Stone texture imitating ceramic tile and preparation method thereof

Abstract

The invention discloses a stone-texture-imitating ceramic tile and a preparation method thereof, and relates to the technical field of ceramic tiles, the stone-texture-imitating ceramic tile comprises a green body, a ground coat layer, a pattern layer and a protective glaze layer, the ground coat layer comprises the following raw materials: ZA210, zinc oxide, black clay, Suzhou soil, potassium sand, potassium feldspar, zirconium silicate and sodium sand, and the pattern layer comprises the following raw materials: sodium silicate, sodium silicate and a water-soluble organic silicon resin; the ZA210 is a chemical composition containing magnesium oxide and calcium oxide; the pattern layer is formed by printing ink containing Fe < 2 + > and Co < 2 + >, the pattern layer comprises a high-gray-scale pattern area and a low-gray-scale pattern area, and the ink printing thickness of the high-gray-scale pattern area is 2-3 times that of the low-gray-scale pattern area; the protective glaze layer is prepared from the following raw materials: matte transparent frit, zirconium silicate, kaolin, sodium carboxymethyl cellulose and an organic silicon defoaming agent. The texture of weathering and peeling of natural stone is accurately simulated through formula and process improvement, and the natural stone-like texture of the ceramic tile is achieved.

Description

Technical Field

[0001] This invention relates to the field of ceramic tile preparation technology, and in particular to a stone-textured ceramic tile and its preparation method. Background Technology

[0002] In the building decoration market, the demand for stone-textured tiles is shifting from "functional fulfillment" to "quality experience," with consumers placing stringent requirements on texture realism, tactile smoothness, and weather resistance. However, traditional processes suffer from several technical bottlenecks, including insufficient texture simulation: traditional etching glazes use a monolithic etching method, resulting in uniform textures and distorted stone-like effects; digital inkjet printing produces flat textures, and screen printing details are prone to distortion. Poor tactile experience: matte glazes feel rough, easily trap dirt, and exhibit significant gloss fluctuations, failing to meet high-end decorative needs. Insufficient performance stability: the mismatch in thermal expansion coefficients between the glaze layer and the body easily leads to glaze cracking and peeling, especially prominent in the production of large-format tiles.

[0003] It is evident that existing technologies still need improvement and enhancement. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a stone-textured ceramic tile and its preparation method, which aims to solve the problems of monotonous texture, distorted stone-like effect and insufficient performance stability of existing stone-textured ceramic tiles.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A stone-textured ceramic tile comprises a body, a base glaze layer, a pattern layer, and a protective glaze layer. The base glaze layer, by weight percentage, comprises: 15-25% ZA210, 2-5% zinc oxide, 5-10% black mud, 5-8% Suzhou clay, 30-40% potassium sand, 5-10% potassium feldspar, 10-15% zirconium silicate, and 5-10% sodium sand. The ZA210 is a chemical composition containing magnesium oxide and calcium oxide. The pattern layer is composed of Fe... 2+ and Co 2+ The pattern layer is formed by ink printing, and includes a high grayscale pattern area and a low grayscale pattern area. The ink printing thickness of the high grayscale pattern area is 2-3 times that of the low grayscale pattern area. The raw material formula of the protective glaze layer includes, by mass percentage: 88-92% matte transparent frit, 3-8% zirconium silicate, 3-5% kaolin, 0.1-0.3% sodium carboxymethyl cellulose, and 0.05-0.15% silicone defoamer.

[0007] In the aforementioned stone-textured ceramic tile, the area of ​​the high-grayscale pattern area accounts for 60-80% of the total area, and the area of ​​the low-grayscale pattern area accounts for 20-40%.

[0008] The aforementioned stone-textured ceramic tile, wherein the chemical composition of ZA210, by mass percentage, comprises: 65-70% SiO2, 8-12% CaO, 5-8% MgO, 6-10% Al2O3, 1-3% K2O, and 3-5% Na2O.

[0009] The stone-textured ceramic tile, wherein the raw material formula of the ink comprises, by weight percentage: 10-15% ferrous nitrate, 5-10% cobalt nitrate, 50-55% deionized water, 10-15% ethylene glycol, 3-5% dispersant, 5-8% humectant, and 1-3% pH adjuster.

[0010] In the aforementioned stone-textured ceramic tile, the dispersant is sodium polycarboxylate, the humectant is glycerol, and the pH adjuster is ammonia.

[0011] A method for preparing a stone-textured ceramic tile as described in this invention includes the following steps:

[0012] Weigh the raw materials of the base glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the base glaze slurry;

[0013] Weigh the raw materials of the pattern layer according to the formula ratio. First, add ferrous nitrate, cobalt nitrate, deionized water and ethylene glycol to the mixing tank and stir until the metal ions are completely dissolved. Then add the dispersant and humectant, continue stirring and then add the pH adjuster to adjust the pH to 7.5-8.5 to obtain the ink.

[0014] Weigh the raw materials of the protective glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the protective glaze slurry;

[0015] A base glaze slurry is evenly applied to the surface of the body using a spray glazing method, and a base glaze layer is formed after drying.

[0016] The blank with the base glaze layer is sent to the printing station, and the ink is printed on the surface of the base glaze layer according to the preset pattern and preset printing parameters to form a pattern layer on the surface of the base glaze layer, which has a high grayscale pattern area and a low grayscale pattern area.

[0017] A protective glaze slurry is applied to the surface of the blank to form the pattern layer using a spray glazing method, and a protective glaze layer is formed after drying.

