An anti - pollution matte antique brick with anti - slip performance and its preparation method

Abstract

The present invention relates to the technical field of architectural ceramics, and discloses an anti-fouling matte antique brick with anti-slip performance and a preparation method thereof, including: A. Prepare a body layer; B. Apply a base glaze on the surface of the body layer; C. Apply an anti-slip and anti-fouling matte glaze on the surface of the base glaze layer; D. After drying, put it into a kiln for firing; the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze, anti-fouling and wear-resistant dry particles and anti-slip dry particles, and the anti-fouling and wear-resistant dry particles are composed of particles with a mesh number of ≥200 meshes and <250 meshes and particles with a mesh number of 250-325 meshes, and the anti-slip dry particles are composed of particles with a mesh number of ≥150 meshes and <160 meshes, particles with a mesh number of ≥160 meshes and <200 meshes, particles with a mesh number of ≥200 meshes and <250 meshes and particles with a mesh number of 250-325 meshes. The anti-fouling matte antique brick with anti-slip performance proposed by this solution can take into account the glossiness, anti-fouling performance, hardness, wear resistance, color development and anti-slip performance under the existing firing conditions, and improve the satisfaction of consumers with the use of antique bricks.

Description

Technical Field

[0001] The invention relates to the technical field of building ceramics, and in particular to an anti-fouling matte antique brick with anti-slip performance and a preparation method thereof. Background Art

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

[0003] Based on considerations of glossiness, cost and flatness, the existing glaze formula structure of antique tiles usually uses a full raw material formula, and the flux system is generally a potassium-sodium system. However, if the potassium-sodium content in the glaze formula structure is high, the glaze is easy to melt and produce a glass phase at the low temperature stage of the firing curve, resulting in the glaze raw materials being sealed in the glaze layer before they can be exhausted during the sintering process, causing bubbles to appear on the glaze surface and causing a decrease in anti-fouling performance.

[0004] In order to improve the anti-fouling performance of existing antique tiles, technicians generally adjust the formula and firing temperature. However, since the firing curve of antique tiles is generally based on the existing body and base glaze being vitrified, only a small range of temperature adjustment can be made, and the room for improvement in anti-fouling performance is very limited. Basically, the formula structure of the glaze is adjusted to adapt to the existing firing conditions.

[0005] Due to the rigidification of the firing system, it is difficult to strike a balance between glossiness, anti-fouling performance, hardness, wear resistance and color development performance for the glaze formula of antique tiles composed entirely of raw materials. Therefore, it is urgent to break the existing glaze formula structure of antique tiles composed entirely of raw materials so that under the existing firing conditions, glossiness, anti-fouling performance, hardness, wear resistance and color development performance can be taken into account at the same time, thereby improving consumers' satisfaction with the use of antique tiles.

[0006] In addition, the anti-slip performance of antique tiles used for floors is increasingly valued by the industry. How to give antique tiles anti-slip properties while ensuring anti-fouling properties has also become a focus of industry attention. Summary of the invention

[0007] The purpose of the present invention is to propose an anti-fouling matte antique tile with anti-slip performance and a preparation method thereof, and to optimize the glaze formula structure of the antique tile so that under the existing firing conditions, the glossiness, anti-fouling performance, hardness, wear resistance, color and anti-slip performance are taken into account at the same time, thereby improving consumers' satisfaction with the use of the antique tile.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] A method for preparing anti-fouling matte antique tiles with anti-slip properties comprises the following steps:

[0010] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

[0011] B. Apply a base glaze to the surface of the green body layer to obtain a 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, fire in a kiln to obtain an anti-fouling matte antique brick with anti-slip performance;

[0014] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze, anti-fouling and wear-resistant dry particles, and anti-slip dry particles. The anti-fouling and wear-resistant dry particles are composed of particles with a mesh number of ≥200 meshes and <250 meshes and particles of 250 - 325 meshes. The anti-slip dry particles are composed of particles with a mesh number of ≥150 meshes and <160 meshes, particles with a mesh number of ≥160 meshes and <200 meshes, particles with a mesh number of ≥200 meshes and <250 meshes, and particles of 250 - 325 meshes;

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

[0016] Calculated by mass percentage, the chemical composition of the anti-fouling and wear-resistant frit 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-fouling and wear-resistant frit is the same as that of the anti-fouling and wear-resistant dry particles;

[0017] Calculated by mass percentage, the chemical composition of the anti-slip dry particles 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 of the firing is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0019] Preferably, the particle size distribution of the anti-fouling and wear-resistant dry particles satisfies: calculated based on the total weight of the anti-fouling and wear-resistant dry particles, particles with a mesh number of ≥200 meshes and <250 meshes account for 70 - 85%, and the remainder are particles of 250 - 325 meshes.

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

[0021] Preferably, by mass ratio, the mixing ratio of the anti-fouling matte glaze and the mixed dry particles in the anti-slip and anti-fouling matte glaze is 10:(1-2), and the mixed dry particles are the anti-fouling and wear-resistant dry particles and the anti-slip dry particles;

[0022] By mass ratio, the mixing ratio of the anti-fouling and wear-resistant dry particles and the anti-slip dry particles in the mixed dry particles is 1:2.

[0023] Preferably, the firing curves of the anti-fouling and wear-resistant frit are all:

[0024] Heating from room temperature to 300°C takes 1.5-2.5 h;

[0025] Heating from 300°C to 1530°C takes 2-3 h;

[0026] 1530°C, holding for 0.5-1.2 h.

