Ceramic dry granule, dry granule glaze, dry granule polishing surface ceramic tile and tile preparation method

Abstract

The application relates to the technical field of ceramic materials, and discloses a ceramic dry particle, a dry particle glaze, a dry particle polishing surface ceramic tile and a ceramic tile preparation method. The ceramic dry particle comprises a first dry particle. The chemical composition of the first dry particle comprises, in percentage by mass, SiO2 51.5-57.5%, Al2O3 9.8-11.8%, CaO 11.3-13.4%, MgO 2.7-3.5%, K2O 5.8-6.8%, Na2O 0.4-0.6%, BaO 2.3-2.8% and ZnO 8.4-10.2%, and the rest is ignition loss and impurities. The content of SiO2 in the first dry particle is increased, and the content of Al2O3 in the first dry particle is adjusted, so that the firing temperature and firing energy consumption of the glaze layer are reduced, the glaze layer is densified and sintered, the excellent wear resistance, stain resistance and acid and alkali resistance of the glaze layer are simultaneously considered, the mechanical strength of the glaze layer is still improved when the content of Al2O3 in the glaze layer is low, and the excellent wear resistance of the glaze layer is maintained.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, and in particular to a method for preparing dry ceramic granules, dry granule glaze, dry granule polished ceramic tiles and ceramic tiles. Background Technology

[0002] In today's ceramic tile market, polished products with smooth surfaces and easy cleaning are more popular with consumers. Among them, fully polished glazed tiles have become the main sales product for ceramic companies due to their cost advantage. However, the wear resistance of the glaze in this type of tile product has shortcomings. The industry often tries to enhance the wear resistance of the glaze by increasing the amount of alumina added or by incorporating wear-resistant aggregates such as corundum and zircon sand. However, these improvement methods can easily cause crystallization in the glaze layer, which not only makes the glaze surface cloudy but also reduces the transparency of the glaze layer, ultimately affecting the presentation of the tile's pattern.

[0003] Some technologies attempt to enhance the wear resistance of glazes by adding dry granules, but the essence remains the same: strengthening the wear resistance of the glaze layer by increasing the Al2O3 content. However, a high Al2O3 content in the glaze layer will increase the firing temperature, which will not only increase firing energy consumption but also increase the difficulty of melting the glaze, easily leading to insufficient melting of the glaze layer. This will reduce the density, acid and alkali resistance, and stain resistance of the glaze layer. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention provides a method for preparing ceramic dry granules, dry granule glaze, dry granule polished ceramic tiles and ceramic tiles, aiming to solve the technical problem that the method of enhancing the wear resistance of the glaze layer by increasing the Al2O3 content in the glaze has the disadvantages of high firing temperature and inability to simultaneously achieve the acid and alkali resistance, stain resistance and wear resistance of the glaze layer.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: The first aspect of the present invention provides a ceramic dry granule, comprising a first dry granule; the first dry granule, by mass percentage, comprises: SiO2 51.5%–57.5%, Al2O3 9.8%–11.8%, CaO 11.3%–13.4%, MgO 2.7%–3.5%, K2O 5.8%–6.8%, Na2O 0.4%–0.6%, BaO 2.3%–2.8%, ZnO 8.4%–10.2%, with the remainder being loss on ignition and impurities.

[0006] The aforementioned ceramic dry granules also include second and third dry granules; the second dry granules, by mass percentage, have the following chemical composition: SiO2 51.2%–57.1%, Al2O3 15.6%–18.2%, CaO 6.5%–7.9%, MgO 2.3%–2.7%, K2O 3.3%–3.8%, Na2O 1.8%–2.2%, SrO 7.2%–8.6%, BaO 0.3%–0.5%, ZnO 4.7%–5.5%, with the remainder being loss on ignition and impurities; The third dry granule, by mass percentage, comprises the following chemical composition: SiO2 48.6%–52.7%, Al2O3 18.5%–21.5%, CaO 16.6%–20.2%, K2O 3.1%–3.6%, ZnO 6.4%–7.6%, with the remainder being loss on ignition and impurities.

[0007] In the aforementioned ceramic dry granules, the mass ratio of the first dry granules, the second dry granules, and the third dry granules is 1:(0.12~0.13):(0.12~0.13).

[0008] In the aforementioned ceramic dry granules, the particle size D90 of the first dry granules is 182µm to 188µm; the particle size D90 of the second dry granules is 151µm to 157µm; and the particle size D90 of the third dry granules is 126µm to 132µm.

[0009] A second aspect of the present invention provides a dry granule glaze, comprising the ceramic dry granules described above.

[0010] The dry granule glaze also includes a protective glaze; the protective glaze, by mass percentage, comprises the following chemical composition: SiO2 54.3%–60.2%, Al2O3 9.8%–11.9%, CaO 2.3%–3.1%, MgO 1.45%–1.95%, K2O 4.1%–4.8%, Na2O 1.3%–1.75%, SrO 2.7%–3.3%, ZnO 9.8%–12.2%, with the remainder being loss on ignition and impurities.

[0011] In the dry granule glaze, the mass ratio of the ceramic dry granules to the protective glaze is 1:(0.19~0.21).

[0012] In the dry granule glaze, the particle size D90 of the protective glaze is 20µm to 25µm.

[0013] A third aspect of the present invention provides a dry-granule polished ceramic tile, which comprises, from bottom to top, a body layer, a surface glaze layer, and a dry-granule glaze layer; the dry-granule glaze layer is made of the aforementioned dry-granule glaze.

[0014] In the aforementioned dry-granule polished ceramic tile, an inkjet pattern layer is formed on the glaze layer.

[0015] In the aforementioned dry-granule polished ceramic tile, the mass percentage of amorphous phase in the dry-granule glaze layer is >99%.

[0016] In the aforementioned dry-granule polished ceramic tile, the surface glaze layer is made of a surface glaze, and the surface glaze, by mass percentage, comprises: SiO2 55.3%–61.3%, Al2O3 28.5%–33.5%, CaO 1.0%–1.2%, MgO 0.7%–0.9%, K2O 1.5%–1.9%, Na2O 3.8%–4.6%, with the remainder being loss on ignition and impurities.

[0017] A fourth aspect of the present invention provides a method for preparing the above-described dry-granule polished ceramic bricks, comprising the following steps: Apply a glaze to the surface of the body layer to form a glaze layer after firing; Apply dry granule glaze to the surface of the body layer that has been glazed with a surface glaze, so as to form a dry granule glaze layer after firing. Firing and cooling ceramic bricks after firing; The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

[0018] Beneficial effects: The first aspect of this invention provides ceramic dry granules. By increasing the SiO2 content and adjusting the Al2O3 content in the first dry granules, the firing temperature and energy consumption of the glaze layer are reduced, and the glaze layer is densified and sintered. Simultaneously, the glaze layer also exhibits excellent wear resistance, stain resistance, and acid and alkali resistance. Furthermore, by increasing the CaO content in the first dry granules, even when the Al2O3 content in the glaze layer is relatively low, the mechanical strength of the glaze layer can still be improved, and the glaze layer can maintain excellent wear resistance.

[0019] The second aspect of the present invention provides a dry granule glaze that, after being fired at high temperature, forms a dry granule glaze layer with a transparent texture, high density, and excellent wear resistance, stain resistance, and acid and alkali resistance, which can significantly improve the surface texture and performance of ceramic tiles.

[0020] The third aspect of this invention provides a dry-granule polished ceramic tile. The surface of the dry-granule polished ceramic tile has a dry-granule glaze layer with a very high proportion of amorphous phase. It has the characteristics of high transparency, high wear resistance, high stain resistance, and high acid and alkali resistance. In addition, the ceramic tile has clear and three-dimensional patterns and excellent gloss and texture, which can significantly improve the product grade and practical value. Attached Figure Description

[0021] Figure 1 This is the XRD phase analysis diagram of the dry granule glaze layer in the dry granule polished ceramic tile prepared in Example 2.

[0022] Figure 2 This is a photograph of the dry-granule polished ceramic tile prepared in Example 2.

[0023] Figure 3 This is a picture of the dry-granule polished ceramic tile prepared according to Comparative Example 1. Detailed Implementation

[0024] This invention provides a method for preparing ceramic dry granules, dry granule glaze, dry granule polished ceramic tiles, and ceramic tiles. 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.

