Super-flat wear-resistant glaze golden velvet ceramic tile and preparation method thereof

Abstract

The invention relates to the technical field of building ceramic materials, and discloses a super-flat wear-resistant glaze golden velvet ceramic tile and a preparation method thereof.The super-flat wear-resistant glaze golden velvet ceramic tile comprises a green body layer, a ground coat layer and a golden velvet glaze layer, and the ground coat layer and the golden velvet glaze layer are arranged on the green body layer; wherein the preparation raw material of the golden velvet glaze layer is golden velvet glaze, and the preparation raw materials of the golden velvet glaze comprise an inorganic raw material, water and an auxiliary agent, the inorganic raw materials comprise the following preparation raw materials in parts by weight: 35-45 parts of quartz, 7-12 parts of calcined kaolin, 3-7 parts of dolomite, 9-11 parts of zinc oxide, 3-5 parts of zirconite, 2-3 parts of barium carbonate, 8-13 parts of boron frit, 1-4 parts of calcium phosphate, 2-6 parts of wollastonite, 15-20 parts of potassium feldspar and 0.5-2 parts of boron nitride. By implementing the method, the ceramic tile which is low in light and not dazzling and has velvet-like light sensation can be obtained, and the ceramic tile has a smooth ultra-flat glaze surface, antifouling property and wear resistance.

Description

Technical Field

[0001] This invention relates to the technical field of building ceramic materials, and in particular to an ultra-flat, wear-resistant glazed gold velvet ceramic tile and its preparation method. Background Technology

[0002] In the home decoration industry, ceramic tiles have long been a core material for floor and wall decoration due to their combination of durability and aesthetics. However, as contemporary consumers demand both a relaxed aesthetic and practicality in their homes, traditional ceramic tiles have gradually revealed their shortcomings, such as limited decorative texture and difficulty in balancing functionality and aesthetics. These issues are particularly prominent in the sub-category of soft-light ceramic tiles.

[0003] While traditional soft-light tiles can create a gentle spatial atmosphere by reducing gloss and avoiding glare from strong light, their surfaces are mostly conventional matte or have simple textures, making it difficult to replicate the delicate touch and high-end feel of natural materials. This results in a highly homogenized decorative effect, failing to meet consumers' demands for upgraded home aesthetics. Furthermore, limited by surface processing techniques, traditional soft-light tiles generally suffer from poor stain resistance and are prone to stain penetration. In daily use, stains easily seep into the tile body, making cleaning difficult. Additionally, some products have a rough surface texture, lacking a comfortable tactile experience, severely restricting their application in high-end home decoration scenarios.

[0004] This year, the industry has launched velvet-textured tiles. The core of velvet soft-light tiles lies in using the "velvet" texture as a visual and tactile medium, precisely replicating the feel of velvet fabric. Building upon ordinary soft-light tiles, through innovative technological upgrades, the surface smoothness is further enhanced, presenting a subtle, velvety sheen, achieving a visual effect of "soft, non-glaring light, and a velvety feel," perfectly matching the relaxed aesthetic of contemporary homes. At the same time, it solves the pain points of traditional soft-light tiles in practical use, such as easy staining and rough texture, making it quickly popular among young consumers. With its velvet texture and practical breakthroughs in stain resistance and waterproofing, velvet soft-light tiles infuse the warm, velvety feel into the tile's texture, and further solve home pain points with its superior stain resistance and waterproofing performance, opening up a new high-value-added track in the industry's homogenized price war.

[0005] However, in existing technologies, conventional processes achieve the velvety feel of velvet soft-light tiles by constructing micron-level protrusions. However, the physical strength of these protrusions is usually lower than that of a completely dense glass phase glaze, which leads to reduced wear resistance and also affects the macroscopic smoothness of the glaze surface. Under certain lighting conditions, tiny ripples or unevenness may be visible. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide an ultra-flat wear-resistant glazed velvet ceramic tile and its preparation method. The ceramic tile has a velvety, subtle luster and a delicate surface texture, as well as a smooth ultra-flat glaze, stain resistance, and wear resistance.

[0007] To address the aforementioned technical problems, the first aspect of this invention provides an ultra-flat, wear-resistant glazed gold velvet ceramic tile, comprising a body layer, a base glaze layer, and a gold velvet glaze layer disposed on the body layer; wherein the raw material for preparing the gold velvet glaze layer is gold velvet glaze, and the raw material for preparing the gold velvet glaze includes inorganic raw materials, water, and additives, wherein the inorganic raw materials, by weight, comprise: Quartz 35-45 parts, calcined kaolin 7-12 parts, dolomite 3-7 parts, zinc oxide 9-11 parts, zircon 3-5 parts, barium carbonate 2-3 parts, boron frit 8-13 parts, calcium phosphate 1-4 parts, wollastonite 2-6 parts, potassium feldspar 15-20 parts, boron nitride 0.5-2 parts.

[0008] As an improvement to the above scheme, the chemical composition of the inorganic raw material, by weight percentage, includes: The composition is as follows: SiO2 61%-70%, Al2O3 5%-8%, ZnO 8%-11%, B2O3 1.5%-2.5%, CaO 2%-4%, MgO 0.5%-1.5%, K2O 0.5%-1.5%, BaO 1%-2%, P2O5 0.5%-1.5%, ZrO2 1%-2%, with the balance being impurities. The ZnO:B2O3:P2O5 ratio is (7-13):(2-4):1.