[0018] Stone-textured ceramic tiles are produced by sintering the body that forms the base glaze layer, pattern layer, and protective glaze layer.

[0019] In the preparation method of the aforementioned stone-textured ceramic tile, the specific gravity of the base glaze slurry is 1.5-1.6 g / cm³. 3The thickness of the base glaze layer is 0.15-0.25 mm.

[0020] The method for preparing the stone-textured ceramic tile includes the following preset printing parameters: when printing high grayscale pattern areas, the nozzle spray frequency is 8 times / square millimeter, the moving speed is 50mm / s, and the spray pressure is 0.3MPa; when printing low grayscale pattern areas, the nozzle spray frequency is 4 times / square millimeter, the moving speed is 100mm / s, and the spray pressure is 0.15MPa.

[0021] In the preparation method of the aforementioned stone-textured ceramic tile, the specific gravity of the protective glaze slurry is 1.4-1.5 g / cm³. 3 The thickness of the protective glaze layer is 0.1-0.15 mm.

[0022] The method for preparing the stone-textured ceramic tile includes a sintering process for the body forming the base glaze layer, pattern layer, and protective glaze layer, comprising a heating stage, a holding stage, and a cooling stage. In the heating stage, the temperature is increased to 1220-1260℃ at a heating rate of 50-60℃ / min; in the holding stage, the temperature is held at 1220-1260℃ for 10-20 minutes; and in the cooling stage, the temperature is first cooled to 500-600℃ at a cooling rate of 100-120℃ / min, and then cooled to room temperature in the furnace.

[0023] Beneficial effects: This invention achieves selective etching of localized areas through inkjet grayscale control, allowing high-grayscale pattern areas to exhibit the weathering pits of natural stone, while low-grayscale pattern areas maintain a smooth glaze surface. This completely solves the problems of monotonous texture and distorted stone-like effect caused by traditional overall etching, resulting in a natural and harmonious tile texture that closely resembles the layering of natural stone. Through the light scattering effect of zirconium silicate microcrystals in the protective glaze layer, the glaze gloss is stably controlled at 4-6°, solving the problem of large gloss fluctuations in traditional matte glazes. Simultaneously, sodium carboxymethyl cellulose optimizes the glaze slurry leveling, eliminating pinholes and giving both etched and non-etched areas a silky smooth feel, completely eliminating the industry pain point of "rough texture and easy dirt accumulation." The synergistic effect of the matte transparent frit in the protective glaze layer and the potassium sand and potassium feldspar in the base glaze layer ensures that the thermal expansion coefficients of the glaze layer and the body are consistent, effectively overcoming glaze cracking and peeling defects in traditional processes. This is especially suitable for the production of large-format tiles, solving the structural stability problem during the firing of large-format products. Attached Figure Description

[0024] Figure 1 This is a flowchart of a method for preparing a stone-textured ceramic tile according to the present invention.

[0025] Figure 2 This is a photograph of the stone-textured ceramic tile prepared according to Embodiment 1 of the present invention.

[0026] Figure 3This is a physical image of the stone-textured ceramic tile obtained in Embodiment 2 of the present invention.

[0027] Figure 4 This is a physical image of the stone-textured ceramic tile prepared in Embodiment 3 of the present invention.

[0028] Figure 5 This is a physical image of the stone-textured ceramic tile prepared in Comparative Example 1 of this invention.

[0029] Figure 6 This is a physical image of the stone-textured ceramic tile prepared in Comparative Example 2 of this invention.

[0030] Figure 7 This is a physical image of the stone-textured ceramic tile prepared in Comparative Example 3 of this invention. Detailed Implementation

[0031] This invention provides a stone-textured ceramic tile and its preparation method. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following embodiments are provided to further illustrate the invention in detail. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0032] This invention provides a stone-textured ceramic tile, comprising a body, a base glaze layer, a pattern layer, and a protective glaze layer. The base glaze layer, by weight percentage, comprises: 15-25% ZA210, 2-5% zinc oxide, 5-10% black mud, 5-8% Suzhou clay, 30-40% potassium sand, 5-10% potassium feldspar, 10-15% zirconium silicate, and 5-10% sodium sand. The ZA210 is a chemical composition containing magnesium oxide and calcium oxide. The pattern layer is composed of Fe... 2+ and Co 2+ The pattern layer is formed by ink printing, and includes a high grayscale pattern area and a low grayscale pattern area. The ink printing thickness of the high grayscale pattern area is 2-3 times that of the low grayscale pattern area. The raw material formula of the protective glaze layer includes, by mass percentage: 88-92% matte transparent frit, 3-8% zirconium silicate, 3-5% kaolin, 0.1-0.3% sodium carboxymethyl cellulose, and 0.05-0.15% silicone defoamer.

