Marble ceramic tile and preparation method thereof

Abstract

The invention belongs to the technical field of ceramic tiles, and particularly discloses a marble ceramic tile and a preparation method thereof. The marble ceramic tile sequentially comprises a green body layer, a cover glaze layer, a pattern layer and a marble glaze layer, the marble glaze layer is formed by marble glaze, and the marble glaze comprises a prefabricated material composed of first dry particles, second dry particles and protective glaze according to a specific proportion, wherein the first dry particles, the second dry particles and the protective glaze are different and have a specific range of initial melting temperature and particle size. By innovating the formula of the glaze layer, the prepared marble ceramic tile has stereoscopic impression and natural sense which are closer to those of natural marble, the glaze surface is fine and smooth, and meanwhile, the marble ceramic tile also has better wear resistance, antifouling property and acid-base resistance and has better application prospects.

Description

Technical Field

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

[0002] Natural stone primarily includes marble and granite. Natural marble, with its unique texture and color, offers a smoother, more beautiful appearance compared to granite, making it more suitable for home decoration. Its natural, indented texture of varying depths and sizes offers a natural aesthetic and texture, making it a favorite decorative material for interior designers, adding a touch of elegance and luxury. However, over-exploitation of natural stone has led to resource scarcity and environmental damage, resulting in ceramic slabs and tiles replacing natural stone as the mainstream decorative material in modern architectural decoration. Driven by people's pursuit of aesthetics and quality in their homes, particularly their appreciation and fondness for the texture, color, and feel of marble, a number of ceramic slabs and tiles designed to mimic marble have emerged within the industry.

[0003] The popular ceramic tiles with imitation natural marble textures in the current market are generally formed by sinking ink to form a pattern layer with concave lines, and then applying a protective glaze on the surface of the pattern layer to obtain a three-dimensional marble texture effect. However, on the one hand, the existing imitation marble tiles have insufficient or even poor three-dimensional and natural marble texture / texture, resulting in a large gap between the surface effect of ceramic tiles and real stone, failing to achieve the beauty and texture of natural marble and unable to meet the aesthetic needs of users; on the other hand, the glaze layer provided on the surface usually has other limitations such as poor wear resistance and prone to pore defects, which also greatly restricts the development of imitation marble ceramic tiles. Summary of the Invention

[0004] The purpose of the present application is to address at least one of the shortcomings of the prior art. Based on this, the first aspect of the present application provides a marble ceramic tile, which comprises a body layer, a surface glaze layer, a pattern layer and a marble glaze layer in sequence; the surface glaze layer is formed of a surface glaze, and the marble glaze layer is formed of a marble glaze, and the marble glaze comprises a prefabricated material, and the prefabricated material comprises a combination of dry particles and a protective glaze, and the combination of dry particles comprises a first dry particle and a second dry particle; the mass ratio of the combination of dry particles to the protective glaze is 1:(0.3-0.34), and the mass ratio of the first dry particles to the second dry particles is 1:(0.45-0.55); The onset melting temperature of the first dry particles is 1145°C-1155°C, the onset melting temperature of the second dry particles is 1200°C-1210°C, and the onset melting temperature of the protective glaze is 1130°C-1140°C; The particle size D97 of the first dry particles is 125 μm-129 μm, the particle size D97 of the second dry particles is 66 μm-70 μm, and the particle size D97 of the protective glaze is 19 μm-23 μm; The chemical composition of the first dry particles comprises, by mass percentage, SiO2 50.5%-56.5%, Al2O3 15.0%-19.0%, CaO 6.4%-7.8%, MgO 2.2%-2.9%, K2O 2.9%-3.8%, Na2O 1.9%-2.5%, SrO 8.4%-10%, ZnO 4.4%-5.6%, and the remainder is loss on ignition and impurities; The chemical composition of the second dry particles comprises, by mass percentage, SiO2 50%-55%, Al2O3 17.5%-21.5%, CaO 3.3%-4%, K2O 3.2%-4.3%, Na2O 2.8%-3.4%, BaO 9%-11%, ZnO 3.3%-4.1%, SrO 3.3%-3.9%, and the remainder is loss on ignition and impurities; The raw materials of the protective glaze include, by weight, 36-41 parts of sodium stone powder, 13-16 parts of kaolin, 13-16 parts of dolomite, 12-14 parts of quartz powder, 7-9 parts of corundum powder, 4-6 parts of strontium carbonate, and 6-8 parts of calcined zinc oxide.

[0005] The present application sets differentiated and specific melting temperatures and particle sizes for the first dry particles, the second dry particles, and the protective glaze. The smaller particle size and the strong flux sodium in the protective glaze enable it to melt at a lower temperature. During the melting process, the first dry particles and the second dry particles also form a eutectic, thereby promoting the melting of the first dry particles and the semi-melting of the second dry particles. The high barium content in the second dry particles facilitates the formation and growth of crystal nuclei. After melting and reorganization, a large amount of barium adularia, strontium feldspar, and potassium-sodium feldspar crystal phases are subsequently formed, with a proportion of up to 50% (the specific mass contents of different phases in the marble glaze layer are: potassium-sodium feldspar 11%-15%, strontium feldspar 12%-16%, and barium adularia 23%-27%), thereby making the glaze surface present a more delicate structure and improving the wear resistance of the glaze layer. In addition, the clinker properties of the dry particles can reduce the intensity of the reaction of the glaze layer, thereby reducing the formation of surface pores. At the same time, the fine and evenly distributed crystals not only improve the elasticity of the glaze surface, making the glaze surface uniform and crack-free, but also further improve the wear resistance of the glaze layer. Furthermore, when the glaze layer of differentiated particle sizes is physically spread out under the influence of sufficient ink grayscale, it forms differentiated grooves from the sides to the bottom. After firing, it has a more delicate and natural micro-convex and concave texture, more similar to the visual and tactile "marks of time" presented by natural marble. Furthermore, due to its relatively high temperature, the semi-melting of the second dry particle acts as a network of fulcrums within the high-temperature fluidity of the glaze layer during the melting process. These distributed fulcrums exert a certain amount of traction on the molten glaze, effectively reducing the formation of slightly larger flattened potholes, thereby achieving a fine and smooth glaze layer with superior smoothness.