[0027] Preferably, step C is specifically:

[0028] C. Spraying the anti-slip and anti-fouling matte glaze on the surface of the bottom glaze layer to obtain an anti-slip and anti-fouling matte glaze layer;

[0029] Among them, the specific gravity of the anti-slip and anti-fouling matte glaze is 1.5-1.55, and the aperture of the spray gun for spraying is 0.62 mm.

[0030] Preferably, calculated by mass percentage, the chemical components of the anti-fouling and wear-resistant frit include 34.81% of SiO2, 18.66% of Al2O3, 19.16% of CaO, 0.81% of K2O, 11.23% of ZnO, 1.76% of BaO, and 13.46% of SrO;

[0031] Calculated by mass percentage, the chemical components of the anti-slip dry particles include 40.72% of SiO2, 23.21% of Al2O3, 18.59% of CaO, 1.04% of MgO, 3.49% of K2O, 0.54% of Na2O, 8.82% of ZnO, 1.72% of BaO, and 1.87% of B2O3.

[0032] Preferably, the anti-fouling and wear-resistant frit and the anti-fouling and wear-resistant dry particles have the same raw materials. Calculated by mass fraction, the raw materials of the anti-fouling and wear-resistant frit 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.

[0033] Preferably, calculated by mass fraction, the raw materials of the anti-slip dry particles are composed of 30-35 parts of kaolin, 8-12 parts of calcined alumina, 3-6 parts of quartz, 30-38 parts of wollastonite, 5-10 parts of zinc oxide, 3-8 parts of dolomite, 3-8 parts of potassium nitrate, 1-4 parts of barium carbonate, and 1-5 parts of borax.

[0034] An anti-fouling matte antique brick with anti-slip performance is prepared by using the preparation method of the anti-fouling matte antique brick with anti-slip performance described above. The glossiness of the glaze surface of the anti-fouling matte antique brick with anti-slip performance is 8-12°, the anti-fouling grade is 5, the Mohs hardness is 7, the wear resistance is ≥4 (6000 revolutions), the dry static friction coefficient is ≥0.75, and the wet static friction coefficient is ≥0.70.

[0035] The technical solution provided by the present invention may include the following beneficial effects:

[0036] 1. In the firing process of the frit, Al 3+ exists in the form of aluminum-oxygen tetrahedrons in silicon-oxygen tetrahedrons, so that part of the silicon dioxide and alumina in the chemical composition form a dense mullite network structure. The above-mentioned mullite network structure specifically includes two crystal forms, namely 3Al2O3·2SiO2 and 2Al2O3.SiO2. When the above crystals are evenly distributed in the glaze layer, it can effectively improve the hardness and wear resistance of the glaze layer; and the high silicon-aluminum content in the chemical composition is also beneficial to improving the acid and alkali resistance of the frit, resisting the erosion of acid and alkaline substances for a long time, and contributing to anti-fouling. In addition, the anti-fouling and wear-resistant frit uses divalent ions Sr 2+ and Zn 2+ as the flux system, which can make the frit form a dense internal structure during the firing process, thus contributing to anti-fouling; at the same time, Sr 2+ and Zn 2+ also help the frit to precipitate anorthite crystals during the firing process. On the one hand, the anorthite crystals can also contribute to improving the hardness and wear resistance of the glaze layer. On the other hand, the anorthite crystals have high transparency, and at the same time, the chemical composition contains a large amount of ZnO. Introducing the frit as a raw material into the glaze can effectively improve the color development performance of the glaze.

[0037] 2. The antifouling matte glaze reduces the addition ratios of potassium feldspar and sodium feldspar in the raw material formula, and at the same time introduces a relatively high proportion of quartz, thereby reducing the contents of low-temperature fluxes K2O and Na2O and the fusible glass phase in the glaze, increasing the softening point temperature of the glaze during the sintering process, making it not easy to form a closed layer prematurely during the glaze firing, allowing sufficient exhaust time for the gases generated during firing to match the existing low-temperature and fast-firing regime of antique tiles. Further, strontium carbonate is additionally introduced into the raw materials of the antifouling matte glaze. Strontium oxide can reduce the softening temperature of the glaze, increase the high-temperature fluidity of the glaze, and increase the firing range of the glaze, thus being more conducive to forming a dense glaze layer structure and enhancing the antifouling performance of the glaze layer. In addition, since the atomic radius of Sr 2+ is larger than that of Ca 2+ , Mg 2+ , the application of a large amount of strontium oxide forms a certain surface roughness between it and the glass phase in the glaze, forms diffuse reflection with the incident light, reduces the surface gloss of the glaze surface, and realizes the matte effect of the antique tile; after the crystal phases formed with other divalent metal ions are evenly distributed on the glaze surface, the surface gloss of the glaze layer can also be controlled at 8-12°, meeting the public aesthetic of consumers for the matte gloss of antique tiles. Furthermore, calcined kaolin and burnt talc are also introduced into the raw materials of the glaze. Therefore, harder mullite and cordierite crystals can be additionally generated during the glaze firing. Coupled with the original crystals in the frit and the unmolten quartz in the raw materials, the glaze surface of the antifouling matte glaze layer is distributed with a variety of harder crystalline substances, which is more conducive to enhancing the hardness and wear resistance of the glaze surface. During the long-term use of the antique tile, it is not easy to damage the surface performance of the glaze layer, realizing long-term antifouling.

[0038] 3. This solution develops a non-slip dry granule that matches the antifouling matte glaze, enabling the anti-slip and antifouling matte glaze to simultaneously take into account excellent antifouling and anti-slip properties. At the same time, the antifouling and wear-resistant frit is re-introduced into the glaze in the form of dry granules to further enhance the antifouling performance of the glaze surface and endow the glaze surface with a delicate and soft touch. This solution also optimizes the particle composition of the antifouling and wear-resistant dry granules and the non-slip dry granules to take into account the antifouling and anti-slip properties while enhancing the delicate and soft touch of the glaze surface.