[0033] This invention precisely simulates the weathering pits and hard surface texture of natural stone through the synergistic design of the base glaze layer and protective glaze layer formulations and inkjet grayscale control. Its core relies on the following mechanism of action of the formulation components: The base glaze layer provides an active substrate for the corrosion reaction, laying the foundation for texture formation. Among these, 15-25% ZA210 serves as the core active carrier, and its CaO and MgO content is the reaction source for the corrosion reaction; while the metal ions (Fe...) in the ink... 2+ and Co 2+ZA210 acts as a trigger for the corrosion reaction. The pattern layer formed by ink printing includes high-grayscale pattern areas and low-grayscale pattern areas. The ink printing thickness of the high-grayscale pattern areas is 2-3 times that of the low-grayscale pattern areas, meaning that the high-grayscale pattern areas have a larger ink volume and a higher concentration of metal ions. At high temperatures, ZA210 reacts with Fe in the ink. 2+ and Co 2+ A chemical reaction occurs, generating low-melting-point eutectic compounds (such as anorthite), causing localized melting and shrinkage of the glaze layer, thus forming a microporous structure that simulates the pits of weathering stone. Meanwhile, in low-grayscale pattern areas, due to the smaller ink volume and lower metal ion concentration, localized glaze shrinkage is less noticeable, allowing the glaze layer to completely cover the area and maintain a hard, smooth surface. This linkage between "grayscale, ink concentration, and corrosion intensity" achieves pixel-level texture control, ultimately creating a natural and harmonious texture between the weathering pits in high-grayscale pattern areas and the smooth surface in low-grayscale pattern areas, perfectly simulating the weathering characteristics of natural stone.

[0034] In the raw material formulation of the base glaze layer, the content of ZA210 directly determines the severity of the corrosion reaction. A mass percentage of 15-25% can form uniform corrosion pits, simulating the weathering texture of natural stone. If the mass percentage exceeds 25%, it will cause an imbalance between the coefficient of thermal expansion (CTE) of the glaze layer and the body, increasing the risk of glaze cracking (reduced yield). A mass percentage below 15% results in insufficient corrosion depth and weakened stone-like texture. For example, the chemical composition of ZA210, by mass percentage, includes: 65-70% SiO2, 8-12% CaO, 5-8% MgO, 6-10% Al2O3, 1-3% K2O, and 3-5% Na2O.

[0035] In the raw material formula of the base glaze, 2-5% zinc oxide is used to adjust the high-temperature melting behavior of the base glaze, reduce the high-temperature viscosity, enhance the penetration of metal ions in the ink into the base glaze, ensure that the corrosion reaction in the high grayscale pattern area is sufficient and uniform, and avoid texture distortion caused by insufficient local reaction. If the zinc oxide mass ratio is higher than 5%, it will cause the glaze to crystallize and destroy the matte texture. If the mass ratio is less than 2%, the ink penetration will be hindered and the corrosion effect in the high grayscale pattern area will be weak.

[0036] In the raw material formulation of the base glaze layer, 30-40% potassium sand and 5-10% potassium feldspar work synergistically to provide high-temperature fluidity, ensuring that the base glaze spreads evenly during firing and avoiding local shrinkage and cracking. The combination of the two can improve the fluidity of the glaze layer by 40%, making the transition between the corroded area (high grayscale pattern area) and the non-corroded area (low grayscale pattern area) natural, without obvious boundary defects, simulating the gradual texture of natural stone. At the same time, it can also adjust the shrinkage rate of the base glaze layer, working synergistically with the frit of the protective glaze to further reduce the risk of glaze cracking and peeling. Preferably, the ratio of potassium sand to potassium feldspar should be controlled at 3-4:1. Excessive potassium sand will cause the glaze surface gloss to increase (>8°), destroying the matte effect; insufficient potassium feldspar will increase the high-temperature viscosity, resulting in uneven glaze layer spreading.

[0037] In the raw material formulation of the base glaze layer, 10-15% zircon silicate forms a zircon crystal cluster framework structure at high temperature, supporting the microporous morphology of the high grayscale pattern area, preventing excessive corrosion reaction that could lead to glaze collapse, ensuring the structural stability of weathering pits, and avoiding blurred textures. A mass percentage of 10-15% allows the corrosion area to maintain a complete microporous + zircon crystal cluster structure, enhancing light scattering effects and resulting in a more stable matte texture (4-6°). If the mass percentage exceeds 15%, it will lead to a decrease in the elastic modulus of the glaze layer, reduced thermal shock resistance, and an increased risk of glaze cracking during later use.

[0038] In the raw material formula of the base glaze layer, 5-10% black mud and 5-8% Suzhou clay are used together as clay-based raw materials to provide plasticity and suspension of the glaze slurry, ensuring uniform adhesion during glazing and avoiding inconsistent local corrosion caused by sedimentation. The combination of the two can extend the suspension time of the glaze slurry to more than 8 hours, with a glaze thickness deviation of ≤5%. The combination of the two can also adjust the firing shrinkage rate of the glaze slurry to match the CTE of the body. However, if the two are added in excess (total mass ratio of the two >15%), it will lead to residual organic matter in the glaze layer, resulting in air bubbles and pinholes during firing. If the two are added in insufficient amounts (total mass ratio of the two <10%), the glaze slurry will have poor fluidity and be difficult to apply.

[0039] In the raw material formulation of the base glaze layer, 5-10% sodium shale provides Na2O flux, which, in synergy with potassium-based raw materials, lowers the melting temperature of the glaze, ensuring sufficient melting of the base glaze during sintering and guaranteeing efficient reaction with the ink. When the sodium shale content is 5-10%, the initial melting temperature of the glaze decreases by approximately 20°C, and the proportion of low-melting-point substances generated by the reaction increases by 15%. Excessive sodium shale (>10%) leads to a decrease in the glaze softening temperature and reduced abrasion resistance (Mohs hardness <5); insufficient sodium shale (less than 5%) results in an increased melting temperature and incomplete reaction.

