Antifouling matte archaized brick with antiskid effect and preparation method of antifouling matte archaized brick

Abstract

The invention relates to the technical field of architectural ceramics, and discloses an anti-fouling matte archaized brick with an anti-skid effect and a preparation method thereof, and the preparation method comprises the following steps: A, preparing a green body layer; b, applying ground coat; c, applying anti-skid and anti-fouling matte glaze; and D, firing. The anti-slip antifouling matte glaze comprises antifouling matte glaze and anti-slip dry particles, the antifouling matte glaze is prepared from 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 calcined talc, 1-3 parts of zinc oxide, 2-5 parts of strontium carbonate and 20-30 parts of antifouling wear-resistant frit; the antiskid dry particles comprise the following chemical components in percentage by weight: 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. According to the scheme, the glossiness, the antifouling property, the hardness, the abrasion resistance, the color development and the skid resistance can be considered under the existing firing condition, and the use satisfaction degree of consumers is improved.

Description

Technical Field

[0001] The invention relates to the technical field of building ceramics, and in particular to an anti-slip and anti-fouling matte antique brick 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 effect 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-slip and anti-fouling matte antique tiles 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. Dry and then fire in a kiln to obtain an anti-fouling matte antique brick with anti-slip function;

[0014] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze and anti-slip dry particles, and according to the mass ratio, the mixing ratio of the anti-fouling matte glaze and the anti-slip dry particles is 10:(1 - 2);

[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 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;

[0017] 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;

[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 particles are composed of particles with a mesh number ≥150 and <160, particles with a mesh number ≥160 and <200, particles with a mesh number ≥200 and <250, and particles with a mesh number of 250 - 325.

[0020] 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 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%.

[0021] Preferably, according to the mass ratio, the mixing ratio of the stain-resistant matte glaze and the anti-slip dry particles is 10:1.5.

[0022] Preferably, the firing curve of the stain-resistant and wear-resistant frit is as follows:

[0023] Heating from room temperature to 300 °C takes 1.5-2.5 h;

[0024] Heating from 300 °C to 1530 °C takes 2-3 h;

[0025] At 1530 °C, keep warm for 0.5-1.2 h.

[0026] Preferably, step C is specifically:

[0027] C. Spraying the anti-slip and stain-resistant matte glaze on the surface of the bottom glaze layer to obtain an anti-slip and stain-resistant matte glaze layer;

[0028] Among them, the specific gravity of the anti-slip and stain-resistant matte glaze is 1.5-1.55, and the aperture of the spraying spray gun is 0.62 mm.

[0029] Preferably, calculated by mass percentage, the chemical composition of the stain-resistant 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;

[0030] 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.

[0031] Preferably, calculated by mass parts, the raw materials of the stain-resistant 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.

[0032] Preferably, 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.

[0033] An anti-fouling matte antique brick with anti-slip function is prepared by using the preparation method of the anti-slip anti-fouling matte antique brick described above, and the glaze glossiness of the anti-slip anti-fouling matte antique brick 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 ≥0.77, and the wet static friction coefficient is ≥0.75.

[0034] The technical solutions provided by the present invention may include the following beneficial effects:

[0035] 1. Al in the frit during the firing process 3+ Exists as 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. And 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, it 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 helps 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.

[0036] 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 content 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, and allowing sufficient exhaust time for the gases generated during firing to match the existing low-temperature and fast-firing system 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 improving the antifouling performance of the glaze layer. In addition, due to the fact that 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 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 within 8 - 12°, meeting the general aesthetic of consumers for the matte gloss of antique tiles. Furthermore, calcined kaolin and burnt talc are introduced into the raw materials of the glaze. Therefore, during the glaze firing, mullite and cordierite crystals with relatively high hardness can be additionally generated. 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 crystals with relatively high hardness, which is more conducive to improving 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.

[0037] 3. The anti-slip dry particles in this solution contain a high content of CaO, making the main crystal phase of the dry particles after firing be anorthite and the secondary crystal phase be mullite. 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 glaze surface flatness of the ceramic tile. The anti-slip dry particle formula 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 crystal quality 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 antifouling 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 particle particles, thus greatly improving the anti-slip performance of the glaze surface.