[0025] The first aspect of this invention provides a ceramic dry granule, which can be used as a core component to achieve the functions of wear resistance, stain resistance, and acid and alkali resistance of glaze. It can utilize the characteristics of its clinker to reduce the violent reaction of the glaze melt, which not only helps to improve the permeability and air tightness of the glaze layer, but also improves the wear resistance, acid and alkali resistance, stain resistance and other properties of the glaze layer of polished glazed tiles.

[0026] Specifically, the ceramic dry granules include a first dry granule. The first dry granule, by mass percentage, comprises: SiO₂ 51.5%–57.5%, Al₂O 39.8%–11.8%, CaO 11.3%–13.4%, MgO 2.7%–3.5%, K₂O 5.8%–6.8%, Na₂O 0.4%–0.6%, BaO 2.3%–2.8%, ZnO 8.4%–10.2%, with the remainder being loss on ignition and impurities.

[0027] The first dry granules mentioned above contain a high SiO2 content, and the Si / Al mass ratio in the first dry granules is lower than that of traditional high-alumina ceramic dry granules. This reduces the Al2O3 content introduced into the glaze, thereby lowering the melting temperature of the glaze, reducing the firing temperature and energy consumption, and promoting full melting of the glaze layer, achieving densification and sintering. This avoids the increase of defects such as pinholes in the glaze layer due to insufficient melting, and also improves the acid and alkali resistance and anti-fouling properties of the glaze layer. The high calcium content in the first dry granules effectively lowers the eutectic point of the glaze, which helps to densify and sinter the glaze layer, thus improving its anti-fouling and acid and alkali resistance. Furthermore, the free oxygen provided by the high calcium content can repair the Si-O-Si network structure, strengthening the glass structure of the glaze layer. This allows the mechanical strength of the glaze layer to be improved even when the Al2O3 content is low, resulting in excellent wear resistance.

[0028] As can be seen, this invention, by increasing the SiO2 content and adjusting the Al2O3 content in the first dry granules, can reduce the Al2O3 content introduced into the glaze. This effectively lowers the glaze melting temperature and firing energy consumption while simultaneously ensuring excellent acid and alkali resistance, stain resistance, and wear resistance. To maintain the excellent physical and chemical properties of the glaze while also preserving its transparency and producing clear, three-dimensional ceramic tile patterns, the first dry granules also contain a high content of K2O. Firstly, K2O increases the viscosity of the glass phase in the glaze, inhibiting melt crystallization. Secondly, K2O effectively reduces the surface tension of the glaze, promoting the formation of the glass phase and thus maintaining the glaze's transparency. Furthermore, compared to Na2O, K2O has a larger ionic radius and is relatively more stable, reducing the likelihood of acid and alkali corrosion and improving the glaze's acid and alkali resistance. In addition, the MgO in the first dry granules weakens the refractive index of the glass phase in the glaze, further enhancing its transparency.

[0029] To ensure the transparency of the wear-resistant glaze layer and make the inkjet pattern beneath it clear and three-dimensional, in a preferred embodiment, the ceramic dry particles further include a second type of dry particles. Specifically, the second type of dry particles, by mass percentage, comprises: SiO2 51.2%–57.1%, Al2O3 15.6%–18.2%, CaO 6.5%–7.9%, MgO 2.3%–2.7%, K2O 3.3%–3.8%, Na2O 1.8%–2.2%, SrO 7.2%–8.6%, BaO 0.3%–0.5%, ZnO 4.7%–5.5%, with the remainder being loss on ignition and impurities.

[0030] The high SrO content in the second dry granules can adsorb tiny air bubbles in the glaze melt, purifying the glaze layer and ensuring its transparency. Simultaneously, the high SrO content in the second dry granules can counteract the high expansion of the glaze layer caused by strong potassium and sodium fluxing components, reducing the occurrence of glaze cracking. Furthermore, by reducing the proportion of CaO and increasing the proportion of Al2O3 in the second dry granules, the firing range of the glaze can be broadened, the viscosity of the glaze melt can be stabilized, and better uniform melting of the glaze can be achieved, helping to eliminate glaze shrinkage and pinhole defects during the glaze firing process.

[0031] To further improve the wear resistance of the glaze layer, in a preferred embodiment, the ceramic dry particles further include a third type of dry particles. The third type of dry particles, by mass percentage, comprises: SiO2 48.6%–52.7%, Al2O3 18.5%–21.5%, CaO 16.6%–20.2%, K2O 3.1%–3.6%, and ZnO 6.4%–7.6%.

[0032] The third dry granule is a high-alumina dry granule. During the high-temperature firing stage of the glaze, Al2O3 can gradually penetrate into the silicon-oxygen network of the glaze melt, effectively stabilizing the glassy skeleton of the glaze layer, suppressing the brittle defects that are prone to occur in the high-silicon network, significantly improving the overall mechanical strength and structural stability of the glaze layer, and making the glaze layer more wear-resistant. At the same time, the third dry granule can moderately control the viscosity of the high-temperature melt, maintain suitable sintering rheological characteristics, effectively suppress crystal nucleation and grain growth, avoid crystallization and devitrification of the glaze layer, and ensure the high transparency and uniform gloss of the glaze surface.

[0033] To enhance the gloss and transparency of the glaze layer in polished ceramic tiles, maintain high transparency, and make the tile surface easier to clean and more resistant to stains, the ceramic dry granules provided in this invention contain a high zinc oxide content in each granule. During the high-temperature firing stage, zinc oxide can effectively improve the surface tension of the glaze melt, increase the smoothness of the glaze layer, and reduce the orange peel phenomenon caused by glaze shrinkage. This allows the glaze layer to maintain better gloss and transparency, and also improves the stain resistance of the glaze layer.

[0034] In the aforementioned ceramic dry granules, the proportion of each granule affects the glaze's transparency, stain resistance, wear resistance, and acid and alkali resistance. If the proportion of the first dry granule is too high, the fluxing components will significantly lower the glaze's melting temperature, causing the granules to soften and melt prematurely. This results in excessively low high-temperature viscosity of the glaze melt, poor melt stability, and a high risk of glaze crystallization and devitrification, leading to a cloudy and opaque glaze surface, a significant decrease in glaze transparency, and severely impacting the tile's color and visual texture. Conversely, if the proportion of the first dry granule is too low, the overall fluxing capacity of the glaze is insufficient, resulting in incomplete sintering. This leads to a loose glaze structure and low density, significantly reducing transparency and creating porosity defects, thus severely degrading the glaze's stain resistance and acid and alkali resistance.

[0035] In the aforementioned ceramic dry granules, if the proportion of the second dry granule is too large, the excessive SrO in the dry granules will destroy the originally stable Si-Al-O network structure in the glaze layer, disrupt the uniformity of the glass phase, and thus induce crystal nuclei precipitation and grain growth, resulting in a cloudy glaze surface, a significant decrease in the transparency of the glaze layer, and a serious impact on the glaze gloss and color clarity. At the same time, after the Si-Al-O network structure is destroyed, the acid and alkali resistance of the glaze layer will also decrease. If the proportion of the second dry granule is too small, it cannot effectively offset the thermal expansion of the glaze layer, resulting in a high coefficient of expansion, poor elasticity and thermal stability of the glaze layer. After firing, the glaze layer is prone to cracking, pinholes, or even breakage defects. At the same time, the insufficient density and loose structure of the glaze layer will weaken the anti-fouling ability and acid and alkali resistance of the glaze layer, and reduce the transparency and gloss of the glaze surface.

[0036] In the aforementioned ceramic dry granules, if the proportion of the third dry granule is too large, the excessive high-alumina component will significantly increase the melting temperature of the glaze, increase the high-temperature viscosity, and cause the glaze melt to have poor fluidity and uneven spreading. The glaze surface is prone to shrinkage and pinholes. At the same time, the glaze layer is not fully sintered and the density decreases, which not only significantly reduces the transparency but also leads to poor anti-fouling and acid and alkali resistance due to increased internal porosity. If the proportion of the third dry granule is too small, during the firing process of the glaze layer, there is a lack of sufficient Al2O3 to penetrate into the silicon-oxygen network to build a complete and stable Si-Al-O glass network. This will lead to problems such as loose glaze structure, insufficient surface strength, and significantly reduced wear resistance. The glaze surface is prone to scratches, wear, and other defects. At the same time, the low density of the glaze layer will lead to a deterioration in the anti-fouling and acid and alkali resistance of the glaze layer.