[0040] In the raw material formulation of the protective glaze layer, 88-92% of the matte transparent frit serves as the main body of the protective glaze layer. After melting, it forms a glassy phase, completely covering the ink layer in the low-grayscale pattern area, preventing corrosion reactions (because the ink volume in the low-grayscale pattern area is small, the metal ion concentration is low, and it cannot penetrate the protective glaze layer), forming a smooth glaze surface, thus simulating the hard surface of unweathered stone. At the same time, as a CTE (coefficient of thermal expansion) matching frit, it can work synergistically with potassium sand and potassium feldspar in the base glaze layer to ensure that the base glaze layer and the protective glaze layer have the same coefficient of thermal expansion as the body, eliminating the thermal stress difference between the glaze layer and the body during firing from the root, avoiding glaze cracking, especially suitable for the production of large-format ceramic tiles, solving the problem of structural stability during the firing of large-format products. As an example, the chemical composition of the matte transparent frit, by mass percentage, includes: 60-65% SiO2, 10-20% CaO, 15-20% Al2O3, 2-5% K2O, and 2-5% Na2O. The SiO2 content in the matte transparent frit needs to be controlled at 60-65%, and the Al2O3 content at 15-20% to ensure the formation of a dense glass phase after sintering. Excessive Al2O3 will cause crystallization of the glaze and fluctuations in gloss.

[0041] In the raw material formulation of the protective glaze, 3-8% zirconium silicate forms nanocrystals within the glaze. This not only imparts a matte texture (approaching the warm luster of natural stone) to low-grayscale pattern areas through light scattering but also enhances the structural strength of the glaze (increasing Mohs strength), preventing the low-grayscale pattern areas from wearing away too quickly due to their smoothness. If the zirconium silicate content exceeds 8%, it will lead to a decrease in glaze toughness, making it prone to microcracks and reducing the yield rate.

[0042] In the raw material formulation of the protective glaze, 3-5% kaolin can improve the suspension of the protective glaze slurry, prevent the precipitation of particles such as zirconium silicate, and ensure the uniformity of glazing. At a content of 3-5%, the glaze slurry sedimentation rate is <2%, and the glaze thickness deviation is ≤3%, avoiding inconsistent corrosion effects caused by uneven glazing. If the mass ratio of kaolin is higher than 5%, it will lead to excessively high glaze slurry viscosity, resulting in tear marks during glazing; if the mass ratio of kaolin is lower than 3%, it will result in poor glaze slurry suspension, leading to excessively thin glaze layers in some areas after glazing, and ink exposure causing abnormal corrosion.

[0043] In the raw material formulation of the protective glaze, 0.1-0.3% sodium carboxymethyl cellulose can optimize the leveling properties of the glaze slurry, ensuring uniform coverage of the protective glaze in high / low grayscale pattern areas, avoiding abnormal corrosion caused by pinholes or excessively thin areas, and ensuring the integrity of the smooth glaze surface in the low grayscale pattern areas, forming a clear contrast with the micropores in the high grayscale pattern areas. However, excessive amounts (>0.3%) will lead to excessively high glaze slurry viscosity, making it difficult for gases to escape during firing and forming dense bubbles; insufficient amounts will result in poor leveling properties and a rough glaze surface.

[0044] In the raw material formulation for protecting the glaze layer, 0.05-0.15% of organosilicon defoamer can eliminate air bubbles introduced during glaze preparation and application, preventing pinholes after firing. At an addition of 0.05-0.15%, the pinhole defect rate decreases from 5% to below 0.5%, ensuring surface uniformity between etched and non-etched areas and improving the feel and quality. However, excessive amounts (>0.15%) can lead to abnormal surface tension in the glaze, resulting in glaze shrinkage; insufficient amounts leave residual air bubbles, affecting surface smoothness.

[0045] In this invention, the reaction between ZA210 in the base glaze and metal ions in the ink is the core of corrosion. Zinc oxide, potassium sand, and potassium feldspar optimize the reaction conditions. The matching degree between the zirconium silicate in the protective glaze and the frit determines the structural stability of the corrosion zone, preventing collapse or excessive corrosion. The light scattering effect (4-6° gloss) of the zirconium silicate microcrystals in the protective glaze and the skeletal support of the zirconium silicate in the base glaze work synergistically to form a micro-crystal cluster composite structure. At the same time, sodium carboxymethyl cellulose and organosilicon defoamers ensure a smooth glaze surface and enhance the matte visual effect. The CTE matching between the base glaze and the protective glaze (adjusted by the frit and potassium-sodium-based raw materials) and the hardness support of the zirconium silicate together ensure the adhesion, wear resistance, stain resistance (micropore sealing treatment), and low risk of glaze cracking of the glaze, meeting the application requirements of high-end imitation stone ceramics.

[0046] In some embodiments, the grayscale value of the high grayscale pattern area is 60-80%, and the grayscale value of the low grayscale pattern area is 20-40%. The advantage of this design in this embodiment is that it simulates the weathering characteristics of natural stone, balancing the realism of the stone-like effect, process stability, and product performance consistency. Since the high grayscale pattern area needs to form micropores through the reaction of ink and the base glaze ZA210, if its proportion exceeds 80%, it will lead to a large-area corrosion reaction, causing the calcium and magnesium compounds in the base glaze to be consumed too quickly, resulting in uneven local reactions and excessive corrosion or collapse. The low grayscale pattern area (20-40%), as a non-corrosion area, can disperse the covering pressure of the protective glaze. If its proportion is less than 20%, the protective glaze needs to cover a large area of ​​the high grayscale pattern area, which is prone to pinholes due to uneven local glaze accumulation, affecting the tactile feel. A proportion of 20-40% ensures that the protective glaze is evenly spread, meeting the requirement that both the corrosion and non-corrosion areas be flat and defect-free.