[0006] The protective glaze and the second dry particle also contain a high alumina content, which increases the high-temperature viscosity of the glaze melt and is more favorable for the functional ink's recessed areas (i.e., the functional ink forms the texture pattern in the pattern layer, which displaces the glaze layer to form recessed lines, resulting in a concave-convex feel. The recessed areas are formed by the functional ink displacing the glaze layer). This prevents the sides of the recesses from collapsing, improves the sintering degree of the glaze melt, and facilitates smooth degassing of the glaze layer, thereby reducing pores and enhancing the glaze's texture. Furthermore, alumina's high surface tension in the glaze melt ensures a smooth, smooth tactile feel. Furthermore, the protective glaze's low silicon-aluminum ratio effectively activates crystallization, allowing sufficient crystalline phases to precipitate from the glaze melt. The high alumina content effectively suppresses crystallization, controlling the particle size (below 5 μm), resulting in fine and uniform crystals. This reduces the elastic modulus of the glaze layer, resulting in greater elasticity and less cracking.

[0007] The first dry granules also contain a high content of calcium oxide, which not only effectively achieves low-temperature melting of the first dry granules themselves, promoting sintering and increasing the density of the glass body, thereby further improving anti-fouling performance, but also effectively reduces the high-temperature viscosity of the molten glass phase. The low-viscosity glass phase facilitates the flow and diffusion of the high-temperature liquid surface, better reflecting the overall flatness, and strengthens the glass structure, improving the mechanical strength and acid and alkali resistance of the glass phase, and providing better stability within the glaze layer. The magnesium oxide introduced into the first dry granules can reduce the viscosity of the glaze melt under high-temperature melting and effectively increase the surface tension.

[0008] In addition, in addition to the special design of the initial melting temperature, composition, particle size, etc. between the above-mentioned first dry particles, second dry particles, and protective glaze being key factors in achieving the effect of this application, the ratio between the first dry particles, the second dry particles and the protective glaze is also an indispensable factor that needs to be specially matched and set; if the proportion of the protective glaze is too large, the overall initial melting temperature will be too low, causing the first dry particles and the second dry particles to undergo a melting reaction in advance, resulting in the precipitated crystals of different sizes and uneven distribution, resulting in a surface that is too smooth and the texture pattern lacks three-dimensionality, and poor wear resistance; and if the proportion of the protective glaze is too small, the overall initial melting temperature will be too high, making it impossible for the first dry particles and the second dry particles to undergo a semi-melting reaction, thereby reducing the amount of crystallization, poor crystal phase formation, and different crystal sizes and uneven distribution, resulting in a noticeable surface roughness, a general three-dimensional texture pattern, and poor wear resistance. In addition, if the proportion of the protective glaze is too small, the dry particles lack filling each other, and the anti-fouling performance is reduced. If the proportion of the second dry particles is too small or the proportion of the first dry particles is too large, the second dry particles will have limited role as a fulcrum for the interlaced mesh in the glaze layer after semi-melting, resulting in large-area flattened potholes on the surface, insufficient fineness, a lack of three-dimensional texture pattern, and poor wear resistance and anti-fouling performance. If the proportion of the second dry particles is too large or the proportion of the first dry particles is too small, the excessive proportion of the second dry particles will form a noticeable roughness on the surface after semi-melting, poor fineness, a lack of three-dimensional texture pattern, and poor wear resistance and anti-fouling performance. At the same time, this application not only requires that the particle sizes of the first dry particles, the second dry particles, and the protective glaze have specific differentiated designs, but also need to be kept within the specific range set by this application. If they are all larger or smaller, the final effect of this application cannot be achieved well. If they are all larger, the particle content will be correspondingly reduced, which will lead to a more obvious roughness and large-area potholes on the surface, a lack of fineness and naturalness in the texture pattern, and poor anti-fouling performance and wear resistance. If they are all smaller, tiny bumps will form on the surface after semi-melting, which will also make the texture pattern lack three-dimensional.

[0009] The pattern layer includes a color pattern and a texture pattern formed by printing, and the texture pattern includes a plurality of concave lines with a width of 0.5 mm to 1.5 mm and a depth of less than 1 mm, and a combination of light and matte.

[0010] The marble glaze includes a solvent, and the mass ratio of the prefabricated material to the solvent is 1:(0.95-1.05). In some implementations, the solvent includes a suspending agent and water in a mass ratio of 1:(0.2-0.3).

[0011] The raw materials for the glaze, by weight, include: 25-30 parts of calcite powder, 8-10 parts of calcined alumina, 6-7 parts of calcined kaolin, 21.5-25.5 parts of quartz powder, 7-9 parts of calcined ball clay, 7-9 parts of nepheline powder, 4-5 parts of wollastonite, 2.5-3 parts of calcined talc, 0.5-0.7 parts of calcined zinc oxide, and 9-11 parts of zirconium silicate. The chemical composition of the glaze, by mass percentage, includes: SiO₂ 56.5%-63.5%, Al₂O₃ 19.2%-23.2%, CaO 1.9%-2.7%, MgO 1.6%-2.4%, K₂O 2.6%-3.5%, Na₂O 1.5%-2.1%, ZrO₂ 5.8%-7.1%, ZnO 0.4%-0.9%, with the remainder being loss on ignition and impurities. The preparation process of the above-mentioned glaze comprises the following steps: mixing the above-mentioned glaze raw materials with water and additives (which may include a thickener such as methyl cellulose and other conventional commercial products, or a dispersant such as sodium tripolyphosphate and other conventional commercial products), grinding, sieving, and aging to obtain the above-mentioned glaze, wherein the specific gravity of the glaze is 1.84 g / cm 3 -1.89 g / cm 3 .