[0038] 4. The chemical composition and crystal system of the anti-slip dry particles result in a not-too-high melting point. 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, this can ensure that the anti-slip dry particles basically maintain their initial particulate state and protrude from the surface of the glaze layer, enhancing the anti-slip coefficient. On the other hand, it can improve the bonding between the dry particles and the glaze layer, avoiding a decline in anti-fouling performance. Additionally, to prevent dirt from hiding between the anti-fouling matte glaze and the anti-slip dry particles, thereby effectively enhancing the easy-cleaning property of the anti-fouling matte antique brick, this solution also limits the mixing ratio between the anti-slip dry particles and the anti-fouling matte glaze to improve the problem of dirt accumulation. Detailed implementation method

[0039] A preparation method of an anti-fouling matte antique brick with anti-slip function includes the following steps:

[0040] A. Prepare a ceramic blank, press the ceramic blank, and obtain a blank layer after drying;

[0041] B. Apply a base glaze on the surface of the blank layer to obtain a base glaze layer;

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

[0043] D. After drying, fire in a kiln to obtain an anti-fouling matte antique brick with anti-slip function;

[0044] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze and anti-slip dry particles, and according to the mass ratio, the mixing ratio of the anti-fouling matte glaze and the anti-slip dry particles is 10:(1 - 2);

[0045] 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;

[0046] 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%;

[0047] Calculated by mass percentage, 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;

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

[0049] In order to make the glaze layer of antique tiles take into account glossiness, stain resistance, 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 stain-resistant matte glaze in the anti-slip and stain-resistant matte glaze, breaking the glaze formula structure composed of all raw materials in existing antique tiles, and can effectively improve the satisfaction of consumers with the use of antique tiles.

[0050] Specifically, the raw material formula structure of the stain-resistant matte glaze in this solution consists of a raw material part and a clinker part, and the clinker part is the stain-resistant and wear-resistant frit. It should be noted that the clinker in the ceramic industry is generally defined as the frit obtained through firing, and the materials in the frit are fully matured before application. Calcined kaolin, calcined 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 raw materials. That is to say, the materials outside the frit are all defined as raw materials.

[0051] Based on the chemical composition of the stain-resistant and wear-resistant frit in this solution, Al in the frit during the firing process 3+ Exists in the silicon oxygen tetrahedron in the form of an aluminum oxygen tetrahedron, so that part of the silicon dioxide and aluminum oxide in the chemical composition form a dense mullite network structure. And 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 contributing to stain resistance.

[0052] In addition, in the chemical composition of the stain-resistant 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 contributing to stain resistance; at the same time, Sr 2+ and Zn 2+It also helps the frit to precipitate anorthite crystals during the firing process. On the one hand, anorthite crystals can also help improve the hardness and wear resistance of the glaze layer. On the other hand, anorthite 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 development performance of the glaze.

[0053] For the raw material part of the anti - stain matte glaze, compared with the raw material formula structure of existing antique bricks, this solution 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 low - temperature and fast - firing regime of existing antique bricks. In addition, the increase in the softening point temperature of the glaze is also beneficial for preventing the anti - stain matte glaze from forming a low - temperature eutectic composition with the anti - slip dry particles, which may cause the dry particles to be melted flat and reduce the anti - slip performance of the glaze surface.

[0054] Furthermore, to effectively prevent strontium oxide from reducing the fluxing activity of the glaze after melting with the glass phase in the frit, strontium carbonate is additionally introduced into the raw materials of the anti - stain matte glaze in this solution. 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 - stain performance of the glaze layer. In addition, due to the 2+ atomic radius of Sr 2+ being larger than that of Ca 2+ and Mg, the application of a large amount of strontium oxide makes it form a certain surface roughness between the glaze and the glass phase, which forms diffuse reflection with incident light, reducing the surface gloss of the glaze surface and achieving the matte effect of antique bricks; 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 general aesthetic of consumers for the matte gloss of antique bricks.

[0055] Even further, since calcined kaolin and calcined talc are also introduced into the raw materials of the glaze, harder mullite and cordierite crystals can be generated additionally during the glaze firing. Together with the original crystals in the frit and the un - melted quartz in the raw materials, the glaze surface of the glaze layer is distributed with multiple high - hardness crystalline substances, which is more conducive to improving the hardness and wear resistance of the glaze surface. During the long - term use of antique bricks, it is not easy to damage the surface performance of the glaze layer, achieving long - term anti - stain performance.

[0056] Secondly, to endow antique bricks with anti - slip performance while ensuring anti - stain performance, this solution also develops an anti - slip dry particle that matches the anti - stain matte glaze, enabling the anti - slip and anti - stain matte glaze to simultaneously possess excellent anti - stain and anti - slip performance.

[0057] Specifically, the anti-slip dry particles of this solution contain a high content of CaO, so that after firing, the dry particles form a crystal system with anorthite as the main crystal phase and mullite as the secondary crystal phase. 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, and the crystal system with anorthite as the main crystal phase can effectively improve the glaze flatness of the ceramic tile.

