Antifouling matte antique brick with anti-skid effect and preparation method thereof

Abstract

This invention relates to the field of architectural ceramics technology, and discloses a non-slip, stain-resistant matte antique-style tile and its preparation method, including: A. preparing the body layer; B. applying the base glaze; C. applying the non-slip and stain-resistant matte glaze; D. firing. The anti-slip and anti-fouling matte glaze includes anti-fouling matte glaze and anti-slip dry granules. The anti-fouling matte glaze is composed of 7-10 parts kaolin, 5-10 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 8-15 parts sodium feldspar, 5-10 parts calcined talc, 1-3 parts zinc oxide, 2-5 parts strontium carbonate, and 20-30 parts anti-fouling and wear-resistant frit. The chemical composition of the anti-slip dry granules includes 38-42% SiO2, 20-24% Al2O3, 18-20% CaO, 0.5-2% MgO, 3-4.5% K2O, 0.2-1% Na2O, 8-10% ZnO, 1-2.5% BaO, and 1-2.5% B2O3. This solution can balance gloss, stain resistance, hardness, wear resistance, color development, and anti-slip properties under existing firing conditions, thereby improving consumer satisfaction.

Description

Technical Field

[0001] This invention relates to the field of building ceramics technology, and in particular to a non-slip, stain-resistant matte antique-style brick and its preparation method. Background Technology

[0002] In the field of architectural ceramics, the glaze surface of antique bricks is generally not polished, so that the glaze surface retains the sintered state and presents a raw matte texture similar to natural stone.

[0003] Considering factors such as gloss, cost, and smoothness, the glaze formulations of existing antique-style tiles typically use all-raw-material formulas, and the fluxing system is generally a potassium-sodium system. However, if the potassium-sodium content in the glaze formulation is high, the glaze is prone to melting and forming a glassy phase at the low-temperature stage of the firing curve. This results in the glaze raw materials being trapped in the glaze layer before they can be degassed during sintering, causing bubbles to appear on the glaze surface and reducing its anti-fouling performance.

[0004] To improve the stain resistance of existing antique-style bricks, technicians typically adjust the formula and firing temperature. However, since the firing curve of antique-style bricks is generally based on the existing vitrification of the body and base glaze, only a small range of temperature adjustments can be made. The room for improvement in stain resistance is very limited, and the improvement is basically achieved by adjusting the glaze formula to adapt to the existing firing conditions.

[0005] Due to the rigidity of the firing process, it is difficult to balance the gloss, stain resistance, hardness, wear resistance and color performance of antique-style brick glaze formulas composed entirely of raw materials. Therefore, it is urgent to break the existing structure of glaze formulas composed entirely of raw materials for antique-style bricks, so that under the existing firing conditions, gloss, stain resistance, hardness, wear resistance and color performance can be taken into account simultaneously, thereby improving consumers' satisfaction with the use of antique-style bricks.

[0006] In addition, the anti-slip performance of antique-style tiles used for flooring is receiving increasing attention from the industry. How to give antique-style tiles anti-slip performance while ensuring stain resistance has also become a key focus of the industry. Summary of the Invention

[0007] The purpose of this invention is to propose a non-slip, stain-resistant matte antique-style tile and its preparation method. By optimizing the glaze formula structure of the antique-style tile, it can simultaneously achieve gloss, stain resistance, hardness, wear resistance, color development and non-slip performance under existing firing conditions, thereby improving consumer satisfaction with the use of antique-style tiles.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] A method for preparing anti-slip, stain-resistant matte antique-style tiles includes the following steps:

[0010] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

[0011] B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer;

[0012] C. Apply an anti-slip and anti-fouling matte glaze to the surface of the base glaze layer to obtain an anti-slip and anti-fouling matte glaze layer;

[0013] D. After drying, the bricks are fired in a kiln to obtain anti-slip, stain-resistant matte antique-style bricks.

[0014] In step C, the anti-slip and anti-fouling matte glaze includes anti-fouling matte glaze and anti-slip dry granules, and the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:(1~2) by mass.

[0015] According to the mass fraction, the raw materials of the anti-fouling matte glaze are composed of 7-10 parts kaolin, 5-10 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 8-15 parts sodium feldspar, 5-10 parts calcined talc, 1-3 parts zinc oxide, 2-5 parts strontium carbonate, and 20-30 parts anti-fouling and wear-resistant frit.

[0016] The chemical composition of the anti-fouling and wear-resistant fused block, calculated by mass percentage, includes SiO2 32-40%, Al2O3 18-20%, CaO 18-20%, K2O 0.5-1.5%, ZnO 10-12%, BaO 1-2.5%, and SrO 12-15%.

[0017] The chemical composition of the anti-slip dry granules, calculated by mass percentage, includes SiO2 38-42%, Al2O3 20-24%, CaO 18-20%, MgO 0.5-2%, K2O 3-4.5%, Na2O 0.2-1%, ZnO 8-10%, BaO 1-2.5%, and B2O3 1-2.5%.

[0018] In step D, the firing temperature is 1180–1205°C, and the firing time is 45–60 min.

