A ceramic tile imitating the surface relief texture of a mushroom stone and a preparation method thereof

Abstract

The present application relates to the technical field of ceramics, and discloses a ceramic tile with a mushroom stone surface relief texture and a preparation method thereof. The ceramic tile with a mushroom stone surface relief texture comprises a tile blank layer and a composite glaze layer arranged above the tile blank layer. The chemical composition of the tile blank layer, by mass percentage, comprises SiO2 71.5-72.5%, Al2O3 16.0-16.5%, K2O 3.0-3.3%, Na2O 1.8-2.0%, MgO 1.2-1.4%, CaO 0.4-0.6%, Fe2O3 0.8-0.9%, and TiO2 0.2-0.3%. By optimizing the amounts of SiO2, Al2O3, K2O, Na2O and MgO in the tile blank layer, the tile blank layer can form a network of mullite-cordierite interwoven crystal phases during the firing of the ceramic tile, greatly improving the high-temperature bending strength of the tile blank layer. Meanwhile, the density and high-temperature deformation resistance of the tile blank layer can be balanced, so that the tile blank layer, especially the irregular tile blank layer, is less likely to warp, deform or collapse during high-temperature firing, ensuring that the surface of the tile blank layer can be finely textured, and the ceramic tile can have low water absorption and high strength.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to a ceramic brick with a mushroom-stone-like surface texture and its preparation method. Background Technology

[0002] Natural mushroom stone, as a classic architectural decorative stone, is widely used in exterior wall cladding, landscape walls, and courtyard paving due to its unique texture and natural feel. However, natural mushroom stone has significant industry drawbacks: high resource and environmental costs, requiring quarrying that damages mountain vegetation and ecological balance, and generating large amounts of dust and waste during extraction. Therefore, in recent years, the demand for environmentally friendly imitation stone materials (such as ceramic tiles) in the architectural decoration industry has continued to increase.

[0003] However, the mainstream technology for imitation stone ceramic tiles is still concentrated in the field of planar inkjet printing, while three-dimensional imitation stone ceramic tile products are in the early stages of development. Existing technologies mainly suffer from the following shortcomings: First, the technology for irregularly shaped body formulations is immature, easily leading to warping, deformation, and collapse of fine lines during high-temperature firing, making it difficult to achieve fine texture formation; second, the decorative effect relies on a combination of molds and printing, resulting in stiff, repetitive textures that cannot simulate the natural mottled feel and contrast of natural mushroom stone; third, matte glaze texture and performance are mutually exclusive, with low-gloss glazes generally exhibiting poor stain resistance, low hardness, and susceptibility to scratches; fourth, the adhesion between the body and glaze is poor, easily resulting in glaze peeling and detachment defects at irregularly shaped edges and corners. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a ceramic tile with a mushroom-stone-like surface texture and its preparation method, which aims to solve the problem that irregularly shaped blanks are prone to warping, deformation, and collapse of fine lines during high-temperature firing, making it difficult to achieve fine texture forming.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: The first aspect of this invention provides a ceramic tile with an undulating texture resembling mushroom stone, comprising a tile body layer and a composite glaze layer disposed above the tile body layer; the chemical composition of the tile body layer, by mass percentage, includes: SiO2 71.5-72.5%, Al2O3 16.0-16.5%, K2O 3.0-3.3%, Na2O 1.8-2.0%, MgO 1.2-1.4%, CaO 0.4-0.6%, Fe2O3 0.8-0.9%, TiO2 0.2-0.3%, with the remainder being loss on ignition and impurities.

[0006] In the ceramic tile with the undulating texture of the mushroom stone surface, the composite glaze layer includes a base glaze layer and a top glaze layer; the raw materials for preparing the base glaze layer include basic glaze and colorant, and the high-temperature viscosity of the base glaze layer is lower than that of the top glaze layer.

[0007] In the ceramic tile with the undulating texture of the imitation mushroom stone surface, the raw materials for preparing the base glaze, by weight, include: 33-37 parts of potassium feldspar, 10-14 parts of sodium feldspar, 21-25 parts of calcite, 7-9 parts of calcined talc, 6-8 parts of calcined zinc oxide, 4-6 parts of zirconium silicate, and 9-11 parts of black mud powder.

[0008] In the ceramic tile with the undulating texture of the imitation mushroom stone surface, the colorant includes at least one of cobalt black material, reddish-brown material, zirconium iron red material, electrolytic manganese, and iron oxide.

[0009] In the ceramic tile with the undulating texture of the mushroom stone surface, the raw materials for preparing the glaze layer, by weight, include: 18-22 parts potassium feldspar, 23-27 parts calcite, 11-15 parts quartz, 4-6 parts calcined zinc oxide, 9-11 parts titanium dioxide, 4-6 parts black mud powder, 11-13 parts high-silicon and high-titanium frit, and 9-11 parts zirconium silicate.

[0010] The ceramic brick with the undulating texture of the mushroom stone surface, by mass percentage, contains the following chemical composition of the high-silicon and high-titanium frit: SiO2 51-53%, Al2O3 6-8%, TiO2 13-15%, CaO 14-16%, K2O 3-5%, Na2O 2-4%, B2O3 2-4%, P2O5 0.4-0.6%, with the remainder being loss on ignition and impurities.

[0011] A second aspect of this invention provides a method for preparing ceramic tiles with the above-described mushroom-stone surface texture, comprising the following steps: S01. Weigh the raw materials for the brick blank layer according to the proportion, mix the raw materials and place them in a press to press them into brick blank layers; S02. The raw materials for preparing the composite glaze layer are put into a ball mill according to the ratio, mixed with water and ball milled to obtain the base glaze slurry and the top glaze slurry respectively. S03. Apply the base glaze slurry to the surface of the brick body to form a base glaze layer; S04. Apply a top glaze slurry onto the base glaze layer to form a top glaze layer; S05. Firing to obtain ceramic bricks with the undulating texture of the mushroom stone surface.