[0012] The raw materials of the first dry particles include, by weight, 15-17 parts of potassium feldspar, 14-16 parts of sodium feldspar, 11-19 parts of quartz, 10-14 parts of limestone, 7-9 parts of kaolin, 4-6 parts of calcined kaolin, 2-4 parts of aluminum oxide, 4-6 parts of zinc oxide, 12-14 parts of strontium carbonate, and 7-9 parts of calcined talc. The preparation process of the first dry particles includes the following steps: mixing the raw materials of the first dry particles, calcining and melting at 1350°C-1450°C, clarifying, and rapidly cooling the glass melt in a water bath or water-cooled metal rollers to produce crushed glass (blocks, flakes, or granules) frits, which are then crushed to obtain first dry particles with a D97 of 125 μm-129 μm.

[0013] The raw materials of the second dry particles include, by weight, 15-17 parts of potassium feldspar, 17-19 parts of sodium feldspar, 16-24 parts of quartz, 9-11 parts of kaolin, 6-8 parts of limestone, 3-7 parts of aluminum oxide, 3.5-4.5 parts of zinc oxide, 5.5-6.5 parts of strontium carbonate, and 12-16 parts of barium carbonate. The preparation process of the second dry particles includes the following steps: mixing the raw materials of the second dry particles, calcining and melting them at 1350°C-1450°C, clarifying them, and rapidly cooling the glass melt in a water bath or with water-cooled metal rollers to produce crushed glass (blocks, flakes, or granules) frits, which are then crushed to obtain second dry particles with a D97 of 66 μm-70 μm.

[0014] The chemical composition of the protective glaze, by mass percentage, includes: SiO2 45.5%-51.0%, Al2O3 17.5%-21.5%, CaO 4.3%-5.4%, MgO 2.5%-3.5%, Na2O 3.5%-4.5%, SrO 3.5%-4.5%, ZnO 4.5%-5.5%, with the remainder being loss on ignition and impurities. The preparation process of the protective glaze includes the following steps: mixing the raw materials of the protective glaze with water and additives (which may include a thickener such as methyl cellulose or a dispersant such as sodium tripolyphosphate), grinding, sieving, and aging to obtain the protective glaze. The specific gravity of the protective glaze is 1.85 g / cm 3 -1.90g / cm 3 .

[0015] The preparation process of the marble glaze comprises the following steps: uniformly mixing the first dry particles, the second dry particles, the protective glaze and the solvent to obtain the marble glaze, wherein the specific gravity of the marble glaze is 1.46 g / cm 3 -1.50 g / cm 3 .

[0016] The second aspect of the present application provides a method for preparing the above-mentioned marble ceramic tiles, comprising the following steps: applying the above-mentioned glaze to the surface of the above-mentioned green body layer, then printing to form the above-mentioned pattern layer, then applying the above-mentioned marble glaze, firing, and obtaining the above-mentioned marble ceramic tiles.

[0017] The amount of glaze applied is 430 g / m 2 -450 g / m 2 The application amount of the marble glaze is 450 g / m 2 -470 g / m 2; In the process of printing and forming the above-mentioned pattern layer, the pixels of the lines printed in the texture pattern are 6-40, the grayscale of the matte engraving ink is 75-85, and the grayscale of the glossy ink is 15-25; the pixels of the through-net (sheet, block and / or other shapes) are 40-60, the grayscale of the matte engraving ink is 60-70, and the grayscale of the glossy ink is 5-15.

[0018] After the firing, the process further includes polishing, which includes using a 600-1500 mesh elastic grinding block and a 400-600 mesh fiber grinding block for polishing and waxing, thereby obtaining marble ceramic tiles with a bright or stone-like finish.

[0019] Before applying the glaze, digital ink is first printed on the surface of the body layer to form a digital mold texture.

[0020] The beneficial effects of this application are: through the innovative glaze layer formula, the marble ceramic tiles produced have a three-dimensional and natural feel that is closer to natural marble, the glaze surface is delicate and smooth, and at the same time have good wear resistance, stain resistance and acid and alkali resistance, and have good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Shown is the XRD phase diagram of the marble glaze layer in the marble ceramic tile prepared in Example 1; Figure 2 Shown is a SEM scanning electron microscope image of the marble glaze layer in the marble ceramic tile prepared in Example 1; Figure 3 Shown is a SEM scanning electron microscope image of the marble glaze layer in the ceramic tile prepared in Comparative Example 1; Figure 4 Shown is a SEM scanning electron microscope image of the marble glaze layer in the ceramic tile prepared in Comparative Example 2; Figure 5 Shown is a physical picture of the marble ceramic tile prepared in Example 1. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments and drawings to clearly and completely describe the concept, specific structure and technical effects of this application to fully understand the purpose, scheme and effect of this application. It should be noted that the embodiments and features in the embodiments of this application can be combined with each other unless there is a conflict.

[0023] Example 1 This embodiment provides a marble ceramic tile, which includes a body layer, a glaze layer, a pattern layer and a marble glaze layer in sequence.

[0024] The marble glaze layer is formed from marble glaze, which includes a prefabricated material and a solvent in a mass ratio of 1:1. The prefabricated material includes combined dry particles (including first dry particles and second dry particles) and a protective glaze. The solvent includes water and a suspending agent (Foshan Sanshui Taiyang New Materials Co., Ltd., suspending agent model: F525). The preparation process of the marble glaze includes the following steps, calculated by weight: 51 parts of the first dry particles, 25 parts of the second dry particles, 24 parts of the protective glaze, 80 parts of the suspending agent, and 20 parts of water are uniformly mixed to obtain the marble glaze. The specific gravity of the marble glaze is 1.48 g / cm 3 The mass ratio of the combined dry particles to the protective glaze is 1:0.316 (rounded to 3 significant figures); the mass ratio of the first dry particles to the second dry particles is 1:0.5 (rounded to 1 significant figure); and the mass ratio of the suspending agent to water is 1:0.25.