[0019] Preferably, the anti-slip dry granules consist of granules with a mesh size ≥150 and <160, granules with a mesh size ≥160 and <200, granules with a mesh size ≥200 and <250, and granules with a mesh size of 250 to 325.

[0020] Preferably, the particle size distribution of the anti-slip dry granules satisfies the following: based on the total weight of the anti-slip dry granules, particles with a mesh size ≥150 and <160 account for 10-20%, particles with a mesh size ≥160 and <200 account for 40-55%, particles with a mesh size ≥200 and <250 account for 20-30%, and particles with a mesh size of 250-325 account for 5-13%.

[0021] Preferably, the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:1.5 by mass.

[0022] Preferably, the firing curve of the anti-fouling and wear-resistant fused block is as follows:

[0023] The time required to heat the temperature from room temperature to 300℃ is 1.5 to 2.5 hours.

[0024] The temperature rises from 300℃ to 1530℃, taking 2-3 hours.

[0025] 1530℃, keep warm for 0.5~1.2h.

[0026] Preferably, step C specifically includes:

[0027] C. Spray an anti-slip and anti-fouling matte glaze onto the surface of the base glaze layer to obtain an anti-slip and anti-fouling matte glaze layer;

[0028] The specific gravity of the anti-slip and anti-fouling matte glaze is 1.5 to 1.55, and the nozzle diameter of the spray gun is 0.62 mm.

[0029] Preferably, the chemical composition of the anti-fouling and wear-resistant frit, calculated by mass percentage, includes 34.81% SiO2, 18.66% Al2O3, 19.16% CaO, 0.81% K2O, 11.23% ZnO, 1.76% BaO, and 13.46% SrO.

[0030] The chemical composition of the anti-slip dry granules, calculated by mass percentage, includes 40.72% SiO2, 23.21% Al2O3, 18.59% CaO, 1.04% MgO, 3.49% K2O, 0.54% Na2O, 8.82% ZnO, 1.72% BaO, and 1.87% B2O3.

[0031] Preferably, the raw materials of the antifouling and wear-resistant frit, calculated by mass parts, consist of 12-18 parts of quartz, 15-20 parts of calcined alumina, 30-38 parts of wollastonite, 8-12 parts of zinc oxide, 18-22 parts of strontium carbonate, and 1-5 parts of barium carbonate.

[0032] Preferably, the raw materials of the anti-slip dry granules, calculated by mass parts, consist of 30-35 parts kaolin, 8-12 parts calcined alumina, 3-6 parts quartz, 30-38 parts wollastonite, 5-10 parts zinc oxide, 3-8 parts dolomite, 3-8 parts potassium nitrate, 1-4 parts barium carbonate, and 1-5 parts borax.

[0033] A non-slip, stain-resistant matte antique-style tile is prepared using the above-mentioned method for preparing non-slip, stain-resistant matte antique-style tiles. The non-slip, stain-resistant matte antique-style tile has a glaze gloss of 8-12°, a stain resistance level of 5, a Mohs hardness of 7, a wear resistance of ≥4 (6000 revolutions), a dry static friction coefficient of ≥0.77, and a wet static friction coefficient of ≥0.75.

[0034] The technical solution provided by this invention may include the following beneficial effects:

[0035] 1. Al in the sintering process of the frit 3+ The presence of aluminum-oxygen tetrahedra within silicon-oxygen tetrahedra creates a dense mullite network structure from the partial silicon oxide and aluminum oxide in the chemical composition. This mullite network structure specifically includes two crystal forms: 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂. When these crystals are uniformly distributed in the glaze layer, they effectively improve the hardness and wear resistance of the glaze. Furthermore, the high silicon-aluminum content in the chemical composition also enhances the acid and alkali resistance of the frit, providing long-term protection against acid and alkali corrosion and contributing to anti-fouling properties. Additionally, the anti-fouling and wear-resistant frit utilizes divalent Sr ions... 2+ and Zn 2+ As a flux system, it can help the frit form a dense internal structure during firing, thus aiding in anti-fouling; at the same time, Sr 2+ and Zn 2+ It also helps the frit to precipitate calcium feldspar crystals during the firing process. On the one hand, calcium feldspar crystals can also help improve the hardness and wear resistance of the glaze. On the other hand, calcium feldspar crystals have high transparency and contain a large amount of ZnO in their chemical composition. Introducing the frit as a raw material into the glaze can effectively improve the color performance of the glaze.