[0012] In the preparation method described above, in step S03, the specific gravity of the base glaze slurry is 1.52–1.54 g / cm³. 3 The application rate of the base glaze slurry is 6.08–6.94 g / dm³. 2 .

[0013] In the preparation method described above, in step S04, the specific gravity of the glaze slurry is 1.64–1.66 g / cm³.3 The application rate of the surface glaze slurry is 10.85–11.72 g / dm³. 2 .

[0014] In the preparation method described above, in step S05, the highest firing temperature is 1200-1250℃, and the firing cycle is 38-42 minutes.

[0015] Beneficial effects: The first aspect of this invention provides a ceramic tile with a mushroom-like surface texture. By optimizing the amount of SiO2, Al2O3, K2O, Na2O, and MgO in the tile body layer, a mullite-cordierite interwoven crystalline phase network can be constructed in the tile body layer during the ceramic tile firing process. This significantly improves the high-temperature flexural strength of the tile body layer. At the same time, the density and high-temperature deformation resistance of the tile body layer can be balanced, making it less prone to warping, deformation, and collapse of fine lines during high-temperature firing, especially for irregularly shaped tile body layers. This ensures that the surface of the tile body layer can achieve fine texture formation, and the ceramic tile can achieve low water absorption and high strength.

[0016] In addition, by introducing TiO2 into the brick body layer, TiO2 and MgO are combined to form a composite nucleating agent and serve as heterogeneous nucleation sites, which can inhibit excessive crystal growth in the brick body layer, refine the grains in the brick body layer, and greatly improve the toughness of the brick body layer. The finished ceramic tiles have excellent thermal stability and are not prone to cracking or breakage after long-term use.

[0017] The second aspect of this invention provides a method for preparing ceramic tiles with a mushroom-stone-like surface texture. The preparation method can be implemented on a large scale using existing ceramic tile production lines, and the process is highly stable, making it easy to promote industrialization and mass production. It can efficiently prepare imitation stone ceramic tiles with a mushroom-stone-like surface texture. Attached Figure Description

[0018] Figure 1 This is a flowchart of the method for preparing ceramic tiles with an imitation mushroom stone surface texture provided by the present invention.

[0019] Figure 2 This is a brick surface image of the ceramic tile with the undulating texture of mushroom stone as described in Example 1.

[0020] Figure 3 This is a brick surface image of the ceramic tile with the undulating texture of mushroom stone as described in Example 2.

[0021] Figure 4 This is a brick surface image of the ceramic tile with the undulating texture of mushroom stone as described in Example 3.

[0022] Figure 5 This is a picture of the ceramic tile with the undulating texture of a mushroom stone surface, as shown in Comparative Example 1.

[0023] Figure 6 This is a picture of the ceramic tile with the undulating texture of mushroom stone surface, shown in Comparative Example 4.

[0024] Figure 7 This is a picture of the ceramic tile with the undulating texture of a mushroom stone surface, shown in Comparative Example 5.

[0025] Figure 8 This is a picture of the ceramic tile with the undulating texture of a mushroom stone surface, shown in Comparative Example 6.

[0026] Figure 9 This is a picture of the ceramic tile with the undulating texture of a mushroom stone surface, shown in Comparative Example 7.

[0027] Figure 10 This is a picture of the ceramic tile with the undulating texture of a mushroom stone surface, shown in Comparative Example 8. Detailed Implementation

[0028] This invention provides a ceramic tile with a mushroom-stone-like surface texture and its preparation method. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0029] like Figures 2 to 4 As shown, the first aspect of the present invention provides a ceramic tile with an undulating texture resembling mushroom stone, comprising a tile body layer and a composite glaze layer disposed above the tile body layer. The chemical composition of the tile body layer, by mass percentage, includes: SiO2 71.5–72.5%, Al2O3 16.0–16.5%, K2O 3.0–3.3%, Na2O 1.8–2.0%, MgO 1.2–1.4%, CaO 0.4–0.6%, Fe2O3 0.8–0.9%, TiO2 0.2–0.3%, with the remainder being loss on ignition and impurities.

[0030] By optimizing the Al / Si ratio in the chemical composition of the brick blank layer, the high-temperature flexural strength of the brick blank layer can be improved. SiO2, as the main refractory component of the brick blank layer, can form a silicon-oxygen network at high temperatures, improving the high-temperature structural strength of the brick blank layer and resisting softening and collapse during firing. The reaction of Al2O3 and SiO2 can generate needle-like mullite, improving the high-temperature flexural strength of the brick blank layer and inhibiting warping, deformation, and fine line collapse. MgO can synergistically generate cordierite with SiO2 and Al2O3, enabling the construction of a mullite-cordierite interwoven crystalline phase network in the brick blank layer, significantly improving the high-temperature flexural strength of the brick blank layer. This makes the brick blank layer, especially irregularly shaped brick blank layers, less prone to warping, deformation, and fine line collapse during high-temperature firing (deformation rate ≤0.1%), ensuring that the surface of the brick blank layer can achieve fine (minimum line width 0.5mm) texture formation.

[0031] In order to balance the density and high-temperature deformation resistance of the brick blank layer, so that the fired ceramic bricks can achieve low water absorption and high strength, while avoiding warping, deformation, and collapse of texture lines, the chemical composition of the brick blank layer is optimized. The content of glass phase in the brick blank layer can be controlled at 25-30 wt%, thereby taking into account the sintering density and high-temperature rigidity of the brick blank layer, and effectively suppressing the warping of the brick blank layer and the collapse of fine textures.