[0025] The raw materials of the first dry particles include, by weight, 16 parts of potassium feldspar, 15 parts of sodium feldspar, 15 parts of quartz, 12 parts of limestone, 8 parts of kaolin, 5 parts of calcined kaolin, 3 parts of aluminum oxide, 5 parts of zinc oxide, 13 parts of strontium carbonate, and 8 parts of calcined talc. The preparation process of the first dry particles includes the following steps: mixing the raw materials of the first dry particles, calcining and melting them at 1400°C, clarifying them, and rapidly cooling the glass melt with water-cooled metal rollers to produce a crushed glass granular frit material, which is then crushed to obtain the first dry particles with a D97 of 125 μm-129 μm. The chemical composition of the first dry particles includes, by mass percentage, 53.37% of SiO2, 16.97% of Al2O3, 7.13% of CaO, 2.52% of MgO, 3.35% of K2O, 2.18% of Na2O, 9.15% of SrO, and 1.08% of ZnO. 4.98%, the rest is loss on ignition and impurities; the initial melting temperature of the first dry granule is 1150 ℃; The raw materials for the second dry granules include, by weight, 16 parts potassium feldspar, 18 parts sodium feldspar, 20 parts quartz, 10 parts kaolin, 7 parts limestone, 5 parts aluminum oxide, 4 parts zinc oxide, 6 parts strontium carbonate, and 14 parts barium carbonate. The preparation process of the second dry granules includes the following steps: mixing the raw materials for the second dry granules, calcining and melting them at 1400°C, clarifying them, rapidly cooling the glass melt with water-cooled metal rollers to produce a crushed glass granular frit, and then crushing them to obtain the second dry granules with a D97 of 66 μm-70 μm. The chemical composition of the second dry granules includes, by mass percentage, 52.6% SiO2, 19.6% Al2O3, 3.6% CaO, 3.8% K2O, 3.1% Na2O, 9.9% BaO, 3.7% ZnO, and 3.6% SrO, with the remainder being loss on ignition and impurities. The onset melting temperature of the second dry granules is 1205°C. The raw materials for the protective glaze include, by weight, 38 parts of sodium stone powder, 14 parts of kaolin, 14 parts of dolomite, 13 parts of quartz powder, 8 parts of corundum powder, 4.5 parts of strontium carbonate, and 7 parts of calcined zinc oxide. The preparation process of the protective glaze includes the following steps: mixing the raw materials for the protective glaze with water, a thickener (methyl cellulose), and a dispersant (sodium tripolyphosphate) in a ratio of 100:30:0.15:0.35, grinding, sieving, and aging to obtain a protective glaze with a particle size D97 of 19 μm-23 μm. The specific gravity of the protective glaze is 1.88 g / cm 3 The chemical composition of the protective glaze, calculated by mass percentage, includes: SiO2 48.23%, Al2O3 19.54%, CaO 4.83%, MgO 3.04%, Na2O 3.97%, SrO 4%, ZnO 4.94%, and the remainder is ignition loss and impurities; the initial melting temperature of the protective glaze is 1135°C; The top glaze layer is formed by the top glaze. The raw materials of the top glaze include, by weight, 27.5 parts of potassium sodium stone powder, 9 parts of calcined aluminum oxide, 6.5 parts of calcined kaolin, 23.5 parts of quartz powder, 8 parts of high white ball clay, 8 parts of nepheline powder, 4.5 parts of wollastonite, 2.5 parts of calcined talc powder, 0.5 parts of calcined zinc oxide, and 10 parts of zirconium silicate. The preparation process of the top glaze includes the following steps: mixing the raw materials of the top glaze with water, a thickener (methyl cellulose), and a dispersant (sodium tripolyphosphate) in a ratio of 100:30:0.15:0.35, grinding, sieving, and aging to obtain the top glaze. The specific gravity of the top glaze is 1.87 g / cm 3 The chemical composition of the glaze, calculated by mass percentage, includes: SiO2 59.96%, Al2O3 21.19%, CaO 2.3%, MgO 1.98%, K2O 3.05%, Na2O 1.8%, ZnO 0.66%, ZrO2 6.47%, and the rest is loss on ignition and impurities.

[0026] The pattern layer includes a color pattern and a texture pattern formed by printing. The texture pattern includes a number of concave lines with a width of 0.5 mm to 1.5 mm and a depth of less than 1 mm, and a combination of light and matte. Among them, the pixels of the lines printed in the texture pattern are 20, the grayscale of the matte engraving ink is 80, and the grayscale of the glossy ink is 20; the pixels of the through-net are 50, the grayscale of the matte engraving ink is 65, and the grayscale of the glossy ink is 10.

[0027] Wherein, the physical picture of the marble ceramic tile obtained in this embodiment is as follows Figure 5 As shown; the XRD phase diagram of the marble glaze layer in the marble ceramic tile is as follows Figure 1 As shown; SEM scanning electron microscope image of marble glaze layer is as follows Figure 2 shown.

[0028] The preparation method of the marble ceramic tile comprises the following steps: (1) Dry the green body layer and control the moisture content within 0.3% (mass percentage); (2) Apply the glaze to the surface of the body layer at a rate of 440 g / m 2 ; (3) Printing to form a pattern layer; (4) Apply marble glaze at a rate of 460 g / m 2 ; (5) Firing in a kiln at a maximum temperature of 1150°C and polishing to obtain the above-mentioned marble ceramic tiles.