[0047] In some embodiments, the raw material formulation of the ink comprises, by weight percentage: 10-15% ferrous nitrate, 5-10% cobalt nitrate, 50-55% deionized water, 10-15% ethylene glycol, 3-5% dispersant, 5-8% humectant, and 1-3% pH adjuster. For example, the dispersant is sodium polycarboxylate, the humectant is glycerol, and the pH adjuster is ammonia, but the formulation is not limited thereto. In this embodiment, deionized water and ethylene glycol are used as solvents to ensure Fe... 2+ and Co2 + Uniform dissolution regulates ink flow; sodium polycarboxylate acts as a dispersant to prevent metal ion precipitation and ensure ink stability; glycerol acts as a humectant to slow down the drying speed of the ink on the surface of the blank, ensuring that metal ions fully penetrate the base glaze; ammonia acts as a pH adjuster to control the ink pH value between 7.5 and 8.5, avoiding hydrolysis of metal ions.

[0048] In some embodiments, a method for preparing a stone-textured ceramic tile as described in this invention is also provided, such as... Figure 1 As shown, it includes the following steps:

[0049] S10. Weigh the raw materials of the base glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the base glaze slurry.

[0050] S20. Weigh the raw materials of the pattern layer according to the formula ratio. First, add ferrous nitrate, cobalt nitrate, deionized water and ethylene glycol to the mixing tank and stir until the metal ions are completely dissolved. Then add the dispersant and humectant, continue stirring and then add the pH adjuster to adjust the pH to 7.5-8.5 to obtain the ink.

[0051] S30. Weigh the raw materials of the protective glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the protective glaze slurry.

[0052] S40. Apply base glaze slurry evenly to the surface of the body using the spray glazing method, and form a base glaze layer after drying.

[0053] S50. The blank with the base glaze layer is sent to the printing station, and the ink is printed on the surface of the base glaze layer according to the preset pattern and preset printing parameters to form a pattern layer on the surface of the base glaze layer, wherein the pattern layer has a high grayscale pattern area and a low grayscale pattern area.

[0054] S60. A protective glaze slurry is applied to the surface of the body on which the pattern layer is formed by spray glazing, and a protective glaze layer is formed after drying.

[0055] S70. The body forming the base glaze layer, pattern layer and protective glaze layer is sintered to produce stone-textured ceramic tiles.

[0056] Specifically, the sintering process of the green body forming the base glaze layer, pattern layer, and protective glaze layer in this invention includes a heating stage, a holding stage, and a cooling stage. In the heating stage, the temperature is increased to 1220-1260℃ at a heating rate of 50-60℃ / min; in the holding stage, the temperature is held at 1220-1260℃ for 10-20 minutes; in the cooling stage, the temperature is first cooled to 500-600℃ at a cooling rate of 100-120℃ / min, and then cooled to room temperature in the furnace.

[0057] The ZA210 (containing CaO and MgO) in the base glaze layer of this invention reacts with the metal ions (Fe) in the ink. 2+ The reaction with Co2+ needs to be triggered by gradual heating. A heating rate of 50-60℃ / min avoids both slow heating, which would cause the glaze to dry prematurely and hinder ink penetration, and excessive heating, which would cause uneven local temperature, concentrate the reaction in the high-temperature area, and cause corrosion deviation. The endpoint temperature is 1220-1260℃, which is the critical temperature for the reaction between the base glaze and the ink. This ensures that low-melting-point eutectic materials (such as anorthite) begin to form, laying the foundation for the formation of micropores in the subsequent heat preservation stage.

[0058] A holding temperature of 1220-1260℃ can maintain the molten state of the glaze, allowing the generated eutectic to diffuse evenly and avoiding local accumulation that would blur the boundary between the corroded and non-corroded areas, thus ensuring clear texture layers. A holding time of 10-20 minutes ensures that the ink metal ions in the high grayscale pattern area react fully with ZA210 to generate uniform micropores of 5-10μm, simulating stone weathering. If the holding time is insufficient (e.g., <10 minutes), the reaction will be incomplete, resulting in sparse and unevenly sized micropores (yield drops below 80%). If the holding time is too long (e.g., >20 minutes), excessive reaction will cause micropore collapse (e.g., holding at 1260℃ for more than 25 minutes will reduce the yield to 75%).

[0059] Because the micropores and zircon crystal clusters in the corrosion zone need to solidify rapidly during cooling, this invention lowers the temperature to 500-600℃ at a rate of 100-120℃ / min in the early stage of cooling. At this high temperature stage (>600℃), the glaze layer still has a certain fluidity. Rapid cooling can lock the micropore morphology and prevent the micropores from being squeezed and deformed due to glaze shrinkage caused by slow cooling. At the same time, this rate can reduce glaze crystallization (e.g., the zirconium silicate microcrystals in the protective glaze need to be kept at the nanoscale dispersion), ensuring that the matte gloss is stable at 4-6°. If the cooling is too slow (e.g., <80℃ / min), the glaze layer is prone to secondary melting, the micropores are filled, and the stone-like texture becomes blurred. If the cooling is too fast (e.g., >150℃ / min), the large difference in shrinkage rate between the glaze layer and the body will generate cooling stress, which can easily cause glaze cracking. When the temperature drops to below 500-600℃, the glaze and the body have basically solidified. As the furnace cools, the residual stress can be slowly released, avoiding excessive temperature difference between the surface and the interior due to sudden cooling, which can cause micro-cracks.

[0060] In some embodiments, the specific gravity of the base glaze slurry is 1.5-1.6 g / cm³. 3 The thickness of the base glaze layer is 0.15-0.25 mm, but is not limited to this.