[0032] Furthermore, the collapse of fine textures in ceramic tiles can be reduced by improving the toughness of the brick blank layer and decreasing the internal stress within it. To enhance the toughness of the brick blank layer, this invention introduces TiO2 into it. During the firing process, TiO2 acts as a heterogeneous nucleation site, resulting in fine and uniform mullite and cordierite crystals in the brick blank layer. This avoids the brittleness and stress concentration caused by coarse crystals, thus improving the toughness of the brick blank layer. In addition, the combination of TiO2 and MgO forms a composite nucleating agent, further inhibiting the formation of coarse mullite crystals and refining the grains in the brick blank layer, significantly improving its toughness.

[0033] The realization of fine textures in imitation stone ceramic tiles is not only related to the high-temperature deformation resistance of the tile body, but also to the properties of the glaze. Therefore, in order to simulate the natural mottled texture and contrast of natural mushroom stone, in a preferred embodiment, the composite glaze layer includes a base glaze layer and a top glaze layer disposed on the base glaze layer. The raw materials for preparing the base glaze layer include basic glaze and colorant, and the high-temperature viscosity of the base glaze layer is lower than that of the top glaze layer.

[0034] This invention utilizes the viscosity difference between the base glaze layer and the top glaze layer. During the high-temperature holding stage of ceramic tile firing, the gas generated by the decomposition of raw materials in the base glaze layer can create internal pressure within the closed base glaze system. This pressure forces the low-viscosity base glaze to penetrate the weak areas of the semi-solid top glaze layer (which has a higher viscosity). Because colorants are added to the raw materials used in the preparation of the base glaze layer, after the base glaze penetrates the top glaze layer, it can form uniform color spots (such as...) within the top glaze layer. Figure 2 (As shown). Furthermore, by utilizing a textured molding die, this invention creates uneven areas on the surface of the brick blank, resulting in natural differences in the thickness of the composite glaze layer in these areas. Therefore, when the base glaze breaks through the top glaze layer, a natural three-dimensional contrast in depth is formed on the glaze surface. Simultaneously, the composite glaze layer at the edge of the brick blank is the thinnest and most uniformly transitioned, making it easier for the base glaze to break through and forming a soft and natural border of the same color. This allows the fired ceramic tiles to highly reproduce the original texture of natural mushroom stone with its mottled and three-dimensional appearance, eliminating the need for additional decorative processes such as inkjet printing and dry granulation. This simplifies the production process and improves the naturalness of the product's appearance and production efficiency.

[0035] In order to make the high-temperature viscosity of the base glaze layer lower than that of the top glaze layer, in a preferred embodiment, the raw materials for preparing the base glaze, by weight, include: 33-37 parts of potassium feldspar, 10-14 parts of sodium feldspar, 21-25 parts of calcite, 7-9 parts of calcined talc, 6-8 parts of calcined zinc oxide, 4-6 parts of zirconium silicate, and 9-11 parts of black mud powder.

[0036] In the raw materials for preparing the basic glaze described above, a high amount of potassium feldspar can lower the melting temperature and high-temperature viscosity of the glaze. Furthermore, potassium feldspar, in combination with sodium feldspar, synergistically weakens the high-temperature rigidity of the base glaze layer, laying the foundation for a low-viscosity base glaze layer. It also forms a stable glassy phase, preventing irregular flow of the glaze. Calcite decomposes at high temperatures to generate CaO, a network modifier that further disrupts the silicon-oxygen framework of the glaze, helping to reduce the viscosity of the base glaze melt. In addition, the CaO generated from calcite decomposition diffuses with the aluminum-silicon components in the brick body and base glaze layer, forming a calcium feldspar-mullite composite intermediate layer at the body-glaze interface. This smooths the thermal expansion difference between the body and glaze, alleviating firing thermal stress, thereby improving the body-glaze bonding performance at the uneven edges of irregularly shaped ceramic tiles and reducing glaze peeling defects. Simultaneously, the CO2 gas generated from calcite decomposition creates internal pressure within the closed base glaze system, pushing the low-viscosity base glaze through the weak areas of the semi-solid surface glaze layer, thus forming uniform color spots.

[0037] For example, the colorant may include at least one of cobalt black, reddish-brown, zirconium iron red, electrolytic manganese, and iron oxide. This invention adds the colorant to the base glaze, allowing it to dissolve in the glassy phase of the base glaze or precipitate stable colored microcrystals during the ceramic tile firing process. The outer glaze layer then forms a dense protective barrier, isolating it from ultraviolet radiation, moisture, and acid / alkali corrosion, significantly improving the product's outdoor weather resistance and color retention.

[0038] To address the challenge of simultaneously achieving both a matte finish and superior performance, and to ensure that the high-temperature viscosity of the top glaze layer is greater than that of the base glaze layer, in a preferred embodiment, the raw materials for preparing the top glaze layer, by weight, include: 18-22 parts potassium feldspar, 23-27 parts calcite, 11-15 parts quartz, 4-6 parts calcined zinc oxide, 9-11 parts titanium dioxide, 4-6 parts black mud powder, 11-13 parts high-silicon, high-titanium frit, and 9-11 parts zirconium silicate.