[0009] As an improvement to the above scheme, the boron nitride is a modified boron nitride modified with a siloxane compound, and the preparation method of the modified boron nitride includes the following steps: Boron nitride is uniformly dispersed in an aqueous ethanol solution, a siloxane compound is added, and the mixture is refluxed at 60℃-80℃ for 2-3 hours. Finally, it is washed and dried. The mass of the siloxane compound added is 1-2 wt% of the mass of the boron nitride added; the boron nitride is nanosheet boron nitride with a size of 2 μm-5 μm and a thickness of 50 nm-200 nm.

[0010] As an improvement to the above solution, the ultra-flat wear-resistant glaze gold velvet ceramic tile further includes a protective layer disposed on the gold velvet glaze layer. The protective layer is formed after the sol prepolymer is cured. The raw materials for preparing the sol prepolymer include: perfluorooctyltriethoxysilane, tetraethyl orthosilicate, catalyst, and solvent. The molar ratio of perfluorooctyltriethoxysilane to tetraethyl orthosilicate is (3.5-4.5):1, and the concentration of perfluorooctyltriethoxysilane is 0.2M-0.25M. The solvent is a mixture of water and ethanol, and the volume ratio of water to ethanol is 1:(7.5-8.5). The catalyst is an acidic catalyst.

[0011] As an improvement to the above solution, the thickness of the protective layer is 90nm-600nm; The method for preparing the sol-prepolymer includes the following steps: Perfluorooctyltriethoxysilane and tetraethyl orthosilicate were dissolved in a solvent, and a catalyst was added to react and form a sol. The sol was then aged at room temperature for 18-36 hours to form a sol prepolymer. When the catalyst is added to carry out the reaction, the pH of the reaction system is controlled to be 2-2.5.

[0012] As an improvement to the above scheme, the weight ratio of the inorganic raw materials, water and additives is 1:(0.2-0.3):(0.35-0.45). The additives are sodium tripolyphosphate and carboxymethyl cellulose, and the weight ratio of sodium tripolyphosphate to carboxymethyl cellulose is 1:(1.5-3.5). The average particle size of the inorganic raw material is 40μm-60μm.

[0013] As an improvement to the above scheme, the raw materials for preparing the green body layer include, by weight: 12-17 parts of porcelain clay, 8-12 parts of kaolin, 2-5 parts of bentonite, 3-7 parts of high-alumina clay, 20-26 parts of quartz sand, 3-6 parts of albite, 13-18 parts of potassium-sodium feldspar, 4-5 parts of wollastonite, 5-10 parts of cordierite, 0.05-2 parts of kyanite, 0.05-0.3 parts of sodium lignosulfonate, and 0.05-0.3 parts of sodium carboxymethyl cellulose; The chemical composition of the blank layer, by weight percentage, includes: SiO2: 67%-73%, Al2O3: 17%-22%, K2O+Na2O: 2.7%-4.7%, CaO+MgO+TiO2: 2.7%-5.2%, Fe2O3: 0.1%-0.4%, with the balance being impurities.

[0014] As an improvement to the above solution, the raw materials for preparing the base glaze layer include, by weight: Quartz 20-30 parts, calcined kaolin 30-40 parts, potassium feldspar 15-20 parts, sodium feldspar 3-6 parts, wollastonite 8-12 parts, zircon 8-12 parts, cordierite 3-7 parts; The chemical composition of the base glaze layer, by weight percentage, includes: SiO2: 55%-65%, Al2O3: 18%-25%, K2O: 1.5%-2.5%, Na2O: 0.3%-0.8%, CaO: 4%-7%, MgO: 0%-0.5%, ZrO2: 4%-6%, with the balance being impurities.

[0015] A second aspect of this invention provides a method for preparing the aforementioned ultra-flat, wear-resistant glazed velvet ceramic tile, comprising the following steps: (1) Prepare the raw materials for the preparation of the blank layer, and obtain the blank layer by spreading and forming; (2) Apply glaze to the body layer to form a base glaze layer; (3) First, inkjet print the pattern on the base glaze layer, and then spray glaze to form a gold velvet glaze layer; (4) The glazed body is sintered at high temperature, removed from the kiln, and cooled.

[0016] As an improvement to the above scheme, in step (4), the high-temperature sintering includes: Sintering at 1180℃-1200℃ for 8-15 minutes forms a uniform glass phase matrix, resulting in an ultra-flat surface. The temperature was reduced from 1180℃-1200℃ to 880℃-920℃, with the cooling rate controlled at 48℃ / min-53℃ / min, while preserving the glassy structure at high temperature. The temperature is lowered from 880℃-920℃ to 720℃-760℃, with the cooling rate controlled at 3℃ / min-5℃ / min, to enter the crystallization window of zinc silicoite, so that the zinc silicoite crystals grow uniformly and fill the gaps between the glass phases; The temperature was reduced from 720℃-760℃ to 630-660℃, with the cooling rate controlled at 2℃ / min-4℃ / min, to separate the borosilicate glass phase and optimize the distribution of microcracks.

[0017] As an improvement to the above scheme, the preparation method further includes the following steps: (5) Spray the semi-finished gold velvet glaze layer onto it and cure it to form a protective layer; The curing temperature for forming the protective layer is 280℃-320℃, and the curing time is 15min-20min.

