Anti-lime stone glazed ceramic tile and preparation method thereof

Abstract

The invention discloses an anti-lime stone glazed ceramic tile and a preparation method thereof, and relates to the technical field of ceramic materials. According to the preparation method of the anti-lime glaze ceramic tile, the raw materials and chemical components of the protective glaze and the firing temperature are limited, so that the smoothness and roughness of the anti-lime glaze ceramic tile are balanced on the microscopic scale, and high stain resistance and high skid resistance are achieved at the same time. The imitated lime stone glaze surface layer formed by the formula design of the cover glaze and the protective glaze has the characteristics of skid resistance and fouling resistance, and is highly similar to natural lime stone. The structure not only meets the use requirements, but also breaks through the mutual restriction relationship between the antifouling performance and the antiskid performance in the traditional technology, and provides a new idea for the design of the high-performance ceramic tile glaze.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, and more specifically, to a limestone-resistant glazed ceramic tile and its preparation method. Background Technology

[0002] Limestone is a natural limestone formed from the remains of marine organisms such as shells and corals from the seabed hundreds of millions of years ago, deposited and compressed through long-term geological processes. Because it often retains fossil traces of these ancient organisms, it has earned the reputation of "stone of life." Limestone has a gentle color, typically in low-saturation shades such as off-white, beige, and gray, with delicate and varied textures. It possesses a retro, elegant quality and a weathered look, making it a favorite element for many designers. Meanwhile, glaze, as a key ceramic material, plays a crucial role in improving the performance of ceramic products. Currently, optimizing the glaze quality while achieving a limestone glaze design, thereby improving the product's quality and grade, has become a core objective for many ceramic companies. In ceramic tiles and other products, the stain resistance and anti-slip properties of the glaze directly determine its actual service life and performance. Insufficient stain resistance leads to stains that are difficult to remove, affecting aesthetics; poor anti-slip properties increase the risk of slipping and endangering personal safety in flooring applications.

[0003] Stain resistance and slip resistance, as two key properties of ceramics, often exhibit a mutually restrictive relationship. This inherent contradiction stems from the different requirements they place on the ceramic glaze: excellent stain resistance typically requires a smooth and dense glaze to resist contaminant adhesion; while good slip resistance often relies on a rough glaze surface to increase friction. However, this structure designed for increased roughness becomes a site for trapping dust and dirt, thus weakening its stain-resistant effect. Current traditional glaze technology struggles to overcome the constraint between high stain resistance and high slip resistance, often resulting in performance compromises in existing ceramic products, making it difficult to achieve an ideal synergistic effect. Therefore, how to simultaneously achieve excellent stain resistance and slip resistance on ceramic tile glazes has become a topic worthy of in-depth research.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a limestone-resistant glazed ceramic tile and its preparation method.

[0006] This invention is implemented as follows: In a first aspect, the present invention provides a method for preparing anti-lime stone glazed ceramic tiles, which includes applying a surface glaze to the surface of a ceramic tile body layer to form a surface glaze layer, printing a pattern on the surface of the surface glaze layer to form an inkjet printing layer, applying a protective glaze to the surface of the inkjet printing layer to form a protective glaze layer, and then firing at 1200-1220 °C. The protective glaze is composed of CBP5005Z slurry, G1099 slurry, and G1099 dry granules in a mass ratio of 1:0.5-1.5:0.5-1.5. The chemical composition of the protective glaze layer, calculated as a percentage by mass, includes: SiO2 49.09-51.26%, Al2O3 16.52-19.77%, Fe2O3 0.11-0.20%, TiO2 0.05-0.15%, CaO 4.81-7.00%, MgO 0.92-1.72%, K2O 1.58-3.15%, Na2O 2.09-3.51%, B2O3 0.08-0.25%, BaO 8.85-10.26%, SrO 0.62-1.55%, ZrO2 0.01-0.06%, ZnO 3.29-4.11%, P2O5 0.03-0.15%, and LOI 2.36-4.64%.

[0007] In an optional embodiment, the firing temperature is 1200-1208 °C and the firing time is 40-45 min; And / or, the mass ratio of the CBP5005Z slurry, the G1099 slurry, and the G1099 dry pellets is 1:0.8-1.2:0.8-1.2.

[0008] In an optional embodiment, the chemical composition of the CBP5005Z slurry, calculated by mass percentage, includes: SiO2 41.64-47.85%, Al2O3 14.35-18.21%, Fe2O3 0.10-0.35%, TiO2 0.05-0.15%, CaO 5.32-7.44%, MgO 1.76-3.05%, K2O 1.05-2.66%, Na2O 2.64-4.01%, B2O3 0.21-0.45%, BaO 9.27-12.88%, SrO 0.15-0.36%, ZnO 4.35-6.53%, ZrO2 0.01-0.05%, and LOI 7.69-9.72%. Preferably, the formulation of the CBP5005Z slurry, calculated by mass parts, includes: 6.5-9 parts nepheline, 10.5-12.5 parts potassium feldspar, 17.5-23.5 parts sodium feldspar, 11.5-13 parts dolomite, 5.5-8 parts calcined clay, 4.5-6.5 parts kaolin, 8-10 parts barium carbonate, 4-6 parts zinc oxide, 10.5-12.5 parts F2 frit, and 9.5-11.5 parts 38808 frit; Preferably, the chemical composition of the 38808 frit, calculated by mass percentage, includes: SiO2 52.68-54.88%, Al2O3 17.26-22.55%, Fe2O3 0.06-0.09%, TiO2 0.03-0.05%, CaO 12.35-15.68%, MgO 0.35-0.52%, K2O 1.02-1.74%, Na2O 2.45-4.61%, B2O3 0.10-0.20%, BaO 0.10-0.30%, SrO 0.05-0.08%, ZnO 2.45-4.59%, ZrO2 0.02-0.04%, and LOI 0.03-0.05%.

[0009] In an optional embodiment, the chemical composition range of the G1099 slurry and the G1099 dry granules, calculated as a percentage by mass, includes: SiO2 50.32-54.61%, Al2O3 17.61-20.55%, Fe2O3 0.11-0.18%, TiO2 0.05-0.10%, CaO 4.55-6.78%, MgO 0.50-1.05%, K2O 1.84-3.15%, Na2O 1.82-3.26%, B2O3 0.03-0.05%, BaO 8.64-10.96%, SrO 1.50-1.86%, ZnO 2.66-3.86%, P2O5 0.09-0.15%, and LOI 0.26-0.45%.

[0010] In an optional embodiment, the chemical composition of the glaze, by mass percentage, includes: SiO2 47.49-52.49%, Al2O3 21.34-24.18%, Fe2O3 0.22-0.25%, TiO2 0.10-0.14%, CaO 3.06-4.66%, MgO 1.51-2.05%, K2O 2.68-3.05%, Na2O 1.94-2.64%, ZrO2 9.59-10.81%, BaO 1.47-1.94%, SrO 0.01-0.58%, B2O3 0.01-0.08%, P2O5 0.01-0.25%, ZnO 0.46-1.50%, and LOI 4.86-6.25%. Preferably, the raw materials of the glaze, by mass parts, include: 6.5-9 parts nepheline, 14.5-19.5 parts potassium feldspar, 7-10 parts dolomite, 8.5-11 parts calcined clay, 7.5-9 parts kaolin, 0.5-1.5 parts zinc oxide, 4-6 parts F2 frit, 1.5-2.5 parts wollastonite, 14.5-20 parts zirconium silicate, 7-9 parts alumina, 17-20 parts quartz, and 4-6 parts GB0306 frit.

[0011] In an optional embodiment, the chemical composition of the F2 frit, calculated as a percentage by mass, includes: SiO2 38.29-41.43%, Al2O3 12.48-14.66%, Fe2O3 0.01-0.03%, TiO2 0.02-0.05%, CaO 0.56-1.24%, MgO 1.54-2.56%, K2O 2.01-2.55%, Na2O 2.76-3.88%, B2O3 0.10-0.20%, BaO 34.15-40.58%, SrO 0.10-0.30%, and LOI 0.04-0.06%. And / or, the chemical composition of the GB0306 frit, calculated as a percentage by mass, includes: SiO2 39.26-43.69%, Al2O3 18.87-23.46%, Fe2O3 0.10-0.20%, TiO2 0.04-0.07%, CaO 3.96-6.32%, MgO 0.10-0.20%, K2O 3.69-5.71%, Na2O 15.59-19.02%, P2O5 0.25-0.39%, BaO 0.06-0.09%, SrO 0.01-0.03%, ZrO2 5.41-7.98%, LOI 1.01-1.50%.