[0039] Compared to the raw materials used in the base glaze layer, the total amount of feldspar (potassium feldspar) in the preparation of the top glaze layer is significantly reduced. This reduces the network-breaking effect of alkali metals, prevents the glaze melt viscosity from being too low, and ensures that the high-temperature viscosity of the top glaze layer is much higher than that of the base glaze layer. Titanium dioxide and high-silicon, high-titanium frit can introduce TiO2 into the top glaze layer. During the firing process of ceramic tiles, TiO2 can precipitate anatase and rutile microcrystals in the top glaze layer, forming a refractive index difference with the glass phase, thereby stably achieving a low-gloss matte effect of 5-10°. Calcined zinc oxide can participate in the TiO2-ZnO-ZrSiO4 multiphase nucleation system in the top glaze layer, promoting the precipitation of zinc spinel microcrystals, forming a diffuse reflection effect, creating a delicate matte texture, and ZnO can improve the sintering density of the glaze, enhancing the wear resistance and stain resistance of the top glaze layer. Zirconium silicate can improve the hardness, wear resistance, and acid and alkali resistance of the top glaze layer.

[0040] As an example, the chemical composition of the high-silicon and high-titanium fused block, by mass percentage, includes: SiO2 51-53%, Al2O3 6-8%, TiO2 13-15%, CaO 14-16%, K2O 3-5%, Na2O 2-4%, B2O3 2-4%, P2O5 0.4-0.6%, with the remainder being loss on ignition and impurities.

[0041] like Figure 1 As shown, a second aspect of the present invention provides a method for preparing ceramic tiles with the above-described mushroom-stone surface texture, comprising the following steps: S01. Weigh the raw materials for the brick blank layer according to the proportion, mix the raw materials and place them in a press and press them into brick blank layers through a textured mold. S02. The raw materials for preparing the composite glaze layer are put into a ball mill according to the ratio, mixed with water and ball milled to obtain the base glaze slurry and the top glaze slurry respectively. S03. Apply the base glaze slurry to the surface of the brick body to form a base glaze layer. The spraying pressure is 0.3 to 0.5 MPa. S04. Spray the top glaze slurry onto the base glaze layer to form the top glaze layer. The spraying pressure is 0.3 to 0.5 MPa. S05. Firing to obtain ceramic bricks with the undulating texture of the mushroom stone surface.

[0042] The preparation method described above can be implemented on a large scale using existing ceramic tile production lines. It has strong process stability, is easy to promote industrialization and mass production, and can efficiently produce imitation stone ceramic tiles with the undulating texture of mushroom stone surface.

[0043] To ensure a uniform thickness of the composite glaze layer on the brick body and a stable final ceramic tile texture, in a preferred embodiment, the specific gravity of the base glaze slurry is 1.52–1.54 g / cm³. 3 The application rate of the base glaze slurry is 6.08–6.94 g / dm³. 2 In step S04, the specific gravity of the glaze slurry is 1.64–1.66 g / cm³. 3 The application rate of the surface glaze slurry is 10.85–11.72 g / dm³. 2 .

[0044] In the preparation method described above, in step S05, the maximum firing temperature is 1200–1250℃, and the firing cycle is 38–42 minutes. When the maximum firing temperature is between 1200 and 1250℃, the densification process of the brick body is sufficient, the mullite and cordierite crystalline phases precipitate normally, and the high-temperature viscosity gradient between the base glaze layer and the top glaze layer is suitable, resulting in a stable texture formation state.

[0045] The present invention will be further illustrated by the following examples and comparative examples.

[0046] Example 1 This embodiment provides a ceramic tile with a mushroom-stone-like surface texture, comprising a tile body layer and a composite glaze layer disposed above the tile body layer; wherein, by mass percentage, the chemical composition of the tile body layer includes: SiO2 72.04%, Al2O3 16.26%, K2O 3.0%, Na2O 1.8%, MgO 1.285%, CaO 0.4%, Fe2O3 0.8%, TiO2 0.259%, and loss on ignition and impurities 4.156%.

[0047] The composite glaze layer comprises a base glaze layer and a top glaze layer. The base glaze layer is prepared from raw materials including a basic glaze and a colorant. By weight, the basic glaze comprises: 35 parts potassium feldspar, 12 parts sodium feldspar, 23 parts calcite, 8 parts calcined talc, 7 parts calcined zinc oxide, 5 parts zirconium silicate, and 10 parts black mud powder, with an additional 1 part colorant. The colorant includes cobalt black, reddish-brown, and zirconium iron red pigments. The mass ratio of cobalt black, reddish-brown, and zirconium iron red pigments is 5:2:3.

[0048] The raw materials for preparing the glaze layer, by weight, include: 20 parts potassium feldspar, 25 parts calcite, 13 parts quartz, 5 parts calcined zinc oxide, 10 parts titanium dioxide, 5 parts black mud powder, 12 parts high-silicon and high-titanium frit, and 10 parts zirconium silicate.

[0049] The chemical composition of the high-silicon and high-titanium molten metal, by mass percentage, includes: 51% SiO2, 36% Al2O3, 13% TiO2, 14% CaO, 3% K2O, 2% Na2O, 32% B2O, 0.4% P2O5, and 8.6% loss on ignition and impurities.

[0050] This embodiment also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, including the following steps: S01. Weigh the raw materials for the brick blank layer according to the proportion, mix the raw materials and place them in a press to press them into brick blank layers; S02. The raw materials for preparing the composite glaze layer are put into a ball mill according to the ratio, mixed with water and ball milled to obtain the base glaze slurry and the top glaze slurry respectively. S03. Apply the base glaze slurry to the surface of the brick body to form a base glaze layer; S04. Apply a top glaze slurry onto the base glaze layer to form a top glaze layer; S05. Firing to obtain ceramic bricks with the undulating texture of the mushroom stone surface.

[0051] In step S03, the specific gravity of the base glaze slurry is 1.53 g / cm³. 3 The application rate of the base glaze slurry is 6.08 g / dm³. 2 .

[0052] In step S04, the specific gravity of the glaze slurry is 1.65 g / cm³. 3 The application rate of the surface glaze slurry is 10.85 g / dm². 2 .