[0058] In the field of architectural ceramics, a system with SiO2 content less than 50% and Al2O3 content higher than 18% in the formula system is usually called a low-silica high-alumina system. The anti-slip dry particle formula system in this case is exactly a low-silica high-alumina system. The setting of the low-silica high-alumina system is beneficial to the formation of crystals 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 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.

[0059] In addition, the mutual matching between the anti-slip dry particles and the anti-fouling matte glaze is also reflected in the melting point. 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 surface of the glaze layer, 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. It should be noted that if the melting point difference between the dry 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 showing an underfired state and forming more dirt-trapping voids around the dry particles; when the firing temperatures of the anti-slip dry particles and the anti-fouling matte glaze match each other, it can ensure that the dry particles are in a state of slight melting but not melting and flattening, combine with the glaze to form a whole and form a dense glaze layer, thereby avoiding the decline of the anti-fouling performance.

[0060] Finally, in order to prevent dirt from hiding between the anti-fouling matte glaze and the anti-slip dry particles and effectively enhance the easy-to-clean property of the anti-fouling matte antique tiles, this solution also limits the mixing ratio between the anti-slip dry particles and the anti-fouling matte glaze to improve the phenomenon of dirt entrapment.

[0061] Preferably, calculated by mass parts, the raw materials of the anti-fouling 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 burnt talc, 2 parts of zinc oxide, 4 parts of strontium carbonate, and 25 parts of anti-fouling and wear-resistant frit.

[0062] It should be noted that the ceramic blank in step A and the base glaze in step B in this solution are both common ceramic blanks and base glazes for antique tiles, and are not limited here.

[0063] Further explanation is as follows. The anti-slip dry particles are composed of particles with a mesh number of ≥150 and <160 meshes, particles with a mesh number of ≥160 and <200 meshes, particles with a mesh number of ≥200 and <250 meshes, and particles with a mesh number of 250 - 325 meshes.

[0064] Since the anti-slip dry particles used in this case vary in size, the small dry particles can perfectly fit with the contact object, improving the phenomenon of dirt entrapment. The fine anti-slip particles can effectively generate resistance and play an anti-slip role; while the large dry particles can form protruding particles on the surface of the glaze layer, effectively enhancing the anti-slip effect and playing both an anti-slip and dirt-entrapment avoidance role.

[0065] In addition, the anti-slip dry particles within this mesh number range can also ensure that the anti-slip and stain-resistant matte glaze can be evenly applied by spraying, and after application, a good hand feeling can be formed on the surface of the glaze layer.

[0066] Further explanation is as follows. 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 of ≥150 and <160 meshes account for 10 - 20%, particles with a mesh number of ≥160 and <200 meshes account for 40 - 55%, particles with a mesh number of ≥200 and <250 meshes account for 20 - 30%, and particles with a mesh number of 250 - 325 meshes account for 5 - 13%.

[0067] As a preference of the above embodiment, this case also optimizes the particle distribution of each mesh number in the anti-slip dry particles to ensure both anti-slip and dirt-entrapment avoidance effects.

[0068] Preferably, 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 of ≥150 and <160 meshes account for 15.31%, particles with a mesh number of ≥160 and <200 meshes account for 48%, particles with a mesh number of ≥200 and <250 meshes account for 26.99%, and particles with a mesh number of 250 - 325 meshes account for 9.7%.

[0069] Further explanation is as follows. According to the mass ratio, the mixing ratio of the stain-resistant matte glaze and the anti-slip dry particles is 10:1.5.

[0070] Further explanation is as follows. The firing curve of the stain-resistant and wear-resistant frit is as follows:

[0071] Heating from room temperature to 300°C takes 1.5 - 2.5 h;

[0072] Heating from 300°C to 1530°C takes 2 - 3 h;

[0073] At 1530°C, keep the temperature for 0.5 - 1.2 h.

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

[0075] Preferably, the firing curve of the stain-resistant and wear-resistant frit is as follows:

[0076] Heat up from room temperature to 300 °C, taking 2 hours;

[0077] Heat up from 300 °C to 1530 °C, taking 2.5 hours;

[0078] Keep the temperature at 1530 °C for 1 hour.

[0079] Further explanation, step C is specifically:

[0080] C. Spray the anti-slip, stain-resistant and matte glaze on the surface of the base glaze layer to obtain an anti-slip, stain-resistant and matte glaze layer;

[0081] Among them, the specific gravity of the anti-slip, stain-resistant and matte glaze is 1.5 - 1.55, and the aperture of the spray gun for spraying is 0.62 mm.

[0082] In another specific embodiment of this technical solution, the anti-slip, stain-resistant and 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 and the aperture of the spray gun are optimized in this solution.