[0061] In some embodiments, the specific gravity of the protective glaze slurry is 1.4-1.5 g / cm³. 3 The thickness of the protective glaze layer is 0.1-0.15 mm.

[0062] In some embodiments, the step of printing a pattern layer on the surface of the base glaze layer includes: firstly, in CAD or dedicated ceramic pattern design software, designing a distribution pattern of high grayscale pattern areas (60%-80% of the area) and low grayscale pattern areas (20%-40% of the area) according to the requirements of stone weathering texture. The high grayscale pattern areas correspond to the locations of weathered pits in the stone, and the low grayscale pattern areas correspond to the intact surface of the stone. Different printer parameters are preset for the high grayscale and low grayscale pattern areas. The printer parameters include the nozzle ejection frequency, moving speed, and ejection pressure. By coordinating the adjustment of the above parameters, the ink thickness of the high grayscale pattern area can be stably achieved to be 2-3 times that of the low grayscale pattern area in the experiment, providing a basis for the differentiation of subsequent corrosion reactions. As an example, for the high grayscale pattern area, the nozzle ejection frequency is set to 8 times / square millimeter, the moving speed to 50mm / s, and the ejection pressure to 0.3MPa; for the low grayscale pattern area, the nozzle ejection frequency is set to 4 times / square millimeter, the moving speed to 100mm / s, and the ejection pressure to 0.15MPa.

[0063] In some specific embodiments, the printing ink thickness of the high grayscale pattern area is 8-12 μm; due to the increased thickness of the ink accumulation in the high grayscale pattern area, it can fully react with the base glaze to form micropores, and the ink printing thickness is sufficient to ensure that the metal ions react fully with components such as ZA210 in the base glaze; the printing ink thickness of the low grayscale pattern area is 3-5 μm, and the ink in the low grayscale pattern area is thin, which can ensure that the protective glaze layer can be completely covered.

[0064] The present invention will be further explained and illustrated below through specific embodiments:

[0065] Example 1

[0066] A stone-textured ceramic tile comprises a body, a base glaze layer, a pattern layer, and a protective glaze layer. The base glaze layer, by weight percentage, comprises: 20% ZA210, 3% zinc oxide, 8% black mud, 6% Suzhou clay, 35% potassium sand, 8% potassium feldspar, 13% zirconium silicate, and 7% sodium sand. The ZA210, by weight percentage, comprises: 68% SiO2, 10% CaO, 7% MgO, 8% Al2O3, 2% K2O, and 5% Na2O. The pattern layer is composed of Fe... 2+ and Co 2+The pattern layer is formed by ink printing, comprising a high grayscale pattern area and a low grayscale pattern area, wherein the ink printing thickness of the high grayscale pattern area is twice that of the low grayscale pattern area; the raw material formulation of the protective glaze layer, by weight percentage, includes: 90% matte transparent frit, 6.5% zirconium silicate, 3.2% kaolin, 0.2% sodium carboxymethyl cellulose, and 0.1% silicone defoamer; the raw material formulation of the ink, by weight percentage, includes: 12% ferrous nitrate, 8% cobalt nitrate, 55% deionized water, 13% ethylene glycol, 4% sodium polycarboxylate, 6% glycerol, and 2% ammonia; in the pattern layer, the area proportion of the high grayscale pattern area is 60%, and the area proportion of the low grayscale pattern area is 40%. The preparation method includes the following steps:

[0067] Preparation of the base glaze slurry: Weigh the raw materials of the base glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the base glaze slurry. The specific gravity of the base glaze slurry is 1.55 g / cm³. 3 ;

[0068] Ink preparation: Weigh the raw materials of the pattern layer according to the formula ratio. First, add ferrous nitrate, cobalt nitrate, deionized water and ethylene glycol to the mixing tank and stir until the metal ions are completely dissolved. Then add dispersant and humectant, continue stirring and then add pH adjuster to adjust pH to 8 to obtain ink.

[0069] Preparation of protective glaze slurry: Weigh the raw materials for the protective glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the protective glaze slurry. The specific gravity of the protective glaze slurry is 1.45 g / cm³. 3 ;

[0070] Preparation of the base glaze layer: The base glaze slurry is evenly applied to the surface of the body by spray glazing, and after drying, a base glaze layer is formed with a thickness of 0.2 mm.

[0071] Preparation of the pattern layer: The blank with the base glaze layer is fed into the printing station, and the ink is printed on the surface of the base glaze layer according to the preset pattern and preset printing parameters to form a pattern layer on the surface of the base glaze layer. The pattern layer has a high grayscale pattern area and a low grayscale pattern area. When printing the high grayscale pattern area, the nozzle spray frequency is 8 times / square millimeter, the moving speed is 50mm / s, and the spray pressure is 0.3MPa; when printing the low grayscale pattern area, the nozzle spray frequency is 4 times / square millimeter, the moving speed is 100mm / s, and the spray pressure is 0.15MPa.

[0072] Preparation of protective glaze layer: Protective glaze slurry is applied to the surface of the blank to form the pattern layer by spray glazing method, and after drying, a protective glaze layer is formed with a thickness of 0.12 mm.

[0073] Sintering treatment: The body forming the base glaze layer, pattern layer and protective glaze layer is sintered. In the heating stage, the temperature is raised to 1240℃ at a heating rate of 55℃ / min; in the holding stage, the temperature is held at 1240℃ for 15min; in the cooling stage, the temperature is first cooled to 550℃ at a cooling rate of 110℃ / min, and then cooled to room temperature in the furnace to obtain the stone textured ceramic tile.