[0039] 4. The anti-slip dry particles in this solution contain a high content of CaO, which enables the formation of a crystal system with anorthite as the main crystal phase and mullite as the secondary crystal phase after firing the dry particles. Since mullite crystals are generally opalescent, the anti-slip dry particles have outstanding advantages in terms of transparency and color development. In addition, the expansion coefficient of anorthite is significantly greater than that of mullite. The crystal system with anorthite as the main crystal phase can effectively improve the flatness of the glaze surface of the ceramic tile. The anti-slip dry particle formulation system in this case is a low-silica and high-alumina system. The setting of the low-silica and high-alumina system is conducive to the formation of crystalline substances in the anti-slip dry particles and reduces the generation of the glass phase, thereby improving the hardness and initial melting point of the dry particles. In addition, both Al2O3 and the formed anorthite crystals have the characteristic of high high-temperature viscosity. After combining the anti-slip dry particles with the anti-fouling matte glaze that also has a relatively large high-temperature viscosity, they are not easily melted and flattened, and can basically remain in the initial state of the dry particle grains, thus greatly improving the anti-slip performance of the glaze surface.

[0040] 5. The chemical composition and crystal system of the anti-slip dry particles make their melting point not too high. When the anti-slip dry particles are combined with the anti-fouling matte glaze, the anti-slip dry particles can slightly melt in the glaze. On the one hand, it can ensure that the anti-slip dry particles basically maintain their initial state of the particles and protrude from the glaze layer surface, improving the anti-slip coefficient. On the other hand, it can improve the bonding property between the dry particles and the glaze layer and avoid the decline of the anti-fouling performance. Specific implementation method

[0041] A preparation method of an anti-fouling matte antique ceramic tile with anti-slip performance includes the following steps:

[0042] A. Prepare a ceramic blank, press the ceramic blank, and obtain a blank layer after drying;

[0043] B. Apply a base glaze to the surface of the blank layer to obtain a base glaze layer;

[0044] 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;

[0045] D. After drying, fire in a kiln to obtain an anti-fouling matte antique ceramic tile with anti-slip performance;

[0046] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze, anti-fouling and wear-resistant dry particles, and anti-slip dry particles. The anti-fouling and wear-resistant dry particles are composed of particles with a mesh number ≥ 200 mesh and < 250 mesh and particles with a mesh number of 250 - 325 mesh. The anti-slip dry particles are composed of particles with a mesh number ≥ 150 mesh and < 160 mesh, particles with a mesh number ≥ 160 mesh and < 200 mesh, particles with a mesh number ≥ 200 mesh and < 250 mesh, and particles with a mesh number of 250 - 325 mesh;

[0047] Calculated by mass parts, the raw materials of the antifouling matte glaze are composed of 7-10 parts of kaolin, 5-10 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of albite, 5-10 parts of calcite, 5-10 parts of burnt talc, 1-3 parts of zinc oxide, 2-5 parts of strontium carbonate, and 20-30 parts of antifouling and wear-resistant frit;

[0048] Calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit 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 antifouling and wear-resistant frit is the same as that of the antifouling and wear-resistant dry granules;

[0049] Calculated by mass percentage, the chemical composition of the anti-slip dry granules 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%;

[0050] In step D, the firing temperature is 1180-1205 °C, and the firing time is 45-60 min.

[0051] In order to make the glaze layer of the antique brick take into account glossiness, antifouling performance, hardness, wear resistance, color development, and anti-slip performance under the existing firing conditions (i.e., the firing temperature is 1180-1205 °C, and the firing time is 45-60 min), this solution first designs and optimizes the antifouling matte glaze in the anti-slip and antifouling matte glaze, breaking the glaze formula structure composed of all raw materials in the existing antique brick, and can effectively improve the satisfaction of consumers with the use of antique bricks.

[0052] Specifically, the raw material formula structure of the antifouling matte glaze in this solution is composed of a raw material part and a clinker part, and the clinker part is the antifouling and wear-resistant frit. It should be noted that the clinker in the ceramic industry is generally defined as the frit obtained after firing, and the materials in the frit are fully matured before application. Calcined kaolin, burnt talc, calcined zinc oxide, etc. are only the single raw materials calcined to volatilize the organic matter of the raw materials and make the crystal form more stable, and they still belong to the raw materials. That is to say, the materials outside the frit are all defined as raw materials.

[0053] Based on the chemical composition of the antifouling and wear-resistant frit in this solution, the Al in the frit during the firing process 3+Exist as alumina tetrahedra in silica tetrahedra, so that part of the silica and alumina in the chemical composition form a dense mullite network structure. Moreover, the above-mentioned mullite network structure specifically includes two crystal forms, namely 3Al2O3·2SiO2 and 2Al2O3·SiO2. When the above crystals are evenly distributed in the glaze layer, it can effectively improve the hardness and wear resistance of the glaze layer; and the high silicon and aluminum content in the chemical composition is also beneficial to improving the acid and alkali resistance of the frit, resisting the erosion of acid and alkaline substances for a long time, and helping to prevent dirt.

[0054] In addition, in the chemical composition of the anti-fouling and wear-resistant frit, divalent ions Sr 2+ and Zn 2+ As the flux system, it can make the frit form a dense internal structure during the firing process, thus helping to prevent dirt; at the same time, Sr 2+ and Zn 2+ Also help the frit to precipitate anorthite crystals during the firing process. On the one hand, the anorthite crystals can also help to improve the hardness and wear resistance of the glaze layer. On the other hand, the anorthite crystals have high transparency, and at the same time, the chemical composition contains a large amount of ZnO. Introducing the frit as a raw material into the glaze can effectively improve the color development performance of the glaze.

