze. On the one hand, the complexity of the void structure in the glaze layer is significantly reduced, the porous matrix is easily exposed after wear, the ink anchoring depth is reduced, the wear resistance is significantly reduced, and the surface pattern is prone to scratches; on the other hand, the zirconia phase (its phase change and volume effect) is missing in the glaze layer, the stress concentration phenomenon in the glaze layer is intensified, and the crack resistance is significantly reduced. At the same time, the mechanical interlocking of the three-dimensional network between the glaze layer and the body is lacking, and the overall mechanical properties of the ceramic tile are significantly deteriorated.

[0148] In Comparative Example 2, the alumina-zirconia composite fiber is not subjected to surface modification treatment. During the preparation of the glaze, the agglomeration degree of the composite fiber increases, and the effective bonding sites on the fiber surface decrease. After sintering, the continuity of the fiber skeleton in the glaze layer is reduced, the distribution uniformity of the three-dimensional network structure is decreased, and the complexity of the void structure on the ceramic tile surface is different, resulting in cracks and scratches in local areas, and the overall mechanical properties of the ceramic tile are reduced.

[0149] In Comparative Example 11, after the glaze is applied to the surface layer of the ceramic tile body, the alumina-zirconia composite fiber in the glaze layer is anchored into the surface layer of the ceramic tile body. The nano calcium carbonate (CaCO3) particles in the surface layer of the body react with the modified composite fiber surface to form Si-O-Ca interface chemical bonding, thereby significantly improving the interfacial bonding strength between the glaze layer and the body layer, preventing the delamination of the glaze layer, and avoiding the peeling of the ink with the glaze layer. After removing the nano calcium carbonate in the ceramic tile body, the connection structure between the body and the glaze layer formed by the three-dimensional network and the chemical bonding is significantly reduced, and the overall performance of the ceramic tile is reduced.

[0150] In Comparative Example 3-6, when the diameter of the alumina-zirconia composite fiber is too small (800 nm), agglomeration occurs easily during the preparation of the slip even after surface modification. After sintering, the local stress of the glaze layer is concentrated obviously, and micro-cracks are easily induced, which reduces the overall performance of the ceramic tile. When the diameter of the composite fiber is too large (1300 nm), the matching degree between the diameter of the composite fiber and the size of the glaze layer micropores is reduced, the continuity of the skeleton in the glaze layer is reduced, and even some glaze layer micropore channels can be blocked, which reduces the ink permeability and causes the surface pattern of the ceramic tile to be easily scratched. In addition, when the number density of the composite fiber is insufficient, the restraining effect of the composite fiber on the crack tip of the glaze layer is weakened during sintering, and even new micro-cracks can be generated due to local excessive extrusion, which reduces the overall performance of the ceramic tile. In summary, the optimal value of the diameter of the alumina-zirconia composite fiber is 1200 nm.

[0151] In Comparative Examples 7-10, when the particle size of the nano-calcium carbonate is too small (40 μm), the nano-calcium carbonate is easily aggregated during the preparation of the ceramic slip, which reduces the melting uniformity of the body during the subsequent sintering process, and easily forms crack sources in the ceramic tile, which reduces the overall performance of the ceramic tile.

[0152] When the particle size of the nano-calcium carbonate is too large (60 μm), the nano-calcium carbonate is easily left un-melted during the subsequent sintering process of the body, which easily forms crack sources in the ceramic tile, which reduces the overall performance of the ceramic tile. Therefore, the optimal value of the particle size of the nano-calcium carbonate is 53.8 μm.

[0153] The above provides a detailed description of the embodiments of the present application. The specific examples are applied to the principles and implementation methods of the present application, and the above description of the embodiments is only used to help understand the method and core idea of the present application. It should be noted that for ordinary skilled persons in the technical field, without departing from the principles of the present application, the present application can be improved and modified, and these improvements and modifications also fall within the protection scope of the claims of the present application.