[0018] Implementing this invention has the following beneficial effects: In this application, quartz and potassium feldspar, as glaze glass network forgers, provide mechanical strength and chemical stability to the velvet glaze layer. Zircon and zinc oxide form a zinc-zirconium composite crystalline phase, enhancing the wear resistance of the velvet glaze layer. Furthermore, the added boron nitride induces the directional crystallization of zinc-aluminum spinel and wollastonite, resulting in a more uniform grain size distribution and improved glaze fineness. Moreover, the boron nitride surface is rich in BO bonds, which can adsorb alkali-rich phases, reducing the interfacial energy and making the separation of silicon-rich and alkali-rich phases more uniform, thus reducing wear. The glaze exhibits minimal localized gloss variations. Furthermore, the synergistic effect of boron frit and calcium phosphate causes the velvet glaze to undergo further liquid-liquid phase separation after crystallization, separating into two immiscible glass phases: one rich in SiO2 and the other rich in B2O3 / P2O2. This constructs a functionalized microstructure within the velvet glaze layer, forming a dense, amorphous glass network between the microcrystals. This seals any potential pores, and the combined effect of boron nitride enhances the glaze's density, thereby achieving the inherent stain resistance of the ceramic tile and creating a nanoscale smooth, ultra-flat glaze surface. Attached Figure Description

[0019] Figure 1 This is a diagram showing the effect of the ultra-flat wear-resistant glazed velvet ceramic tile obtained in Example 5 of the present invention under indoor lighting conditions; Figure 2 This is a diagram showing the effect of the ultra-flat, wear-resistant glazed velvet ceramic tile obtained in Example 5 under sunlight. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the present invention clearer, specific embodiments will be described in further detail below.

[0021] To address the aforementioned problems, the present invention provides an ultra-flat, wear-resistant glazed velvet ceramic tile, comprising a body layer, a base glaze layer, and a velvet glaze layer disposed on the body layer.

[0022] Preferably, the raw materials for preparing the green body layer include, by weight: 12-17 parts porcelain clay, 8-12 parts kaolin, 2-5 parts bentonite, 3-7 parts high-alumina clay, 20-26 parts quartz sand, 3-6 parts albite, 13-18 parts potassium-sodium feldspar, 4-5 parts wollastonite, 5-10 parts cordierite, 0.05-2 parts kyanite, 0.05-0.3 parts sodium lignosulfonate, and 0.05-0.3 parts sodium carboxymethyl cellulose. The green body obtained after sintering the above raw materials has good mechanical strength and good flatness.

[0023] Furthermore, the chemical composition of the green body layer, by weight percentage, includes: SiO2: 67%-73%, Al2O3: 17%-22%, K2O+Na2O: 2.7%-4.7%, CaO+MgO+TiO2: 2.7%-5.2%, Fe2O3: 0.1%-0.4%, with the balance being impurities. This composition can effectively promote densification during the sintering process, thereby reducing the water absorption rate of the ceramic product green body and improving its mechanical properties such as pressure resistance and hardness.

[0024] Preferably, the raw materials for preparing the base glaze layer include, by weight: 20-30 parts quartz, 30-40 parts calcined kaolin, 15-20 parts potassium feldspar, 3-6 parts sodium feldspar, 8-12 parts wollastonite, 8-12 parts zircon, and 3-7 parts cordierite. The addition of potassium feldspar, zinc oxide, and other raw materials can effectively control the coefficient of thermal expansion of the glaze in the base glaze layer, placing it between the body layer and the velvet glaze layer to form a rational stress gradient. Furthermore, the addition of wollastonite, calcium carbonate, dolomite, sodium feldspar, etc., can adjust the sintering temperature of the base glaze, allowing it to melt first to form a dense and smooth base layer, providing an ideal platform for the "crystallization-phase separation" of the velvet glaze.

[0025] Furthermore, the chemical composition of the base glaze layer, by weight percentage, includes: SiO2: 55%-65%, Al2O3: 18%-25%, K2O: 1.5%-2.5%, Na2O: 0.3%-0.8%, CaO 4%-7%, MgO 0%-0.5%, ZrO2: 4%-6%, with the balance being impurities. More preferably, the SiO2 / Al2O3 ratio is 8-10, and the optimized ratio and the introduction of 0.5%-1.5% MgO further improve the glaze slurry properties and firing tolerance of the base glaze.

[0026] Preferably, the raw material for preparing the velvet glaze layer is velvet glaze, which includes inorganic raw materials, water, and additives. The weight ratio of the inorganic raw materials, water, and additives is 1:(0.2-0.3):(0.35-0.45). The additives are sodium tripolyphosphate and carboxymethyl cellulose, and the weight ratio of sodium tripolyphosphate and carboxymethyl cellulose is 1:(1.5-3.5). This ensures that the velvet glaze forms a uniform glass phase matrix during high-temperature sintering, reducing microcrack defects. At the same time, it can control the surface tension difference between the inorganic raw material glaze and the digital deep ink, forming a matte three-dimensional texture, enhancing the velvet feel, and achieving a fine embossed effect.

[0027] The inorganic raw materials, by weight, include: 35-45 parts quartz, 7-12 parts calcined kaolin, 3-7 parts dolomite, 9-11 parts zinc oxide, 3-5 parts zircon, 2-3 parts barium carbonate, 8-13 parts boron frit, 1-4 parts calcium phosphate, 2-6 parts wollastonite, 15-20 parts potassium feldspar, and 0.5-2 parts boron nitride. In this application, quartz and potassium feldspar, as glaze glass network forgings, provide mechanical strength and chemical stability to the velvet glaze layer. Zircon and zinc oxide can form a zinc-zirconium composite crystalline phase, enhancing the wear resistance of the velvet glaze layer. Furthermore, the added boron nitride induces the directional crystallization of zinc-aluminum spinel and wollastonite, resulting in a more uniform grain size distribution and improved glaze fineness. Moreover, the boron nitride surface is rich in BO bonds, which can adsorb alkaline phases, reducing the interfacial energy and making the separation of silicon-rich and alkaline-rich phases more uniform, reducing localized glaze surface defects. The difference in gloss; and the synergistic effect of boron frit and calcium phosphate causes the velvet glaze to undergo further "liquid-liquid phase separation" after crystallization, separating into two immiscible glass phases rich in SiO2 and B2O3 / P2O2, which construct a functional microstructure inside the velvet glaze layer, forming a dense, amorphous glass network between the microcrystals, sealing any possible pores, and with the cooperation of boron nitride, improving the density of the glaze surface, thereby achieving the inherent stain resistance of the ceramic tile, making it extremely difficult for stains to penetrate, and forming a nanoscale smooth ultra-flat glaze surface.