[0053] In step S05, the maximum firing temperature is 1200℃ (the maximum temperature is held for 10 minutes), and the firing cycle is 40 minutes.

[0054] Example 2 This embodiment provides a ceramic tile with a mushroom-stone-like surface texture, comprising a tile body layer and a composite glaze layer disposed above the tile body layer; wherein, by mass percentage, the chemical composition of the tile body layer includes: SiO2 71.5%, Al2O3 16.0%, K2O 3.3%, Na2O 1.9%, MgO 1.3%, CaO 0.5%, Fe2O3 0.9%, TiO2 0.2%, loss on ignition and impurities 4.4%.

[0055] The composite glaze layer includes a base glaze layer and a top glaze layer. The base glaze layer is prepared from base glaze materials and colorants. By weight, the base glaze materials include: 33 parts potassium feldspar, 10 parts sodium feldspar, 21 parts calcite, 7 parts calcined talc, 6 parts calcined zinc oxide, 4 parts zirconium silicate, and 9 parts black mud powder, with an additional 1.5 parts of colorant. The colorants include cobalt black, reddish-brown, zirconium iron red, and electrolytic manganese. The mass ratio of cobalt black, reddish-brown, zirconium iron red, and electrolytic manganese is 6:2:3:4.

[0056] The raw materials for preparing the glaze layer, by weight, include: 18 parts potassium feldspar, 23 parts calcite, 11 parts quartz, 4 parts calcined zinc oxide, 9 parts titanium dioxide, 4 parts black mud powder, 11 parts high-silicon and high-titanium frit, and 9 parts zirconium silicate.

[0057] The chemical composition of the high-silicon and high-titanium molten metal, by mass percentage, includes: 51% SiO2, 36% Al2O3, 13% TiO2, 14% CaO, 3% K2O, 2% Na2O, 32% B2O, 0.4% P2O5, and 8.6% loss on ignition and impurities.

[0058] This embodiment also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, including the following steps: S01. Weigh the raw materials for the brick blank layer according to the proportion, mix the raw materials and place them in a press to press them into brick blank layers; S02. The raw materials for preparing the composite glaze layer are put into a ball mill according to the ratio, mixed with water and ball milled to obtain the base glaze slurry and the top glaze slurry respectively. S03. Apply the base glaze slurry to the surface of the brick body to form a base glaze layer; S04. Apply a top glaze slurry onto the base glaze layer to form a top glaze layer; S05. Firing to obtain ceramic bricks with the undulating texture of the mushroom stone surface.

[0059] In step S03, the specific gravity of the base glaze slurry is 1.54 g / cm³. 3 The application rate of the base glaze slurry is 6.08 g / dm³. 2 .

[0060] In step S04, the specific gravity of the glaze slurry is 1.66 g / cm³. 3 The application rate of the surface glaze slurry is 10.85 g / dm². 2 .

[0061] In step S05, the maximum firing temperature is 1200℃ (the maximum temperature is held for 12 minutes), and the firing cycle is 38 minutes.

[0062] Example 3 This embodiment provides a ceramic tile with a mushroom-stone-like surface texture, comprising a tile body layer and a composite glaze layer disposed above the tile body layer; wherein, by mass percentage, the chemical composition of the tile body layer includes: SiO2 72.5%, Al2O3 16.5%, K2O 3.1%, Na2O 2.0%, MgO 1.4%, CaO 0.6%, Fe2O3 0.8%, TiO2 0.3%, loss on ignition and impurities 2.8%.

[0063] The composite glaze layer includes a base glaze layer and a top glaze layer. The base glaze layer is prepared from base glaze materials and colorants. By weight, the base glaze materials include: 37 parts potassium feldspar, 14 parts sodium feldspar, 25 parts calcite, 9 parts calcined talc, 8 parts calcined zinc oxide, 6 parts zirconium silicate, and 11 parts black mud powder, with an additional 2.2 parts of colorant. The colorant includes cobalt black pigment, zirconium iron red pigment, electrolytic manganese, and iron oxide. The mass ratio of cobalt black pigment, zirconium iron red pigment, electrolytic manganese, and iron oxide is 6:3:5:8.

[0064] The raw materials for preparing the glaze layer, by weight, include: 22 parts potassium feldspar, 27 parts calcite, 15 parts quartz, 6 parts calcined zinc oxide, 11 parts titanium dioxide, 6 parts black mud powder, 13 parts high-silicon and high-titanium frit, and 11 parts zirconium silicate.

[0065] The chemical composition of the high-silicon and high-titanium molten metal, by mass percentage, includes: 51% SiO2, 36% Al2O3, 13% TiO2, 14% CaO, 3% K2O, 2% Na2O, 32% B2O, 0.4% P2O5, and 8.6% loss on ignition and impurities.

[0066] This embodiment also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, including the following steps: S01. Weigh the raw materials for the brick blank layer according to the proportion, mix the raw materials and place them in a press to press them into brick blank layers; S02. The raw materials for preparing the composite glaze layer are put into a ball mill according to the ratio, mixed with water and ball milled to obtain the base glaze slurry and the top glaze slurry respectively. S03. Apply the base glaze slurry to the surface of the brick body to form a base glaze layer; S04. Apply a top glaze slurry onto the base glaze layer to form a top glaze layer; S05. Firing to obtain ceramic bricks with the undulating texture of the mushroom stone surface.

[0067] In step S03, the specific gravity of the base glaze slurry is 1.52 g / cm³. 3 The application rate of the base glaze slurry is 6.94 g / dm³. 2 .

[0068] In step S04, the specific gravity of the glaze slurry is 1.64 g / cm³. 3 The application rate of the surface glaze slurry is 11.72 g / dm². 2 .