[0012] In an optional embodiment, the ceramic brick body layer is made by mixing 100 parts of body material with 35-50 parts of water, 0.1-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after a first ball milling, and subsequently pressed and dried. Preferably, the raw materials of the billet material include, by mass fraction: 2-5 parts of low-temperature sand, 25-29 parts of sodium calcite powder, 13-18 parts of ball clay, 12-16 parts of ultra-white sand, 20-35 parts of high-white sand, 3-8 parts of potassium-sodium sand, 2-7 parts of bentonite, and 2-5 parts of talc. Preferably, the first ball milling time is 2-4 hours; Preferably, the particle size distribution after ball milling is as follows: ≤2.0% for particles larger than 20 mesh, 45%-55% for particles larger than 40 mesh, 80%-90% for particles larger than 60 mesh, and ≤2.2% for particles smaller than 100 mesh. Preferably, the pressing pressure is 350-370 bar, the pressing cycle is 92.6-102.6 times / h, and the thickness of the ceramic tile body layer after pressing is 6-12 mm.

[0013] In an optional embodiment, the surface glaze layer is made by mixing 100 parts of the surface glaze material with 35-45 parts of water, 0.2-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after a second ball milling and after a first aging process. The mixture is then applied to the surface of the ceramic tile body layer and dried. Preferably, the second ball milling time is 4-6 hours, and the residue after passing through a 160-180 mesh sieve is 0.6%-0.9%. Preferably, the first aging time is 24-48 hours; Preferably, the specific gravity of the glaze slurry during glazing is 1.45-1.55 g / cm³. 3 The glaze application rate can be 220-260 g / m². 2 .

[0014] In an optional embodiment, the protective glaze layer is made by mixing 100 parts of the protective glaze with 35-45 parts of water, 0.2-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, ball milling for a third time, sieving, and aging for a second time before spraying the glaze onto the surface of the inkjet printing layer and drying. Preferably, the third ball milling time is 8-10 hours, and the material is passed through a 250-325 mesh sieve with a residue of 0.4-0.6%. Preferably, the second aging time is 24-48 hours; Preferably, the specific gravity of the glaze slurry during glazing is 1.25-1.35 g / cm³. 3 The glaze application rate is 90-110 g / m². 2 .

[0015] Secondly, the present invention provides a limestone-resistant glazed ceramic tile, which is prepared by the method for preparing limestone-resistant glazed ceramic tiles as described in any of the foregoing embodiments.

[0016] The present invention has the following beneficial effects: The method for preparing anti-lime stone glazed ceramic tiles provided by this invention limits the chemical composition of the surface glaze, the raw materials and chemical composition of the protective glaze, and the firing temperature. Among them, the surface glaze has a high content of SiO2 and Al2O3, which can form the glass phase skeleton of the glaze layer and ensure the basic density of the glaze. ZrO2 improves the chemical and thermal stability of the glaze, reduces high-temperature defects, and improves the hardness and impermeability of the glaze, effectively preventing dirt from penetrating. Alkali metal oxides (K2O, Na2O) and alkaline earth metal oxides (CaO, MgO) act as fluxes, lowering the melting temperature and allowing the surface glaze to fully melt during firing, forming a continuous and dense surface layer. The loss on ignition is low, and there are few residual volatile components after firing. The surface glaze substrate is relatively flat and dense, providing a uniform adhesion substrate for the protective glaze and avoiding dirt from penetrating and accumulating due to an excessively loose substrate. The protective glaze is a mixture of CBP5005Z slurry, G1099 slurry, and G1099 dry granules in a ratio of 1:0.5-1.5:0.5-1.5. This design aims to leverage the complementary strengths of the structure-controlled CBP5005Z slurry and the dense, stable G1099 slurry and dry granules. The CBP5005Z slurry is rich in BaO and ZnO, which act as strong fluxes, lowering the melting temperature of the protective glaze, promoting glass phase formation, and simultaneously reducing the surface energy of the glaze, thus decreasing the adhesion of contaminants. It has a high loss on ignition and contains a significant amount of high-temperature volatile / decomposed components. During firing, these volatile components release gases, forming micro-pits and phase-separated structures within the glaze layer, introducing a moderate roughness to the surface. Furthermore, during firing, the G1099 dry granules only partially melt or retain their granular shape, resulting in micron-level protrusions on the surface. The CBP5005Z and G1099 slurries melt to form a glass matrix that fills the gaps between particles, preventing dirt from accumulating. This provides friction points without the tendency for dirt to accumulate as easily as on a rough surface. Furthermore, the controlled firing temperature ensures that the dry particles in the protective glaze partially melt, maintaining their morphology and bonding firmly to the glass matrix, preventing particle detachment. These features balance smoothness and roughness at the microscale, achieving both high stain resistance and high slip resistance. The limestone-like glaze layer formed through the above-designed formulation of the surface glaze and protective glaze components possesses both slip and stain-resistant properties and is highly similar to natural limestone. This structure not only meets usage requirements but also overcomes the traditional trade-off between stain resistance and slip resistance, providing a new approach to the design of high-performance ceramic tile glazes. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of the surface of the imitation limestone glazed ceramic tile provided in Embodiment 1 of the present invention; Figure 2 This is a schematic diagram of the microstructure of the imitation limestone glazed ceramic tile provided in Embodiment 1 of the present invention. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0020] This invention provides a method for preparing anti-lime stone glazed ceramic tiles, which includes: applying a surface glaze to the surface of a ceramic tile body layer to form a surface glaze layer; printing a pattern on the surface of the surface glaze layer to form an inkjet printing layer; applying a protective glaze to the surface of the inkjet printing layer to form a protective glaze layer; and then firing at 1200-1220 °C.

[0021] Specifically, it includes the following steps: S1. Prepare the ceramic brick body layer.

[0022] The ceramic tile body layer is made by mixing 100 parts of body material with 35-50 parts of water, 0.1-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after the first ball milling, and subsequently pressed and dried.

[0023] The green body material can be made from commonly used green body raw materials in the field. The present invention provides a typical but non-limiting example: the raw materials of the green body material include, by mass fraction: 2-5 parts of low temperature sand, 25-29 parts of sodium calcite powder, 13-18 parts of ball clay, 12-16 parts of super white sand, 20-35 parts of high white sand, 3-8 parts of potassium sodium sand, 2-7 parts of bentonite and 2-5 parts of talc.

[0024] Weigh the above-mentioned green body material according to the formula composition. Add 35-50 parts of water, 0.1-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate to 100 parts of green body material and mix. After ball milling for 2-4 hours, sieve the mixture. The particle size distribution after ball milling is as follows: ≤2.0% for particles above 20 mesh, 45%-55% for particles above 40 mesh, 80%-90% for particles above 60 mesh, and ≤2.2% for particles below 100 mesh.

[0025] "Particle size distribution" refers to the proportion of particles of different sizes in the raw material of the green body. ≤2.0% of particles larger than 20 mesh indicates that coarse particles that cannot pass through a 20-mesh sieve account for no more than 2.0% of the total mass. 45-55% of particles larger than 40 mesh indicates that particles that cannot pass through a 40-mesh sieve (including coarse particles larger than 20 mesh) account for 45%-55% of the total mass. 80-90% of particles larger than 60 mesh indicates that particles that cannot pass through a 60-mesh sieve (including particles larger than 20 and 40 mesh) account for 80%-90% of the total mass. ≤2.2% of particles smaller than 100 mesh indicates that fine particles that can pass through a 100-mesh sieve account for no more than 2.2% of the total mass.

[0026] The above particle size distribution ensures the uniformity of raw materials and the subsequent molding effect.

[0027] The pressing is carried out using a 30,000-ton System press at a pressure of 350-370 bar, with a pressing cycle of 92.6-102.6 times / hour. The thickness of the ceramic tile body layer after pressing is 6-12 mm.

[0028] S2. Apply a surface glaze to the surface of the ceramic tile body to form a surface glaze layer.

[0029] The surface glaze layer is formed by applying surface glaze material to the ceramic tile body layer. Specifically, the surface glaze layer is made by mixing 100 parts surface glaze material with 35-45 parts water, 0.2-0.3 parts methylcellulose and 0.2-0.4 parts sodium tripolyphosphate, which is then sieved after a second ball milling and after a first aging process. The mixture is then poured onto the surface of the ceramic tile body layer and dried.