[0029] Example 2 This embodiment provides a marble ceramic tile, which is different from the embodiment 1 in that: in this embodiment, (1) The raw materials of the first dry granules include, by weight, 17 parts of potassium feldspar, 16 parts of sodium feldspar, 11 parts of quartz, 10 parts of limestone, 9 parts of kaolin, 4 parts of calcined kaolin, 4 parts of aluminum oxide, 6 parts of zinc oxide, 14 parts of strontium carbonate, and 9 parts of calcined talc; the chemical composition of the first dry granules includes, by mass percentage, 50.68% of SiO2, 18.73% of Al2O3, 6.55% of CaO, 2.84% of MgO, 3% of K2O, 2.41% of Na2O, 9.85% of SrO, and 5.52% of ZnO, with the remainder being loss on ignition and impurities; the initial melting temperature of the first dry granules is 1155°C; (2) The raw materials of the second dry granules include, by weight, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 16 parts of quartz, 11 parts of kaolin, 8 parts of limestone, 7 parts of aluminum oxide, 4.5 parts of zinc oxide, 5.5 parts of strontium carbonate, and 12 parts of barium carbonate; the chemical composition of the second dry granules includes, by mass percentage, 50.26% of SiO2, 21.3% of Al2O3, 3.9% of CaO, 4.21% of K2O, 3.32% of Na2O, 9.17% of BaO, 4% of ZnO, and 3.34% of SrO, with the remainder being loss on ignition and impurities; the initial melting temperature of the second dry granules is 1200°C; (3) The raw materials of the protective glaze include, by weight, 36 parts of sodium stone powder, 16 parts of kaolin, 13 parts of dolomite, 12 parts of quartz powder, 9 parts of corundum powder, 6 parts of strontium carbonate, and 8 parts of calcined zinc oxide; the chemical composition of the protective glaze includes, by mass percentage, 46.07% of SiO2, 21.23% of Al2O3, 4.41% of CaO, 2.65% of MgO, 3.7% of Na2O, 4.44% of SrO, and 5.43% of ZnO, with the remainder being ignition loss and impurities; the initial melting temperature of the protective glaze is 1130°C; The rest is the same as Example 1.

[0030] Example 3 This embodiment provides a marble ceramic tile, which is different from the embodiment 1 in that: in this embodiment, (1) The raw materials of the first dry granules include, by weight, 15 parts of potassium feldspar, 14 parts of sodium feldspar, 19 parts of quartz, 14 parts of limestone, 7 parts of kaolin, 6 parts of calcined kaolin, 2 parts of aluminum oxide, 4 parts of zinc oxide, 12 parts of strontium carbonate, and 7 parts of calcined talc; the chemical composition of the first dry granules includes, by mass percentage, 56.06% of SiO2, 15.25% of Al2O3, 7.57% of CaO, 2.3% of MgO, 3.63% of K2O, 1.91% of Na2O, 8.48% of SrO, and 4.51% of ZnO, with the remainder being loss on ignition and impurities; the melting point of the first dry granules is 1145°C; (2) The raw materials of the second dry granules include, by weight, 15 parts of potassium feldspar, 17 parts of sodium feldspar, 24 parts of quartz, 9 parts of kaolin, 6 parts of limestone, 3 parts of aluminum oxide, 3.5 parts of zinc oxide, 6.5 parts of strontium carbonate, and 16 parts of barium carbonate; the chemical composition of the second dry granules includes, by mass percentage, 54.23% of SiO2, 17.68% of Al2O3, 3.39% of CaO, 3.23% of K2O, 2.82% of Na2O, 10.77% of BaO, 3.39% of ZnO, and 3.83% of SrO, with the remainder being loss on ignition and impurities; the initial melting temperature of the second dry granules is 1210°C; (3) The raw materials of the protective glaze include, by weight, 40 parts of sodium stone powder, 13 parts of kaolin, 16 parts of dolomite, 14 parts of quartz powder, 7 parts of corundum powder, 4 parts of strontium carbonate, and 6 parts of calcined zinc oxide; the chemical composition of the protective glaze includes, by mass percentage, 50.53% of SiO2, 17.81% of Al2O3, 5.32% of CaO, 3.39% of MgO, 4.32% of Na2O, 3.56% of SrO, and 4.58% of ZnO, with the remainder being ignition loss and impurities; the initial melting temperature of the protective glaze is 1140°C; The rest is the same as Example 1.

[0031] Example 4 This embodiment provides a marble ceramic tile, which differs from Example 1 in that: in the marble glaze of this embodiment, the weight portion of the first dry particles is 51 parts, the weight portion of the second dry particles is 23 parts, and the mass ratio of the first dry particles to the second dry particles is 1:0.45; the rest is the same as Example 1.

[0032] Example 5 This embodiment provides a marble ceramic tile, which differs from Example 1 in that: in the marble glaze of this embodiment, the weight of the first dry particles is 51 parts, the weight of the second dry particles is 28 parts, and the mass ratio of the first dry particles to the second dry particles is 1:0.55 (rounded to 2 significant figures); the rest is the same as Example 1.

[0033] Example 6 This embodiment provides a marble ceramic tile, which differs from Example 1 in that: in the marble glaze of this embodiment, the weight of the combined dry particles is 76 parts, the weight of the protective glaze is 23 parts, and the mass ratio of the combined dry particles to the protective glaze is 1:0.30 (rounded to 2 significant figures); the rest is the same as Example 1.

[0034] Example 7 This embodiment provides a marble ceramic tile, which differs from Example 1 in that: in the marble glaze of this embodiment, the weight of the combined dry particles is 76 parts, the weight of the protective glaze is 25.5 parts, and the mass ratio of the combined dry particles to the protective glaze is 1:0.34 (rounded to 2 significant figures); the rest is the same as Example 1.

[0035] Comparative Example 1 This comparative example provides a ceramic tile, which is different from Example 1 in that: in the marble glaze of this comparative example, the weight proportion of the first dry particles is 51 parts, the weight proportion of the second dry particles is 25 parts, and the weight proportion of the protective glaze is 32 parts, wherein the mass ratio of the combined dry particles to the protective glaze is 1:0.42 (rounded to 2 significant figures); the rest is the same as Example 1 (i.e., the proportion of the protective glaze is too large compared to Example 1).