[0028] Accordingly, the chemical composition of the inorganic raw materials, by weight percentage, includes: SiO2 61%-70%, Al2O3 5%-8%, ZnO 8%-11%, B2O3 1.5%-2.5%, CaO 2%-4%, MgO 0.5%-1.5%, K2O 0.5%-1.5%, BaO 1%-2%, P2O5 0.5%-1.5%, ZrO2 1%-2%, with the balance being impurities. Among them, the ZnO:B2O3:P2O5 ratio is (7-13):(2-4):1, which can precisely guide the formation of micron-sized zinc silicoeite crystals, producing soft light diffuse reflection and a velvety feel. Subsequently, a nano-sized liquid-liquid phase separation structure is formed, achieving a dense and smooth surface, intrinsic stain resistance, and soft gloss, making the gloss of the gold velvet textured ceramic tile approximately 33°±3°. If the ZnO content is too high, it will promote the precipitation of zinc silicosite, resulting in crystal growth that is too fast and too large. It will also inhibit the phase separation tendency of the boron-phosphorus system, resulting in ceramic tiles with a normal matte or soft-gloss surface and a slight sandy feel rather than a velvety feel. If the B2O3 content is too high or the P2O5 content is too low, excessive phase separation will occur, inhibiting the formation of crystal nuclei and the growth of crystals. This will cause the glaze melt to quickly enter a stable phase-separated glassy state. Although this improves the stain resistance of the glaze, it lacks sufficient micron-sized crystals to produce a velvety feel and specific diffuse reflection.

[0029] Furthermore, the boron nitride is modified boron nitride modified with siloxane compounds. Modified boron nitride has good dispersibility in velvet glaze, avoiding uneven crystallization caused by agglomeration, ensuring that zinc silicoite microcrystals precipitate in a fine, dense and uniform manner, obtaining a submicron-level microstructure, forming a uniformly dispersed core of velvety diffuse reflection, and obtaining a delicate and uniform velvety touch.

[0030] Optionally, the boron nitride is nanosheet boron nitride, whose nanosheet structure can form a micron-level tactile gradient, simulating the smoothness of natural velvet. Furthermore, the sheet structure can absorb thermal stress, reducing the risk of glaze cracking in the velvet enamel layer. The boron nitride has a size of 2μm-5μm and a thickness of 50nm-200nm. The siloxane compound includes, but is not limited to, the silane coupling agent KH-550.

[0031] Specifically, the preparation method of the modified boron nitride includes the following steps: uniformly dispersing boron nitride in an aqueous ethanol solution, adding a siloxane compound, refluxing at 60℃-80℃ for 2-3 hours, and finally washing and drying. The mass of the siloxane compound added is 1-2 wt% of the mass of boron nitride added. When washing and drying the reaction product, the product can be centrifuged first, then washed 2-3 times with ethanol to remove unreacted siloxane compounds, and finally dried under vacuum at 70℃-80℃.

[0032] Furthermore, the average particle size of the inorganic raw material is 40μm-60μm. If the particle size of the inorganic raw material is too small, it will flow during high-temperature sintering, destroying the velvet texture structure; if the particle size of the inorganic raw material is too large, it will lead to a decrease in the smoothness of the glaze surface and affect the ultra-flat effect.

[0033] The ultra-flat, wear-resistant glaze velvet ceramic tile further includes a protective layer disposed on the velvet glaze layer, the thickness of which is 90nm-600nm. Preferably, the protective layer is formed after the curing of a sol-gel prepolymer, the raw materials for preparing the sol-gel prepolymer including: perfluorooctyltriethoxysilane, tetraethyl orthosilicate, catalyst, and solvent. In this application, a protective coating with a Si-O-Si inorganic network as the framework and low surface energy organic chains grafted onto the surface is generated in situ on the glaze surface by the sol-gel method, providing sufficient hardness and wear resistance to the velvet glaze layer. Moreover, the low surface energy fluorine-containing structure on the surface can provide excellent hydrophobic and oleophobic properties for the velvet ceramic tile, improving its impermeability and extending its durability. In addition, the sol prepolymer has good leveling and wetting properties, which can seamlessly fill every gap in the microstructure of the velvet glaze. After curing, it is completely attached to the surface of the velvet, maintaining its microstructure. When exposed to light, the original micron-level crystallization-phase separation structure of the velvet glaze layer still takes effect, producing the same diffuse reflection, thus preserving its gloss and the unique delicate feel of velvet.

[0034] Further, the molar ratio of perfluorooctyltriethoxysilane to tetraethyl orthosilicate is (3.5-4.5):1, and the concentration of perfluorooctyltriethoxysilane is 0.2M-0.25M; the solvent is a mixture of water and ethanol, and the volume ratio of water to ethanol is 1:(7.5-8.5). Of course, other organic solvents can also be used, as long as they dissolve perfluorooctyltriethoxysilane and tetraethyl orthosilicate and are compatible with water.