[0083] Further explanation, calculated by mass percentage, the chemical composition of the stain-resistant and wear-resistant frit includes SiO2 34.81%, Al2O3 18.66%, CaO 19.16%, K2O 0.81%, ZnO 11.23%, BaO 1.76% and SrO 13.46%;

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

[0085] Further explanation, calculated by mass parts, the raw materials of the stain-resistant 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.

[0086] In a preferred embodiment of the present technical solution, the anti-fouling 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.

[0087] Furthermore, 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.

[0088] In a preferred embodiment of the present technical solution, the anti-slip dry particles can be fired from kaolin, calcined alumina, quartz, wollastonite, zinc oxide, dolomite, potassium nitrate, barium carbonate and borax and then quenched into an anti-slip frit, and then broken by the anti-slip frit.

[0089] An anti-fouling matte antique brick with anti-slip function is prepared by using the preparation method of the anti-fouling matte antique brick with anti-slip function described above, and the glaze glossiness of the anti-fouling matte antique brick with anti-slip function is 8-12°, the anti-fouling grade is 5, the Mohs hardness is 7, the wear resistance is ≥4 grades (6000 revolutions), the dry static friction coefficient is ≥0.77, and the wet static friction coefficient is ≥0.75.

[0090] The anti-fouling matte antique brick with anti-slip function proposed in this scheme 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.

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

[0092] Example 1

[0093] A. Prepare a ceramic blank, press the ceramic blank, and obtain a blank layer after drying;

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

[0095] C. Spray the anti-slip and anti-fouling matte glaze with a specific gravity of 1.5 on the surface of the base glaze layer by using a spray gun with a pore diameter of 0.62 mm to obtain an anti-slip and anti-fouling matte glaze layer;

[0096] D. After drying, fire in a kiln to obtain an anti-fouling matte antique brick with anti-slip function;

[0097] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze and anti-slip dry particles. By mass ratio, the mixing ratio of the anti-fouling matte glaze to the anti-slip dry particles is 10:1. 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 ≥ 150 and < 160 account for 15%, the particles with a mesh number ≥ 160 and < 200 account for 45%, the particles with a mesh number ≥ 200 and < 250 account for 30%, and the particles with a mesh number of 250 - 325 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 particles is shown in Table 3 below. In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0098] Example 2

[0099] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

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

[0101] 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;

[0102] D. After drying, put it into the kiln for firing to obtain an anti-fouling matte antique brick with anti-slip function;

[0103] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze and anti-slip dry particles. By mass ratio, the mixing ratio of the anti-fouling matte glaze to the anti-slip dry particles is 10:1.5. 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 ≥ 150 and < 160 account for 15.31%, the particles with a mesh number ≥ 160 and < 200 account for 48%, the particles with a mesh number ≥ 200 and < 250 account for 26.99%, and the particles with a mesh number of 250 - 325 account for 9.7%; 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 particles is shown in Table 3 below. In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0104] Example 3

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

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

[0107] C. Spray the anti-slip and anti-fouling matte glaze with a specific gravity of 1.5 onto the surface of the underglaze layer using a spray gun with a pore size of 0.62 mm to obtain an anti-slip and anti-fouling matte glaze layer;

[0108] D. After drying, fire it in a kiln to obtain an anti-fouling matte antique brick with anti-slip function;

[0109] Among them, in step C, the anti-slip and anti-fouling matte glaze includes an anti-fouling matte glaze and anti-slip dry particles. By mass ratio, the mixing ratio of the anti-fouling matte glaze and the anti-slip dry particles is 10:2. 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 ≥ 150 and < 160 account for 20%, the particles with a mesh number ≥ 160 and < 200 account for 50%, the particles with a mesh number ≥ 200 and < 250 account for 25%, and the particles with a mesh number of 250 - 325 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 particles is shown in Table 3 below. In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

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

[0111]

[0112]

[0113] Table 2 Chemical composition of each anti-fouling and wear-resistant frit 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 particle 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, and the remaining formulations and parameters are the same.

[0119] 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 calcined talc, 2 parts of zinc oxide, 4 parts of strontium carbonate, and 25 parts of existing matte frit;

[0120] Calculated by mass percentage, the chemical composition of the existing matte frit includes SiO2 55%, Al2O3 17%, BaO10%, 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] The antifouling matte glaze in Example 2 was replaced by glaze B, and the other formulas and parameters were the same.

[0123] Among them, calculated by mass, the raw materials of 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 burned talc, 6 parts of wollastonite and 4 parts of barium carbonate.

[0124] Comparative Example 3

[0125] The anti-skid dry particles in Example 2 were replaced with ordinary anti-skid dry particles, and the other formulas and parameters were the same.