[0037] To address this issue, in order to ensure that the glaze layer using ceramic dry granules simultaneously achieves high transparency, high wear resistance, high stain resistance, and high acid and alkali resistance, in a preferred embodiment, the mass ratio of the first, second, and third dry granules is 1:(0.12-0.13):(0.12-0.13). When the ceramic dry granules in this ratio are added to the glaze, they do not significantly increase the Al2O3 content in the glaze, maintaining the Si / Al mass ratio within a suitable range. This reduces the firing temperature and energy consumption of the ceramic tiles while promoting complete melting of the glaze layer, achieving dense sintering, and ensuring high transparency without affecting the tile's surface color, while also providing excellent wear resistance, stain resistance, and acid and alkali resistance.

[0038] In the ceramic dry granules, the particle size distribution of each granule affects the density, surface quality, stain resistance, and acid and alkali resistance of the glaze layer. When the particle size distribution of each dry granule is consistent or similar, accumulated voids, pores, and glaze bubbles will form in the glaze layer. After polishing the ceramic tile, pores will appear on the glaze surface, significantly reducing the stain resistance and acid and alkali resistance of the glaze layer. Therefore, in a preferred embodiment, the particle size D90 of the first dry granule is 182µm to 188µm; the particle size D90 of the second dry granule is 151µm to 157µm; and the particle size D90 of the third dry granule is 126µm to 132µm. This embodiment uses a gradient distribution of large, medium and small particle sizes to make the dry particles interlock and fill each other tightly, which can effectively reduce the voids and pores inside the glaze layer, improve the density and smoothness of the glaze layer, and prevent the pores from being exposed after polishing. Therefore, it can improve the anti-fouling performance and acid and alkali resistance of the glaze surface, while ensuring the high transparency of the glaze layer.

[0039] A second aspect of this invention provides a dry-granule glaze, comprising a protective glaze and the aforementioned ceramic dry granules. This dry-granule glaze can be applied to a ceramic tile body with a surface glaze. After high-temperature firing, it forms a dry-granule glaze layer with a transparent texture, high density, and excellent wear resistance, stain resistance, and acid and alkali resistance, significantly improving the surface texture and performance of the ceramic tile. Furthermore, the protective glaze in the dry-granule glaze facilitates the co-melting of the dry granules, refines the glaze structure, fills the gaps between the dry granule particles, promotes uniform melting of the glaze layer, and achieves dense sintering, further improving the smoothness, gloss, and transparency of the glaze surface. It can also reduce defects such as glaze shrinkage and pinholes, ensuring the stable overall performance of the glaze layer.

[0040] To further enhance the wear resistance of the glaze, in a preferred embodiment, the protective glaze, by mass percentage, comprises: SiO2 54.3%–60.2%, Al2O3 9.8%–11.9%, CaO 2.3%–3.1%, MgO 1.45%–1.95%, K2O 4.1%–4.8%, Na2O 1.3%–1.75%, SrO 2.7%–3.3%, ZnO 9.8%–12.2%, with the remainder being loss on ignition and impurities. By weight, the raw materials for preparing the protective glaze include 33–37.5 parts potassium feldspar, 7–11 parts sodium feldspar, 5–10 parts kaolin, 4–5.5 parts limestone, 19–25.5 parts quartz, 4–6 parts talc, 4–5.5 parts strontium carbonate, and 10–13 parts calcined zinc oxide.

[0041] In the raw materials for preparing the protective glaze, quartz is used in a relatively high amount. During the high-temperature firing process, the quartz gradually melts and transforms into amorphous SiO2 after entering the glaze melt. This greatly improves the wear resistance of the glaze layer, and the amorphous SiO2 also ensures the high transparency of the glaze layer. In addition, the addition amount of calcined zinc oxide in the raw materials for preparing the protective glaze is relatively high, which can effectively improve the surface tension of the glaze melt, enhance the smoothness of the glaze layer, and reduce the orange peel phenomenon, thereby ensuring better gloss and transparency of the glaze layer.

[0042] In order to further improve the wear resistance of the glaze, in a preferred embodiment, fused silica can be used as the raw material for preparing the protective glaze. Fused silica does not melt during the firing process of the glaze and can exist in the form of quartz particles. It can act as a network support in the entire glaze layer to improve the hardness and wear resistance of the glaze surface. At the same time, the amorphous properties of fused silica can keep the glaze layer highly transparent.

[0043] In the aforementioned dry-granule glaze, the ratio of ceramic dry granules to protective glaze affects the glaze's anti-fouling performance, acid and alkali resistance, and transparency. If the proportion of protective glaze is too high, it will cause premature melting of the glaze layer, resulting in excessively low high-temperature viscosity, insufficient melt stability, and a high tendency to induce crystallization, causing the glaze surface to appear cloudy and significantly reducing its transparency. If the proportion of protective glaze is too low, there is a lack of effective filling and encapsulation between the dry granules, leading to increased porosity and air pockets within the glaze layer, insufficient glaze density, and decreased anti-fouling and acid / alkali resistance. Therefore, in a preferred embodiment, the mass ratio of ceramic dry granules to protective glaze is 1:(0.19–0.21). This ratio balances the melting characteristics and particle packing structure of the glaze layer, allowing the glaze layer to achieve high transparency, high density, and excellent anti-fouling and acid / alkali resistance.

[0044] Furthermore, in order to prepare dry granule glaze, the raw materials for preparing dry granule glaze also include a suspending agent and water. The suspending agent can be suspending agent 92991 (Foshan Zhongxingye Ceramics Technology Co., Ltd.).

[0045] In a preferred embodiment, the particle size D90 of the protective glaze is 20µm to 25µm. Here, particle size refers to the particle size of the solid particles in the protective glaze slurry. Protective glazes within this particle size range can fully fill the gaps between dry particles, promoting low-temperature uniform eutectic melting of the dry particle layer, thereby effectively improving the transparency and density of the glaze layer and enhancing the smoothness of the glaze surface.

[0046] The third aspect of this invention provides a dry-granule polished ceramic tile, which comprises, from bottom to top, a body layer, a glaze layer, and a dry-granule glaze layer; the dry-granule glaze layer is made of the aforementioned dry-granule glaze, and the mass ratio of amorphous phase in the dry-granule glaze layer is >99%, ensuring that the glaze surface is pure and free of crystal points, has a strong sense of transparency, high color reproduction, and clear layers. At the same time, the glaze layer has a dense structure, excellent wear resistance, stain resistance, and acid and alkali resistance, making the dry-granule polished ceramic tile have a delicate and high-end texture while significantly improving its overall performance.

[0047] Furthermore, inkjet printing can be used to create inkjet pattern layers on the glaze layer, based on the decorative needs of ceramic tiles.

[0048] The surface glaze layer is made of a surface glaze. For example, the chemical composition of the surface glaze, by mass percentage, may include: SiO2 55.3%–61.3%, Al2O3 28.5%–33.5%, CaO 1.0%–1.2%, MgO 0.7%–0.9%, K2O 1.5%–1.9%, Na2O 3.8%–4.6%, with the remainder being loss on ignition and impurities. In this surface glaze, the high content of Al2O3 and SiO2 can form a continuous and dense aluminum-silicon network structure. This network can effectively block the migration and diffusion of color-developing impurity ions such as iron and manganese in the brick body layer to the upper glaze layer at high temperatures. This can prevent problems such as color pollution, dark hue, and local color spots caused by the mutual interference between impurity ions and color-developing ions in ceramic ink from the source, thereby significantly improving the color purity, color uniformity, and visual transparency of the pattern.

[0049] A fourth aspect of the present invention provides a method for preparing the above-described dry-granule polished ceramic bricks, comprising the following steps: Apply a glaze to the surface of the body layer to form a glaze layer after firing; Apply dry granule glaze to the surface of the body layer that has been glazed with a surface glaze, so as to form a dry granule glaze layer after firing. Firing and cooling ceramic bricks after firing; The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

[0050] The present invention will be further described in detail below with examples and comparative examples. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention.

[0051] Example 1 This embodiment provides a ceramic dry granule, including a first dry granule. The first dry granule, by mass percentage, comprises: SiO2 54.51%, Al2O3 10.81%, CaO 12.34%, MgO 3.08%, K2O 6.29%, Na2O 0.49%, BaO 2.56%, ZnO 9.32%, with a loss on ignition and impurities of 0.6%.

[0052] The raw materials for preparing the first dry granules, by weight, include: 40 parts potassium feldspar, 2 parts sodium feldspar, 14 parts quartz, 18.5 parts limestone, 5 parts kaolin, 2.5 parts dolomite, 7 parts calcined talc, 3 parts barium carbonate, and 8 parts calcined zinc oxide.