[0035] Specifically, the preparation method of the sol prepolymer includes the following steps: dissolving perfluorooctyltriethoxysilane and tetraethyl orthosilicate in a solvent, adding a catalyst to react and form a sol, followed by aging at room temperature for 18-36 hours to form a sol prepolymer. When adding the catalyst, the pH of the reaction system is controlled at 2-2.5 to facilitate better hydrolysis of perfluorooctyltriethoxysilane and tetraethyl orthosilicate. After aging, a Si-OH-rich sol prepolymer can be formed. Optionally, the catalyst is an acidic catalyst, including but not limited to hydrochloric acid.

[0036] A second aspect of this invention provides a method for preparing the aforementioned ultra-flat, wear-resistant glazed velvet ceramic tile, comprising the following steps: (1) Prepare the raw materials for the preparation of the blank layer, and obtain the blank layer by spreading and forming; (2) Apply glaze to the body layer to form a base glaze layer; (3) First, inkjet print the pattern on the base glaze layer, and then spray glaze to form a gold velvet glaze layer; (4) The glazed body is sintered at high temperature, removed from the kiln, and cooled.

[0037] Preferably, in step (4), the high-temperature sintering includes: (41) Sinter at 1180℃-1200℃ for 8min-15min to form a uniform glass phase matrix and obtain an ultra-flat surface; In this step, the quartz, potassium feldspar, boron frit, and other components in the velvet glaze are completely melted to form a continuous and uniform glass phase. The body layer and the base glaze layer will not be over-fired or deformed due to excessive temperature. Moreover, the air bubbles in the velvet glaze are completely expelled, avoiding pinholes or depressions after sintering, and finally forming an ultra-flat glaze base.

[0038] (42) Cooling from 1180℃-1200℃ to 880℃-920℃, controlling the cooling rate at 48℃ / min-53℃ / min, while preserving the glassy structure at high temperature; In this step, rapid cooling can temporarily lock the glaze in a glassy state, preparing it for precise crystallization in the future. At the same time, it can suppress premature crystallization, reduce the temperature difference between the inside and outside of each layer, and reduce macroscopic cracks caused by thermal stress. If the cooling is too slow, zinc ore will precipitate in large quantities in the high-temperature range, resulting in a rough glaze surface and loss of the velvet texture in the velvet glaze layer.

[0039] (43) Cool down from 880℃-920℃ to 720℃-760℃, control the cooling rate to 3℃ / min-5℃ / min, enter the crystallization window of zinc silico, so that the zinc silico crystals grow uniformly and fill the gaps between the glass phases; In this step, the slow cooling rate of 3℃ / min-5℃ / min enters the crystallization window of zinc silicosite, providing sufficient crystallization time for the Zn in the glass phase to crystallize. 2+ With SiO4 4- The crystals are fully combined to form uniformly distributed zinc silicoeite crystals; at the same time, this rate can avoid agglomeration or uneven glaze caused by excessively rapid crystal growth, forming a delicate velvet-like microstructure. (44) Cooling from 720℃-760℃ to 630-660℃, controlling the cooling rate to 2℃ / min-4℃ / min, the borosilicate glass phase separates and the microcrack distribution is optimized.

[0040] In this step, the slower cooling rate of 2℃ / min to 4℃ / min allows the borosilicate glass to fully separate into a "silicon-rich phase" and a "boron-rich phase," achieving phase separation. At the same time, it makes the microcracks generated by the forces between the crystal and the glass uniformly distributed, further optimizing the light scattering effect and enhancing the velvet texture.

[0041] In this application, the segmented slow cooling sintering process can maintain the ultra-flat appearance of the velvet ceramic tile, and the crystal scattering of light can present a soft and non-glaring velvet texture. The gloss can be kept stable within the range of 33°±3°. At the same time, the uniform glass phase matrix and crystal filling structure reduce the porosity of the glaze layer and improve the wear resistance, stain resistance and impermeability of the glaze surface.

[0042] Furthermore, the preparation method further includes the following steps: (5) spraying the semi-finished gold velvet glaze layer and curing it to form a protective layer; wherein the curing temperature for forming the protective layer is 280℃-320℃ and the curing time is 15min-20min. Under these curing conditions, the Si-OH groups in the sol prepolymer react with the Si-OH groups on the glaze surface in the gold velvet glaze layer to form strong Si-O-Si covalent bonds, providing sufficient hardness and wear resistance to the gold velvet glaze layer. Moreover, since it is a chemical bond, its durability far exceeds that of physically adsorbed coatings.

[0043] In some specific and preferred embodiments, the ceramic tiles after firing can undergo a very light surface mirroring treatment using a high-mesh grinding head, removing only a very thin layer that floats on the surface due to crystallization, further ensuring flatness and a consistent feel without damaging the underlying structure. Simultaneously, before applying the protective coating, the tile surface can be treated with plasma or UV-ozone cleaning to increase the surface Si-OH density, thereby enhancing the chemical bonding between the velvet glaze layer and the protective layer.

[0044] The present invention will be further described below with reference to specific embodiments: Example 1 This embodiment provides an ultra-flat wear-resistant glazed gold velvet ceramic tile, including a body layer, a base glaze layer, a gold velvet glaze layer and a protective layer disposed on the body layer; The raw materials for preparing the body layer include, by weight: 15 parts porcelain clay, 10 parts kaolin, 3 parts bentonite, 5 parts high-alumina clay, 23 parts quartz sand, 5 parts sodium feldspar, 15 parts potassium sodium feldspar, 4 parts wollastonite, 7 parts cordierite, 1 part kyanite, 0.1 parts sodium lignosulfonate, and 0.15 parts sodium carboxymethyl cellulose; the chemical composition by weight percentage includes: SiO2: 71.3%, Al2O3: 20.2%, K2O+Na2O: 4.1%, CaO+MgO+TiO2: 3.9%, Fe2O3: 0.23%, with the remainder being impurities.