[0036] 2. The anti-fouling matte glaze reduces the proportion of potassium feldspar and sodium feldspar in the raw material formula, while introducing a higher proportion of quartz. This reduces the content of low-temperature fluxes K2O and Na2O, as well as the fusible glass phase, in the glaze. This increases the softening temperature of the glaze during sintering, preventing premature formation of a sealed layer during firing and allowing sufficient time for gas degassing, matching the low-temperature, fast-firing firing regime of existing antique-style tiles. Furthermore, strontium carbonate and strontium oxide are added to the anti-fouling matte glaze raw materials. Strontium carbonate lowers the softening temperature of the glaze, increases its high-temperature fluidity, and expands its firing range, thus promoting the formation of a dense glaze layer structure and improving its anti-fouling performance. Additionally, due to Sr... 2+ The atomic radius of Ca is greater than that of Ca 2+ Mg 2+ The large radius and extensive use of strontium oxide create a certain surface roughness between it and the glass phase in the glaze. This roughness, combined with incident light, causes diffuse reflection, reducing the surface gloss and achieving the matte effect of antique-style tiles. Furthermore, the uniform distribution of crystalline phases formed with other divalent metal ions on the glaze surface further controls the surface gloss to 8-12°, meeting the popular aesthetic preference for matte finishes in antique-style tiles. Moreover, calcined kaolin and calcined talc are incorporated into the glaze raw materials. This allows for the additional formation of high-hardness mullite and cordierite crystals during firing. Combined with the existing crystals in the frit and unmelted quartz in the raw materials, the matte glaze layer exhibits a variety of high-hardness crystals, enhancing its hardness and wear resistance. This ensures that the glaze surface properties are not easily damaged during long-term use, achieving lasting stain resistance.

[0037] 3. The anti-slip dry granules in this solution contain a high CaO content, resulting in a crystal system after firing with calcium feldspar as the main crystalline phase and mullite as the auxiliary crystalline phase. Since mullite crystals are generally opaque, the anti-slip dry granules have significant advantages in transparency and color development. Furthermore, the coefficient of thermal expansion of calcium feldspar is significantly greater than that of mullite; the calcium feldspar-dominant crystal system effectively improves the smoothness of the tile glaze. The anti-slip dry granule formula in this solution is a low-silicon, high-alumina system. This low-silicon, high-alumina system promotes crystal formation in the anti-slip dry granules while reducing the formation of the glass phase, thereby increasing the hardness and initial melting point of the dry granules. Additionally, Al2O3 and the formed calcium feldspar crystals both have high viscosity at high temperatures. When the anti-slip dry granules are combined with a matte anti-fouling glaze that also has high viscosity at high temperatures, they are less likely to melt and remain largely in their initial state, thus greatly improving the anti-slip performance of the glaze.

[0038] 4. The chemical composition and crystal system of the anti-slip granules result in a relatively low melting point. When combined with the anti-fouling matte glaze, the anti-slip granules can slightly melt into the glaze. This ensures that the granules retain their initial particle state and protrude from the glaze surface, improving the anti-slip coefficient. Furthermore, it enhances the bonding between the granules and the glaze, preventing a decrease in anti-fouling performance. Additionally, to prevent dirt from accumulating between the anti-fouling matte glaze and the anti-slip granules, thus effectively enhancing the easy-to-clean properties of the anti-fouling matte antique tiles, this solution also limits the mixing ratio of the anti-slip granules and the anti-fouling matte glaze to mitigate dirt trapping. Detailed Implementation

[0039] A method for preparing anti-slip, stain-resistant matte antique-style tiles includes the following steps:

[0040] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

[0041] B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer;

[0042] C. Apply an anti-slip and anti-fouling matte glaze to the surface of the base glaze layer to obtain an anti-slip and anti-fouling matte glaze layer;

[0043] D. After drying, the bricks are fired in a kiln to obtain anti-slip, stain-resistant matte antique-style bricks.

[0044] In step C, the anti-slip and anti-fouling matte glaze includes anti-fouling matte glaze and anti-slip dry granules, and the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:(1~2) by mass.

[0045] According to the mass fraction, the raw materials of the anti-fouling matte glaze are composed of 7-10 parts kaolin, 5-10 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 8-15 parts sodium feldspar, 5-10 parts calcined talc, 1-3 parts zinc oxide, 2-5 parts strontium carbonate, and 20-30 parts anti-fouling and wear-resistant frit.

[0046] The chemical composition of the anti-fouling and wear-resistant fused block, calculated by mass percentage, includes SiO2 32-40%, Al2O3 18-20%, CaO 18-20%, K2O 0.5-1.5%, ZnO 10-12%, BaO 1-2.5%, and SrO 12-15%.

[0047] The chemical composition of the anti-slip dry granules, calculated by mass percentage, includes SiO2 38-42%, Al2O3 20-24%, CaO 18-20%, MgO 0.5-2%, K2O 3-4.5%, Na2O 0.2-1%, ZnO 8-10%, BaO 1-2.5%, and B2O3 1-2.5%.

[0048] In step D, the firing temperature is 1180–1205°C, and the firing time is 45–60 min.

[0049] In order to ensure that the glaze layer of antique-style tiles simultaneously achieves gloss, stain resistance, hardness, wear resistance, color development, and anti-slip properties under existing firing conditions (i.e., firing temperature of 1180–1205℃ and firing time of 45–60 min), this solution first designs and optimizes the anti-stain matte glaze in the anti-slip and anti-fouling matte glaze. This breaks the existing glaze formula structure of antique-style tiles, which is composed entirely of raw materials, and can effectively improve consumers' satisfaction with the use of antique-style tiles.