[0036] The SEM scanning electron microscope image of the marble glaze layer of the ceramic tile prepared in this comparative example is as follows: Figure 3 shown.

[0037] Comparative Example 2 This comparative example provides a ceramic tile, which is different from Example 1 in that: in the marble glaze of this comparative example, the weight proportion of the first dry particles is 51 parts, the weight proportion of the second dry particles is 25 parts, and the weight proportion of the protective glaze is 16 parts, wherein the mass ratio of the combined dry particles to the protective glaze is 1:0.21 (rounded to 2 significant figures); the rest is the same as Example 1 (i.e., the proportion of the protective glaze is too small compared to Example 1).

[0038] The SEM scanning electron microscope image of the marble glaze layer of the ceramic tile prepared in this comparative example is as follows: Figure 4 shown.

[0039] Comparative Example 3 This comparative example provides a ceramic tile, which is different from Example 1 in that: in the marble glaze of this comparative example, the weight portion of the first dry particles is 51 parts, and the weight portion of the second dry particles is 15 parts, wherein the mass ratio of the first dry particles to the second dry particles is 1:0.29 (rounded to 2 significant figures); the rest is the same as Example 1 (i.e., the proportion of the second dry particles is too small compared to Example 1).

[0040] Comparative Example 4 This comparative example provides a ceramic tile, which differs from Example 1 in that: in the marble glaze of this comparative example, the weight proportion of the first dry particles is 51 parts, and the weight proportion of the second dry particles is 36 parts, wherein the mass ratio of the first dry particles to the second dry particles is 1:0.71 (rounded to 2 significant figures); the rest is the same as Example 1 (i.e., the proportion of the second dry particles is too large compared to Example 1).

[0041] Comparative Example 5 This comparative example provides a ceramic tile, which differs from Example 1 in that: in the marble glaze of this comparative example, the particle size D97 of the first dry particles is 130 μm-134 μm, the particle size D97 of the second dry particles is 71 μm-75 μm, and the particle size D97 of the protective glaze is 24 μm-28 μm; the rest is the same as Example 1 (that is, compared with Example 1, the particle sizes D97 of the first dry particles, the second dry particles and the protective glaze are all too large).

[0042] Comparative Example 6 This comparative example provides a ceramic tile, which differs from Example 1 in that: in the marble glaze of this comparative example, the particle size D97 of the first dry particles is 120 μm-124 μm, the particle size D97 of the second dry particles is 61 μm-65 μm, and the particle size D97 of the protective glaze is 14 μm-18 μm; the rest is the same as Example 1 (that is, compared with Example 1, the particle sizes D97 of the first dry particles, the second dry particles and the protective glaze are all too small).

[0043] Comparative Example 7 This comparative example provides a ceramic tile, which is different from Example 1 in that: (1) The raw materials of the first dry granules include, by weight, 17 parts of potassium feldspar, 17 parts of sodium feldspar, 16 parts of quartz, 6 parts of limestone, 10 parts of kaolin, 5 parts of calcined kaolin, 3 parts of aluminum oxide, 5 parts of zinc oxide, 13 parts of strontium carbonate, and 8 parts of calcined talc; the chemical composition of the first dry granules includes, by mass percentage, 53.86% of SiO2, 17.68% of Al2O3, 3.67% of CaO, 2.65% of MgO, 3.44% of K2O, 2.73% of Na2O, 9.3% of SrO, and 5.08% of ZnO, with the remainder being loss on ignition and impurities; the initial melting temperature of the first dry granules is 1160°C; (2) The raw materials of the second dry granules include, by weight, 18 parts of potassium feldspar, 20 parts of sodium feldspar, 21 parts of quartz, 11 parts of kaolin, 8 parts of limestone, 5 parts of aluminum oxide, 4 parts of zinc oxide, 6 parts of strontium carbonate, and 7 parts of barium carbonate; the chemical composition of the second dry granules includes, by mass percentage, 52.78% of SiO2, 19.89% of Al2O3, 4.34% of CaO, 4.45% of K2O, 3.57% of Na2O, 6.03% of BaO, 4.4% of ZnO, and 4.33% of SrO, with the remainder being loss on ignition and impurities; the initial melting temperature of the second dry granules is 1215°C; (3) The raw materials of the protective glaze include, by weight, 28 parts of sodium stone powder, 18 parts of kaolin, 17 parts of dolomite, 16 parts of quartz powder, 9 parts of corundum powder, 5 parts of strontium carbonate, and 7 parts of calcined zinc oxide; the chemical composition of the protective glaze includes, by mass percentage, 48.8% of SiO2, 20.05% of Al2O3, 4.94% of CaO, 3.1% of MgO, 1.98% of Na2O, 4.07% of SrO, and 5.15% of ZnO, with the remainder being ignition loss and impurities; the initial melting point of the protective glaze is 1145°C; The rest is the same as Example 1 (that is, compared with Example 1, the calcium oxide content in the first dry particles is lower, the barium content in the second dry particles is lower, and the sodium content in the protective glaze is lower).