[0053] The first dry granules are prepared by mixing the raw materials used to prepare the first dry granules, calcining and melting them at 1400℃ to obtain a glass melt, and then cooling and crushing the molten glass melt with water-cooled metal rollers to obtain the first dry granules. The particle size D90 of the first dry granules is 185µm.

[0054] This embodiment also provides a dry granule glaze, wherein the raw materials for preparing the dry granule glaze include 20 parts of protective glaze, 100 parts of ceramic dry granules (all of which are first dry granules), 50 parts of suspending agent and 12 parts of water, by weight.

[0055] The protective glaze, by mass percentage, comprises the following chemical components: SiO2 57.33%, Al2O3 10.87%, CaO 2.62%, MgO 1.69%, K2O 4.48%, Na2O 1.48%, SrO 3.01%, ZnO 11.18%, with loss on ignition and impurities at 7.34%.

[0056] The raw materials for preparing the protective glaze, by weight, include: 35 parts potassium feldspar, 9 parts sodium feldspar, 7.5 parts kaolin, 5 parts limestone, 22.5 parts quartz, 5 parts talc, 4.5 parts strontium carbonate, and 11.5 parts calcined zinc oxide.

[0057] The preparation method of the protective glaze includes the following steps: mixing the raw materials for the protective glaze, water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate), followed by ball milling, sieving, and aging to obtain the protective glaze. The specific gravity of the protective glaze is 1.88 g / cm³. 3 The particle size D90 of the solid particles in the protective glaze slurry is 22µm.

[0058] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, includes a body layer, a glaze layer, a pattern layer, and a dry-granule glaze layer.

[0059] The surface glaze layer is made of a surface glaze, and the surface glaze, by mass percentage, has the following chemical composition: SiO2 58.31%, Al2O3 30.75%, CaO 1.09%, MgO 0.81%, K2O 1.72%, Na2O 4.23%, loss on ignition and impurities 3.09%.

[0060] The raw materials for preparing the glaze, by weight, include: 8 parts potassium feldspar, 13 parts sodium feldspar, 10.5 parts kaolin, 27 parts quartz, 2 parts wollastonite, 18 parts nepheline, 5.5 parts calcined kaolin, 2 parts calcined talc, and 14 parts calcined alumina.

[0061] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, including the following steps: To obtain a green body layer with a moisture content of less than 0.3% by mass; A surface glaze is applied to the surface of the body layer to form a glaze layer after firing, wherein the specific gravity of the surface glaze is 1.86 g / cm³. 3 The amount of glaze applied is 460g / m². 2 ; A pattern is printed by inkjet printing on the surface of the body layer covered with a glaze to form a pattern layer; A dry-grain glaze is applied to the pattern layer to form a dry-grain glaze layer after firing, wherein the specific gravity of the dry-grain glaze is 1.48 g / cm³. 3 The application rate of dry granular glaze is 700g / m². 2 ; The ceramic bricks are fired and cooled after firing, with a maximum firing temperature of 1130℃. The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

[0062] Example 2 This embodiment provides a ceramic dry granule, including a first dry granule, a second dry granule, and a third dry granule; the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.125:0.125.

[0063] The chemical composition of the first dry granules, by mass percentage, includes: SiO2 54.51%, Al2O3 10.81%, CaO 12.34%, MgO 3.08%, K2O 6.29%, Na2O 0.49%, BaO 2.56%, ZnO 9.32%, loss on ignition and impurities 0.6%.

[0064] The raw materials for preparing the first dry granules, by weight, include: 40 parts potassium feldspar, 2 parts sodium feldspar, 14 parts quartz, 18.5 parts limestone, 5 parts kaolin, 2.5 parts dolomite, 7 parts calcined talc, 3 parts barium carbonate, and 8 parts calcined zinc oxide.

[0065] The second dry granules, by mass percentage, have the following chemical composition: SiO2 54.13%, Al2O3 16.91%, CaO 7.2%, MgO 2.5%, K2O 3.55%, Na2O 2.03%, SrO 7.91%, BaO 0.41%, ZnO 5.12%, loss on ignition and impurities 0.24%.

[0066] The raw materials for preparing the second dry granules, by weight, include: 26 parts potassium feldspar, 13 parts sodium feldspar, 15 parts quartz, 9 parts limestone, 10 parts kaolin, 4 parts dolomite, 4 parts calcined talc, 4 parts calcined alumina, 10 parts strontium carbonate, 0.5 parts barium carbonate, and 4.5 parts calcined zinc oxide.

[0067] The chemical composition of the third dry granules, by mass percentage, includes: 50.16% SiO2, 19.98% Al2O3, 18.4% CaO, 3.37% K2O, 7.03% ZnO, and 1.06% loss on ignition and impurities.

[0068] The raw materials for preparing the third dry granules, by weight, include: Potassium feldspar 25 parts, quartz 17 parts, limestone 20 parts, wollastonite 10.5 parts, kaolin 12.5 parts, calcined alumina 8.5 parts, calcined zinc oxide 6.5 parts.

[0069] The preparation methods for the first, second, and third dry granules are the same: the raw materials used to prepare the dry granules are mixed and calcined at 1400°C to obtain a glass melt, and then the molten glass melt is cooled and crushed by water-cooled metal rollers to obtain dry granules.

[0070] The first dry granule has a particle size D90 of 185µm; the second dry granule has a particle size D90 of 154µm; and the third dry granule has a particle size D90 of 129µm.

[0071] This embodiment also provides a dry granule glaze. By weight, the raw materials for preparing the dry granule glaze include 20 parts of protective glaze, 100 parts of ceramic dry granules (the mass ratio of ceramic dry granules to protective glaze is 1:0.2), 50 parts of suspending agent, and 12 parts of water. The ceramic dry granules include 80 parts of first dry granules, 10 parts of second dry granules, and 10 parts of third dry granules.

[0072] The protective glaze, by mass percentage, comprises the following chemical components: SiO2 57.33%, Al2O3 10.87%, CaO 2.62%, MgO 1.69%, K2O 4.48%, Na2O 1.48%, SrO 3.01%, ZnO 11.18%, with loss on ignition and impurities at 7.34%.

[0073] The raw materials for preparing the protective glaze, by weight, include: 35 parts potassium feldspar, 9 parts sodium feldspar, 7.5 parts kaolin, 5 parts limestone, 22.5 parts quartz, 5 parts talc, 4.5 parts strontium carbonate, and 11.5 parts calcined zinc oxide.

[0074] The preparation method of the protective glaze includes the following steps: mixing the raw materials for the protective glaze, water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate), followed by ball milling, sieving, and aging to obtain the protective glaze. The specific gravity of the protective glaze is 1.88 g / cm³. 3 The particle size D90 of the solid particles in the protective glaze slurry is 22µm.

[0075] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, includes a body layer, a glaze layer, a pattern layer, and a dry-granule glaze layer.

[0076] The surface glaze layer is made of a surface glaze, and the surface glaze, by mass percentage, has the following chemical composition: SiO2 58.31%, Al2O3 30.75%, CaO 1.09%, MgO 0.81%, K2O 1.72%, Na2O 4.23%, loss on ignition and impurities 3.09%.

[0077] The raw materials for preparing the glaze, by weight, include: 8 parts potassium feldspar, 13 parts sodium feldspar, 10.5 parts kaolin, 27 parts quartz, 2 parts wollastonite, 18 parts nepheline, 5.5 parts calcined kaolin, 2 parts calcined talc, and 14 parts calcined alumina.

[0078] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, including the following steps: To obtain a green body layer with a moisture content of less than 0.3% by mass; A surface glaze is applied to the surface of the body layer to form a glaze layer after firing, wherein the specific gravity of the surface glaze is 1.86 g / cm³. 3 The amount of glaze applied is 460g / m². 2 ; A pattern is printed by inkjet printing on the surface of the body layer covered with a glaze to form a pattern layer; A dry-grain glaze is applied to the pattern layer to form a dry-grain glaze layer after firing, wherein the specific gravity of the dry-grain glaze is 1.48 g / cm³. 3 The application rate of dry granular glaze is 700g / m². 2 ; The ceramic bricks are fired and cooled after firing, with a maximum firing temperature of 1130℃. The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

[0079] Example 3 This embodiment provides a ceramic dry granule, including a first dry granule, a second dry granule, and a third dry granule; the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.125:0.125.

[0080] The chemical composition of the first dry granules, by mass percentage, includes: 52.08% SiO2, 11.86% Al2O3, 11.82% CaO, 2.78% MgO, 6.68% K2O, 0.41% Na2O, 2.79% BaO, 10.18% ZnO, and 1.4% loss on ignition and impurities.