[0030] The chemical composition of the glaze, by mass percentage, includes: SiO2 47.49-52.49%, Al2O3 21.34-24.18%, Fe2O3 0.22-0.25%, TiO2 0.10-0.14%, CaO 3.06-4.66%, MgO 1.51-2.05%, K2O 2.68-3.05%, Na2O 1.94-2.64%, ZrO2 9.59-10.81%, BaO 1.47-1.94%, SrO 0.01-0.58%, B2O3 0.01-0.08%, P2O5 0.01-0.25%, ZnO 0.46-1.50%, and LOI 4.86-6.25%. From the chemical composition of the glaze provided by this invention, the glaze contains high levels of SiO2 and Al2O3, which form the glassy phase framework of the glaze layer, ensuring the basic density of the glaze surface. ZrO2 enhances the chemical and thermal stability of the glaze, reduces high-temperature defects, and improves the hardness and impermeability of the glaze surface, effectively preventing dirt from penetrating. Alkali metal oxides (K2O, Na2O) and alkaline earth metal oxides (CaO, MgO) act as fluxes, lowering the melting temperature and allowing the glaze to fully melt during firing, forming a continuous and dense surface layer. The loss on ignition is low, resulting in fewer residual volatile components after firing. The glaze substrate is relatively flat and dense, providing a uniform adhesion substrate for the protective glaze and preventing dirt from penetrating and accumulating due to an excessively loose substrate.

[0031] The raw materials for the glaze can be common chemical raw materials used in the field, as long as their proportions meet the above-mentioned chemical composition of the glaze. The present invention provides a typical but not limiting example: the raw materials of the glaze include, by mass parts: 6.5-9 parts of nepheline, 14.5-19.5 parts of potassium feldspar, 7-10 parts of dolomite, 8.5-11 parts of calcined clay, 7.5-9 parts of kaolin, 0.5-1.5 parts of zinc oxide, 4-6 parts of F2 frit, 1.5-2.5 parts of wollastonite, 14.5-20 parts of zirconium silicate, 7-9 parts of alumina, 17-20 parts of quartz, and 4-6 parts of GB0306 frit.

[0032] The chemical composition of the F2 ingot, calculated by mass percentage, includes: SiO2 38.29-41.43%, Al2O3 12.48-14.66%, Fe2O3 0.01-0.03%, TiO2 0.02-0.05%, CaO 0.56-1.24%, MgO 1.54-2.56%, K2O 2.01-2.55%, Na2O 2.76-3.88%, B2O3 0.10-0.20%, BaO 34.15-40.58%, SrO 0.10-0.30%, and LOI 0.04-0.06%.

[0033] The chemical composition of GB0306 frit, calculated as a percentage by mass, includes: SiO2 39.26-43.69%, Al2O3 18.87-23.46%, Fe2O3 0.10-0.20%, TiO2 0.04-0.07%, CaO 3.96-6.32%, MgO 0.10-0.20%, K2O 3.69-5.71%, Na2O 15.59-19.02%, P2O5 0.25-0.39%, BaO 0.06-0.09%, SrO 0.01-0.03%, ZrO2 5.41-7.98%, and LOI 1.01-1.50%.

[0034] In this invention, the above-mentioned raw materials are subjected to a second ball milling. Ball milling can refine the raw materials, which is conducive to the uniformity of subsequent glazing. The second ball milling time is 4-6 hours, and the material is passed through a 160-180 mesh sieve with a sieve residue of 0.6%-0.9%.

[0035] In this invention, the raw materials after ball milling and sieving undergo a first aging process to improve the properties of the slurry and lay the foundation for subsequent molding and sintering. The first aging period is 24-48 hours. The specific gravity of the glaze slurry during glazing is 1.45-1.55 g / cm³. 3 The glaze application rate can be 220-260 g / m². 2 .

[0036] Among them, "specific gravity" refers to the density of the slurry (mass of slurry per unit volume), which directly affects the flow properties of the glaze slurry; "glaze application amount" refers to the total amount of glaze slurry applied to the surface of the ceramic body, which determines the final thickness and uniformity of the glaze layer. Both together affect the quality of the glaze surface.

[0037] S3. Print patterns on the surface of the glaze layer to form an inkjet printing layer.

[0038] Using a KEDA inkjet printer, the printhead height can be adjusted from 6.5 to 12.5 mm. The printhead height should be adjusted to be slightly greater than the thickness of the ceramic tile body. The desired pattern is printed on the surface of the glaze layer. The ceramic tile body with the glaze and printed pattern is then conveyed by belt to the drying kiln for drying, ensuring the ceramic tile body temperature is 150-200 °C.

[0039] S4. Apply a protective glaze to the surface of the inkjet printing layer to form a protective glaze layer.

[0040] The protective glaze layer is formed by applying protective glaze to the inkjet printing layer. Specifically, the protective glaze layer is made by mixing 100 parts of protective glaze with 35-45 parts of water, 0.2-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after a third ball milling and a second aging process. The mixture is then sprayed onto the surface of the inkjet printing layer and dried. The protective glaze is composed of CBP5005Z slurry, G1099 slurry, and G1099 dry granules in a mass ratio of 1:0.5-1.5:0.5-1.5. The chemical composition of the protective glaze layer, calculated as a percentage by mass, includes: SiO2 49.09-51.26%, Al2O3 16.52-19.77%, Fe2O3 0.11-0.20%, TiO2 0.05-0.15%, CaO 4.81-7.00%, MgO 0.92-1.72%, K2O 1.58-3.15%, Na2O 2.09-3.51%, B2O3 0.08-0.25%, BaO 8.85-10.26%, SrO 0.62-1.55%, ZrO2 0.01-0.06%, ZnO 3.29-4.11%, P2O5 0.03-0.15%, and LOI 2.36-4.64%.

[0041] In this invention, the protective glaze is a compound of CBP5005Z slurry, G1099 slurry, and G1099 dry granules. The invention utilizes the complementary structural control of CBP5005Z slurry and the dense stability of G1099 slurry and dry granules. CBP5005Z slurry is rich in BaO and ZnO, which act as strong fluxes, lowering the melting temperature of the protective glaze, promoting glass phase formation, and simultaneously reducing the surface energy of the glaze, thus reducing the adhesion of contaminants. It has a high loss on ignition and contains a significant amount of high-temperature volatile / decomposed components. During firing, these volatile components release gases, forming micro-pits and phase-separated structures in the glaze layer, introducing appropriate roughness to the glaze surface. Furthermore, during firing, the G1099 dry granules only partially melt or maintain their particle shape, thereby forming micron-level protrusions on the surface. The melting of CBP5005Z slurry and G1099 slurry forms a glass matrix that fills the gaps between particles, preventing contaminant retention sites.

[0042] Preferably, the mass ratio of CBP5005Z slurry, G1099 slurry, and G1099 dry granules is 1:0.8-1.2:0.8-1.2. In this invention, the stain resistance and anti-slip properties can be adjusted by regulating the mass ratio of CBP5005Z slurry, G1099 slurry, and G1099 dry granules.

[0043] The chemical composition of CBP5005Z slurry, calculated by mass percentage, includes: SiO2 41.64-47.85%, Al2O3 14.35-18.21%, Fe2O3 0.10-0.35%, TiO2 0.05-0.15%, CaO 5.32-7.44%, MgO 1.76-3.05%, K2O 1.05-2.66%, Na2O 2.64-4.01%, B2O3 0.21-0.45%, BaO 9.27-12.88%, SrO 0.15-0.36%, ZnO 4.35-6.53%, ZrO2 0.01-0.05%, and LOI 7.69-9.72%. The formulation of CBP5005Z slurry, by mass parts, includes: 6.5-9 parts nepheline, 10.5-12.5 parts potassium feldspar, 17.5-23.5 parts sodium feldspar, 11.5-13 parts dolomite, 5.5-8 parts calcined clay, 4.5-6.5 parts kaolin, 8-10 parts barium carbonate, 4-6 parts zinc oxide, 10.5-12.5 parts F2 frit, and 9.5-11.5 parts 38808 frit. The chemical composition of the 38808 frit, by mass percentage, includes: 52.68-54.88% SiO2, 17.26-22.55% Al2O3, 0.06-0.09% Fe2O3, 0.03-0.05% TiO2, 12.35-15.68% CaO, 0.35-0.52% MgO, and K2O. 1.02-1.74%, Na2O 2.45-4.61%, B2O30.10-0.20%, BaO 0.10-0.30%, SrO 0.05-0.08%, ZnO 2.45-4.59%, ZrO20.02-0.04%, LOI 0.03-0.05%. The chemical composition of G1099 slurry and G1099 dry granules, calculated as a percentage by mass, includes: SiO2 50.32-54.61%, Al2O3 17.61-20.55%, Fe2O3 0.11-0.18%, TiO2 0.05-0.10%, CaO 4.55-6.78%, MgO 0.50-1.05%, K2O 1.84-3.15%, Na2O 1.82-3.26%, B2O3 0.03-0.05%, BaO 8.64-10.96%, SrO 1.50-1.86%, ZnO 2.66-3.86%, P2O5 0.09-0.15%, and LOI 0.26-0.45%.