[0050] Specifically, the raw material formula of the anti-fouling matte glaze in this solution consists of a raw material component and a calcined material component, with the calcined material being the anti-fouling and wear-resistant frit. It should be noted that in the ceramics industry, calcined material is generally defined as a frit obtained through firing, where the materials are fully matured before application. Calcination of kaolin, talc, and zinc oxide, etc., simply involves calcining a single raw material to allow the organic matter to volatilize and the crystal form to become more stable; these are still considered raw materials. In other words, all materials other than the frit are defined as raw materials.

[0051] Based on the chemical composition of the anti-fouling and wear-resistant fused block in this solution, the Al content of the fused block during the firing process... 3+ The presence of aluminum-oxygen tetrahedra within silicon-oxygen tetrahedra results in a dense mullite network structure formed from some of the silicon oxide and aluminum oxide in the chemical composition. This mullite network structure specifically includes two crystal forms: 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂. When these crystals are uniformly distributed in the glaze layer, they can effectively improve the hardness and wear resistance of the glaze layer. Furthermore, the high silicon-aluminum content in the chemical composition also helps to improve the acid and alkali resistance of the frit, providing long-term protection against the erosion of acidic and alkaline substances and aiding in stain prevention.

[0052] In addition, the chemical composition of the anti-fouling and wear-resistant fused block is dominated by divalent ions Sr. 2+ and Zn 2+ As a flux system, it can help the frit form a dense internal structure during firing, thus aiding in anti-fouling; at the same time, Sr 2+ and Zn 2+It also helps the frit to precipitate calcium feldspar crystals during the firing process. On the one hand, calcium feldspar crystals can also help improve the hardness and wear resistance of the glaze. On the other hand, calcium feldspar crystals have high transparency and contain a large amount of ZnO in their chemical composition. Introducing the frit as a raw material into the glaze can effectively improve the color performance of the glaze.

[0053] For the raw material portion of the anti-fouling matte glaze, compared to the existing raw material formula structure of antique tiles, this solution reduces the proportion of potassium feldspar and sodium feldspar in the raw material formula, while introducing a higher proportion of quartz. This reduces the content of low-temperature fluxes K2O and Na2O, as well as the fusible glass phase in the glaze, thereby increasing the softening point temperature of the glaze during sintering. This prevents the premature formation of a sealed layer during glaze firing, allowing sufficient time for the gases generated during firing to escape, matching the low-temperature, fast-firing firing regime of existing antique tiles. Furthermore, the increased softening point temperature of the glaze also helps prevent the anti-fouling matte glaze from forming a low-temperature eutectic composition with the anti-slip dry granules, which would cause the dry granules to melt and reduce the anti-slip performance of the glaze surface.

[0054] Furthermore, to effectively prevent strontium oxide from melting with the glassy phase in the frit and reducing its fluxing activity in the glaze, this solution also introduces strontium carbonate into the anti-fouling matte glaze raw material. Strontium oxide can lower the softening temperature of the glaze, increase its high-temperature fluidity, and expand its firing range, thus facilitating the formation of a dense glaze layer structure and improving its anti-fouling performance. Additionally, due to Sr... 2+ The atomic radius of Ca is greater than that of Ca 2+ Mg 2+ The large radius and extensive use of strontium oxide create a certain surface roughness between the glaze and the glass phase, resulting in diffuse reflection of incident light and reducing the surface gloss of the glaze, thus achieving a matte effect for antique-style tiles. Furthermore, the uniform distribution of the crystalline phase formed with other divalent metal ions on the glaze surface can control the surface gloss of the glaze layer to 8–12°, which meets the general aesthetic preference of consumers for the matte gloss of antique-style tiles.

[0055] Furthermore, since calcined kaolin and calcined talc are also introduced into the raw materials of the glaze, mullite and cordierite crystals with higher hardness can be generated additionally during the firing of the glaze. Combined with the original crystals in the frit and the unmelted quartz in the raw materials, the glaze surface has a variety of crystals with higher hardness, which is more conducive to improving the hardness and wear resistance of the glaze surface. Under the long-term use of antique bricks, the surface performance of the glaze layer is not easily damaged, achieving long-lasting stain resistance.

[0056] Secondly, in order to give antique tiles anti-slip properties while ensuring anti-fouling performance, this solution also developed an anti-slip dry granule that matches the anti-fouling matte glaze, so that the anti-slip and anti-fouling matte glaze can simultaneously achieve excellent anti-fouling and anti-slip performance.

[0057] Specifically, the anti-slip dry granules of this solution contain a high content of CaO, which causes the dry granules to form a crystal system with calcium feldspar as the main crystalline phase and mullite as the auxiliary crystalline phase after firing. Since mullite crystals are generally opaque, the anti-slip dry granules have outstanding advantages in terms of transparency and color development. In addition, the expansion coefficient of calcium feldspar is significantly greater than that of mullite. The crystal system with calcium feldspar as the main crystalline phase can effectively improve the flatness of the glaze of the ceramic tile.