[0055] For the raw material part of the anti-fouling matte glaze, compared with the raw material formula structure of the existing antique tiles, this scheme reduces the addition ratio of potassium feldspar and sodium feldspar in the raw material formula, and at the same time introduces a relatively high proportion of quartz, thereby reducing the content of low-temperature fluxes K2O, Na2O, and easily fusible glass phase in the glaze, increasing the softening point temperature of the glaze during the sintering process, and making it not easy to form a closed layer prematurely during the firing of the glaze, so that the gases generated during firing have sufficient exhaust time to match the low-temperature and fast-firing firing system of the existing antique tiles. In addition, the increase in the softening point temperature of the glaze is also beneficial to preventing the anti-fouling matte glaze from forming a low-temperature eutectic composition with the anti-slip dry particles, which may cause the anti-slip dry particles to be melted flat and reduce the anti-slip performance of the glaze surface.

[0056] Furthermore, to effectively prevent strontium oxide from reducing the fluxing activity of the strontium oxide to the glaze after melting with the glass phase in the frit, strontium carbonate is additionally introduced into the raw materials of the anti-fouling matte glaze in this scheme. Strontium oxide can reduce the softening temperature of the glaze, increase the high-temperature fluidity of the glaze, and increase the firing range of the glaze, thus being more conducive to forming a dense glaze layer structure and improving the anti-fouling performance of the glaze layer. In addition, due to the atomic radius of Sr 2+ being larger than that of Ca 2+ and Mg 2+With a large radius, the application of a large amount of strontium oxide forms a certain surface roughness between it and the glass phase in the glaze. When interacting with incident light, it forms diffuse reflection, reducing the surface gloss of the glaze and achieving the matte effect of antique tiles. After the crystal phases formed with other divalent metal ions are evenly distributed on the glaze surface, the surface gloss of the glaze layer can also be controlled within 8 - 12°, meeting the public aesthetic of consumers for the matte gloss of antique tiles.

[0057] Furthermore, since calcined kaolin and burnt talc are also introduced into the raw materials of the glaze, during the firing of the glaze, harder mullite and cordierite crystals can be generated additionally. Coupled with the original crystals in the frit and the unmolten quartz in the raw materials, the glaze layer has a variety of harder crystalline substances on its surface, which is more conducive to improving the hardness and wear resistance of the glaze surface. During the long-term use of antique tiles, it is not easy to damage the surface properties of the glaze layer, achieving long-lasting anti-fouling.

[0058] Secondly, in order to endow antique tiles with anti-slip performance while ensuring anti-fouling performance, this solution also develops an anti-slip dry granule that matches the anti-fouling matte glaze, enabling the anti-slip and anti-fouling matte glaze to simultaneously take into account excellent anti-fouling and anti-slip performance. At the same time, the anti-fouling and wear-resistant frit is introduced into the glaze again in the form of dry granules to further enhance the anti-fouling performance of the glaze surface and also endow the glaze surface with a delicate and soft touch.

[0059] Specifically, the anti-slip dry granule of this solution contains a high content of CaO, making the dry granule form a crystal system with anorthite as the main crystal phase and mullite as the secondary crystal phase after firing. Since mullite crystals are generally opalescent, the anti-slip dry granule has outstanding advantages in terms of transparency and color development. In addition, the expansion coefficient of anorthite is significantly greater than that of mullite, and the crystal system with anorthite as the main crystal phase can effectively improve the glaze surface flatness of the ceramic tile.

[0060] In the field of building ceramics, a system with a SiO2 content lower than 50% and an Al2O3 content higher than 18% in the formula system is usually called a low-silica and high-alumina system. The anti-slip dry granule formula system in this case is exactly a low-silica and high-alumina system. The setting of the low-silica and high-alumina system is conducive to the formation of crystalline substances in the anti-slip dry granule and reduces the generation of the glass phase, thereby improving the hardness and initial melting point of the dry granule. In addition, both Al2O3 and the formed anorthite crystals have the characteristic of high high-temperature viscosity. After combining the anti-slip dry granule with the anti-fouling matte glaze that also has a large high-temperature viscosity, they are not easy to melt flat and can basically remain in the initial state of the dry granule particles, thus greatly improving the anti-slip performance of the glaze surface.

[0061] In addition, the mutual matching between the anti-skid dry particles and the anti-fouling matte glaze is also reflected in the melting point. The chemical composition and crystal system of the anti-skid dry particles make their melting point not too high. When the anti-skid dry particles are combined with the anti-fouling matte glaze, the anti-skid dry particles can be slightly melted in the glaze. On the one hand, it can ensure that the anti-skid dry particles basically maintain their initial state and protrude from the surface of the glaze layer, thereby improving the anti-skid coefficient. On the other hand, it can improve the bonding between the dry particles and the glaze layer, thereby avoiding the decline of the anti-fouling performance. It should be noted that when the melting point difference between some particles and the glaze is too large, that is, when the melting point of the dry particles is too high, it is difficult to combine with the glaze, resulting in the dry particles being in a raw fired state, and forming more dirt-hiding gaps around the dry particles; and when the firing temperature of the anti-skid dry particles and the anti-fouling matte glaze matches each other, it can ensure that the dry particles are in a state of melting in small amounts but not melting flat, and combine with the glaze into a whole and form a dense glaze layer, thereby avoiding the decline of the anti-fouling performance.