[0126] Among them, calculated by mass percentage, the chemical composition of ordinary anti-slip dry particles 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%.

[0127] 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:

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

[0129]

[0130] 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.

[0131] 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 method for preparing anti-slip and anti-fouling matte antique tiles, characterized in that: The following steps are involved: A. preparing a ceramic blank, pressing the ceramic blank, and obtaining a blank layer after drying; B. applying a base glaze to the surface of the green body layer to obtain a base glaze layer; C. applying an anti-skid and anti-fouling matte glaze cloth to the surface of the base glaze layer to obtain an anti-skid and anti-fouling matte glaze layer; D. After drying, put it into the kiln for firing to obtain anti-slip and anti-fouling matte antique tiles; Wherein, in step C, the anti-slip and anti-fouling matte glaze comprises anti-fouling matte glaze and anti-slip dry particles, and the mixing ratio of the anti-fouling matte glaze and the anti-slip dry particles is 10:(1-2) in terms of mass ratio; Calculated by weight, the raw materials of the antifouling matte glaze are composed of 7 to 10 parts of kaolin, 5 to 10 parts of calcined kaolin, 4 to 8 parts of quartz, 20 to 30 parts of potassium feldspar, 8 to 15 parts of sodium feldspar, 5 to 10 parts of calcite, 5 to 10 parts of burned talc, 1 to 3 parts of zinc oxide, 2 to 5 parts of strontium carbonate and 20 to 30 parts of antifouling and wear-resistant frit; 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%; Calculated by mass percentage, the chemical composition of the anti-skid 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%; In step D, the firing temperature is 1180-1205° C., and the firing time is 45-60 min.

2. The method for preparing the anti-slip and anti-fouling matte antique brick according to claim 1, characterized in that: The anti-skid 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.

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

4. The method for preparing the anti-slip and anti-fouling matte antique 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 particles is 10:1.

5.

5. The method for preparing the anti-slip and anti-fouling matte antique brick according to claim 1, characterized in that: The firing curve of the anti-fouling and wear-resistant frit is: It takes 1.5 to 2.5 hours to heat from room temperature to 300°C; It takes 2 to 3 hours to heat from 300°C to 1530°C; 1530℃, keep warm for 0.5~1.2h.

6. The method for preparing the anti-slip and anti-fouling matte antique brick according to claim 1, characterized in that: Step C is specifically as follows: C. spraying the anti-skid and anti-fouling matte glaze on the surface of the base glaze layer to obtain an anti-skid 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 is 0.62 mm.

7. The method for preparing the anti-slip and anti-fouling matte antique brick according to claim 1, characterized in that: Calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit includes SiO234.81%, Al2O3 18.66%, CaO 19.16%, K2O 0.81%, ZnO 11.23%, BaO 1.76% and SrO13.46%; Calculated by mass percentage, the chemical composition of the anti-slip dry particles includes SiO2 40.72%, Al2O3 23.21%, CaO 18.59%, MgO 1.04%, K2O 3.49%, Na2O 0.54%, ZnO 8.82%, BaO 1.72% and B2O3 1.87%.

8. The method for preparing the anti-slip and anti-fouling matte antique brick according to claim 1, characterized in that: Calculated by weight, the raw materials of the antifouling and wear-resistant frit are composed of 12 to 18 parts of quartz, 15 to 20 parts of calcined alumina, 30 to 38 parts of wollastonite, 8 to 12 parts of zinc oxide, 18 to 22 parts of strontium carbonate and 1 to 5 parts of barium carbonate.

9. The method for preparing the anti-slip and anti-fouling matte antique brick according to claim 1, characterized in that: Calculated by weight, the raw materials of the anti-skid dry particles are composed of 30 to 35 parts of kaolin, 8 to 12 parts of calcined alumina, 3 to 6 parts of quartz, 30 to 38 parts of wollastonite, 5 to 10 parts of zinc oxide, 3 to 8 parts of dolomite, 3 to 8 parts of potassium nitrate, 1 to 4 parts of barium carbonate and 1 to 5 parts of borax.

10. A non-slip and anti-fouling matte antique tile, characterized in that: The anti-fouling matte antique brick with anti-skid effect is prepared by the preparation method of any one of claims 1 to 9, and the anti-fouling matte antique brick with anti-skid effect has a glaze gloss of 8 to 12°, an anti-fouling grade of level 5, a Mohs hardness of level 7, a wear resistance of ≥ level 4 (6000 revolutions), a dry static friction coefficient of ≥ 0.77, and a wet static friction coefficient of ≥ 0.75.

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