[0058] In the field of architectural ceramics, systems with SiO2 content below 50% and Al2O3 content above 18% are generally referred to as low-silicon, high-alumina systems. The anti-slip dry granule formulation in this case is precisely a low-silicon, high-alumina system. This low-silicon, high-alumina configuration facilitates crystal formation in the anti-slip dry granules while reducing the formation of the glassy phase, thereby increasing the hardness and initial melting point of the dry granules. Furthermore, Al2O3 and the resulting anorthite crystals both exhibit high viscosity at high temperatures. When the anti-slip dry granules are combined with a similarly high-temperature viscosity anti-fouling matte glaze, they are less likely to melt and remain largely in their initial state, thus significantly enhancing the anti-slip performance of the glaze surface.

[0059] Furthermore, the compatibility between anti-slip granules and anti-fouling matte glaze is also reflected in their melting points. The chemical composition and crystal system of the anti-slip granules result in a relatively low melting point. When combined with the anti-fouling matte glaze, the anti-slip granules can slightly melt into the glaze. This ensures that the granules retain their initial particle state and protrude from the glaze surface, improving the anti-slip coefficient. Simultaneously, it enhances the bonding between the granules and the glaze, preventing a decrease in anti-fouling performance. It should be noted that if the melting point difference between the granules and the glaze is too large (i.e., the granules' melting point is too high), they are difficult to bond with the glaze, resulting in an underfired state and creating numerous voids around the granules that trap dirt. However, when the firing temperatures of the anti-slip granules and the anti-fouling matte glaze are matched, the granules can be partially melted but not completely melted, bonding with the glaze to form a dense glaze layer, thus preventing a decrease in anti-fouling performance.

[0060] Finally, to prevent dirt from getting trapped between the anti-fouling matte glaze and the anti-slip dry granules, thereby effectively enhancing the easy-to-clean properties of the anti-fouling matte antique tiles, this solution also limits the mixing ratio between the anti-slip dry granules and the anti-fouling matte glaze to improve the problem of dirt trapping.

[0061] Preferably, the raw materials of the anti-fouling matte glaze, calculated by mass parts, consist of 8 parts kaolin, 6 parts calcined kaolin, 5 parts quartz, 25 parts potassium feldspar, 10 parts sodium feldspar, 7 parts calcite, 8 parts calcined talc, 2 parts zinc oxide, 4 parts strontium carbonate, and 25 parts anti-fouling and wear-resistant frit.

[0062] It should be noted that the ceramic body in step A and the base glaze in step B of this scheme are both ceramic bodies and base glazes commonly used in antique bricks, and are not limited here.

[0063] To further explain, the anti-slip dry granules are composed of granules with a mesh size of ≥150 mesh and <160 mesh, granules with a mesh size of ≥160 mesh and <200 mesh, granules with a mesh size of ≥200 mesh and <250 mesh, and granules with a mesh size of 250 to 325 mesh.

[0064] Because the anti-slip granules used in this case are of various sizes, the small granules can perfectly adhere to the contact object, improving the problem of dirt getting stuck. The fine anti-slip granules can effectively generate resistance and play an anti-slip role; while the large granules can form protruding particles on the glaze surface, effectively enhancing the anti-slip effect, while also playing an anti-slip and dirt-avoiding role.

[0065] In addition, the anti-slip dry granules in this mesh range can ensure that the anti-slip and anti-fouling matte glaze can be applied evenly by spraying, and after application, it can also form a good feel on the glaze surface.

[0066] Furthermore, the particle size distribution of the anti-slip dry granules satisfies the following: based on the total weight of the anti-slip dry granules, particles with a mesh size ≥150 and <160 account for 10-20%, particles with a mesh size ≥160 and <200 account for 40-55%, particles with a mesh size ≥200 and <250 account for 20-30%, and particles with a mesh size of 250-325 account for 5-13%.

[0067] As a preferred embodiment of the above, this case further optimizes the particle distribution of each mesh size in the anti-slip dry granules to ensure that they simultaneously provide anti-slip and prevent dirt from getting stuck.

[0068] Preferably, the particle size distribution of the anti-slip dry granules satisfies the following: based on the total weight of the anti-slip dry granules, particles with a mesh size ≥150 mesh and <160 mesh account for 15.31%, particles with a mesh size ≥160 mesh and <200 mesh account for 48%, particles with a mesh size ≥200 mesh and <250 mesh account for 26.99%, and particles with a mesh size of 250 to 325 mesh account for 9.7%.

[0069] To further explain, the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:1.5 by mass.

[0070] To further explain, the firing curve of the anti-fouling and wear-resistant fused block is as follows:

[0071] The time required to heat the temperature from room temperature to 300℃ is 1.5 to 2.5 hours.

[0072] The temperature rises from 300℃ to 1530℃, taking 2-3 hours.

[0073] 1530℃, keep warm for 0.5~1.2h.

[0074] In this way, the softening point temperature of the frit can be matched with the existing firing system of antique bricks, so that the tiny frit particles after ball milling can create a tiny rough surface between them and the glass phase plane formed after the glaze is fired, further ensuring the formation of a matte glaze.