[0044] Comparative Example 8 This comparative example provides a ceramic tile, which is different from Example 1 in that: (1) The raw materials of the first dry granules include, by weight, 14 parts of potassium feldspar, 14 parts of sodium feldspar, 13 parts of quartz, 18 parts of limestone, 8 parts of kaolin, 4 parts of calcined kaolin, 3 parts of aluminum oxide, 5 parts of zinc oxide, 13 parts of strontium carbonate, and 8 parts of calcined talc; the chemical composition of the first dry granules includes, by mass percentage, 51.95% of SiO2, 18.02% of Al2O3, 10.13% of CaO, 2% of MgO, 2.83% of K2O, 1.78% of Na2O, 8.34% of SrO, and 4.23% of ZnO, with the remainder being loss on ignition and impurities; the initial melting temperature of the first dry granules is 1140°C; (2) The raw materials of the second dry granules include, by weight, 15 parts of potassium feldspar, 17 parts of sodium feldspar, 19 parts of quartz, 10 parts of kaolin, 6 parts of limestone, 5 parts of aluminum oxide, 4 parts of zinc oxide, 5 parts of strontium carbonate, and 19 parts of barium carbonate; the chemical composition of the second dry granules includes, by mass percentage, 52.01% of SiO2, 18.9% of Al2O3, 3% of CaO, 3.05% of K2O, 2.62% of Na2O, 14.1% of BaO, 3.1% of ZnO, and 3.03% of SrO, with the remainder being loss on ignition and impurities; the initial melting temperature of the second dry granules is 1195°C; (3) The raw materials of the protective glaze include, by weight, 48 parts of sodium stone powder, 12 parts of kaolin, 12 parts of dolomite, 11 parts of quartz powder, 7 parts of corundum powder, 4 parts of strontium carbonate, and 6 parts of calcined zinc oxide. The chemical composition of the protective glaze includes, by mass percentage, 46.71% of SiO2, 18.52% of Al2O3, 4.63% of CaO, 3% of MgO, 6.18% of Na2O, 3.86% of SrO, and 4.78% of ZnO, with the remainder being ignition loss and impurities. The melting point of the protective glaze is 1125°C. The rest is the same as Example 1 (that is, compared with Example 1, the calcium oxide content in the first dry particles is higher, the barium content in the second dry particles is higher, and the sodium content in the protective glaze is higher).

[0045] Test Example 1 For the marble ceramic tiles prepared in Examples 1-7 and the ceramic tiles prepared in Comparative Examples 1-2, the marble glaze layers were subjected to semi-quantitative phase analysis using X-ray diffraction analysis (XRD). The results are shown in Table 1.

[0046] Table 1 refer to Figure 1 Combined with the test data in Table 1, it can be seen that the protective glaze in the marble glaze layer formula of the present application melts at a lower temperature due to its smaller particle size and the presence of strong flux sodium. During the melting process, it also causes eutectic melting of the first dry particles and the second dry particles, prompting the melting of the first dry particles and the semi-melting of the second dry particles. After melting and reorganization, a large amount of barium feldspar, strontium feldspar, and potassium sodium feldspar crystals are subsequently formed, and the entire glaze layer has good wear resistance and acid and alkali resistance.

[0047] Test Example 2 The marble ceramic tiles prepared in Examples 1-7 and the ceramic tiles prepared in Comparative Examples 1-8 were tested for wear resistance, stain resistance, and surface quality. The surface wear resistance was tested using the method in GB / T3810.7, and the surface stain resistance and surface quality were tested using the method in GB / T3810.14-2016. The results are shown in Table 2.

[0048] Table 2 It can be seen from the test data in Table 2 above that the marble ceramic tiles prepared using the technical solution of the present application have good wear resistance and stain resistance (both reaching level 5), and have a natural texture pattern and a fine and smooth surface.

[0049] With reference to Table 2, it can be seen from the comparison of Example 1 and Comparative Examples 1-2 that when the proportion of the protective glaze is too large, its initial melting temperature will be too low, and thus the overall initial melting temperature will be too low, prompting the first dry particles and the second dry particles to undergo a melting reaction before the maximum temperature of 1150°C, resulting in the precipitated crystals of different sizes and uneven distribution, resulting in a too smooth surface and a lack of three-dimensional texture pattern, and poor wear resistance; when the proportion of the protective glaze is small, its initial melting temperature will be too high, and thus the overall initial melting temperature will be too high. At the maximum temperature of 1150°C, the first dry particles cannot be melted and the second dry particles cannot undergo a semi-melting reaction, resulting in a reduced amount of crystallization, poor crystal phase formation, and different crystal sizes and uneven distribution, resulting in a noticeable surface roughness, a general three-dimensional texture pattern, and poor wear resistance. In addition, a small proportion of the protective glaze will also cause a lack of filling between the dry particles, resulting in a decrease in anti-fouling performance.

[0050] From the comparison of Example 1 and Comparative Examples 3-4, it can be seen that when the proportion of the second dry particles is small, the weight ratio of the first dry particles to the second dry particles will be too large. Under the same firing conditions, because the second dry particles are at a relatively high temperature and the first dry particles are at a relatively low temperature, the second dry particles with a relatively small proportion play a limited role as a fulcrum for the network interlacing in the glaze layer after semi-melting, resulting in a large range of flattened potholes on the surface, and insufficient fineness. Although the potholes have become lighter after polishing, the texture pattern lacks three-dimensional sense, and the wear resistance and anti-fouling properties are poor; when the proportion of the second dry particles is large, the weight ratio of the first dry particles to the second dry particles will be too small. Under the same firing conditions, because the second dry particles are at a relatively high temperature and the first dry particles are at a relatively low temperature, the second dry particles with a relatively large proportion form an obvious roughness on the surface after semi-melting, and the fineness is poor. Although the roughness and fineness are improved after polishing, the texture pattern lacks three-dimensional sense, and the wear resistance and anti-fouling properties are poor.

[0051] From the comparison of Example 1 and Comparative Examples 5-6, it can be seen that when the particle size D97 of the first dry particles, the second dry particles and the protective glaze are all large, the particle content is reduced accordingly, which will cause the second dry particles to form a more obvious roughness and a larger range of potholes on the surface after semi-melting. Although the roughness and potholes are slightly improved after polishing, the texture pattern lacks a natural feel, and the anti-fouling and wear resistance are poor; when the particle size D97 of the first dry particles, the second dry particles and the protective glaze are all small, the particle content is increased accordingly, resulting in the formation of tiny bumps on the surface after semi-melting of the second dry particles. Although the surface is smoother and flatter after polishing, and the anti-fouling and wear resistance are better, the texture pattern lacks a three-dimensional sense.