Claims

1. A method for producing a ceramic tile having a granite texture, characterized by, It comprises the following steps: Step 101. The prepared ceramic tile powder is pressed into a first embryo; Step 102. The prepared glaze is applied to the surface of the first embryo prepared in step 101, and a second embryo is obtained; Step 103. The prepared ink is sprayed on the surface of the second embryo prepared in step 102, and a third embryo is obtained; Step 104. The third embryo prepared in step 103 is transferred to a kiln for firing, and after firing, a finished ceramic tile with granite texture is obtained; In step 102, the glaze consists of the following components by weight fraction: 15-18 parts of sodium feldspar, 5-10 parts of potassium feldspar, 8-12 parts of aluminum oxide-zirconium oxide composite fiber, 25-32 parts of waste clay brick, and 12-18 parts of quartz; The aluminum oxide-zirconium oxide composite fiber is surface modified; The surface modification of the aluminum oxide-zirconium oxide composite fiber comprises the following steps: Aluminum oxide-zirconium oxide composite fiber, n-butyl trimethyl silicate, distilled water and anhydrous ethanol are sequentially added to a reaction kettle, and ultrasonic treatment is carried out under the conditions of water bath 40℃ and ultrasonic frequency 20kHz-25kHz. During the ultrasonic treatment, 1.5mol / L nitric acid solution is added dropwise to the reaction system. After ultrasonic treatment for 20-30min, the reaction system is sequentially filtered and dried to obtain surface modified aluminum oxide-zirconium oxide composite fiber; The cross-sectional diameter of the aluminum oxide-zirconium oxide composite fiber is 1200nm, and the aspect ratio is (11.5-14.8):1; In step 101, the ceramic tile powder consists of the following components by weight fraction: 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; The median particle size of the nano calcium carbonate is 53.8μm.

2. The method of claim 1, wherein the ceramic tile having a granite texture is prepared by the steps of: The preparation method of the aluminum oxide-zirconium oxide composite fiber comprises the following steps: Step 201. Ethyl acetoacetate and isopropanol are sequentially added to a magnetic stirring kettle, and stirred uniformly at room temperature and 800-1200rpm. Then, zirconium oxychloride is added, and stirred at room temperature and 1300rpm until the zirconium oxychloride is uniformly dispersed, and the liquid system is milky white, to obtain reaction liquid A; Step 202. Tert-butyl alcohol aluminum and N,N-dimethylformamide are sequentially added to the reaction liquid A prepared in step 201, and stirred at room temperature, water bath 33℃ and 1000rpm until the liquid system is transparent, to obtain reaction liquid B; Step 203. Polyvinylpyrrolidone is added to the reaction liquid B prepared in step 201, and stirred at room temperature and 500rpm for 5-10h to obtain the spinning liquid C; Step 204. The spinning liquid C prepared in step 203 is transferred to an electrospinning device for spinning, and dried to obtain the aluminum oxide-zirconium oxide composite fiber.

3. The method for preparing a ceramic tile with granite texture according to claim 2, characterized in that, In step 201, the mass ratio of ethyl acetoacetate, isopropanol and zirconium oxychloride is (1.2-1.7):(8.9-9.5):(0.1-0.3). In step 202, the mass ratio of reaction liquid 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 liquid B and polyvinylpyrrolidone is 1:(0.17-0.21).

4. The method of claim 2, wherein the ceramic tile having a granite texture is prepared by the steps of: In step 102, the preparation method of the glaze slurry comprises the following steps: After the components of the glaze slurry are sequentially added into the ball mill according to the preset proportions, 0.3wt% of carboxymethyl cellulose is added into the ball mill as a suspending agent, and the glaze slurry is obtained after ball milling for 40-60 minutes. During the ball milling process, the mass ratio of the glaze material, the suspending agent, the grinding balls and water in the ball mill is 1:(1.25-1.5):(10-15):(3-5).

5. The method for preparing a ceramic tile with granite texture according to claim 2, characterized in that, In step 101, the preparation method of the ceramic tile powder comprises the following steps: After the components of the ceramic tile powder are sequentially added into the grinding machine according to the preset proportions, the first powder is obtained after the ball milling is completed, and the ceramic tile powder is obtained after the first powder is sequentially sieved through a 50-mesh screen and sealed and aged.

6. A ceramic tile having a granite texture, characterized by, The ceramic tile with granite texture is prepared by the preparation method of the ceramic tile with granite texture according to any one of claims 1-5.

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