[0069] In step S05, the maximum firing temperature is 1250℃ (the maximum temperature is held for 8 minutes), and the firing cycle is 38 minutes.

[0070] Comparative Example 1 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture, differing from Example 1 only in the chemical composition of the tile body layer. By mass percentage, the chemical composition of the tile body layer includes: SiO2 73.8%, Al2O3 14.5%, K2O 3.0%, Na2O 1.8%, MgO 1.285%, CaO 0.4%, Fe2O3 0.8%, TiO2 0.259%, with a loss on ignition and impurities of 4.156%.

[0071] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, which is the same as the method provided in Example 1.

[0072] Comparative Example 2 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture, differing from Example 1 only in the chemical composition of the tile body layer. By mass percentage, the chemical composition of the tile body layer includes: SiO2 72.04%, Al2O3 16.26%, K2O 3.259%, Na2O 1.8%, MgO 1.285%, CaO 0.4%, Fe2O3 0.8%, with a loss on ignition and impurities of 4.156%.

[0073] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, which is the same as the method provided in Example 1.

[0074] Comparative Example 3 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture. The only difference between this example and Example 1 is the chemical composition of the tile body layer. By mass percentage, the chemical composition of the tile body layer includes: SiO2 72.04%, Al2O3 16.26%, K2O 2.0%, Na2O 2.8%, MgO 1.285%, CaO 0.4%, Fe2O3 0.8%, TiO2 0.259%, and loss on ignition and impurities 4.156%.

[0075] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, which is the same as the method provided in Example 1.

[0076] Comparative Example 4 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture. The only difference from Example 1 is that the raw materials for preparing the base glaze are different in the base glaze layer. By weight, the raw materials for preparing the base glaze include: 35 parts potassium feldspar, 12 parts sodium feldspar, 28 parts calcite, 8 parts calcined talc, 7 parts calcined zinc oxide, 5 parts zirconium silicate, and 10 parts black mud powder.

[0077] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, which is the same as the method provided in Example 1.

[0078] Comparative Example 5 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture. The only difference from Example 1 is that the raw materials for preparing the base glaze are different in the base glaze layer. By weight, the raw materials for preparing the base glaze include: 35 parts potassium feldspar, 12 parts sodium feldspar, 18 parts calcite, 8 parts calcined talc, 7 parts calcined zinc oxide, 5 parts zirconium silicate, and 10 parts black mud powder.

[0079] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, which is the same as the method provided in Example 1.

[0080] Comparative Example 6 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture, which differs from Example 1 only in the raw materials used to prepare the glaze layer.

[0081] The raw materials for preparing the glaze layer, by weight, include: 20 parts potassium feldspar, 25 parts calcite, 13 parts quartz, 5 parts calcined zinc oxide, 10 parts titanium dioxide, 5 parts black mud powder, 16 parts high-silicon and high-titanium frit, and 6 parts zirconium silicate.

[0082] The chemical composition of the high-silicon and high-titanium molten metal, by mass percentage, includes: 51% SiO2, 36% Al2O3, 13% TiO2, 14% CaO, 3% K2O, 2% Na2O, 32% B2O, 0.4% P2O5, and 8.6% loss on ignition and impurities.

[0083] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone, which is the same as the method provided in Example 1.

[0084] Comparative Example 7 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture. The raw materials used to prepare this ceramic tile are the same as those used to prepare the ceramic tile in Example 1.

[0085] This comparative example also provides a method for preparing ceramic tiles with a textured surface resembling mushroom stone. Compared with the preparation method provided in Example 1, the only difference is that in step S05, the maximum firing temperature is 1280℃ (the maximum temperature is held for 15 minutes), and the firing cycle is 40 minutes.

[0086] Comparative Example 8 This comparative example provides a ceramic tile with a mushroom-stone-like surface texture. The raw materials used to prepare this ceramic tile are the same as those used to prepare the ceramic tile in Example 1.

[0087] This comparative example also provides a method for preparing ceramic tiles with a mushroom-stone-like surface texture. Compared with the preparation method provided in Example 1, the only difference is that in step S03, the specific gravity of the base glaze slurry is 1.48 g / cm³. 3 The application rate of the base glaze slurry is 6.08 g / dm³. 2 The glazing pressure is 0.6 MPa.

[0088] In step S04, the specific gravity of the glaze slurry is 1.60 g / cm³. 3 The application rate of the surface glaze slurry is 10.85 g / dm². 2 The glazing pressure is 0.6 MPa.

[0089] Performance tests were conducted on the ceramic tiles with the undulating texture of mushroom stone surface provided in Examples 1 to 3, specifically testing the wear resistance, acid and alkali corrosion resistance, and stain resistance of the glaze. The tests were conducted according to the standard GB / T 4100-2015 "Ceramic Tiles". The test results (same test results for Examples 1 to 3) are as follows: wear resistance ≥6000 revolutions with no obvious scratches; acid and alkali corrosion resistance grade AA; stain resistance grade 5. The test results demonstrate that the ceramic tiles with the undulating texture of mushroom stone surface provided by this invention can simultaneously achieve both a matte glaze texture and physicochemical properties, effectively solving the problem of traditional imitation stone ceramic tiles where a matte glaze texture and performance cannot be simultaneously achieved.

[0090] Furthermore, the ceramic tiles with the undulating texture of mushroom stone surface provided in the above embodiments and comparative examples were visually observed to determine the deformation of the ceramic tile body, the state of the glaze texture, and the presence of glaze defects. The results are shown in the table below.

[0091]

[0092] As can be seen from the judgment results in the table above, the ceramic tiles with the undulating texture of mushroom stone provided in Examples 1 to 3 have no obvious deformation on the surface of the tile body, and the glaze spots are uniform, rich in color, and have clear contrast between light and dark. This indicates that the ceramic tiles provided by the present invention can stably achieve low deformation and fine concave-convex texture, and can replicate the natural three-dimensional mottled decorative effect of natural mushroom stone.