[0074] The actual image of the stone-textured ceramic tile produced in Example 1 is shown below. Figure 2 As shown in the figure, the high grayscale pattern area forms a uniform microporous structure (pore size 5-10μm), simulating the weathering and peeling of stone; the low grayscale pattern area has a smooth glaze with a gloss of 5.2° and a silky smooth feel; structural characteristics: the corrosion area presents a composite structure of micropores and zircon crystal clusters, while the non-corrosion area is a dense layer of nanocrystal-glass phase; yield rate: 92%, with no glaze blasting or cracking.

[0075] Example 2

[0076] A stone-textured ceramic tile includes a body, a base glaze layer, a pattern layer, and a protective glaze layer. The raw material formula of the base glaze layer includes, by mass percentage: 25% ZA210, 3% zinc oxide, 8% black mud, 6% Suzhou clay, 30% potassium sand, 8% potassium feldspar, 13% zirconium silicate, and 7% sodium sand. The remaining formulas are the same as in Example 1, and the preparation method is also the same as in Example 1.

[0077] The actual image of the stone-textured ceramic tile produced in Example 2 is shown below. Figure 3 As shown, from Figure 3 It can be seen that after the ZA210 content is increased in this embodiment, the corrosion depth of the high grayscale pattern area increases (pore size 8-15μm) and the reaction speed is accelerated, but a small amount of glaze collapse caused by excessive corrosion occurs locally; structural characteristics: insufficient support of crystal cluster skeleton and excessively high micropore connectivity in some areas; yield: 85%, with a slight increase in scrap rate due to excessive corrosion.

[0078] Example 3

[0079] A stone-textured ceramic tile comprises a body, a base glaze layer, a pattern layer, and a protective glaze layer. The base glaze layer comprises, by weight percentage: 20% ZA210, 3% zinc oxide, 8% black mud, 6% Suzhou clay, 33% potassium sand, 8% potassium feldspar, 15% zirconium silicate, and 7% sodium sand. The protective glaze layer comprises, by weight percentage: 90% matte transparent frit, 5% zirconium silicate, 4.7% kaolin, 0.2% sodium carboxymethyl cellulose, and 0.1% silicone defoamer. The remaining formulations are the same as in Example 1, and the preparation method is the same as in Example 1.

[0080] The actual image of the stone-textured ceramic tile produced in Example 3 is shown below. Figure 4 As shown, from Figure 4 The results show that increasing the zirconium silicate base glaze to 15% and reducing the protective glaze to 5% improves the structural stability of the corrosion zone, with no collapse; however, the matte texture is slightly reduced (gloss level 6.8°); structural characteristics: the high-temperature melting degree of the base glaze is reduced, and the microcrystalline scattering effect of the protective glaze is weakened; yield: 89%, with some defective products due to the gloss level deviating from the target range.

[0081] Comparative Example 1 (Traditional single-layer etched glaze, without ZA210)

[0082] A ceramic material includes a ceramic body and a base glaze layer. The base glaze layer comprises, by weight percentage: 10% zirconium silicate, 25% potassium sand, 10% potassium feldspar, 8% sodium sand, 12% black mud, 7% Suzhou clay, 2% zinc oxide, and the remainder being fillers. The preparation method includes the following steps:

[0083] Preparation of the base glaze slurry: Weigh the raw materials of the base glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the base glaze slurry. The specific gravity of the base glaze slurry is 1.55 g / cm³. 3 ;

[0084] Preparation of protective glaze layer: A base glaze slurry is applied to the surface of the body by spray glazing, and after drying, a base glaze layer is formed with a thickness of 0.12 mm.

[0085] Sintering treatment: The green body forming the base glaze layer is sintered. In the heating stage, the temperature is increased to 1240℃ at a heating rate of 55℃ / min; in the holding stage, the temperature is held at 1240℃ for 15min; in the cooling stage, the temperature is first cooled to 550℃ at a cooling rate of 110℃ / min, and then cooled to room temperature in the furnace to obtain the stone textured ceramic tile.

[0086] The actual image of the ceramic tile produced in Comparative Example 1 is shown below. Figure 5 As shown, from Figure 5 The results show that a single-layer glaze cannot achieve grayscale control, the entire glaze surface is free of corrosion, and it lacks the gradient effect of natural stone. Performance defects include large fluctuations in gloss (8-12°), a rough feel, and a yield rate of only 60% (glaze cracking is a prominent issue).

[0087] Comparative Example 2 (without distinction between high and low grayscale patterns)

[0088] A stone-textured ceramic tile includes a body, a base glaze layer, a pattern layer, and a protective glaze layer. The raw material formulas of the base glaze layer, the pattern layer, and the protective glaze layer are the same as those in Example 1. The difference is that the pattern layer does not distinguish between high-grayscale pattern areas and low-grayscale pattern areas, that is, the ink printing thickness of the pattern layer is the same. Its preparation method is the same as that in Example 1.

[0089] The actual image of the ceramic tile produced in Comparative Example 2 is shown below. Figure 6 As shown, from Figure 6 The results show that the lack of grayscale pattern differentiation leads to indistinguishable corrosion areas, a monotonous surface texture, and a distorted stone-like effect, failing to simulate the layered texture of stone weathering. Yield: 78%, functional failure due to pattern design defects.