[0062] Finally, in order to prevent dirt from hiding between the anti-fouling matte glaze and the anti-fouling wear-resistant dry particles and anti-slip dry particles, thereby effectively enhancing the cleanability of the anti-fouling matte antique tiles, this solution also optimizes the particle composition of the anti-fouling wear-resistant dry particles and the anti-slip dry particles, so as to take into account the anti-fouling and anti-slip performance, while improving the delicate and soft touch of the glaze. Specifically, the mixed dry particles of this solution have a multi-level particle composition. On the one hand, the small-particle dry particles can fit perfectly with the contact object to improve the dirt sticking phenomenon, and the fine anti-slip particles can effectively generate resistance and play an anti-slip role; while the large-particle dry particles can form protruding particles on the surface of the glaze layer, effectively enhancing the anti-slip effect, while playing an anti-slip and anti-fouling role. On the other hand, the mixed dry particles physically form a more diverse stepped structure, so that the glaze will not feel prickly while being anti-slip, thereby improving the touch.

[0063] Preferably, calculated by mass, the raw materials of the antifouling matte glaze are composed of 8 parts of kaolin, 6 parts of calcined kaolin, 5 parts of quartz, 25 parts of potassium feldspar, 10 parts of sodium feldspar, 7 parts of calcite, 8 parts of burned talc, 2 parts of zinc oxide, 4 parts of strontium carbonate and 25 parts of antifouling and wear-resistant frit.

[0064] It should be noted that the ceramic blank in step A and the base glaze in step B in this solution are both ceramic blanks and base glazes commonly used for antique tiles, and are not limited here.

[0065] Further, the particle size distribution of the antifouling and wear-resistant dry particles satisfies: based on the total weight of the antifouling and wear-resistant dry particles, particles with a mesh size of ≥200 mesh and <250 mesh account for 70-85%, and the rest are particles with a mesh size of 250-325 mesh.

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

[0067] As a preference of the above embodiments, the present case also optimizes the particle distribution of each mesh number in the stain-resistant and wear-resistant dry particles and the anti-slip dry particles to ensure the simultaneous functions of anti-slip, preventing dirt from getting stuck, and improving the touch feeling.

[0068] Preferably, the particle size distribution of the stain-resistant and wear-resistant dry particles satisfies: calculated based on the total weight of the stain-resistant and wear-resistant dry particles, the particles with a mesh number of ≥200 mesh and <250 mesh account for 78.8%, and the particles with a mesh number of 250 - 325 mesh account for 21.2%.

[0069] Preferably, the particle size distribution of the anti-slip dry particles satisfies: calculated based on the total weight of the anti-slip dry particles, the particles with a mesh number of ≥150 mesh and <160 mesh account for 15.31%, the particles with a mesh number of ≥160 mesh and <200 mesh account for 48%, the particles with a mesh number of ≥200 mesh and <250 mesh account for 26.99%, and the particles with a mesh number of 250 - 325 mesh account for 9.7%.

[0070] Further explanation, by mass ratio, the mixing ratio of the stain-resistant matte glaze and the mixed dry particles in the anti-slip and stain-resistant matte glaze is 10:(1 - 2), and the mixed dry particles are the stain-resistant and wear-resistant dry particles and the anti-slip dry particles;

[0071] By mass ratio, the mixing ratio of the stain-resistant and wear-resistant dry particles and the anti-slip dry particles in the mixed dry particles is 1:2.

[0072] In this way, the performance of stain resistance, anti-slip, and touch feeling can be further balanced.

[0073] Further explanation, the firing curves of the stain-resistant and wear-resistant frit are all:

[0074] Heating from room temperature to 300°C takes 1.5 - 2.5h;

[0075] Heating from 300°C to 1530°C takes 2 - 3h;

[0076] At 1530°C, keep the temperature for 0.5 - 1.2h.

[0077] In this way, the softening point temperature of the stain-resistant and wear-resistant frit can also be matched with the firing system of the existing antique bricks, so that the tiny particles of the frit after ball milling and pulping can generate a tiny rough surface between the glass phase plane formed after firing with the glaze, further ensuring the formation of the matte glaze surface.

[0078] Preferably, the firing curves of the antifouling and wear-resistant frit are as follows:

[0079] Heat up from room temperature to 300 °C, taking 2 hours;

[0080] Heat up from 300 °C to 1530 °C, taking 2.5 hours;

[0081] Keep the temperature at 1530 °C for 1 hour.

[0082] For further illustration, step C is specifically as follows:

[0083] C. Spray the anti-slip and antifouling matte glaze on the surface of the base glaze layer to obtain an anti-slip and antifouling matte glaze layer;

[0084] Among them, the specific gravity of the anti-slip and antifouling matte glaze is 1.5 - 1.55, and the aperture of the spray gun for spraying is 0.62 mm.

[0085] In another specific embodiment of this technical solution, the anti-slip and antifouling matte glaze can be applied by spraying. However, in order to make the anti-slip dry particles evenly distributed on the surface of the glaze layer, the specific gravity of the glaze material and the aperture of the spray gun during spraying are also optimized in this solution.

[0086] For further illustration, calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit includes 34.81% of SiO2, 18.66% of Al2O3, 19.16% of CaO, 0.81% of K2O, 11.23% of ZnO, 1.76% of BaO, and 13.46% of SrO;

[0087] Calculated by mass percentage, the chemical composition of the anti-slip dry particles includes 40.72% of SiO2, 23.21% of Al2O3, 18.59% of CaO, 1.04% of MgO, 3.49% of K2O, 0.54% of Na2O, 8.82% of ZnO, 1.72% of BaO, and 1.87% of B2O3.