[0045] The raw materials for preparing the base glaze layer include, by weight: 25 parts quartz, 35 parts calcined kaolin, 17 parts potassium feldspar, 5 parts sodium feldspar, 10 parts wollastonite, 11 parts zircon, and 5 parts cordierite; the chemical composition by weight percentage includes: SiO2: 59%, Al2O3: 21.2%, K2O: 2.1%, Na2O: 0.6%, CaO: 5.8%, MgO: 0.2%, ZrO2: 5.2%, with the remainder being impurities.

[0046] The raw material for preparing the velvet glaze layer is velvet glaze, which includes inorganic raw materials, water, and additives. The inorganic raw materials, by weight, include: 40 parts quartz, 9 parts calcined kaolin, 5 parts dolomite, 9 parts zinc oxide, 3 parts zircon, 2 parts barium carbonate, 10 parts boron frit, 3 parts calcium phosphate, 4 parts wollastonite, 18 parts potassium feldspar, and 1.4 parts boron nitride. The chemical composition, by weight percentage, includes: 66.5% SiO2, 7.2% Al2O3, 9.8% ZnO, 2.1% B2O3, 3.2% CaO, 1.2% MgO, 1.1% K2O, 1.6% BaO, 1.5% P2O5, and 1.4% ZrO2, with the balance being impurities. The ratio of ZnO:B2O3:P2O5 is 6.5:1.4:1.

[0047] The preparation method of the ultra-flat wear-resistant glazed gold velvet ceramic tile is as follows: (1) Prepare the raw materials for the preparation of the blank layer, and obtain the blank layer by spreading and forming; (2) Apply glaze to the body layer to form a base glaze layer; (3) First, inkjet print the pattern on the base glaze layer, and then spray glaze to form a gold velvet glaze layer; (4) The glazed body is sintered at high temperature, removed from the kiln, and cooled to obtain a semi-finished product; (5) Apply the gold velvet glaze layer to the semi-finished product and cure it to form a protective layer.

[0048] In step (4), the high-temperature sintering includes: The surface was sintered at 1200℃ for 12 minutes to form a uniform glass phase matrix and obtain an ultra-flat surface; then cooled to 660℃ at a rate of 5℃ / min.

[0049] Example 2 This embodiment provides an ultra-flat, wear-resistant glazed gold velvet ceramic tile, which is basically the same as that in Embodiment 1, except that: The raw material for preparing the velvet glaze layer is velvet glaze, which includes inorganic raw materials, water, and additives. The inorganic raw materials, by weight, include: 42 parts quartz, 9 parts calcined kaolin, 6 parts dolomite, 10 parts zinc oxide, 4 parts zircon, 2 parts barium carbonate, 12 parts boron frit, 2 parts calcium phosphate, 4 parts wollastonite, 17 parts potassium feldspar, and 1 part boron nitride. The chemical composition, by weight percentage, includes: 66.8% SiO2, 7.4% Al2O3, 9.8% ZnO, 2.2% B2O3, 3.4% CaO, 1.3% MgO, 1% K2O, 1.6% BaO, 1% P2O5, and 1.6% ZrO2, with the balance being impurities. The ratio of ZnO:B2O3:P2O5 is 9.8:2.2:1.

[0050] The preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile is the same as in Example 1.

[0051] Example 3 This embodiment provides an ultra-flat, wear-resistant glazed gold velvet ceramic tile, which is basically the same as embodiment 2, except that: The boron nitride is a modified boron nitride that has been modified with a siloxane compound, and its preparation method includes the following steps: The boron nitride nanosheets were uniformly dispersed in an ethanol aqueous solution, and silane coupling agent KH-550 was added. The mixture was refluxed at 70°C for 3 hours, and then washed and dried. The mass of silane coupling agent KH-550 added was 1.5 wt% of the mass of boron nitride nanosheets. The boron nitride nanosheets had a size of 3 μm and a thickness of approximately 120 nm, and the siloxane compound was silane coupling agent KH-550.

[0052] The preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile is the same as in Example 1.

[0053] Example 4 This embodiment provides an ultra-flat, wear-resistant glazed gold velvet ceramic tile, which is basically the same as embodiment 3, except that: The ultra-flat, wear-resistant glazed gold velvet ceramic tile also includes a protective layer disposed on the gold velvet glaze layer, with a cured thickness of 300 nm. The protective layer is formed by curing a sol-prepolymer, and the raw materials for preparing the sol-prepolymer include: perfluorooctyltriethoxysilane, tetraethyl orthosilicate, catalyst, and solvent. The preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile includes: dissolving perfluorooctyltriethoxysilane and tetraethyl orthosilicate in a molar ratio of 3.8:1 in a solvent formed by water and ethanol, adding hydrochloric acid as a catalyst to carry out the reaction, controlling the pH of the reaction system to 2.2, forming a sol, and then aging it at room temperature for 24 hours to form a sol prepolymer, wherein the concentration of perfluorooctyltriethoxysilane added is 0.23M, and the volume ratio of water to ethanol added is 1:8.

[0054] The preparation method of the ultra-flat wear-resistant glazed gold velvet ceramic tile also includes: (5) Spray the semi-finished gold velvet glaze layer onto it and cure it to form a protective layer; The curing temperature for forming the protective layer is 300°C, and the curing time is 18 minutes.