[0044] After determining the above protective glaze, the protective glaze is mixed with water, methylcellulose and sodium tripolyphosphate, and then subjected to a third ball milling for 8-10 hours. Ball milling can refine the slurry, which is conducive to the uniformity of subsequent glazing. Then it is passed through a 250-325 mesh sieve, and the sieve residue is 0.4-0.6%.

[0045] In this invention, the slurry after ball milling and sieving is subjected to a second aging process to improve the slurry's properties and lay the foundation for subsequent molding and sintering. The second aging process takes 24-48 hours.

[0046] The specific gravity of the glaze slurry during spray glazing is 1.25-1.35 g / cm³. 3 The glaze application rate is 90-110 g / m². 2 .

[0047] The ceramic tile blanks, which have been coated with surface glaze, printed with patterns, and coated with protective glaze, are conveyed by belt to the drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150-200 °C.

[0048] S5. Firing is carried out at 1200-1220 °C.

[0049] Ceramic tile blanks, which have been coated with surface glaze, printed with patterns, and coated with protective glaze, are conveyed by belt to a roller kiln for firing. The firing temperature on both sides of the blank can be 1200-1220 °C, and the firing time can be 40-45 minutes. After firing, the ceramic tiles are ground at the edges; quality inspection and packaging are then carried out to obtain the finished product.

[0050] Preferably, the firing temperature is 1200-1208 °C. In this invention, the firing temperature is further controlled so that the firing temperature can be matched with the raw materials of each layer to achieve the best firing effect.

[0051] The limestone-resistant glazed ceramic tiles prepared by the above-mentioned method balance smoothness and roughness at the microscale, thereby achieving both high stain resistance and high anti-slip performance, and are highly similar to natural limestone.

[0052] The features and performance of the present invention will be further described in detail below with reference to embodiments. LOI represents loss on ignition. Oxides of elements such as C, N, S, and H are in a gaseous state under high-temperature conditions. Those skilled in the art should know that in the actual firing process, undetectable impurities may be present, resulting in the total weight of the raw material's chemical composition being less than 100%. Furthermore, because each oxide component is rounded to two decimal places, the sum of the percentages of various components may deviate slightly from 100%.

[0053] Example 1 This embodiment provides a method for preparing limestone-resistant glazed ceramic tiles, which includes the following steps: S1. Weigh the green body material according to the formula composition. The green body material formula composition includes the following by mass parts: the raw materials of the green body layer include: Dahe low temperature sand: 3 parts, Jiangshui sodium stone powder: 27 parts, Fengze ball clay: 18 parts, Jiefeng super white sand: 12 parts, Mingyuan high white sand: 27 parts, Jianxin potassium sodium sand: 7 parts, Hongnan bentonite: 4 parts, and selected talc 2 parts.

[0054] 100 parts of green body material were mixed with 40 parts of water, 0.2 parts of methylcellulose, and 0.3 parts of sodium tripolyphosphate, and ball-milled for 3 hours. The particle size distribution was: 1.0% of particles above 20 mesh, 50% of particles above 40 mesh, 85% of particles above 60 mesh, and 2.0% of particles below 100 mesh. The green body was pressed using a 30,000-ton System press at a pressure of 360 bar and a pressing cycle of 100.6 times / hour to obtain a ceramic tile green body with a thickness of 9 mm. The ceramic tile green body was then conveyed by belt to the No. 1 drying kiln for drying, ensuring that the temperature of the ceramic tile green body was 150 °C.

[0055] S2. Weigh the surface glaze according to the formula composition. The surface glaze composition, calculated by mass parts, includes: nepheline: 8 parts, potassium feldspar: 15 parts, dolomite: 7 parts, calcined clay: 10 parts, kaolin: 7.5 parts, zinc oxide: 0.5 parts, F2 frit: 4 parts, wollastonite: 1.5 parts, zirconium silicate: 14.5 parts, alumina: 9 parts, quartz: 17 parts, GB0306 frit: 6 parts.

[0056] The chemical composition of F2 ingot, calculated by mass percentage, includes: SiO2 38.31%, Al2O3 14.06%, Fe2O3 0.02%, TiO2 0.03%, CaO 1.05%, MgO 2.04%, K2O 2.42%, Na2O 3.12%, B2O3 0.15%, BaO 38.43%, SrO 0.20%, and LOI 0.05%. The chemical composition of GB0306 frit, calculated by mass percentage, includes: SiO2 41.51%, Al2O3 21.90%, Fe2O3 0.18%, TiO2 0.06%, CaO 5.29%, MgO 0.15%, K2O 4.59%, Na2O 17.93%, P2O5 0.32%, BaO 0.08%, SrO 0.02%, ZrO2 6.40%, and LOI 1.34%.

[0057] The chemical composition of the glaze, calculated by mass percentage, includes: SiO2 48.41%, Al2O3 23.32%, Fe2O3 0.24%, TiO2 0.14%, CaO 3.46%, MgO 1.62%, K2O 2.77%, Na2O 2.53%, ZrO2 9.78%, BaO 1.54%, SrO 0.09%, B2O3 0.06%, P2O5 0.19%, ZnO 0.50%, and LOI 5.09%.

[0058] 100 parts of glaze were mixed with 40 parts water, 0.2 parts methylcellulose, and 0.3 parts sodium tripolyphosphate. After ball milling for 6 hours, the mixture was passed through an 180-mesh sieve, with a residue of 0.6%. The mixture was then aged for 24 hours. The glaze was applied to the surface of the ceramic tile body using a glazing method, with a specific gravity of 1.5 g / cm³. 3 The glaze application rate is 240 g / m². 2 The ceramic tile blanks with the surface glaze applied are conveyed by belt to the No. 2 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0059] S3. Using a Keda inkjet printer, the printhead height can be adjusted to 11.5 mm to print the desired pattern on the surface of the glaze layer; the ceramic tile blanks with the glaze and printed patterns are conveyed by belt to the No. 3 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0060] S4. Weigh the protective glaze according to the formula. The protective glaze is made by weighing CBP5005Z slurry, G1099 slurry, and G1099 dry granules in a 1:1:1 ratio. The formula of CBP5005Z slurry, calculated by mass parts, includes: nepheline: 8.5 parts, potassium feldspar: 11.5 parts, sodium feldspar: 20 parts, dolomite: 12 parts, calcined kaolin: 7.5 parts, kaolin: 5.5 parts, barium carbonate: 9 parts, zinc oxide: 5 parts, F2 frit: 11 parts, and 38808 frit: 10 parts. The chemical composition of the 38808 frit, calculated as a percentage by mass, includes: SiO2 54.88%, Al2O3 20.21%, Fe2O3 0.08%, TiO2 0.04%, CaO 14.33%, MgO 0.44%, K2O 1.59%, Na2O 3.70%, B2O3 0.15%, BaO 0.20%, SrO 0.07%, ZnO 3.90%, ZrO2 0.03%, and LOI 0.04%. The chemical composition of CBP5005Z slurry, calculated by mass percentage, includes: SiO2 42.95%, Al2O3 16.54%, Fe2O3 0.24%, TiO2 0.11%, CaO 5.38%, MgO 2.68%, K2O 2.50%, Na2O 3.60%, B2O3 0.32%, BaO 11.17%, SrO 0.29%, ZnO 5.37%, ZrO2 0.03%, LOI 8.57%; The chemical composition of G1099 slurry and G1099 dry granules, calculated by mass percentage, includes: SiO2 52.16%, Al2O3 19.36%, Fe2O3 0.14%, TiO2 0.09%, CaO 5.87%, MgO 0.96%, K2O 2.70%, Na2O 2.26%, B2O3 0.04%, BaO 9.81%, SrO 1.66%, ZnO 3.32%, P2O5 0.11%, LOI 0.39%; The chemical composition of the protective glaze, calculated by mass percentage, includes: SiO2 49.09%, Al2O3 18.42%, Fe2O3 0.17%, TiO2 0.10%, CaO 5.71%, MgO 1.53%, K2O 2.63%, Na2O 2.71%, B2O3 0.13%, BaO 10.26%, SrO 1.20%, ZrO2 0.01%, ZnO 4.00%, P2O5 0.07%, LOI 3.12%; 100 parts of protective glaze were mixed with 40 parts water, 0.2 parts methylcellulose, and 0.3 parts sodium tripolyphosphate, ball-milled for 10 hours, and passed through a 325-mesh standard sieve, with a residue of 0.4%. The mixture was then aged for 48 hours. The protective glaze was then applied to the surface of the pattern layer using a spray glaze method, with a specific gravity of 1.30 g / cm³. 3 Glazing amount is 100 g / m 2 The ceramic tile blanks, which have been coated with surface glaze, printed with patterns, and coated with protective glaze, are conveyed by belt to the No. 4 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0061] S5. The ceramic tile blanks with applied surface glaze, printed patterns, and applied protective glaze are conveyed by belt to the roller kiln for firing. The firing temperature of the blanks on both sides is 1200-1208 °C, and the firing time is 42 min. The fired ceramic tiles are then ground at the edges. After quality inspection and packaging, the finished products are obtained.