[0088] For further illustration, the raw materials of the antifouling and wear-resistant frit and the anti-slip and antifouling dry particles are the same. Calculated by mass parts, the raw materials of the antifouling and wear-resistant frit 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.

[0089] In a preferred embodiment of this technical solution, the antifouling and wear-resistant frit can be obtained by firing quartz, calcined alumina, wollastonite, zinc oxide, strontium carbonate, and barium carbonate and then quenching with water.

[0090] Further explanation, calculated by mass parts, the raw materials of the anti-slip dry granules are composed of 30-35 parts of kaolin, 8-12 parts of calcined alumina, 3-6 parts of quartz, 30-38 parts of wollastonite, 5-10 parts of zinc oxide, 3-8 parts of dolomite, 3-8 parts of potassium nitrate, 1-4 parts of barium carbonate, and 1-5 parts of borax.

[0091] In a preferred embodiment of this technical solution, the anti-slip dry granules can be obtained by firing kaolin, calcined alumina, quartz, wollastonite, zinc oxide, dolomite, potassium nitrate, barium carbonate, and borax, followed by water quenching to form anti-slip frit, and then crushing the anti-slip frit.

[0092] An anti-fouling matte antique brick with anti-slip performance is prepared by using the preparation method of the anti-fouling matte antique brick with anti-slip performance described above. The glossiness of the glaze surface of the anti-fouling matte antique brick with anti-slip performance is 8-12°, the anti-fouling grade is 5, the Mohs hardness is 7, the abrasion resistance is ≥4 (6000 revolutions), the dry static friction coefficient is ≥0.75, and the wet static friction coefficient is ≥0.70.

[0093] The anti-fouling matte antique brick with anti-slip performance proposed in this solution can take into account the glossiness, anti-fouling performance, hardness, abrasion resistance, color development, and anti-slip performance under the existing firing conditions, improving the satisfaction of consumers with the use of antique bricks.

[0094] The technical solution of the present invention will be further described below through specific embodiments.

[0095] Example 1

[0096] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

[0097] B. Apply the base glaze to the surface of the green body layer to obtain a base glaze layer;

[0098] C. Spray the anti-slip and anti-fouling matte glaze with a specific gravity of 1.5 onto the surface of the base glaze layer using a spray gun with a pore size of 0.62 mm to obtain an anti-slip and anti-fouling matte glaze layer;

[0099] D. After drying, fire in a kiln to obtain an anti-fouling matte antique brick with anti-slip performance;

[0100] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze, anti-fouling and wear-resistant dry granules, and anti-slip dry granules. And by mass ratio, the mixing ratio of the anti-fouling matte glaze and the mixed dry granules (i.e., anti-fouling and wear-resistant dry granules and anti-slip dry granules) is 10:1, and by mass ratio, the mixing ratio of the anti-fouling and wear-resistant dry granules and the anti-slip dry granules in the mixed dry granules is 1:2;

[0101] In addition, the particle size distribution of the stain-resistant and wear-resistant dry particles satisfies: calculated based on the total weight of the stain-resistant and wear-resistant dry particles, the particles with a mesh number of ≥200 and <250 account for 70%, and the particles with a mesh number of 250 - 325 account for 30%; the particle size distribution of the anti-slip dry particles satisfies: calculated based on the total weight of the anti-slip dry particles, the particles with a mesh number of ≥150 and <160 account for 15%, the particles with a mesh number of ≥160 and <200 account for 45%, the particles with a mesh number of ≥200 and <250 account for 30%, and the particles with a mesh number of 250 - 325 account for 10%;

[0102] The raw material composition of the stain-resistant matte glaze is shown in Table 1 below. The chemical compositions of the stain-resistant and wear-resistant frit and the stain-resistant and wear-resistant dry particles are the same. The chemical composition of the stain-resistant and wear-resistant frit is shown in Table 2 below, and the chemical composition of the anti-slip dry particles is shown in Table 3 below.

[0103] In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0104] Example 2

[0105] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

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

[0107] C. Spray the anti-slip and stain-resistant matte glaze with a specific gravity of 1.5 on the surface of the base glaze layer using a spray gun with a pore diameter of 0.62 mm to obtain an anti-slip and stain-resistant matte glaze layer;

[0108] D. After drying, put it into the kiln for firing to obtain an anti-slip and stain-resistant matte antique brick;

[0109] Among them, in step C, the anti-slip and stain-resistant matte glaze includes a stain-resistant matte glaze, stain-resistant and wear-resistant dry particles, and anti-slip dry particles. And by mass ratio, the mixing ratio of the stain-resistant matte glaze and the mixed dry particles (i.e., stain-resistant and wear-resistant dry particles and anti-slip dry particles) is 10:1.5, and by mass ratio, the mixing ratio of the stain-resistant and wear-resistant dry particles and the anti-slip dry particles in the mixed dry particles is 1:2;

[0110] In addition, the particle size distribution of the stain-resistant and wear-resistant dry particles satisfies: calculated based on the total weight of the stain-resistant and wear-resistant dry particles, the particles with a mesh number of ≥200 and <250 account for 78.8%, and the particles with a mesh number of 250 - 325 account for 21.2%; the particle size distribution of the anti-slip dry particles satisfies: calculated based on the total weight of the anti-slip dry particles, the particles with a mesh number of ≥150 and <160 account for 15.31%, the particles with a mesh number of ≥160 and <200 account for 48%, the particles with a mesh number of ≥200 and <250 account for 26.99%, and the particles with a mesh number of 250 - 325 account for 9.7%;

[0111] The raw material composition of the antifouling matte glaze is shown in Table 1 below. The chemical compositions of the antifouling and wear-resistant frit and the antifouling and wear-resistant dry particles are the same. The chemical composition of the antifouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the anti-slip dry particles is shown in Table 3 below.