[0081] The raw materials for preparing the first dry granules, by weight, include: 42 parts potassium feldspar, 1 part sodium feldspar, 11.5 parts quartz, 16.5 parts limestone, 7 parts kaolin, 4 parts dolomite, 5 parts calcined talc, 3.5 parts barium carbonate, and 9.5 parts calcined zinc oxide.

[0082] The second dry granules, by mass percentage, have the following chemical composition: SiO2 51.5%, Al2O3 18.12%, CaO 6.58%, MgO 2.37%, K2O 3.75%, Na2O 1.85%, SrO 8.48%, BaO 0.45%, ZnO 5.45%, loss on ignition and impurities 1.45%.

[0083] The raw materials for preparing the second dry granules, by weight, include: 27 parts potassium feldspar, 15 parts sodium feldspar, 12 parts quartz, 7.5 parts limestone, 8 parts kaolin, 5 parts dolomite, 3 parts calcined talc, 5.5 parts calcined alumina, 11 parts strontium carbonate, 1 part barium carbonate, and 5 parts calcined zinc oxide.

[0084] The chemical composition of the third dry granules, by mass percentage, includes: 48.79% SiO2, 21.32% Al2O3, 16.78% CaO, 3.56% K2O, 7.55% ZnO, and 2% loss on ignition and impurities.

[0085] The raw materials for preparing the third dry granules, by weight, include: Potassium feldspar 27 parts, quartz 15.5 parts, limestone 17 parts, wollastonite 12 parts, kaolin 11.5 parts, calcined alumina 10 parts, calcined zinc oxide 7 parts.

[0086] The preparation methods for the first, second, and third dry granules are the same: the raw materials used to prepare the dry granules are mixed and calcined at 1400°C to obtain a glass melt, and then the molten glass melt is cooled and crushed by water-cooled metal rollers to obtain dry granules.

[0087] The first dry granule has a particle size D90 of 188µm; the second dry granule has a particle size D90 of 157µm; and the third dry granule has a particle size D90 of 132µm.

[0088] This embodiment also provides a dry granule glaze. By weight, the raw materials for preparing the dry granule glaze include 20 parts of protective glaze, 100 parts of ceramic dry granules (the mass ratio of ceramic dry granules to protective glaze is 1:0.2), 50 parts of suspending agent, and 12 parts of water. The ceramic dry granules include 80 parts of first dry granules, 10 parts of second dry granules, and 10 parts of third dry granules.

[0089] The protective glaze, by mass percentage, comprises the following chemical components: SiO2 54.53%, Al2O3 11.78%, CaO 2.35%, MgO 1.52%, K2O 4.71%, Na2O 1.33%, SrO 3.26%, ZnO 12.04%, with a loss on ignition and impurities of 8.48%.

[0090] The raw materials for preparing the protective glaze, by weight, include: 37.5 parts potassium feldspar, 7 parts sodium feldspar, 10 parts kaolin, 4 parts limestone, 19 parts quartz, 4 parts talc, 5.5 parts strontium carbonate, and 13 parts calcined zinc oxide.

[0091] The preparation method of the protective glaze includes the following steps: mixing the raw materials for the protective glaze, water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate), followed by ball milling, sieving, and aging to obtain the protective glaze. The specific gravity of the protective glaze is 1.85 g / cm³. 3 The particle size D90 of the solid particles in the protective glaze slurry is 25µm.

[0092] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, includes a body layer, a glaze layer, a pattern layer, and a dry-granule glaze layer.

[0093] The surface glaze layer is made of a surface glaze, and the surface glaze, by mass percentage, has the following chemical composition: SiO2 55.8%, Al2O3 32.73%, CaO 1.01%, MgO 0.87%, K2O 1.87%, Na2O 3.74%, loss on ignition and impurities 3.98%.

[0094] The raw materials for preparing the glaze, by weight, include: 10 parts potassium feldspar, 15 parts sodium feldspar, 8.5 parts kaolin, 23 parts quartz, 3 parts wollastonite, 15 parts nepheline, 3.5 parts calcined kaolin, 4 parts calcined talc, and 18 parts calcined alumina.

[0095] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, including the following steps: To obtain a green body layer with a moisture content of less than 0.3% by mass; A surface glaze is applied to the surface of the body layer to form a glaze layer after firing, wherein the specific gravity of the surface glaze is 1.85 g / cm³. 3 The amount of glaze applied is 470g / m². 2 ; A pattern is printed by inkjet printing on the surface of the body layer covered with a glaze to form a pattern layer; A dry-grain glaze is applied to the pattern layer to form a dry-grain glaze layer after firing, wherein the specific gravity of the dry-grain glaze is 1.46 g / cm³. 3 The application rate of dry granular glaze is 710g / m³. 2 ; The ceramic bricks are fired and cooled after firing, with a maximum firing temperature of 1135℃. The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

[0096] Example 4 This embodiment provides a ceramic dry granule, including a first dry granule, a second dry granule, and a third dry granule; the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.125:0.125.

[0097] The chemical composition of the first dry granules, by mass percentage, includes: 56.51% SiO2, 9.82% Al2O3, 13.04% CaO, 3.34% MgO, 5.85% K2O, 0.56% Na2O, 2.34% BaO, 8.45% ZnO, and 0.09% loss on ignition and impurities.

[0098] The raw materials for preparing the first dry granules, by weight, include: 38 parts potassium feldspar, 4 parts sodium feldspar, 16 parts quartz, 20 parts limestone, 3 parts kaolin, 1 part dolomite, 8.5 parts calcined talc, 2.5 parts barium carbonate, and 7 parts calcined zinc oxide.

[0099] The second dry granules, by mass percentage, have the following chemical composition: SiO2 56.26%, Al2O3 15.62%, CaO 7.67%, MgO 2.61%, K2O 3.33%, Na2O 2.12%, SrO 7.22%, BaO 0.39%, ZnO 4.71%, with a loss on ignition and impurities of 0.07%.

[0100] The raw materials for preparing the second dry granules, by weight, include: 24.5 parts potassium feldspar, 11 parts sodium feldspar, 17.5 parts quartz, 10 parts limestone, 13 parts kaolinite, 3 parts dolomite, 5 parts calcined talc, 2.5 parts calcined alumina, 9 parts strontium carbonate, 0.5 parts barium carbonate, and 4 parts calcined zinc oxide.

[0101] The chemical composition of the third dry granules, by mass percentage, includes: 52.07% SiO2, 18.51% Al2O3, 19.85% CaO, 3.12% K2O, 6.41% ZnO, with a loss on ignition and impurities of 0.04%.

[0102] The raw materials for preparing the third dry granules, by weight, include: 23 parts potassium feldspar, 19 parts quartz, 23 parts limestone, 8 parts wollastonite, 15.5 parts kaolin, 6 parts alumina, and 5.5 parts calcined zinc oxide.

[0103] The preparation methods for the first, second, and third dry granules are the same: the raw materials used to prepare the dry granules are mixed and calcined at 1400°C to obtain a glass melt, and then the molten glass melt is cooled and crushed by water-cooled metal rollers to obtain dry granules.

[0104] The first dry granule has a particle size D90 of 182µm; the second dry granule has a particle size D90 of 151µm; and the third dry granule has a particle size D90 of 126µm.

[0105] This embodiment also provides a dry granule glaze. By weight, the raw materials for preparing the dry granule glaze include 20 parts of protective glaze, 100 parts of ceramic dry granules (the mass ratio of ceramic dry granules to protective glaze is 1:0.2), 50 parts of suspending agent, and 12 parts of water. The ceramic dry granules include 80 parts of first dry granules, 10 parts of second dry granules, and 10 parts of third dry granules.

[0106] The chemical composition of the protective glaze, by mass percentage, includes: SiO2 59.89%, Al2O3 9.96%, CaO 3.08%, MgO 1.91%, K2O 4.29%, Na2O 1.7%, SrO 2.8%, ZnO 9.9%, and loss on ignition and impurities 6.47%.

[0107] The raw materials for preparing the protective glaze, by weight, include: 33 parts potassium feldspar, 11 parts sodium feldspar, 5 parts kaolin, 5.5 parts limestone, 25.5 parts quartz, 6 parts talc, 4 parts strontium carbonate, and 10 parts calcined zinc oxide.