[0055] Example 5 This embodiment provides an ultra-flat, wear-resistant glazed gold velvet ceramic tile, which is basically the same as embodiment 4, except that: In the preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile, step (4) includes the following high-temperature sintering: Sintering at 1190℃ for 8-15 minutes forms a uniform glass phase matrix, resulting in an ultra-flat surface. The temperature was reduced from 1190℃ to 900℃, with the cooling rate controlled at 50℃ / min, to preserve the glassy structure at high temperature. The temperature is lowered from 900℃ to 735℃ at a rate of 4℃ / min to allow the zinc silicoite crystallization window to grow uniformly and fill the glass phase gaps. The temperature was reduced from 735℃ to 650℃ at a controlled rate of 3℃ / min to separate the borosilicate glass phase and optimize the distribution of microcracks.

[0056] Comparative Example 1 This comparative example provides an ultra-flat, wear-resistant glazed velvet ceramic tile, which is basically the same as Example 1, except that: The inorganic raw materials, by weight, include: 40 parts quartz, 9 parts calcined kaolin, 5 parts dolomite, 9 parts zinc oxide, 3 parts zircon, 2 parts barium carbonate, 3 parts calcium phosphate, 4 parts wollastonite, 18 parts potassium feldspar, and 1.4 parts boron nitride; the chemical composition, by weight percentage, includes: 66.5% SiO2, 7.2% Al2O3, 9.8% ZnO, 3.2% CaO, 1.2% MgO, 1.1% K2O, 1.6% BaO, 1.5% P2O5, and 1.4% ZrO2, with the balance being impurities.

[0057] The preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile is the same as in Example 1.

[0058] Performance testing The ultra-flat, wear-resistant glazed velvet ceramic tiles obtained in the examples and comparative examples were cut into 75mm × 75mm samples for performance testing, specifically including: 1. Light Irradiation Experiment: Under the same indoor environment, the gold velvet ceramic tiles obtained in Example 5 were subjected to both artificial light and sunlight to observe their surface effect. See details below. Figure 1 and Figure 2 .

[0059] Depend on Figure 1 and Figure 2 It is known that the velvet ceramic tile in this application has an ultra-flat glaze, good gloss, and high fineness. Under light or sunlight, the crystal scatters light to present a soft, non-glaring velvet texture.

[0060] 2. Surface roughness Ra: Ra is a measure of the arithmetic mean of the roughness depths. It is the average of five individual roughness depths over five consecutive measurement lengths, where each individual roughness depth is the vertical distance between the highest point and the centerline. 3. Gloss: Measured using a gloss meter; 4. Abrasion resistance: Tested according to the test standard GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of abrasion resistance of glazed tile surfaces". Abrasion resistance is divided into 0-5 levels, with level 0 indicating the worst abrasion resistance and level 5 indicating the best abrasion resistance. For the same level, the higher the number of revolutions, the better the abrasion resistance. 5. Stain resistance: Tested according to the standard GB / T 3810.14-2016 "Test Methods for Ceramic Tiles - Part 14: Determination of Stain Resistance"; 6. Flatness: Determined according to the test standard GB / T 3810.2-2016 "Test Methods for Ceramic Tiles - Part 2: Inspection of Dimensions and Surface Quality"; The test results are shown in Table 1 below.

[0061] Table 1 Performance test results of the examples and comparative examples

[0062] The results above show that, in this application, the added boron nitride can induce the directional crystallization of zinc aluminum spinel and wollastonite, resulting in a more uniform grain size distribution, improved glaze fineness, and reduced local gloss differences. The synergistic effect of boron frit and calcium phosphate can construct a functionalized microstructure within the velvet glaze layer, forming a dense, amorphous glass network between the microcrystals, achieving the inherent stain resistance of the tile and creating a nanoscale smooth, ultra-flat glaze surface. Furthermore, the protective layer can further improve the tile's wear resistance.

[0063] The above description is merely a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. Therefore, any equivalent variations made in accordance with the claims of the present invention are still within the scope of the present invention.

Claims

1. A super-flat, wear-resistant glazed velvet ceramic tile, characterized in that, The material includes a body layer, a base glaze layer, and a velvet glaze layer disposed on the body layer; wherein the raw material for preparing the velvet glaze layer is velvet glaze, and the raw material for preparing the velvet glaze includes inorganic raw materials, water, and additives, and the inorganic raw materials include, by weight: Quartz 35-45 parts, calcined kaolin 7-12 parts, dolomite 3-7 parts, zinc oxide 9-11 parts, zircon 3-5 parts, barium carbonate 2-3 parts, boron frit 8-13 parts, calcium phosphate 1-4 parts, wollastonite 2-6 parts, potassium feldspar 15-20 parts, boron nitride 0.5-2 parts.

2. The ultra-flat, wear-resistant glazed gold velvet ceramic tile as described in claim 1, characterized in that, The chemical composition of the inorganic raw material, by weight percentage, includes: The composition is as follows: SiO2 61%-70%, Al2O3 5%-8%, ZnO 8%-11%, B2O3 1.5%-2.5%, CaO 2%-4%, MgO 0.5%-1.5%, K2O 0.5%-1.5%, BaO 1%-2%, P2O5 0.5%-1.5%, ZrO2 1%-2%, with the balance being impurities. The ZnO:B2O3:P2O5 ratio is (7-13):(2-4):

1.