[0112] In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0113] Example 3

[0114] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

[0115] B. Apply the base glaze on the surface of the green body layer to obtain a base glaze layer;

[0116] C. Spray the anti-slip and antifouling matte glaze with a specific gravity of 1.5 onto the surface of the base glaze layer using a spray gun with a pore size of 0.62 mm to obtain an anti-slip and antifouling matte glaze layer;

[0117] D. After drying, put it into the kiln for firing to obtain an antifouling matte antique brick with anti-slip performance;

[0118] Among them, in step C, the anti-slip and antifouling matte glaze includes an antifouling matte glaze, antifouling and wear-resistant dry particles, and anti-slip dry particles. And by mass ratio, the mixing ratio of the antifouling matte glaze and the mixed dry particles (i.e., the antifouling and wear-resistant dry particles and the anti-slip dry particles) is 10:2, and by mass ratio, the mixing ratio of the antifouling and wear-resistant dry particles and the anti-slip dry particles in the mixed dry particles is 1:2;

[0119] In addition, the particle size distribution of the antifouling and wear-resistant dry particles satisfies: calculated based on the total weight of the antifouling and wear-resistant dry particles, particles with a mesh number ≥ 200 mesh and < 250 mesh account for 85%, and particles with a mesh number of 250 - 325 mesh account for 15%; the particle size distribution of the anti-slip dry particles satisfies: calculated based on the total weight of the anti-slip dry particles, particles with a mesh number ≥ 150 mesh and < 160 mesh account for 20%, particles with a mesh number ≥ 160 mesh and < 200 mesh account for 50%, particles with a mesh number ≥ 200 mesh and < 250 mesh account for 25%, and particles with a mesh number of 250 - 325 mesh account for 5%;

[0120] The raw material composition of the antifouling matte glaze is shown in Table 1 below. The chemical compositions of the antifouling and wear-resistant frit and the antifouling and wear-resistant dry particles are the same. The chemical composition of the antifouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the anti-slip dry particles is shown in Table 3 below.

[0121] In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0122] Table 1 Raw material composition of each antifouling matte glaze in Examples 1 - 3

[0123]

[0124] Table 2 Chemical Compositions of Each Anti-Stain and Wear-Resistant Frit (Anti-Stain and Wear-Resistant Dry Granules) in Examples 1-3

[0125]

[0126] Table 3 Chemical Compositions of Each Anti-Slip Dry Granule in Examples 1-3

[0127]

[0128] Comparative Example 1

[0129] Replace the anti-stain matte glaze in Example 2 with glaze A, and keep the rest of the formula and parameters the same.

[0130] Among them, calculated by mass parts, the raw materials of the glaze A are composed of 8 parts of kaolin, 6 parts of calcined kaolin, 5 parts of quartz, 25 parts of potassium feldspar, 10 parts of sodium feldspar, 7 parts of calcite, 8 parts of burnt talc, 2 parts of zinc oxide, 4 parts of strontium carbonate, and 25 parts of existing matte frit.

[0131] Calculated by mass percentage, the chemical composition of the existing matte frit includes 55% SiO2, 17% Al2O3, 10% BaO, 4% ZnO, 4.5% SrO, 2.65% K2O, 3.7% Na2O, 2.5% CaO, 0.05% MgO, 0.3% P2O5, and 0.3% CaF2.

[0132] Comparative Example 2

[0133] Replace the anti-stain matte glaze in Example 2 with glaze B, and keep the rest of the formula and parameters the same.

[0134] Among them, calculated by mass parts, the raw materials of the glaze B are composed of 15 parts of kaolin, 18 parts of calcined kaolin, 30 parts of potassium feldspar, 20 parts of sodium feldspar, 2 parts of zinc oxide, 6 parts of wollastonite, 5 parts of burnt talc, 6 parts of wollastonite, and 4 parts of barium carbonate.

[0135] Comparative Example 3

[0136] Replace the mixed dry granules in Example 2 with ordinary anti-slip dry granules, and keep the rest of the formula and parameters the same.

[0137] Among them, calculated by mass percentage, the chemical composition of the ordinary anti-slip dry granules 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, and the loss on ignition is 0.82%.

[0138] The antique bricks prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to conventional hardness, wear resistance, glaze gloss, antifouling grade and anti-slip tests in the field of architectural ceramics. The results are shown in Table 4 below:

[0139] Table 4 Performance test results of antique tiles in Examples 1-3 and Comparative Examples 1-3

[0140]

[0141] From the performance test results in Table 4, it can be seen that the anti-slip and anti-fouling matte antique tiles prepared by this scheme can take into account gloss, anti-fouling performance, hardness, wear resistance, color and anti-slip performance under the existing firing conditions, thereby improving consumers' satisfaction with the use of antique tiles.