[0062] Please see Figure 1 and Figure 2 ,from Figure 1 It can be seen that the surface of the limestone-resistant glazed ceramic tile provided in this embodiment is highly similar to that of natural limestone. From Figure 2 As can be seen, the glass matrix and multi-particle characteristics of the anti-lime stone glazed ceramic tile provided in this embodiment are a manifestation of this structure - the particle size is small (micrometer level) and uniformly distributed, the glass matrix is ​​continuous, and the smoothness and roughness are balanced at the microscale. This provides friction points and does not easily accumulate dirt like a rough surface, thus achieving both high stain resistance and high anti-slip performance.

[0063] Example 2 This embodiment provides a method for preparing limestone-resistant glazed ceramic tiles, which includes the following steps: S1. Weigh the green body material according to the formula composition. The green body material formula composition includes the following by mass parts: the raw materials of the green body layer include: Dahe low temperature sand: 2 parts, Jiangshui sodium stone powder: 25 parts, Fengze ball clay: 13 parts, Jiefeng super white sand: 16 parts, Mingyuan high white sand: 29 parts, Jianxin potassium sodium sand: 8 parts, Hongnan bentonite: 2 parts, and selected talc: 5 parts.

[0064] 100 parts of green body material were mixed with 35 parts water, 0.1 parts methylcellulose, and 0.2 parts sodium tripolyphosphate, and ball-milled for 2 hours. The particle size distribution was: 2.0% of particles above 20 mesh, 55% of particles above 40 mesh, 90% of particles above 60 mesh, and 1.0% of particles below 100 mesh. The green body was pressed using a 30,000-ton System press at a pressure of 350 bar and a pressing cycle of 92.6 times / hour to obtain a ceramic tile green body with a thickness of 12 mm. The ceramic tile green body was then conveyed by belt to the No. 1 drying kiln for drying, ensuring that the temperature of the ceramic tile green body was 150 °C.

[0065] S2. Weigh the surface glaze according to the formula composition. The surface glaze formula composition, calculated by mass parts, includes: nepheline: 9 parts, potassium feldspar: 14.5 parts, dolomite: 7 parts, calcined clay: 10 parts, kaolin: 9 parts, zinc oxide: 1 part, F2 frit: 5 parts, wollastonite: 2 parts, zirconium silicate: 14.5 parts, alumina: 7 parts, quartz: 17 parts, GB0306 frit: 4 parts.

[0066] The chemical composition of F2 ingot, calculated by mass percentage, includes: SiO2 41.43%, Al2O3 14.66%, Fe2O3 0.03%, TiO2 0.05%, CaO 1.24%, MgO 2.54%, K2O 2.55%, Na2O 3%, B2O3 0.20%, BaO 34.15%, SrO 0.10%, and LOI 0.05%.

[0067] The chemical composition of GB0306 ingot, calculated by mass percentage, includes: SiO2 43.69%, Al2O3 23.46%, Fe2O3 0.10%, TiO2 0.04%, CaO 3.96%, MgO 0.10%, K2O 3.69%, Na2O 18.22%, P2O5 0.25%, BaO 0.06%, SrO 0.01%, ZrO2 5.41%, and LOI 1.01%.

[0068] The chemical composition of the glaze, calculated by mass percentage, includes: SiO2 49.21%, Al2O3 21.87%, Fe2O3 0.25%, TiO2 0.13%, CaO 3.58%, MgO 1.68%, K2O 2.71%, Na2O 2.33%, BaO 1.71%, SrO 0.01%, B2O3 0.01%, P2O5 0.01%, ZnO 0.99%, ZrO2 9.61%, LOI 5.34%; 100 parts of glaze were mixed with 35 parts water, 0.2 parts methylcellulose, and 0.2 parts sodium tripolyphosphate. After ball milling for 4 hours, the mixture was passed through an 180-mesh sieve, with a residue of 0.9%. The mixture was then aged for 36 hours. The glaze was applied to the surface of the ceramic tile body using a glazing method, with a specific gravity of 1.45 g / cm³. 3 The glaze application rate is 220 g / m². 2 The ceramic tile blanks with the surface glaze applied are conveyed by belt to the No. 2 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0069] S3. Using a Keda inkjet printer, the printhead height can be adjusted to 12.5 mm to print the desired pattern on the surface of the glaze layer; the ceramic tile blanks with the glaze and printed patterns are conveyed by belt to the No. 3 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0070] S4. Weigh the protective glaze according to the formula. The protective glaze is made by weighing CBP5005Z slurry, G1099 slurry and G1099 dry granules in a ratio of 1:0.5:0.5.

[0071] The formulation of CBP5005Z slurry, calculated by mass parts, includes: nepheline: 6.5 parts, potassium feldspar: 10.5 parts, sodium feldspar: 23.5 parts, dolomite: 13 parts, calcined kaolin: 8 parts, kaolin: 6.5 parts, barium carbonate: 8 parts, zinc oxide: 4 parts, F2 frit: 10.5 parts, and 38808 frit: 9.5 parts. The chemical composition of the 38808 ingot, calculated as a percentage by mass, includes: SiO2 54.78%, Al2O3 17.26%, Fe2O3 0.09%, TiO2 0.05%, CaO 15.68%, MgO 0.52%, K2O 1.74%, Na2O 4.61%, B2O3 0.20%, BaO 0.3%, SrO 0.08%, ZnO 4.59%, ZrO2 0.04%, LOI 0.05%; The chemical composition of CBP5005Z slurry, calculated by mass percentage, includes: SiO2 44.65%, Al2O3 16.49%, Fe2O3 0.26%, TiO2 0.12%, CaO 5.63%, MgO 2.93%, K2O 2.34%, Na2O 3.69%, B2O3 0.40%, BaO 9.77%, SrO 0.18%, ZrO2 0.04%, ZnO 4.42%, LOI 8.81%; The chemical composition of G1099 slurry and G1099 dry granules, calculated by mass percentage, includes: SiO2 54.61%, Al2O3 20.55%, Fe2O3 0.11%, TiO2 0.05%, CaO 4.55%, MgO 0.50%, K2O 1.84%, Na2O 1.82%, B2O3 0.03%, BaO 10.64%, SrO 1.50%, ZnO 3.45%, P2O5 0.09%, and LOI 0.26%. The chemical composition of the protective glaze, calculated by mass percentage, includes: SiO2 49.63%, Al2O3 18.52%, Fe2O3 0.19%, TiO2 0.09%, CaO 5.09%, MgO 1.72%, K2O 2.09%, Na2O 2.76%, B2O3 0.22%, BaO 10.21%, SrO 0.84%, ZrO2 0.02%, ZnO 3.94%, P2O5 0.05%, and LOI 4.54%. 100 parts of protective glaze were mixed with 35 parts water, 0.2 parts methylcellulose, and 0.2 parts sodium tripolyphosphate, ball-milled for 10 hours, and passed through a 325-mesh standard sieve, with a residue of 0.4%. The mixture was then aged for 48 hours. The protective glaze was then applied to the surface of the pattern layer using a spray glaze method, with a specific gravity of 1.25 g / cm³. 3 Glazing amount is 90 g / m2 The ceramic tile blanks, which have been coated with surface glaze, printed with patterns, and coated with protective glaze, are conveyed by belt to the No. 4 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0072] S5. The ceramic tile blanks with applied surface glaze, printed patterns, and applied protective glaze are conveyed by belt to the roller kiln for firing. The firing temperature of the blanks on both sides is 1200-1208 °C, and the firing time is 42 min. The fired ceramic tiles are then ground at the edges. After quality inspection and packaging, the finished products are obtained.