[0108] The preparation method of the protective glaze includes the following steps: mixing the raw materials for the protective glaze, water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate), followed by ball milling, sieving, and aging to obtain the protective glaze. The specific gravity of the protective glaze is 1.90 g / cm³. 3 The particle size D90 of the solid particles in the protective glaze slurry is 20µm.

[0109] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, includes a body layer, a glaze layer, a pattern layer, and a dry-granule glaze layer.

[0110] The surface glaze layer is made of a surface glaze, and the surface glaze, by mass percentage, has the following chemical composition: SiO2 61.07%, Al2O3 28.66%, CaO 1.09%, MgO 0.72%, K2O 1.51%, Na2O 4.57%, loss on ignition and impurities 2.38%.

[0111] The raw materials for preparing the glaze, by weight, include: 6 parts potassium feldspar, 10 parts sodium feldspar, 12 parts kaolin, 31 parts quartz, 1 part wollastonite, 21 parts nepheline, 7.5 parts calcined kaolin, 1 part calcined talc, and 10.5 parts calcined alumina.

[0112] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, including the following steps: To obtain a green body layer with a moisture content of less than 0.3% by mass; A surface glaze is applied to the surface of the body layer to form a glaze layer after firing, wherein the specific gravity of the surface glaze is 1.89 g / cm³. 3The amount of glaze applied is 450g / m². 2 ; A pattern is printed by inkjet printing on the surface of the body layer covered with a glaze to form a pattern layer; A dry-grain glaze is applied to the pattern layer to form a dry-grain glaze layer after firing, wherein the specific gravity of the dry-grain glaze is 1.50 g / cm³. 3 The application rate of dry granular glaze is 690 g / m³. 2 ; The ceramic bricks are fired and cooled after firing, with a maximum firing temperature of 1125℃. The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

[0113] Example 5 This embodiment provides a ceramic dry granule, which is the same as the ceramic dry granule provided in Embodiment 2.

[0114] This embodiment also provides a dry granule glaze, which differs from the dry granule glaze provided in Embodiment 2 only in that the amount of protective glaze is 19 parts and the mass ratio of ceramic dry granules to protective glaze is 1:0.19.

[0115] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this embodiment. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0116] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0117] Example 6 This embodiment provides a ceramic dry granule, which is the same as the ceramic dry granule provided in Embodiment 2.

[0118] This embodiment also provides a dry granule glaze, which differs from the dry granule glaze provided in Embodiment 2 only in that the amount of protective glaze is 21 parts and the mass ratio of ceramic dry granules to protective glaze is 1:0.21.

[0119] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this embodiment. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0120] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0121] Example 7 This embodiment provides a ceramic dry granule, which differs from the ceramic dry granule provided in Embodiment 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.12:0.13.

[0122] This embodiment also provides a dry granule glaze, the raw material composition of which is the same as that of the dry granule glaze provided in Embodiment 2.

[0123] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this embodiment. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0124] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0125] Example 8 This embodiment provides a ceramic dry granule, which differs from the ceramic dry granule provided in Embodiment 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.13:0.12.

[0126] This embodiment also provides a dry granule glaze, the raw material composition of which is the same as that of the dry granule glaze provided in Embodiment 2.

[0127] This embodiment also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this embodiment. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0128] This embodiment also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0129] Comparative Example 1 This comparative example provides a ceramic dry granule, which is the same as the ceramic dry granule provided in Example 2.

[0130] This comparative example also provides a dry granule glaze, which differs from the dry granule glaze provided in Example 2 only in that the amount of protective glaze is 30 parts and the mass ratio of ceramic dry granules to protective glaze is 1:0.3.

[0131] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0132] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0133] Comparative Example 2 This comparative example provides a ceramic dry granule, which is the same as the ceramic dry granule provided in Example 2.

[0134] This comparative example also provides a dry granule glaze, which differs from the dry granule glaze provided in Example 2 only in that the amount of protective glaze is 10 parts and the mass ratio of ceramic dry granules to protective glaze is 1:0.1.

[0135] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0136] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0137] Comparative Example 3 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1.2: 0.125: 0.125.

[0138] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0139] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0140] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0141] Comparative Example 4 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 0.8:0.125:0.125.

[0142] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0143] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0144] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0145] Comparative Example 5 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.2:0.125.

[0146] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0147] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0148] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0149] Comparative Example 6 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.08:0.125.

[0150] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0151] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0152] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0153] Comparative Example 7 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.125:0.2.

[0154] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0155] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0156] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0157] Comparative Example 8 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 1:0.125:0.08.

[0158] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0159] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0160] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0161] Comparative Example 9 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule of Example 2 only in that the third dry granule is different. In this comparative example, the chemical composition of the third dry granule, by mass percentage, includes: SiO2 54.7%, Al2O3 20.3%, CaO 8.01%, MgO 6.62%, K2O 3.43%, ZnO 6.54%, loss on ignition and impurities 0.4%.

[0162] The raw materials for preparing the third dry granules, by weight, include: Potassium feldspar 24 parts, quartz 15 parts, limestone 13 parts, kaolin 16 parts, calcined talc powder 18 parts, calcined alumina 8 parts, zinc oxide 6 parts.

[0163] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0164] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0165] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0166] Comparative Example 10 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule of Example 2 only in that the particle size D90 of the first dry granule, the second dry granule, and the third dry granule is 182 µm.

[0167] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0168] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0169] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0170] Comparative Example 11 This comparative example provides a ceramic dry granule, which is the same as the ceramic dry granule provided in Example 2.

[0171] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent, and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2. However, the particle size D90 of the solid particles in the protective glaze is greater than 35µm.

[0172] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0173] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0174] Comparative Example 12 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule of Example 2 only in that the first dry granule is different. In this comparative example, the chemical composition of the first dry granule, by mass percentage, includes: SiO2 57.63%, Al2O3 11.4%, CaO 7.67%, MgO 3.47%, K2O 6.26%, Na2O 0.9%, BaO 2.81%, ZnO 9.55%, loss on ignition and impurities 0.31%.

[0175] The raw materials for preparing the first dry granules, by weight, include: 40 parts potassium feldspar, 2 parts sodium feldspar, 14 parts quartz, 10 parts limestone, 5 parts kaolin, 2.5 parts dolomite, 7 parts calcined talc, 3 parts barium carbonate, and 8 parts calcined zinc oxide.

[0176] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0177] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0178] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0179] Comparative Example 13 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule of Example 2 only in that the first dry granule is different. In this comparative example, the chemical composition of the first dry granule, by mass percentage, includes: SiO2 63.81%, Al2O3 13.62%, CaO 8.24%, K2O 4.09%, Na2O 1.30%, ZnO 8.31%, loss on ignition and impurities 0.63%.

[0180] The raw materials for preparing the first dry granules, by weight, include: 23 parts potassium feldspar, 7 parts sodium feldspar, 12 parts kaolin, 27.5 parts quartz, 8 parts wollastonite, 10 parts limestone, 4 parts alumina, and 8.5 parts zinc oxide.

[0181] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0182] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0183] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0184] Comparative Example 14 This comparative example provides a ceramic dry granule, which differs from the ceramic dry granule provided in Example 2 only in that the mass ratio of the first dry granule, the second dry granule, and the third dry granule is 0.3:1:1.

[0185] This comparative example also provides a dry granule glaze, which uses the ceramic dry granules provided in this comparative example, and the ratio of protective glaze, ceramic dry granules, suspending agent and water in the dry granule glaze is the same as that of the dry granule glaze provided in Example 2.

[0186] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0187] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0188] Comparative Example 15 This comparative example provides a ceramic dry granule, which is the same as the ceramic dry granule provided in Example 2.

[0189] This comparative example also provides a dry granule glaze. Compared with the dry granule glaze provided in Example 2, the difference is that, in this comparative example, the protective glaze, by mass percentage, has the following chemical composition: SiO2 45.02%, Al2O3 10.87%, CaO 2.62%, MgO 1.69%, K2O 4.48%, Na2O 1.48%, SrO 3.01%, ZnO 11.18%, and loss on ignition and impurities 19.65%.

[0190] The raw materials for preparing the protective glaze, by weight, include: 35 parts potassium feldspar, 9 parts sodium feldspar, 7.5 parts kaolin, 5 parts limestone, 10 parts quartz, 5 parts talc, 4.5 parts strontium carbonate, and 11.5 parts calcined zinc oxide.

[0191] This comparative example also provides a dry-granule polished ceramic tile, which, from bottom to top, comprises a body layer, a surface glaze layer, a pattern layer, and a dry-granule glaze layer. The dry-granule glaze layer is prepared using the dry-granule glaze provided in this comparative example. The surface glaze layer is prepared using the surface glaze provided in Example 2.