[0142] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A preparation method of an anti - slip and anti - pollution matte antique brick, characterized in that, It includes the following steps: A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying; B. Apply a base glaze to the surface of the green body layer to obtain a 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, fire in a kiln to obtain an anti-fouling matte antique brick with anti-slip performance; Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze, anti-fouling and wear-resistant dry particles, and anti-slip dry particles. The anti-fouling and wear-resistant dry particles are composed of particles with a mesh number of ≥200 mesh and <250 mesh and particles of 250 - 325 mesh. The anti-slip dry particles are composed of particles with a mesh number of ≥150 mesh and <160 mesh, particles with a mesh number of ≥160 mesh and <200 mesh, particles with a mesh number of ≥200 mesh and <250 mesh, and particles of 250 - 325 mesh; Calculated by mass fraction, the raw materials of the anti-fouling matte glaze are composed of 7 - 10 parts of kaolin, 5 - 10 parts of calcined kaolin, 4 - 8 parts of quartz, 20 - 30 parts of potassium feldspar, 8 - 15 parts of sodium feldspar, 5 - 10 parts of calcite, 5 - 10 parts of burnt talc, 1 - 3 parts of zinc oxide, 2 - 5 parts of strontium carbonate, and 20 - 30 parts of anti-fouling and wear-resistant frit; Calculated by mass percentage, the chemical composition of the anti-fouling and wear-resistant frit includes 32 - 40% of SiO2, 18 - 20% of Al2O3, 18 - 20% of CaO, 0.5 - 1.5% of K2O, 10 - 12% of ZnO, 1 - 2.5% of BaO, and 12 - 15% of SrO. The chemical composition of the anti-fouling and wear-resistant frit is the same as that of the anti-fouling and wear-resistant dry particles; Calculated by mass percentage, the chemical composition of the anti-slip dry particles includes 38 - 42% of SiO2, 20 - 24% of Al2O3, 18 - 20% of CaO, 0.5 - 2% of MgO, 3 - 4.5% of K2O, 0.2 - 1% of Na2O, 8 - 10% of ZnO, 1 - 2.5% of BaO, and 1 - 2.5% of B2O3; In step D, the firing temperature for the firing is 1180 - 1205 °C, and the firing time is 45 - 60 min.

2. The preparation method of an anti-slip and anti-fouling matte antique brick with anti-slip performance according to claim 1, characterized in that, The particle size distribution of the anti-fouling and wear-resistant dry particles satisfies that calculated based on the total weight of the anti-fouling and wear-resistant dry particles, particles with a mesh number of ≥200 mesh and <250 mesh account for 70 - 85%, and the rest are particles of 250 - 325 mesh.

3. The preparation method of an anti-slip and anti-fouling matte antique brick with anti-slip performance according to claim 1, characterized in that, The particle size distribution of the anti-slip dry particles satisfies that calculated based on the total weight of the anti-slip dry particles, particles with a mesh number of ≥150 mesh and <160 mesh account for 10 - 20%, particles with a mesh number of ≥160 mesh and <200 mesh account for 40 - 55%, particles with a mesh number of ≥200 mesh and <250 mesh account for 20 - 30%, and particles of 250 - 325 mesh account for 5 - 13%.

4. The preparation method of an anti-slip and anti-fouling matte antique brick with anti-slip performance according to claim 1, characterized in that, Calculated by mass ratio, the mixing ratio of the anti-fouling matte glaze and the mixed dry particles in the anti-slip and anti-fouling matte glaze is 10:(1 - 2), and the mixed dry particles are the anti-fouling and wear-resistant dry particles and the anti-slip dry particles; Calculated by mass ratio, the mixing ratio of the anti-fouling and wear-resistant dry particles and the anti-slip dry particles in the mixed dry particles is 1:

2.

5. The preparation method of an anti-slip and anti-fouling matte antique brick with anti-slip performance according to claim 1, characterized in that The firing curve of the anti-fouling and wear-resistant frit is as follows: Heat up from room temperature to 300 °C, which takes 1.5 - 2.5 h; Heat up from 300 °C to 1530 °C, which takes 2 - 3 h; Keep the temperature at 1530 °C for 0.5 - 1.2 h.

6. The preparation method of an anti-slip and stain-resistant matte antique brick with anti-slip performance according to claim 1, characterized in that, Step C is specifically as follows: C. Spray the anti-slip and anti-fouling matte glaze on the surface of the underglaze layer to obtain an anti-slip and anti-fouling matte glaze layer; Among them, the specific gravity of the anti-slip and anti-fouling matte glaze is 1.5 - 1.55, and the aperture of the spray gun for spraying is 0.62 mm.

7. The preparation method of an anti-slip and anti-fouling matte antique brick with anti-slip performance according to claim 1, characterized in that, Calculated by mass percentage, the chemical composition of the anti-fouling and wear-resistant frit includes 34.81% of SiO2, 18.66% of Al2O3, 19.16% of CaO, 0.81% of K2O, 11.23% of ZnO, 1.76% of BaO, and 13.46% of SrO; Calculated by mass percentage, the chemical composition of the anti-slip dry particles includes 40.72% of SiO2, 23.21% of Al2O3, 18.59% of CaO, 1.04% of MgO, 3.49% of K2O, 0.54% of Na2O, 8.82% of ZnO, 1.72% of BaO, and 1.87% of B2O3.

8. The preparation method of an anti-slip and stain-proof matte antique brick with anti-slip performance according to claim 1, characterized in that, The raw materials of the anti-fouling and wear-resistant frit and the anti-fouling and wear-resistant dry particles are the same. Calculated by mass parts, the raw materials of the anti-fouling and wear-resistant frit 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. The preparation method of an anti-slip and stain-proof matte antique brick with anti-slip performance according to claim 1, characterized in that, Calculated by mass parts, the raw materials of the anti-slip dry particles are composed of 30 - 35 parts of kaolin, 8 - 12 parts of calcined alumina, 3 - 6 parts of quartz, 30 - 38 parts of wollastonite, 5 - 10 parts of zinc oxide, 3 - 8 parts of dolomite, 3 - 8 parts of potassium nitrate, 1 - 4 parts of barium carbonate, and 1 - 5 parts of borax.

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