[0073] Example 3 This embodiment provides a method for preparing limestone-resistant glazed ceramic tiles, which includes the following steps: S1. Weigh the green body material according to the formula composition. The green body material formula composition includes the following by mass parts: the raw materials of the green body layer include: Dahe low temperature sand: 5 parts, Jiangshui sodium stone powder: 29 parts, Fengze ball clay: 15 parts, Jiefeng super white sand: 14 parts, Mingyuan high white sand: 24 parts, Jianxin potassium sodium sand: 3 parts, Hongnan bentonite: 7 parts, and selected talc: 3 parts.

[0074] 100 parts of green body material were mixed with 50 parts of water, 0.3 parts of methylcellulose, and 0.4 parts of sodium tripolyphosphate, and ball-milled for 4 hours. The particle size distribution was: 0.5% of particles above 20 mesh, 45% of particles above 40 mesh, 80% of particles above 60 mesh, and 2.2% of particles below 100 mesh. The green body was pressed using a 30,000-ton System press at a pressure of 370 bar and a pressing cycle of 102.6 times / hour to obtain a ceramic tile green body with a thickness of 6 mm. The ceramic tile green body was then conveyed by belt to the No. 1 drying kiln for drying, ensuring that the temperature of the ceramic tile green body was maintained at 150 °C.

[0075] S2. Weigh the surface glaze according to the formula composition. The surface glaze composition, calculated by mass parts, includes: nepheline: 6.5 parts, potassium feldspar: 16 parts, dolomite: 9 parts, calcined clay: 8.5 parts, kaolin: 7.5 parts, zinc oxide: 1.5 parts, F2 frit: 4 parts, wollastonite: 2.5 parts, zirconium silicate: 14.5 parts, alumina: 8 parts, quartz: 17 parts, GB0306 frit: 5 parts.

[0076] The chemical composition of F2 ingot, calculated by mass percentage, includes: SiO2 38.79%, Al2O3 12.93%, Fe2O3 0.01%, TiO2 0.02%, CaO 0.56%, MgO 1.59%, K2O 2.52%, Na2O 2.76%, B2O3 0.10%, BaO 40.58%, SrO 0.10%, and LOI 0.04%.

[0077] The chemical composition of GB0306 frit, calculated by mass percentage, includes: SiO2 39.62%, Al2O3 18.87%, Fe2O3 0.20%, TiO2 0.07%, CaO 6.32%, MgO 0.20%, K2O 5.71%, Na2O 19.02%, P2O5 0.39%, BaO 0.09%, SrO 0.03%, ZrO2 7.98%, and LOI 1.50%.

[0078] The chemical composition of the glaze, calculated by mass percentage, includes: SiO2 47.57%, Al2O3 21.07%, Fe2O3 0.24%, TiO2 0.11%, CaO 4.21%, MgO 2.02%, K2O 2.81%, Na2O 2.21%, BaO 1.63%, SrO 0.55%, B2O3 0.04%, P2O5 0.20%, ZnO 1.49%, ZrO2 9.80%, LOI 6.02%; 100 parts of glaze were mixed with 45 parts water, 0.3 parts methylcellulose, and 0.4 parts sodium tripolyphosphate. After ball milling for 5 hours, the mixture was passed through an 180-mesh sieve, with a residue of 0.6%. The mixture was then aged for 48 hours. The glaze was applied to the surface of the ceramic tile body using a glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 260 g / m 2 The ceramic tile blanks with the surface glaze applied are conveyed by belt to the No. 2 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0079] S3. Using a Keda inkjet printer, the printhead height can be adjusted to 6.5 mm to print the desired pattern on the surface of the glaze layer; the ceramic tile blanks with the glaze and printed patterns are conveyed by belt to the No. 3 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0080] S4. Weigh the protective glaze according to the formula. The protective glaze is made by weighing CBP5005Z slurry, G1099 slurry and G1099 dry granules in a ratio of 1:1.5:1.5.

[0081] The formulation of CBP5005Z slurry, calculated by mass parts, includes: nepheline: 9 parts, potassium feldspar: 12.5 parts, sodium feldspar: 17.5 parts, dolomite: 11.5 parts, calcined kaolin: 5.5 parts, kaolin: 4.5 parts, barium carbonate: 10 parts, zinc oxide: 6 parts, F2 frit: 12 parts, and 38808 frit: 11.5 parts. The chemical composition of the 38808 ingot, calculated as a percentage by mass, includes: SiO2 54.68%, Al2O3 22.34%, Fe2O3 0.06%, TiO2 0.03%, CaO 14.35%, MgO 0.35%, K2O 1.02%, Na2O 4.42%, B2O3 0.10%, BaO 0.1%, SrO 0.05%, ZnO 2.45%, ZrO2 0.02%, LOI 0.03%; The chemical composition of CBP5005Z slurry, calculated by mass percentage, includes: SiO2 41.64%, Al2O3 15.85%, Fe2O3 0.22%, TiO2 0.09%, CaO 5.43%, MgO 2.54%, K2O 2.59%, Na2O 3.56%, B2O3 0.24%, BaO 12.57%, SrO 0.18%, ZrO2 0.02%, ZnO 6.25%, LOI 8.45%; The chemical composition of G1099 slurry and G1099 dry granules, calculated by mass percentage, includes: SiO2 52.32%, Al2O3 18.61%, Fe2O3 0.18%, TiO2 0.10%, CaO 6.78%, MgO 1.05%, K2O 3.15%, Na2O 3.26%, B2O3 0.05%, BaO 8.64%, SrO 1.86%, ZnO 3.40%, P2O5 0.15%, and LOI 0.45%. The chemical composition of the protective glaze, calculated by mass percentage, includes: SiO2 49.65%, Al2O3 17.92%, Fe2O3 0.19%, TiO2 0.10%, CaO 6.44%, MgO 1.42%, K2O 3.01%, Na2O 3.34%, B2O3 0.10%, BaO 9.62%, SrO 1.44%, ZrO2 0.01%, ZnO 4.11%, P2O5 0.11%, and LOI 2.45%. 100 parts of protective glaze were mixed with 45 parts water, 0.3 parts methylcellulose, and 0.4 parts sodium tripolyphosphate, ball-milled for 10 hours, and passed through a 325-mesh standard sieve, with a residue of 0.4%. The mixture was then aged for 48 hours. The protective glaze was then applied to the surface of the pattern layer using a spray glaze method, with a specific gravity of 1.35 g / cm³. 3 The glaze application rate is 110 g / m².2 The ceramic tile blanks, which have been coated with surface glaze, printed with patterns, and coated with protective glaze, are conveyed by belt to the No. 4 drying kiln for drying, ensuring that the temperature of the ceramic tile blanks is 150 °C.

[0082] S5. The ceramic tile blanks with applied surface glaze, printed patterns, and applied protective glaze are conveyed by belt to the roller kiln for firing. The firing temperature of the blanks on both sides is 1200-1208 °C, and the firing time is 42 min. The fired ceramic tiles are then ground at the edges. After quality inspection and packaging, the finished products are obtained.