[0192] This comparative example also provides a method for preparing dry-granule polished ceramic tiles, which is the same as the method for preparing dry-granule polished ceramic tiles provided in Example 2.

[0193] Figure 1 The XRD phase analysis diagram of the dry granule glaze layer in the dry granule polished ceramic tile prepared in Example 2 is shown. The diagram shows only broadened diffuse peaks, indicating that the dry granule glaze layer prepared in this invention has almost no crystalline phase precipitation, and the amorphous phase accounts for a very high proportion, with the overall structure being dominated by a uniform and stable glassy phase.

[0194] The dry-granule polished ceramic tiles provided in the above embodiments and comparative examples were subjected to performance tests, including abrasion resistance, stain resistance, and transparency. The surface quality of the ceramic tiles was also visually inspected. The test results are shown in Table 1 below.

[0195] The abrasion resistance test was conducted according to the standard GB3810.7-2006 Ceramic Tile Test Methods Part 7: Determination of Abrasion Resistance of Glazed Tile Surfaces; the stain resistance test was conducted according to the standard GBT 3810.14-2016 Ceramic Tile Test Methods Part 14: Determination of Stain Resistance; the acid and alkali resistance test was conducted according to the standard Ceramic Tile Test Methods: Determination of Chemical Corrosion Resistance; and the transparency test was conducted according to the standard GB2680-94 Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Parameters of Architectural Glass (requiring the determination of the direct solar transmittance by firing dry granule glaze slurry into 1mm glaze sheets).

[0196] Table 1:

[0197] As can be seen from the test results in the table above, the dry-granule polished ceramic tiles provided in Examples 1 to 8 have high transparency (the transparency of the dry-granule glaze layer is above 85%), clear tile surface patterns, and the acid and alkali resistance level of the glaze layer reaches Grade A, the stain resistance level reaches Grade 5, and the wear resistance level is above Grade 4. This indicates that the ceramic dry granules and matching dry-granule glaze system used in this invention can effectively balance the light transmission texture, stain resistance, wear resistance, and acid and alkali resistance of ceramic tiles.

[0198] Comparing the dry-granule polished ceramic tiles and their dry-granule glaze layers provided in Examples 2 to 4 with those in Example 1, it was found that by simultaneously using the first dry granule, the second dry granule, and the third dry granule in the ceramic dry granules used in Examples 2 to 4, the transparency of the dry-granule glaze layer can be further improved while ensuring the anti-fouling, wear-resistant, and acid and alkali-resistant properties of the glaze layer. This results in more distinct layers of inkjet patterns on the ceramic tile surface, higher color fidelity, and significantly optimized visual texture.

[0199] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 1 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 1 all decreased. Furthermore, the transparency of the dry-granule glaze layer decreased, resulting in poor translucency and clarity. This is because the proportion of protective glaze in the dry-granule glaze used in Comparative Example 1 was relatively high, leading to premature melting of the dry-granule glaze layer, excessively low high-temperature viscosity, and insufficient melt stability. This easily induces internal crystallization within the dry-granule glaze layer, reducing its density and causing the glaze layer to appear cloudy and opaque (see Example 2). Figure 2 The transparency, stain resistance, wear resistance, and acid and alkali resistance of the glaze layer decrease.

[0200] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 2 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 2 all decreased. Furthermore, the transparency of the dry-granule glaze layer decreased, resulting in poor translucency and clarity. This is because the proportion of protective glaze in the dry-granule glaze used in Comparative Example 2 was low, and there was a lack of effective filling and encapsulation between the dry granules, leading to an increase in internal pores and air pockets in the dry-granule glaze layer, insufficient glaze density, and a decrease in stain resistance, wear resistance, and acid and alkali resistance. The increased internal pores and air pockets in the dry-granule glaze layer also affect its transparency, resulting in poor translucency and clarity of the ceramic tile surface.

[0201] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 3 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 3 were all reduced. Furthermore, the transparency of the dry-granule glaze layer decreased, resulting in poor translucency and clarity. This is because the proportion of high-calcium, high-silicon primary dry granules in the ceramic dry granules used in Comparative Example 3 was relatively high, leading to premature softening and melting of the dry-granule glaze. The low viscosity of the glaze melt at high temperatures induced crystallization and devitrification of the dry-granule glaze layer, causing the glaze surface to become cloudy and the transparency of the glaze layer to significantly decrease. Simultaneously, when the dry-granule glaze layer devitrifies, stress defects exist at the crystal-glass phase interface, and the density of the dry-granule glaze layer decreases, resulting in a reduction in the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer.

[0202] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 4 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 4 were significantly reduced, and the transparency of the dry-granule glaze layer was significantly reduced, resulting in poor transparency and clarity. This is because the proportion of high-calcium and high-silicon first dry granules in the ceramic dry granules used in Comparative Example 4 was relatively small, and the sintering reaction was insufficient, resulting in a loose structure and low density of the dry-granule glaze layer. Not only was the transparency of the glaze layer significantly reduced, but pore defects were also formed, leading to a significant deterioration in the stain resistance, wear resistance, and acid and alkali resistance of the glaze layer.

[0203] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 5 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 5 were all reduced. In addition, the transparency of the dry-granule glaze layer was reduced, and the transparency and clarity were poor. This is because the proportion of the second dry granule in the ceramic dry granules used in Comparative Example 5 was relatively high. Excessive SrO in the dry granules would destroy the originally stable Si-Al-O network structure in the glaze layer, disturb the uniformity of the glass phase, and thus induce crystal nuclei precipitation and grain growth, resulting in crystallization and cloudiness of the glaze surface, and a significant decrease in the density and transparency of the glaze layer.

[0204] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 6 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 6 were significantly reduced. In addition, the transparency of the dry-granule glaze layer decreased, and the transparency and clarity were poor. This is because the proportion of the second dry granule in the ceramic dry granules used in Comparative Example 6 was relatively low, which could not effectively offset the thermal expansion of the glaze layer, resulting in a high coefficient of expansion of the glaze layer, poor elasticity and thermal stability. After firing, the glaze layer is prone to cracking, pinholes, or even breakage defects. At the same time, the glaze layer has insufficient density and a loose structure, which not only weakens the stain resistance, wear resistance, and acid and alkali resistance of the glaze layer, but also reduces the transparency and gloss of the glaze surface.

[0205] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 7 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 7 were significantly reduced. In addition, the transparency of the dry-granule glaze layer decreased, and the transparency and clarity were poor. This is because the proportion of high-alumina third dry granules in the ceramic dry granules used in Comparative Example 7 was relatively high. Excessive high-alumina components will significantly increase the melting temperature of the dry-granule glaze and increase the high-temperature viscosity, resulting in poor glaze melt fluidity, uneven spreading, and easy formation of glaze shrinkage and pinholes on the glaze surface. At the same time, the dry-granule glaze layer was not fully sintered and the density decreased, which not only significantly reduced the transparency but also led to a decrease in stain resistance, wear resistance, and acid and alkali resistance due to the increase in internal pores.

[0206] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 8 with those in Example 2, it was found that the wear resistance, stain resistance, and acid and alkali resistance of the dry-granule polished ceramic tile provided in Comparative Example 8 were significantly reduced, and the transparency of the dry-granule glaze layer was reduced, resulting in poor transparency and clarity. This is because the proportion of high-alumina third dry granules in the ceramic dry granules used in Comparative Example 8 was relatively small. During the firing process of the dry-granule glaze layer, there was a lack of sufficient Al2O3 to penetrate into the silicon-oxygen network to construct a complete and stable Si-Al-O glass network. Not only was the dry-granule glaze layer prone to crystallization, leading to a decrease in the transparency of the dry-granule glaze layer, but it also resulted in problems such as a loose structure, insufficient surface strength, and a significant decrease in wear resistance, stain resistance, and acid and alkali resistance.

[0207] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 9 with those in Example 2, it was found that the stain resistance and acid / alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 9 were significantly reduced, and the transparency of the dry-granule glaze layer was also reduced, resulting in poor transparency and clarity. This is because the CaO content in the third dry granule used in Comparative Example 9 was lower than that in the third dry granule used in Example 2. At the same time, a higher content of MgO was introduced into the third dry granule used in Comparative Example 9. MgO easily reacts with Al2O3 to form magnesium aluminum spinel, which reduces the transparency of the dry-granule glaze layer. Furthermore, the introduction of MgO further increases the surface tension of the glaze melt, easily causing glaze shrinkage defects, resulting in a significant decrease in the stain resistance and acid / alkali resistance of the dry-granule glaze layer.