[0093] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 1 with the ceramic tile provided in Example 1, it was found that the ceramic tile provided in Comparative Example 1 exhibited significant warping and deformation, with the fine lines of the textured surface collapsing (see...). Figure 5 The lines are blurred, and some corner areas show (composite) glaze cracking and peeling, resulting in numerous overall appearance defects. This is because, compared to the brick body layer of Example 1, the proportion of Al2O3 in the brick body layer of Comparative Example 1 is lower, while the proportion of SiO2 is higher. This leads to a significant reduction in the number of mullite crystal phases generated in the brick body layer during the ceramic brick firing process, making it impossible to form a continuous three-dimensional skeleton structure. Consequently, the high-temperature flexural strength of the brick body layer decreases significantly. At the same time, the amount of cordierite microcrystals generated in the brick body layer also decreases, failing to effectively offset the thermal stress of quartz crystal transformation. Furthermore, when the proportion of Al2O3 decreases and the proportion of SiO2 increases, the proportion of glass phase in the brick body layer relatively increases, exacerbating the softening of the body at high temperatures. This results in overall warping and fine line collapse of the brick body layer under the combined action of its own weight and thermal stress. Moreover, the increased deformation of the brick body layer exceeds the suitable range of the thermal expansion coefficient of the body and glaze, ultimately leading to glaze cracking and peeling.

[0094] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 2 with the ceramic tile provided in Example 1, it was found that the ceramic tile provided in Comparative Example 2 exhibited slight warping, slight collapse at the edges of the fine texture, and a disordered distribution of glaze spots, weakened three-dimensional contrast, and cracking and peeling of the (composite) glaze layer in the corner areas. This is because TiO2 was not used in the brick body layer of Comparative Example 2, resulting in a decrease in the high-temperature toughness of the brick body layer.

[0095] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 3 with the ceramic tile provided in Example 1, it was found that the ceramic tile provided in Comparative Example 3 was significantly warped, with collapsed lines, and exhibited (composite) glaze cracking and peeling at the ceramic corners. This is because the alkali metal ratio in the brick body of Comparative Example 3 was unbalanced, with a decrease in K2O content and an increase in Na2O content, resulting in a higher content of glass phase inside the brick body. Under high temperatures, the brick body softened severely, lacking rigidity, thus causing obvious warping and collapse of fine lines. Moreover, the thermal expansion coefficient of the brick body layer could not match that of the base glaze layer, leading to glaze cracking and peeling.

[0096] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 4 with the ceramic tile provided in Example 1, it was found that the diameter of the glaze spots on the ceramic tile provided in Comparative Example 4 was generally larger, and in some areas the spots merged into patches, with a messy and irregular distribution; the glaze surface showed a large number of pinholes and micropores, and the matte texture was rough (see...). Figure 6 This is because the calcite mass fraction in the base glaze of Comparative Example 4 increased to 28%. With the increased calcite content, the amount of CO2 gas generated by the decomposition inside the base glaze during the high-temperature heat preservation stage increased significantly. The internal gas pressure exceeded the viscosity bearing threshold of the surface glaze, causing the area where the base glaze broke through the surface glaze to expand abnormally. The diameter of the spots increased out of control, and adjacent spots merged into patches. After a large amount of gas escaped from the glaze surface rapidly, the viscosity of the glaze surface rose during the cooling stage and could not close the gas channels in time, forming a large number of pinholes and interconnected pores. This not only destroyed the delicate texture of the glaze surface but also led to an increase in the porosity of the glaze, making it easier for pollutants to penetrate into the pores and reducing the anti-fouling performance.

[0097] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 5 with the ceramic tile provided in Example 1, it was found that the ceramic tile provided in Comparative Example 5 had a sparse number of glaze spots, insufficient distribution density, generally small spot diameter, and indistinct mottled texture; the contrast between light and dark areas in the uneven areas was weak, the overall glaze surface was monotonous, and it lacked the unique texture characteristics of mushroom stone (see...). Figure 7 This is because in Comparative Example 5, the calcite content in the base glaze layer decreased to 18%. With the reduction in calcite content, the amount of gas generated by the decomposition of the base glaze layer was insufficient, and the internal pressure could not overcome the viscous resistance of the surface glaze. Only a few thin areas of the surface glaze layer had the base glaze showing through, resulting in fewer spots and smaller sizes, making it impossible to form a uniform mottled effect. The composite glaze layer was dominated by the surface glaze color, and the thickness difference of the glaze layer in the uneven areas of the brick body could not be reflected by the base glaze color. The contrast between light and dark was weakened, and the unique three-dimensional texture of mushroom stone disappeared.

[0098] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 6 with the ceramic tile provided in Example 1, it was found that in the glaze layer of Comparative Example 6, after the proportion of high-silicon and high-titanium frit increased and the proportion of zirconium silicate decreased, the melting temperature of the glaze layer decreased, and the high-temperature viscosity dropped to a level similar to that of the base glaze layer, making it impossible to form an effective viscosity gradient. Moreover, the high-temperature glaze was too fluid and accumulated towards the concave areas of the tile body under the influence of gravity, resulting in glaze accumulation in the concave areas and exposure of the base layer in the convex areas. In addition, when the high-temperature viscosity of the glaze layer was too low, the base glaze would quickly spread outwards after breaking through, resulting in blurred spots and loss of texture layering. At the same time, the amount of zirconium silicate particles and microcrystals precipitated decreased, the diffuse reflection effect was greatly weakened, the glaze gloss increased, and the matte texture disappeared (see...). Figure 8 ).