[0083] Example 4 This embodiment is basically the same as Embodiment 1, except that the composition of the surface glaze layer, calculated by mass parts, includes: nepheline: 6.5 parts, potassium feldspar: 18 parts, dolomite: 7 parts, calcined clay: 8.5 parts, kaolin: 7.5 parts, zinc oxide: 1 part, F2 frit: 5 parts, wollastonite: 2 parts, zirconium silicate: 14.5 parts, alumina: 7 parts, quartz: 19 parts, GB0306 frit: 4 parts. The chemical composition of the glaze, calculated by mass percentage, includes: SiO2 50.62%, Al2O3 21.60%, Fe2O3 0.23%, TiO2 0.12%, CaO 3.51%, MgO 1.65%, K2O 2.96%, Na2O 2.06%, BaO 1.92%, SrO 0.11%, B2O3 0.01%, P2O5 0.01%, ZnO 1.00%, ZrO2 9.65%, and LOI 5.10%. The composition of the GB0306 frit is consistent with that of Example 1.

[0084] Example 5 The difference between this embodiment and Embodiment 1 is that the firing temperature of the upper and lower surfaces of the blank is changed to 1210-1220 °C.

[0085] Comparative Example 1 The difference between this comparative example and Example 1 is that G1099 dry particles were not added to the protective glaze. The chemical composition, calculated as a percentage by mass, includes: SiO2 47.56%, Al2O3 17.95%, Fe2O3 0.19%, TiO2 0.10%, CaO 5.63%, MgO 1.82%, K2O 2.60%, Na2O 2.93%, B2O3 0.18%, BaO 10.49%, SrO 0.98%, ZrO2 0.02%, ZnO 4.35%, P2O5 0.06%, and LOI 4.48%.

[0086] Comparative Example 2 The difference between this comparative example and Example 1 is that G1099 paste was not added to the protective glaze.

[0087] Comparative Example 3 The difference between this comparative example and Example 1 is that CBP5005Z paste was not added to the protective glaze.

[0088] Comparative Example 4 The difference between this comparative example and Example 1 is that G1099 slurry and G1099 dry granules were not added to the protective glaze.

[0089] Comparative Example 5 The difference between this comparative example and Example 1 is that in this comparative example, the mass ratio of CBP5005Z slurry, G1099 slurry, and G1099 dry granules is 1:2:1. The chemical composition, calculated as a percentage by mass, includes: SiO2 49.86%, Al2O3 18.66%, Fe2O3 0.17%, TiO2 0.10%, CaO 5.75%, MgO 1.39%, K2O 2.65%, Na2O 2.60%, B2O3 0.11%, ZrO2 0.01%, P2O5 0.08%, BaO 10.15%, ZnO 3.83%, SrO 1.32%, and LOI 2.46%.

[0090] Comparative Example 6 The difference between this comparative example and Example 1 is that the F2 frit and GB0306 frit in the glaze are omitted in this comparative example. In this case, the chemical composition of the glaze, by mass percentage, includes: SiO2 49.32%, Al2O3 23.83%, Fe2O3 0.26%, TiO2 0.15%, CaO 3.44%, MgO 1.69%, K2O 2.66%, Na2O 1.48%, ZrO2 10.44%, ZnO 0.55%, and LOI 5.57%.

[0091] Comparative Example 7 The difference between this comparative example and Example 1 is that the firing temperature of the upper and lower surfaces of the green body was changed to 1222-1230 °C.

[0092] Experimental Example The ceramic tiles provided in the above embodiments and comparative examples were subjected to stain resistance and slip resistance tests. The stain resistance performance of the ceramic tile glaze was tested according to GB / T3810.14-2016 "Ceramic Tiles Test Methods Part 14: Determination of Stain Resistance". At the same time, the slip resistance performance of the ceramic slab glaze was determined using an 89100 pendulum slip resistance tester according to GB / T37798-2019 "Evaluation of Slip Resistance Performance Grade of Ceramic Tiles".

[0093] The testing methods included: In the stain resistance test, standard pollutants such as light oil containing a green pollutant, 13g / L iodine tincture, and olive oil were used to contaminate the ceramic tile glaze. After 24 hours, the surface was cleaned, and the stain level was assessed according to a 5-level standard (Table 1). The slip resistance test used the pendulum method to determine the frictional resistance value (PTV) of the glaze surface in a wet state, and the level was also assessed according to a 5-level standard (Table 1). The results of all tests are summarized in Table 2.

[0094] Table 1. Grading Table for Stain Resistance and Slip Resistance

[0095] Table 2. Statistical table of test results for stain resistance and slip resistance levels of different examples

[0096] As can be seen from the table above, the anti-lime stone glazed ceramic tiles provided in the embodiments of the present invention all have good stain resistance and anti-slip properties.

[0097] In Comparative Examples 1-4, omitting certain raw materials of the protective glaze significantly reduced the anti-slip effect. Specifically, in Comparative Example 1, without the addition of G1099 dry granules, the stain resistance was high, but the anti-slip effect was low; in Comparative Example 2, without the addition of G1099 paste, the stain resistance was high, but the anti-slip effect was low; in Comparative Example 3, without the addition of CBP5005Z paste, the stain resistance was high, but the anti-slip effect was low; and in Comparative Example 4, without the addition of both G1099 paste and G1099 dry granules, the stain resistance was high, but the anti-slip effect was at its lowest. This demonstrates that these components cannot be arbitrarily omitted and that they have a synergistic effect. In Comparative Example 5, changing the ratio of CBP5005Z paste, G1099 paste, and G1099 dry granules in the protective glaze to 1:2:1 resulted in a higher anti-slip effect but a lower stain resistance; this proves that the proportions of these components are crucial. Comparative Example 6: When the F2 frit and GB0306 frit in the glaze were omitted, the stain resistance was lower, but the slip resistance was higher. Comparative Example 7: When the firing temperature was significantly increased, the stain resistance was higher, but the slip resistance was lower.

[0098] In summary, the preparation method of the anti-lime stone glazed ceramic tile provided by this invention limits the chemical composition of the surface glaze, the raw materials and chemical composition of the protective glaze, and the firing temperature. Among them, the surface glaze has a high content of SiO2 and Al2O3, which can form the glass phase skeleton of the glaze layer and ensure the basic density of the glaze surface; ZrO2 improves the chemical and thermal stability of the glaze, reduces high-temperature defects, and at the same time improves the hardness and impermeability of the glaze surface, effectively preventing dirt from penetrating; alkali metal oxides (K2O, Na2O) and alkaline earth metal oxides (CaO, MgO) act as fluxes, lowering the melting temperature, allowing the surface glaze to fully melt during firing and form a continuous and dense surface layer; the loss on ignition is low, and there are few residual volatile components after firing. The surface glaze substrate is relatively flat and dense, providing a uniform adhesion substrate for the protective glaze and avoiding dirt from penetrating and accumulating due to an excessively loose substrate. The protective glaze is a mixture of CBP5005Z slurry, G1099 slurry, and G1099 dry granules in a ratio of 1:0.5-1.5:0.5-1.5. This design aims to leverage the complementary strengths of the structure-controlled CBP5005Z slurry and the dense, stable G1099 slurry and dry granules. The CBP5005Z slurry is rich in BaO and ZnO, which act as strong fluxes, lowering the melting temperature of the protective glaze, promoting glass phase formation, and simultaneously reducing the surface energy of the glaze, thus decreasing the adhesion of contaminants. It has a high loss on ignition and contains a significant amount of high-temperature volatile / decomposed components. During firing, these volatile components release gases, forming micro-pits and phase-separated structures within the glaze layer, introducing a moderate roughness to the surface. Furthermore, during firing, the G1099 dry granules only partially melt or retain their granular shape, resulting in micron-level protrusions on the surface. The CBP5005Z and G1099 slurries melt to form a glass matrix that fills the gaps between particles, preventing dirt from accumulating. This provides friction points without the tendency for dirt to accumulate as easily as on a rough surface. Furthermore, the controlled firing temperature ensures that the dry particles in the protective glaze partially melt, maintaining their morphology and bonding firmly to the glass matrix, preventing particle detachment. These features balance smoothness and roughness at the microscale, achieving both high stain resistance and high slip resistance. The limestone-like glaze layer formed through the above-designed formulation of the surface glaze and protective glaze components possesses both slip and stain-resistant properties and is highly similar to natural limestone. This structure not only meets usage requirements but also overcomes the traditional trade-off between stain resistance and slip resistance, providing a new approach to the design of high-performance ceramic tile glazes.

[0099] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing limestone-resistant glazed ceramic tiles, characterized in that, It includes applying a surface glaze to the surface of the ceramic tile body layer to form a surface glaze layer, printing a pattern on the surface of the surface glaze layer to form an inkjet printing layer, applying a protective glaze to the surface of the inkjet printing layer to form a protective glaze layer, and then firing at 1200-1220°C. The protective glaze is composed of CBP5005Z slurry, G1099 slurry, and G1099 dry granules in a mass ratio of 1:0.5-1.5:0.5-1.