[0208] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 10 with those in Example 2, it was found that the stain resistance and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 10 decreased significantly, and the transparency and clarity of the dry-granule glaze layer were also generally poor. This is because the particle size distribution of each dry particle in the ceramic dry granules used in Comparative Example 10 is consistent, which will form accumulated voids, pores and glaze bubble defects in the dry-granule glaze layer. After the ceramic tile is polished, pores will appear on the glaze surface, which will significantly reduce the stain resistance and acid and alkali resistance of the glaze layer.

[0209] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 11 with those in Example 2, it was found that the anti-fouling performance and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 11 decreased significantly, and the transparency and clarity of the dry-granule glaze layer were also poor. This is because the particle size of the protective glaze in the dry-granule glaze used in Comparative Example 11 was too large, which could not fill the gaps between the dry particles well, making it difficult to promote the uniform melting of the dry-granule glaze layer. This resulted in a decrease in the flatness and transparency of the dry-granule glaze layer, which in turn affected the anti-fouling and acid and alkali resistance of the dry-granule glaze layer.

[0210] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 12 with those in Example 2, it was found that the anti-fouling performance and acid and alkali resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 12 were significantly reduced. Furthermore, the transparency and clarity of the dry-granule glaze layer were poor, and its wear resistance was somewhat reduced. This is because the CaO content in the first dry granule used in Comparative Example 12 was lower than that in the first dry granule of Example 2. As CaO is a key flux and a reinforcing component for the glass structure of the glaze layer, insufficient CaO content will increase the overall melting temperature of the glaze and increase the high-temperature viscosity of the glaze melt. This results in insufficient melting and uneven spreading of the glaze during firing, making it prone to forming micropores and pinholes inside the dry-granule glaze layer, significantly reducing the overall density. Simultaneously, the low CaO content cannot effectively repair Si-Al-O. The network structure weakens the mechanical strength of the dry granule glaze layer, resulting in poor wear resistance. Furthermore, the loose porous structure of the dry granule glaze layer becomes a channel for the penetration of stains and acid and alkali media, directly causing a deterioration in its stain resistance and acid and alkali resistance. In addition, uneven melting of the glaze can also cause local crystal nuclei to form and crystals to precipitate in the dry granule glaze layer, destroying the continuous glass phase structure of the dry granule glaze layer. Ultimately, this leads to a decrease in the transparency of the dry granule glaze layer and a reduction in the clarity of the brick surface pattern.

[0211] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 13 with those in Example 2, it was found that the anti-fouling performance, acid and alkali resistance, and wear resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 13 were significantly reduced. Furthermore, the transparency and clarity of the dry-granule glaze layer were poor. This is because the chemical composition of the first dry granule used in Comparative Example 13 is different from that of the first dry granule used in Example 2. In the first dry granule used in Comparative Example 13, the Si / Al mass ratio was reduced, and functional components such as CaO and BaO were reduced. This increased the melting temperature and high-temperature viscosity of the glaze, resulting in incomplete melting and insufficient sintering density of the glaze. This not only allowed stains and acid and alkali media to easily penetrate, significantly reducing the anti-fouling and acid and alkali resistance of the dry-granule glaze layer, but also damaged the overall structural strength of the dry-granule glaze layer, resulting in poor wear resistance. At the same time, the unbalanced chemical composition broke the original stable glass phase system, which easily induced crystallization of the glaze layer, destroying the transparent texture of the glaze layer. Ultimately, this resulted in insufficient transparency and significantly reduced clarity of the tile surface pattern.

[0212] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 14 with those in Example 2, it was found that the anti-fouling performance, acid and alkali resistance, and wear resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 14 were significantly reduced. Furthermore, the transparency and clarity of the dry-granule glaze layer were poor. This is because in the ceramic dry granules used in Comparative Example 14, the proportion of the first dry granule was significantly reduced, while the proportion of the second and third dry granules was relatively high. This resulted in an increase in the aluminum content of the glaze system, which not only increased the melting temperature of the glaze, leading to insufficient sintering of the glaze melt and a decrease in the density of the dry-granule glaze layer, directly weakening its anti-fouling and acid and alkali resistance, but also resulted in insufficient mechanical strength of the dry-granule glaze layer due to the lack of sufficient high-calcium components to reinforce the glass network, and a significant decline in wear resistance. At the same time, the excessive amount of second and third dry granules easily caused crystal nuclei to precipitate, destroying the continuous and uniform amorphous phase structure, causing the dry-granule glaze layer to become cloudy and opaque, ultimately resulting in poor transparency and clarity of the tile surface pattern.

[0213] Comparing the dry-granule polished ceramic tile and its dry-granule glaze layer provided in Comparative Example 15 with those in Example 2, it was found that the anti-fouling performance, acid and alkali resistance, and wear resistance of the dry-granule glaze layer of the dry-granule polished ceramic tile provided in Comparative Example 15 were all reduced. In addition, the transparency and clarity of the dry-granule glaze layer were generally poor. This is because the amount of quartz used in the protective glaze of Comparative Example 15 was reduced, which reduced the amount of SiO2 that could be transformed into amorphous state after entering the glaze melt, resulting in limited improvement in the overall performance of the dry-granule glaze layer.

[0214] 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 type of dry ceramic granules, characterized in that, The first dry granules, by mass percentage, contain the following chemical composition: SiO2 51.5%–57.5%, Al2O3 9.8%–11.8%, CaO 11.3%–13.4%, MgO 2.7%–3.5%, K2O 5.8%–6.8%, Na2O 0.4%–0.6%, BaO 2.3%–2.8%, ZnO 8.4%–10.2%, with the remainder being loss on ignition and impurities.

2. The ceramic dry granules according to claim 1, characterized in that, It also includes a second dry granule; the chemical composition of the second dry granule, by mass percentage, includes: SiO2 51.2%–57.1%, Al2O3 15.6%–18.2%, CaO 6.5%–7.9%, MgO 2.3%–2.7%, K2O 3.3%–3.8%, Na2O 1.8%–2.2%, SrO 7.2%–8.6%, BaO 0.3%–0.5%, ZnO 4.7%–5.5%, with the remainder being loss on ignition and impurities; the mass ratio of the first dry granule to the second dry granule is 1:(0.12–0.13).

3. The ceramic dry granules according to claim 2, characterized in that, It also includes a third dry granule; the chemical composition of the third dry granule, by mass percentage, includes: SiO2 48.6%–52.7%, Al2O3 18.5%–21.5%, CaO 16.6%–20.2%, K2O 3.1%–3.6%, ZnO 6.4%–7.6%, with the remainder being loss on ignition and impurities; the mass ratio of the first dry granule to the third dry granule is 1:(0.12–0.13).

4. The ceramic dry granules according to claim 3, characterized in that, The first dry granules have a particle size D90 of 182µm to 188µm; the second dry granules have a particle size D90 of 151µm to 157µm; and the third dry granules have a particle size D90 of 126µm to 132µm.

5. A dry-granule glaze, characterized in that, Includes the ceramic dry granules as described in any one of claims 1-4.

6. The dry-granule glaze according to claim 5, characterized in that, The dry granule glaze also includes a protective glaze; the protective glaze, by mass percentage, comprises: SiO2 54.3%–60.2%, Al2O3 9.8%–11.9%, CaO 2.3%–3.1%, MgO 1.45%–1.95%, K2O 4.1%–4.8%, Na2O 1.3%–1.75%, SrO 2.7%–3.3%, ZnO 9.8%–12.2%, with the remainder being loss on ignition and impurities.

7. The dry-granule glaze according to claim 6, characterized in that, The mass ratio of the ceramic dry granules to the protective glaze is 1:(0.19~0.21).

8. The dry-granule glaze according to claim 6, characterized in that, The particle size D90 of the protective glaze is 20µm to 25µm.

9. A dry-granule polished ceramic tile, characterized in that, It includes a body layer and a dry granule glaze layer disposed on the body layer; the dry granule glaze layer is made of the dry granule glaze according to any one of claims 5-8, and the mass ratio of amorphous phase in the dry granule glaze layer is >99%.

10. A method for preparing dry-granule polished ceramic tiles as described in claim 9, characterized in that, Includes the following steps: Apply dry granule glaze to the body layer to form a dry granule glaze layer after firing; Firing and cooling ceramic bricks after firing; The ceramic tile is polished to obtain the dry-granule polished ceramic tile.

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