[0052] From the comparison of Example 1 and Comparative Example 7, it can be seen that when the calcium oxide content of the first dry particles is low, the barium content of the second dry particles is low, and the sodium content of the protective glaze is low, it will lead to poor high-temperature sintering properties, poor meltability, resulting in poor fluidity of the entire liquid surface at high temperatures, and affecting the formation of the crystal phase, thereby reducing the anti-fouling, wear resistance, strength, acid and alkali resistance and other properties, and the texture pattern lacks a natural feel.

[0053] From the comparison of Example 1 and Comparative Example 8, it can be seen that when the calcium oxide content of the first dry particles is too high, the barium oxide content of the second dry particles is too high, and the sodium content of the protective glaze is too high, the entire glaze layer will melt prematurely, resulting in excessive fluidity of the entire liquid surface at high temperatures, poor stability of the glaze layer, increased defects, and a lack of three-dimensional texture.

[0054] The above is only a preferred embodiment of the present application. The present application is not limited to the above-mentioned embodiments. As long as the technical effects of the present application are achieved by the same means, they shall fall within the scope of protection of the present application. Within the scope of protection of the present application, the technical solutions and / or implementation methods may be modified and varied in various ways.

Claims

1. A marble ceramic tile, characterized in that: The invention sequentially comprises a body layer, a surface glaze layer, a pattern layer and a marble glaze layer; the surface glaze layer is formed of a surface glaze, the marble glaze layer is formed of a marble glaze, the marble glaze comprises a prefabricated material, the prefabricated material comprises a combination of dry particles and a protective glaze, the combination of dry particles comprises a first dry particle and a second dry particle; the mass ratio of the combination of dry particles to the protective glaze is 1:(0.3-0.34), and the mass ratio of the first dry particle to the second dry particle is 1:(0.45-0.55); The first dry particles have an initial melting temperature of 1145°C-1155°C, the second dry particles have an initial melting temperature of 1200°C-1210°C, and the protective glaze has an initial melting temperature of 1130°C-1140°C; The particle size D97 of the first dry particles is 125 μm-129 μm, the particle size D97 of the second dry particles is 66 μm-70 μm, and the particle size D97 of the protective glaze is 19 μm-23 μm; The chemical composition of the first dry particles comprises, by mass percentage, SiO2 50.5%-56.5%, Al2O3 15.0%-19.0%, CaO 6.4%-7.8%, MgO 2.2%-2.9%, K2O 2.9%-3.8%, Na2O 1.9%-2.5%, SrO 8.4%-10%, ZnO 4.4%-5.6%, and the remainder is loss on ignition and impurities; The chemical composition of the second dry particles comprises, by mass percentage, SiO2 50%-55%, Al2O3 17.5%-21.5%, CaO 3.3%-4%, K2O 3.2%-4.3%, Na2O 2.8%-3.4%, BaO 9%-11%, ZnO 3.3%-4.1%, SrO 3.3%-3.9%, and the remainder is loss on ignition and impurities; The raw materials of the protective glaze include, by weight, 36-41 parts of sodium stone powder, 13-16 parts of kaolin, 13-16 parts of dolomite, 12-14 parts of quartz powder, 7-9 parts of corundum powder, 4-6 parts of strontium carbonate, and 6-8 parts of calcined zinc oxide.

2. The marble ceramic tile according to claim 1, characterized in that: The pattern layer includes a color pattern and a texture pattern formed by printing, and the texture pattern includes a plurality of concave lines with a width of 0.5 mm to 1.5 mm and a depth of less than 1 mm, and a combination of light and matte.

3. The marble ceramic tile according to claim 1, characterized in that: The marble glaze includes a solvent, and the mass ratio of the prefabricated material to the solvent is 1:(0.95-1.05).

4. The marble ceramic tile according to claim 3, characterized in that: The solvent includes a suspending agent and water in a mass ratio of 1:(0.2-0.3).

5. The marble ceramic tile according to claim 1, characterized in that: Calculated by mass percentage, the physical phases in the marble glaze layer include: 11%-15% potassium-sodium feldspar, 12%-16% strontium feldspar, and 23%-27% barium adularia.

6. The marble ceramic tile according to claim 1, characterized in that: The raw materials of the glaze include, by weight, 25-30 parts of potassium sodium stone powder, 8-10 parts of calcined alumina, 6-7 parts of calcined kaolin, 21.5-25.5 parts of quartz powder, 7-9 parts of high white ball clay, 7-9 parts of nepheline powder, 4-5 parts of wollastonite, 2.5-3 parts of calcined talc powder, 0.5-0.7 parts of calcined zinc oxide, and 9-11 parts of zirconium silicate.

7. A method for preparing a marble ceramic tile according to any one of claims 1 to 6, characterized in that: The following steps are involved: The top glaze is applied to the surface of the green body layer, and then the pattern layer is formed by printing. Subsequently, the marble glaze is applied and the ceramic tile is fired to obtain the marble ceramic tile.

8. The preparation method according to claim 7, characterized in that The amount of glaze applied was 430 g / m 2 -450 g / m 2 ; and / or, the application amount of the marble glaze is 450 g / m 2 -470 g / m 2 ; and / or, in the process of printing to form the pattern layer, the pixels of the lines printed in the texture pattern are 6-40, the grayscale of the matte engraving ink is 75-85, and the grayscale of the glossy ink is 15-25; the pixels of the through-net are 40-60, the grayscale of the matte engraving ink is 60-70, and the grayscale of the glossy ink is 5-15.

9. The preparation method according to claim 7, characterized in that After the firing, polishing is also included.

10. The preparation method according to claim 7, characterized in that Before applying the top glaze, digital ink is printed on the surface of the body layer.

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