5. The chemical composition of the protective glaze layer, calculated as a percentage by mass, includes: SiO2 49.09-51.26%, Al2O3 16.52-19.77%, Fe2O3 0.11-0.20%, TiO2 0.05-0.15%, CaO 4.81-7.00%, MgO 0.92-1.72%, K2O 1.58-3.15%, Na2O 2.09-3.51%, B2O3 0.08-0.25%, BaO 8.85-10.26%, SrO 0.62-1.55%, ZrO2 0.01-0.06%, ZnO 3.29-4.11%, P2O5 0.03-0.15% and LOI 2.36-4.64%.

2. The method for preparing anti-lime stone glazed ceramic tiles according to claim 1, characterized in that, The firing temperature is 1200-1208 °C, and the firing time is 40-45 min; And / or, the mass ratio of the CBP5005Z slurry, the G1099 slurry, and the G1099 dry pellets is 1:0.8-1.2:0.8-1.

2.

3. The method for preparing anti-lime stone glazed ceramic tiles according to claim 1, characterized in that, The chemical composition of the CBP5005Z slurry, calculated by mass percentage, includes: SiO2 41.64-47.85%, Al2O3 14.35-18.21%, Fe2O3 0.10-0.35%, TiO2 0.05-0.15%, CaO 5.32-7.44%, MgO 1.76-3.05%, K2O 1.05-2.66%, Na2O 2.64-4.01%, B2O3 0.21-0.45%, BaO 9.27-12.88%, SrO 0.15-0.36%, ZnO 4.35-6.53%, ZrO2 0.01-0.05%, and LOI 7.69-9.72%. Preferably, the formulation of the CBP5005Z slurry, calculated by mass parts, includes: 6.5-9 parts nepheline, 10.5-12.5 parts potassium feldspar, 17.5-23.5 parts sodium feldspar, 11.5-13 parts dolomite, 5.5-8 parts calcined clay, 4.5-6.5 parts kaolin, 8-10 parts barium carbonate, 4-6 parts zinc oxide, 10.5-12.5 parts F2 frit, and 9.5-11.5 parts 38808 frit; Preferably, the chemical composition of the 38808 frit, calculated by mass percentage, includes: SiO2 52.68-54.88%, Al2O3 17.26-22.55%, Fe2O3 0.06-0.09%, TiO2 0.03-0.05%, CaO 12.35-15.68%, MgO 0.35-0.52%, K2O 1.02-1.74%, Na2O 2.45-4.61%, B2O3 0.10-0.20%, BaO 0.10-0.30%, SrO 0.05-0.08%, ZnO 2.45-4.59%, ZrO2 0.02-0.04%, and LOI 0.03-0.05%.

4. The method for preparing anti-lime stone glazed ceramic tiles according to claim 1, characterized in that, The chemical composition range of the G1099 slurry and the G1099 dry granules, calculated as a percentage by mass, includes: SiO2 50.32-54.61%, Al2O3 17.61-20.55%, Fe2O3 0.11-0.18%, TiO2 0.05-0.10%, CaO 4.55-6.78%, MgO 0.50-1.05%, K2O 1.84-3.15%, Na2O 1.82-3.26%, B2O3 0.03-0.05%, BaO 8.64-10.96%, SrO 1.50-1.86%, ZnO 2.66-3.86%, P2O5 0.09-0.15%, and LOI 0.26-0.45%.

5. The method for preparing anti-lime stone glazed ceramic tiles according to claim 1, characterized in that, The chemical composition of the glaze, by mass percentage, includes: SiO2 47.49-52.49%, Al2O3 21.34-24.18%, Fe2O3 0.22-0.25%, TiO2 0.10-0.14%, CaO 3.06-4.66%, MgO 1.51-2.05%, K2O 2.68-3.05%, Na2O 1.94-2.64%, ZrO2 9.59-10.81%, BaO 1.47-1.94%, SrO 0.01-0.58%, B2O3 0.01-0.08%, P2O5 0.01-0.25%, ZnO 0.46-1.50%, and LOI 4.86-6.25%. Preferably, the raw materials of the glaze, by mass parts, include: 6.5-9 parts nepheline, 14.5-19.5 parts potassium feldspar, 7-10 parts dolomite, 8.5-11 parts calcined clay, 7.5-9 parts kaolin, 0.5-1.5 parts zinc oxide, 4-6 parts F2 frit, 1.5-2.5 parts wollastonite, 14.5-20 parts zirconium silicate, 7-9 parts alumina, 17-20 parts quartz, and 4-6 parts GB0306 frit.

6. The method for preparing anti-lime stone glazed ceramic tiles according to claim 5, characterized in that, The chemical composition of the F2 frit, calculated by mass percentage, includes: SiO2 38.29-41.43%, Al2O3 12.48-14.66%, Fe2O3 0.01-0.03%, TiO2 0.02-0.05%, CaO 0.56-1.24%, MgO 1.54-2.56%, K2O 2.01-2.55%, Na2O 2.76-3.88%, B2O3 0.10-0.20%, BaO 34.15-40.58%, SrO 0.10-0.30%, and LOI 0.04-0.06%. And / or, the chemical composition of the GB0306 frit, calculated as a percentage by mass, includes: SiO2 39.26-43.69%, Al2O3 18.87-23.46%, Fe2O3 0.10-0.20%, TiO2 0.04-0.07%, CaO 3.96-6.32%, MgO 0.10-0.20%, K2O 3.69-5.71%, Na2O 15.59-19.02%, P2O5 0.25-0.39%, BaO 0.06-0.09%, SrO 0.01-0.03%, ZrO2 5.41-7.98%, and LOI 1.01-1.50%.

7. The limestone-resistant glazed ceramic tile according to claim 1, characterized in that, The ceramic brick body layer is made by mixing 100 parts of body material with 35-50 parts of water, 0.1-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after a first ball milling, and subsequently pressed and dried. Preferably, the raw materials of the billet material include, by mass fraction: 2-5 parts of low-temperature sand, 25-29 parts of sodium calcite powder, 13-18 parts of ball clay, 12-16 parts of ultra-white sand, 20-35 parts of high-white sand, 3-8 parts of potassium-sodium sand, 2-7 parts of bentonite, and 2-5 parts of talc. Preferably, the first ball milling time is 2-4 hours; Preferably, the particle size distribution after ball milling is as follows: ≤2.0% for particles larger than 20 mesh, 45%-55% for particles larger than 40 mesh, 80%-90% for particles larger than 60 mesh, and ≤2.2% for particles smaller than 100 mesh. Preferably, the pressing pressure is 350-370 bar, the pressing cycle is 92.6-102.6 times / h, and the thickness of the ceramic tile body layer after pressing is 6-12 mm.

8. The anti-lime stone glazed ceramic tile according to claim 1, characterized in that, The surface glaze layer is made by mixing 100 parts of the surface glaze material with 35-45 parts of water, 0.2-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after a second ball milling and after a first aging process. The mixture is then applied to the surface of the ceramic tile body layer and dried. Preferably, the second ball milling time is 4-6 hours, and the residue after passing through a 160-180 mesh sieve is 0.6%-0.9%. Preferably, the first aging time is 24-48 hours; Preferably, the specific gravity of the glaze slurry during glazing is 1.45-1.55 g / cm³. 3 The glaze application rate can be 220-260 g / m². 2 .

9. The anti-lime stone glazed ceramic tile according to claim 1, characterized in that, The protective glaze layer is made by mixing 100 parts of the protective glaze material with 35-45 parts of water, 0.2-0.3 parts of methylcellulose and 0.2-0.4 parts of sodium tripolyphosphate, which is then sieved after a third ball milling and a second aging process. The mixture is then sprayed onto the surface of the inkjet printing layer and dried. Preferably, the third ball milling time is 8-10 hours, and the material is passed through a 250-325 mesh sieve with a residue of 0.4-0.6%. Preferably, the second aging time is 24-48 hours; Preferably, the specific gravity of the glaze slurry during glazing is 1.25-1.35 g / cm³. 3 The glaze application rate is 90-110 g / m². 2 .

10. A type of limestone-resistant glazed ceramic tile, characterized in that, It is prepared using the method for preparing anti-lime stone glazed ceramic tiles as described in any one of claims 1-9.

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