[0099] Furthermore, comparing the ceramic tile with the mushroom-stone-like surface texture provided in Comparative Example 7 with the ceramic tile provided in Example 1, it was found that when the firing temperature was too high and the holding time was too long, the glass phase content in the tile body increased, the degree of high-temperature softening intensified, the deformation resistance of the tile body decreased, and the fine lines became rounded and collapsed under the action of gravity and surface tension; in addition, the viscosity of the glaze further decreased with the increase of temperature, the binding effect of the bottom glaze broke through the glaze behind it disappeared, and the spots spread and merged rapidly; some microcrystals in the surface glaze melted back, the grain size and proportion decreased, the diffuse reflection effect weakened, the gloss of the glaze surface increased, and the matte texture was destroyed. In addition, the overall fluidity of the glaze increased, and glaze flow marks appeared in the corner areas of the tile body (see Figure 9 ).

[0100] Furthermore, comparing the ceramic tile with the mushroom-stone texture provided in Comparative Example 8 with the ceramic tile provided in Example 1, it was found that the specific gravity of the base glaze and top glaze decreased. When the spraying pressure increased, the degree of glaze atomization was too high, resulting in an overall decrease in the amount of glaze adhering to the uneven areas of the tile body. Specifically, in the convex areas, which are directly exposed to the spray, the glaze is prone to splashing and loss, resulting in insufficient glaze thickness and the inability of the base glaze to effectively cover the body, leading to exposed base defects. In the concave areas, the amount of glaze deposited is insufficient, reducing the thickness difference of the glaze layer in the uneven areas and weakening the contrast between light and dark areas. In addition, the base glaze and top glaze have excessive fluidity, and during the drying process, the glaze easily flows along the surface of the body, forming water ripple defects, ultimately ruining the overall texture effect.

[0101] 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 ceramic tile with a mushroom-stone-like surface texture, characterized in that, It includes a brick blank layer and a composite glaze layer disposed on top of the brick blank layer; the chemical composition of the brick blank layer, by mass percentage, includes: SiO2 71.5-72.5%, Al2O3 16.0-16.5%, K2O 3.0-3.3%, Na2O 1.8-2.0%, MgO 1.2-1.4%, CaO 0.4-0.6%, Fe2O3 0.8-0.9%, TiO2 0.2-0.3%, with the remainder being loss on ignition and impurities.

2. The ceramic tile with an undulating surface texture resembling mushroom stone according to claim 1, characterized in that, The composite glaze layer includes a base glaze layer and a top glaze layer; the raw materials for preparing the base glaze layer include basic glaze and colorant, and the high-temperature viscosity of the base glaze layer is lower than that of the top glaze layer.

3. The ceramic tile with an undulating surface texture resembling mushroom stone according to claim 2, characterized in that, The raw materials for preparing the base glaze, by weight, include: 33-37 parts potassium feldspar, 10-14 parts sodium feldspar, 21-25 parts calcite, 7-9 parts calcined talc, 6-8 parts calcined zinc oxide, 4-6 parts zirconium silicate, and 9-11 parts black mud powder.

4. The ceramic tile with an undulating surface texture resembling mushroom stone according to claim 2, characterized in that, The colorant includes at least one of cobalt black, reddish-brown, zirconium iron red, electrolytic manganese, and iron oxide.

5. The ceramic tile with an undulating surface texture resembling mushroom stone according to claim 2, characterized in that, The raw materials for preparing the glaze layer, by weight, include: 18-22 parts potassium feldspar, 23-27 parts calcite, 11-15 parts quartz, 4-6 parts calcined zinc oxide, 9-11 parts titanium dioxide, 4-6 parts black mud powder, 11-13 parts high-silicon and high-titanium frit, and 9-11 parts zirconium silicate.

6. The ceramic tile with an undulating surface texture resembling mushroom stone according to claim 5, characterized in that, The chemical composition of the high-silicon, high-titanium fused ingot, by mass percentage, includes: 51-53% SiO2, 1% Al2O3, 1 ... 6-8%, TiO2 13-15%, CaO 14-16%, K2O 3-5%, Na2O 2-4%, B2O3 2-4%, P2O5 0.4-0.6%, the remainder being loss on ignition and impurities.

7. A method for preparing a ceramic tile with an imitation mushroom stone surface texture as described in any one of claims 1-6, characterized in that, Includes the following steps: S01. Weigh the raw materials for the brick blank layer according to the proportion, mix the raw materials and place them in a press to press them into brick blank layers; S02. The raw materials for preparing the composite glaze layer are put into a ball mill according to the ratio, mixed with water and ball milled to obtain the base glaze slurry and the top glaze slurry respectively. S03. Apply the base glaze slurry to the surface of the brick body to form a base glaze layer; S04. Apply a top glaze slurry onto the base glaze layer to form a top glaze layer; S05. Firing to obtain ceramic bricks with the undulating texture of the mushroom stone surface.

8. The method for preparing ceramic tiles with an undulating texture resembling mushroom stone surface according to claim 7, characterized in that, In step S03, the specific gravity of the base glaze slurry is 1.52–1.54 g / cm³. 3 The application rate of the base glaze slurry is 6.08–6.94 g / dm³. 2 .

9. The method for preparing ceramic tiles with an undulating texture resembling mushroom stone surface according to claim 7, characterized in that, In step S04, the specific gravity of the glaze slurry is 1.64–1.66 g / cm³. 3 The application rate of the surface glaze slurry is 10.85–11.72 g / dm³. 2 .

10. The method for preparing ceramic tiles with an undulating surface texture resembling mushroom stone according to claim 7, characterized in that, In step S05, the maximum firing temperature is 1200-1250℃, and the firing cycle is 38-42 minutes.

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