[0075] Preferably, the firing curve of the anti-fouling and wear-resistant fused block is as follows:

[0076] It takes 2 hours to heat the temperature from room temperature to 300℃.

[0077] The temperature was raised from 300℃ to 1530℃ in 2.5 hours.

[0078] 1530℃, keep warm for 1 hour.

[0079] To elaborate further, step C specifically involves:

[0080] C. Spray an anti-slip and anti-fouling matte glaze onto the surface of the base glaze layer to obtain an anti-slip and anti-fouling matte glaze layer;

[0081] The specific gravity of the anti-slip and anti-fouling matte glaze is 1.5 to 1.55, and the nozzle diameter of the spray gun is 0.62 mm.

[0082] In another specific embodiment of this technical solution, the anti-slip and anti-fouling matte glaze can be applied by spraying. However, in order to ensure the uniform distribution of the anti-slip dry particles on the glaze surface, this solution also optimizes the specific gravity of the glaze and the nozzle diameter of the spray gun during spraying.

[0083] To further explain, the chemical composition of the anti-fouling and wear-resistant frit, calculated by mass percentage, includes 34.81% SiO2, 18.66% Al2O3, 19.16% CaO, 0.81% K2O, 11.23% ZnO, 1.76% BaO, and 13.46% SrO.

[0084] The chemical composition of the anti-slip dry granules, calculated by mass percentage, includes 40.72% SiO2, 23.21% Al2O3, 18.59% CaO, 1.04% MgO, 3.49% K2O, 0.54% Na2O, 8.82% ZnO, 1.72% BaO, and 1.87% B2O3.

[0085] To further explain, the raw materials of the antifouling and wear-resistant frit, calculated by mass, consist of 12-18 parts quartz, 15-20 parts calcined alumina, 30-38 parts wollastonite, 8-12 parts zinc oxide, 18-22 parts strontium carbonate, and 1-5 parts barium carbonate.

[0086] In a preferred embodiment of this technical solution, the anti-fouling and wear-resistant frit can be made by calcining quartz, calcined alumina, wollastonite, zinc oxide, strontium carbonate and barium carbonate and then water quenching.

[0087] To further explain, the raw materials of the anti-slip dry granules, calculated by mass, consist of 30-35 parts kaolin, 8-12 parts calcined alumina, 3-6 parts quartz, 30-38 parts wollastonite, 5-10 parts zinc oxide, 3-8 parts dolomite, 3-8 parts potassium nitrate, 1-4 parts barium carbonate, and 1-5 parts borax.

[0088] In a preferred embodiment of this technical solution, the anti-slip dry granules can be made by calcining kaolin, calcined alumina, quartz, wollastonite, zinc oxide, dolomite, potassium nitrate, barium carbonate and borax, followed by water quenching to form an anti-slip frit, and then crushing the anti-slip frit.

[0089] A non-slip, stain-resistant matte antique-style tile is prepared using the above-mentioned method for preparing non-slip, stain-resistant matte antique-style tiles. The non-slip, stain-resistant matte antique-style tile has a glaze gloss of 8-12°, a stain resistance level of 5, a Mohs hardness of 7, a wear resistance of ≥4 (6000 revolutions), a dry static friction coefficient of ≥0.77, and a wet static friction coefficient of ≥0.75.

[0090] The proposed solution provides anti-slip, stain-resistant matte antique-style tiles that, under existing firing conditions, simultaneously achieve good gloss, stain resistance, hardness, wear resistance, color development, and anti-slip properties, thereby improving consumer satisfaction with antique-style tiles.

[0091] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0092] Example 1

[0093] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

[0094] B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer;

[0095] C. Apply a non-slip and anti-fouling matte glaze with a specific gravity of 1.5 to the surface of the base glaze layer using a spray gun with an aperture of 0.62mm to obtain a non-slip and anti-fouling matte glaze layer.

[0096] D. After drying, the bricks are fired in a kiln to obtain anti-slip, stain-resistant matte antique-style bricks.

[0097] In step C, the anti-slip and anti-fouling matte glaze comprises anti-fouling matte glaze and anti-slip dry granules, and the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:1 by mass. The particle size distribution of the anti-slip dry granules meets the following requirements based on the total weight of the anti-slip dry granules: particles with a mesh size ≥150 and <160 mesh account for 15%, particles with a mesh size ≥160 and <200 mesh account for 45%, particles with a mesh size ≥200 and <250 mesh account for 30%, and particles with a mesh size of 250 to 325 mesh account for 10%. The raw material composition of the anti-fouling matte glaze is shown in Table 1 below, the chemical composition of the anti-fouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the anti-slip dry granules is shown in Table 3 below. In step D, the firing temperature is 1180–1205℃, and the firing time is 45–60 min.

[0098] Example 2

[0099] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

[0100] B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer;

[0101] C. Apply a non-slip and anti-fouling matte glaze with a specific gravity of 1.5 to the surface of the base glaze layer using a spray gun with an aperture of 0.62mm to obtain a non-slip and anti-fouling matte glaze layer.

[0102] D. After drying, the bricks are fired in a kiln to obtain anti-slip, stain-resistant matte antique-style bricks.