3. The ultra-flat, wear-resistant glazed gold velvet ceramic tile as described in claim 1, characterized in that, The boron nitride is a modified boron nitride that has been modified with a siloxane compound, and the preparation method of the modified boron nitride includes the following steps: Boron nitride is uniformly dispersed in an aqueous ethanol solution, a siloxane compound is added, and the mixture is refluxed at 60℃-80℃ for 2-3 hours. Finally, it is washed and dried. The mass of the siloxane compound added is 1-2 wt% of the mass of the boron nitride added; the boron nitride is nanosheet boron nitride with a size of 2 μm-5 μm and a thickness of 50 nm-200 nm.

4. The ultra-flat, wear-resistant glazed gold velvet ceramic tile as described in claim 1, characterized in that, The ultra-flat wear-resistant glaze gold velvet ceramic tile also includes a protective layer disposed on the gold velvet glaze layer. The protective layer is formed after the sol prepolymer is cured. The raw materials for preparing the sol prepolymer include: perfluorooctyltriethoxysilane, tetraethyl orthosilicate, catalyst, and solvent. The molar ratio of perfluorooctyltriethoxysilane to tetraethyl orthosilicate is (3.5-4.5):1, and the concentration of perfluorooctyltriethoxysilane is 0.2M-0.25M. The solvent is a mixture of water and ethanol, and the volume ratio of water to ethanol is 1:(7.5-8.5). The catalyst is an acidic catalyst.

5. The ultra-flat, wear-resistant glazed gold velvet ceramic tile as described in claim 4, characterized in that, The thickness of the protective layer is 90nm-600nm; The method for preparing the sol-prepolymer includes the following steps: Perfluorooctyltriethoxysilane and tetraethyl orthosilicate were dissolved in a solvent, and a catalyst was added to react and form a sol. The sol was then aged at room temperature for 18-36 hours to form a sol prepolymer. When the catalyst is added to carry out the reaction, the pH of the reaction system is controlled to be 2-2.

5.

6. The ultra-flat, wear-resistant glazed velvet ceramic tile as described in claim 1, characterized in that, The weight ratio of the inorganic raw materials, water, and additives is 1:(0.2-0.3):(0.35-0.45). The additives are sodium tripolyphosphate and carboxymethyl cellulose, and the weight ratio of sodium tripolyphosphate to carboxymethyl cellulose is 1:(1.5-3.5). The average particle size of the inorganic raw material is 40μm-60μm.

7. The ultra-flat, wear-resistant glazed velvet ceramic tile as described in claim 1, characterized in that, The raw materials for preparing the green body layer include, by weight: 12-17 parts porcelain clay, 8-12 parts kaolin, 2-5 parts bentonite, 3-7 parts high-alumina clay, 20-26 parts quartz sand, 3-6 parts albite, 13-18 parts potassium albite, 4-5 parts wollastonite, 5-10 parts cordierite, 0.05-2 parts kyanite, 0.05-0.3 parts sodium lignosulfonate, and 0.05-0.3 parts sodium carboxymethyl cellulose. The chemical composition of the blank layer, by weight percentage, includes: SiO2: 67%-73%, Al2O3: 17%-22%, K2O+Na2O: 2.7%-4.7%, CaO+MgO+TiO2: 2.7%-5.2%, Fe2O3: 0.1%-0.4%, with the balance being impurities.

8. The ultra-flat, wear-resistant glazed gold velvet ceramic tile as described in claim 1, characterized in that, The raw materials for preparing the base glaze layer include, by weight: Quartz 20-30 parts, calcined kaolin 30-40 parts, potassium feldspar 15-20 parts, sodium feldspar 3-6 parts, wollastonite 8-12 parts, zircon 8-12 parts, cordierite 3-7 parts; The chemical composition of the base glaze layer, by weight percentage, includes: SiO2: 55%-65%, Al2O3: 18%-25%, K2O: 1.5%-2.5%, Na2O: 0.3%-0.8%, CaO: 4%-7%, MgO: 0%-0.5%, ZrO2: 4%-6%, with the balance being impurities.

9. The method for preparing ultra-flat wear-resistant glazed velvet ceramic tiles as described in any one of claims 1-8, characterized in that, Includes the following steps: (1) Prepare the raw materials for the preparation of the blank layer, and obtain the blank layer by spreading and forming; (2) Apply glaze to the body layer to form a base glaze layer; (3) First, inkjet print the pattern on the base glaze layer, and then spray glaze to form a gold velvet glaze layer; (4) The glazed body is sintered at high temperature, removed from the kiln, and cooled.

10. The preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile as described in claim 9, characterized in that, In step (4), the high-temperature sintering includes: Sintering at 1180℃-1200℃ for 8-15 minutes forms a uniform glass phase matrix, resulting in an ultra-flat surface. The temperature was reduced from 1180℃-1200℃ to 880℃-920℃, with the cooling rate controlled at 48℃ / min-53℃ / min, while preserving the glassy structure at high temperature. The temperature is lowered from 880℃-920℃ to 720℃-760℃, with the cooling rate controlled at 3℃ / min-5℃ / min, to enter the crystallization window of zinc silicoite, so that the zinc silicoite crystals grow uniformly and fill the gaps between the glass phases; The temperature was reduced from 720℃-760℃ to 630-660℃, with the cooling rate controlled at 2℃ / min-4℃ / min, to separate the borosilicate glass phase and optimize the distribution of microcracks.

11. The preparation method of the ultra-flat wear-resistant glazed velvet ceramic tile as described in claim 9, characterized in that, The preparation method further includes the following steps: (5) Spray the semi-finished gold velvet glaze layer onto it and cure it to form a protective layer; The curing temperature for forming the protective layer is 280℃-320℃, and the curing time is 15min-20min.

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