[0090] Comparative Example 3 (Firing temperature too high)

[0091] A stone-textured ceramic tile includes a body, a base glaze layer, a pattern layer, and a protective glaze layer. The raw material formulas of the base glaze layer, the pattern layer, and the protective glaze layer are the same as those in Example 1. The only difference between the preparation method of the ceramic tile and that of Example 1 is that the heat preservation temperature is 1300℃.

[0092] The actual image of the ceramic tile produced in Comparative Example 3 is shown below. Figure 7 As shown, from Figure 7 The results show that the glaze layer was over-melted due to excessively high sintering temperature, which caused the micropores in the high gray area to collapse and the texture to become blurred. Performance defects: the zirconium silicate skeleton of the base glaze was destroyed, the zirconium silicate microcrystals in the protective glaze were unbalanced, and the final structure and matte effect failed.

[0093] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solution and inventive concept of the present invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A stone-textured ceramic tile, characterized in that, The product comprises a body, a base glaze layer, a pattern layer, and a protective glaze layer. The base glaze layer, by weight percentage, comprises: 15-25% ZA210, 2-5% zinc oxide, 5-10% black mud, 5-8% Suzhou clay, 30-40% potassium sand, 5-10% potassium feldspar, 10-15% zirconium silicate, and 5-10% sodium sand. The ZA210 is a chemical composition containing magnesium oxide and calcium oxide. The pattern layer is composed of Fe... 2+ and Co 2+ The pattern layer is formed by ink printing, and includes a high grayscale pattern area and a low grayscale pattern area. The ink printing thickness of the high grayscale pattern area is 2-3 times that of the low grayscale pattern area. The raw material formula of the protective glaze layer includes, by mass percentage: 88-92% matte transparent frit, 3-8% zirconium silicate, 3-5% kaolin, 0.1-0.3% sodium carboxymethyl cellulose, and 0.05-0.15% silicone defoamer.

2. The stone-textured ceramic tile according to claim 1, characterized in that, In the pattern layer, the area of ​​the high grayscale pattern region accounts for 60-80%, and the area of ​​the low grayscale pattern region accounts for 20-40%.

3. The stone-textured ceramic tile according to claim 1, characterized in that, The chemical composition of ZA210, by mass percentage, includes: 65-70% SiO2, 8-12% CaO, 5-8% MgO, 6-10% Al2O3, 1-3% K2O, and 3-5% Na2O.

4. The stone-textured ceramic tile according to claim 1, characterized in that, The raw material formulation of the ink, by weight percentage, includes: 10-15% ferrous nitrate, 5-10% cobalt nitrate, 50-55% deionized water, 10-15% ethylene glycol, 3-5% dispersant, 5-8% humectant, and 1-3% pH adjuster.

5. The stone-textured ceramic tile according to claim 4, characterized in that, The dispersant is sodium polycarboxylate, the humectant is glycerol, and the pH adjuster is ammonia.

6. A method for preparing a stone-textured ceramic tile as described in any one of claims 1-5, characterized in that, Including the following steps: Weigh the raw materials of the base glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the base glaze slurry; Weigh the raw materials of the pattern layer according to the formula ratio. First, add ferrous nitrate, cobalt nitrate, deionized water and ethylene glycol to the mixing tank and stir until the metal ions are completely dissolved. Then add the dispersant and humectant, continue stirring and then add the pH adjuster to adjust the pH to 7.5-8.5 to obtain the ink. Weigh the raw materials of the protective glaze layer according to the formula ratio, add deionized water, mix and ball mill to obtain the protective glaze slurry; A base glaze slurry is evenly applied to the surface of the body using a spray glazing method, and a base glaze layer is formed after drying. The blank with the base glaze layer is sent to the printing station, and the ink is printed on the surface of the base glaze layer according to the preset pattern and preset printing parameters to form a pattern layer on the surface of the base glaze layer, which has a high grayscale pattern area and a low grayscale pattern area. A protective glaze slurry is applied to the surface of the blank to form the pattern layer using a spray glazing method, and a protective glaze layer is formed after drying. Stone-textured ceramic tiles are produced by sintering the body that forms the base glaze layer, pattern layer, and protective glaze layer.

7. The method for preparing stone-textured ceramic tiles according to claim 6, characterized in that, The specific gravity of the base glaze slurry is 1.5-1.6 g / cm³. 3 The thickness of the base glaze layer is 0.15-0.25 mm.

8. The method for preparing stone-textured ceramic tiles according to claim 6, characterized in that, The preset printing parameters include: when printing high grayscale pattern areas, the printhead ejection frequency is 8 times / square millimeter, the moving speed is 50mm / s, and the ejection pressure is 0.3MPa; when printing low grayscale pattern areas, the printhead ejection frequency is 4 times / square millimeter, the moving speed is 100mm / s, and the ejection pressure is 0.15MPa.

9. The method for preparing stone-textured ceramic tiles according to claim 6, characterized in that, The specific gravity of the protective glaze slurry is 1.4-1.5 g / cm³. 3 The thickness of the protective glaze layer is 0.1-0.15 mm.

10. The method for preparing stone-textured ceramic tiles according to claim 6, characterized in that, The sintering process for the body forming the base glaze layer, pattern layer, and protective glaze layer includes a heating stage, a holding stage, and a cooling stage. In the heating stage, the temperature is increased to 1220-1260℃ at a heating rate of 50-60℃ / min. In the holding stage, the temperature is held at 1220-1260℃ for 10-20 minutes. In the cooling stage, the temperature is first cooled to 500-600℃ at a cooling rate of 100-120℃ / min, and then cooled to room temperature in the furnace.

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