[0103] In step C, the anti-slip and anti-fouling matte glaze comprises anti-fouling matte glaze and anti-slip dry granules, with a mass ratio of 10:1.5. The particle size distribution of the anti-slip dry granules meets the following criteria: based on the total weight of the anti-slip dry granules, particles with a mesh size ≥150 and <160 account for 15.31%, particles with a mesh size ≥160 and <200 account for 48%, particles with a mesh size ≥200 and <250 account for 26.99%, and particles with a mesh size of 250–325 account for 9.7%. The raw material composition of the anti-fouling matte glaze is shown in Table 1, the chemical composition of the anti-fouling and wear-resistant frit is shown in Table 2, and the chemical composition of the anti-slip dry granules is shown in Table 3. In step D, the firing temperature is 1180–1205℃, and the firing time is 45–60 min.

[0104] Example 3

[0105] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

[0106] B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer;

[0107] C. Apply a non-slip and anti-fouling matte glaze with a specific gravity of 1.5 to the surface of the base glaze layer using a spray gun with an aperture of 0.62mm to obtain a non-slip and anti-fouling matte glaze layer.

[0108] D. After drying, the bricks are fired in a kiln to obtain anti-slip, stain-resistant matte antique-style bricks.

[0109] In step C, the anti-slip and anti-fouling matte glaze comprises anti-fouling matte glaze and anti-slip dry granules, and the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:2 by mass. The particle size distribution of the anti-slip dry granules meets the following requirements based on the total weight of the anti-slip dry granules: particles with a mesh size ≥150 and <160 mesh account for 20%, particles with a mesh size ≥160 and <200 mesh account for 50%, particles with a mesh size ≥200 and <250 mesh account for 25%, and particles with a mesh size of 250 to 325 mesh account for 5%. The raw material composition of the anti-fouling matte glaze is shown in Table 1 below, the chemical composition of the anti-fouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the anti-slip dry granules is shown in Table 3 below. In step D, the firing temperature is 1180–1205℃, and the firing time is 45–60 min.

[0110] Table 1. Raw material composition of each antifouling matte glaze in Examples 1-3

[0111]

[0112]

[0113] Table 2. Chemical composition of each antifouling and wear-resistant fused block in Examples 1-3

[0114] Chemical composition (%) Example 1 Example 2 Example 3 <![CDATA[SiO2]]> 33.63 34.81 36.85 <![CDATA[Al2O3]]> 18.02 18.66 18.76 CaO 18.22 19.16 19.03 <![CDATA[K2O]]> 0.53 0.81 1.42 ZnO 11.89 11.23 10.16 BaO 2.48 1.76 1.18 SrO 14.96 13.46 12.31

[0115] Table 3 Chemical composition of each anti-slip dry granule in Examples 1-3

[0116] Chemical composition (%) Example 1 Example 2 Example 3 <![CDATA[SiO2]]> 38.56 40.72 41.98 <![CDATA[Al2O3]]> 23.96 23.21 20.16 CaO 18.52 18.59 19.85 MgO 0.56 1.04 1.86 <![CDATA[K2O]]> 3.02 3.49 4.45 <![CDATA[Na2O]]> 0.95 0.54 0.3 ZnO 9.86 8.82 8.19 BaO 2.36 1.72 1.63 <![CDATA[B2O3]]> 2.21 1.87 1.58

[0117] Comparative Example 1

[0118] Replace the anti-fouling matte glaze in Example 2 with glaze A, while keeping the rest of the formula and parameters the same.

[0119] According to the mass fraction, the raw materials of the glaze A consist of 8 parts kaolin, 6 parts calcined kaolin, 5 parts quartz, 25 parts potassium feldspar, 10 parts sodium feldspar, 7 parts calcite, 8 parts calcined talc, 2 parts zinc oxide, 4 parts strontium carbonate, and 25 parts of existing matte frit.

[0120] The chemical composition of existing matte ingots, calculated by mass percentage, includes SiO2 55%, Al2O3 17%, BaO 10%, ZnO 4%, SrO 4.5%, K2O 2.65%, Na2O 3.7%, CaO 2.5%, MgO 0.05%, P2O5 0.3%, and CaF2 0.3%.

[0121] Comparative Example 2

[0122] Replace the anti-fouling matte glaze in Example 2 with glaze B, while keeping the rest of the formula and parameters the same.

[0123] According to the mass fraction, the raw materials of glaze B consist of 15 parts kaolin, 18 parts calcined kaolin, 30 parts potassium feldspar, 20 parts sodium feldspar, 2 parts zinc oxide, 6 parts wollastonite, 5 parts calcined talc, 6 parts wollastonite and 4 parts barium carbonate.

[0124] Comparative Example 3

[0125] Replace the anti-slip dry granules in Example 2 with ordinary anti-slip dry granules, while keeping the rest of the formula and parameters the same.

[0126] The chemical composition of ordinary anti-slip dry granules, calculated by mass percentage, includes 62.11% SiO2, 21.55% Al2O3, 0.05% Fe2O3, 0.22% TiO2, 8.72% CaO, 1.2% MgO, 1.66% K2O, and 3.67% NaO, with a loss on ignition of 0.82%.

[0127] The antique-style bricks prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to conventional tests in the field of building ceramics, including hardness, wear resistance, glaze gloss, stain resistance, and slip resistance. The results are shown in Table 4 below.

[0128] Table 4. Performance test results of antique bricks in Examples 1-3 and Comparative Examples 1-3

[0129]

[0130] As can be seen from the performance test results in Table 4, the anti-slip and stain-resistant matte antique-style tiles prepared by this method can simultaneously achieve good gloss, stain resistance, hardness, wear resistance, color development, and anti-slip performance under existing firing conditions, thereby improving consumer satisfaction with the use of antique-style tiles.

[0131] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a stain-resistant matte antique-style tile with anti-slip properties, characterized in that, Includes the following steps: A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer; C. Apply an anti-slip and anti-fouling matte glaze to the surface of the base glaze layer to obtain an anti-slip and anti-fouling matte glaze layer; D. After drying, the bricks are fired in a kiln to obtain anti-slip, stain-resistant matte antique-style bricks. In step C, the anti-slip and anti-fouling matte glaze includes anti-fouling matte glaze and anti-slip dry granules, and the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:(1~2) by mass. According to the mass fraction, the raw materials of the anti-fouling matte glaze are composed of 7-10 parts kaolin, 5-10 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 8-15 parts sodium feldspar, 5-10 parts calcined talc, 1-3 parts zinc oxide, 2-5 parts strontium carbonate, and 20-30 parts anti-fouling and wear-resistant frit. The chemical composition of the anti-fouling and wear-resistant frit, calculated by mass percentage, includes SiO2 32-40%, Al2O3 18-20%, CaO 18-20%, K2O 0.5-1.5%, ZnO 10-12%, BaO 1-2.5%, and SrO 12-15%. The chemical composition of the anti-slip dry granules, calculated by mass percentage, includes SiO2 38-42%, Al2O3 20-24%, CaO 18-20%, MgO 0.5-2%, K2O 3-4.5%, Na2O 0.2-1%, ZnO 8-10%, BaO 1-2.5%, and B2O3 1-2.5%. In step D, the firing temperature is 1180–1205°C, and the firing time is 45–60 min.

2. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, The anti-slip dry granules consist of granules with a mesh size ≥150 and <160, granules with a mesh size ≥160 and <200, granules with a mesh size ≥200 and <250, and granules with a mesh size of 250 to 325.

3. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 2, characterized in that, The particle size distribution of the anti-slip dry granules satisfies the following: based on the total weight of the anti-slip dry granules, particles with a mesh size ≥150 and <160 account for 10-20%, particles with a mesh size ≥160 and <200 account for 40-55%, particles with a mesh size ≥200 and <250 account for 20-30%, and particles with a mesh size of 250-325 account for 5-13%.

4. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, According to the mass ratio, the mixing ratio of the anti-fouling matte glaze and the anti-slip dry granules is 10:1.

5.

5. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, The firing curve of the antifouling and wear-resistant fused block is as follows: The time required to heat the temperature from room temperature to 300℃ is 1.5 to 2.5 hours. The temperature rises from 300℃ to 1530℃, taking 2-3 hours. 1530℃, keep warm for 0.5~1.2h.

6. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, Step C specifically involves: C. Spray an anti-slip and anti-fouling matte glaze onto the surface of the base glaze layer to obtain an anti-slip and anti-fouling matte glaze layer; The specific gravity of the anti-slip and anti-fouling matte glaze is 1.5 to 1.55, and the nozzle diameter of the spray gun is 0.62 mm.

7. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, The chemical composition of the anti-fouling and wear-resistant frit, calculated by mass percentage, includes SiO2 34.81%, Al2O3 18.66%, CaO 19.16%, K2O 0.81%, ZnO 11.23%, BaO 1.76%, and SrO 13.46%. The chemical composition of the anti-slip dry granules, calculated by mass percentage, includes 40.72% SiO2, 23.21% Al2O3, 18.59% CaO, 1.04% MgO, 3.49% K2O, 0.54% Na2O, 8.82% ZnO, 1.72% BaO, and 1.87% B2O3.

8. The method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, According to the mass fractions, the raw materials of the antifouling and wear-resistant fused block are composed of 12-18 parts of quartz, 15-20 parts of calcined alumina, 30-38 parts of wollastonite, 8-12 parts of zinc oxide, 18-22 parts of strontium carbonate and 1-5 parts of barium carbonate.

9. A method for preparing a non-slip, stain-resistant matte antique-style brick according to claim 1, characterized in that, According to the mass fractions, the raw materials of the anti-slip dry granules consist of 30-35 parts kaolin, 8-12 parts calcined alumina, 3-6 parts quartz, 30-38 parts wollastonite, 5-10 parts zinc oxide, 3-8 parts dolomite, 3-8 parts potassium nitrate, 1-4 parts barium carbonate, and 1-5 parts borax.

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