Highly transparent, wear-resistant and antibacterial dry particles, glaze, ceramic tiles and preparation methods thereof

Abstract

The present invention discloses a kind of high-transmittance wear-resistant antibacterial dry granules, glaze, ceramic tile and preparation method thereof, and belongs to the field of building materials technology. The raw materials of the high-transmittance wear-resistant antibacterial dry granules of the present invention include by mass: 15-25 parts of potassium feldspar, 12-20 parts of lithium feldspar, 6-12 parts of dolomite, 4-12 parts of calcined earth, 2-10 parts of corundum, 0.2-1.0 parts of silver oxide, 0.2-1.0 parts of tungsten trioxide, 2-6 parts of zinc oxide, 20-30 parts of cubic boron nitride, and 5-15 parts of aluminum nitride; the high-transmittance wear-resistant antibacterial dry granules are obtained by firing and heat-insulating the raw materials at 1500-1600°C for 30-60 minutes and then quenching, and the water used for quenching is circulating cooling water. The glaze layer and high-transmittance wear-resistant ceramic tile prepared by the high-transmittance wear-resistant antibacterial glaze added with the high-transmittance wear-resistant antibacterial dry granules of the present invention have good transparency and color development, high hardness and wear resistance, and antibacterial properties.

Description

Technical Field

[0001] The invention belongs to the technical field of building materials, and particularly relates to high-transmittance, wear-resistant and antibacterial dry particles, glaze, ceramic tiles and a preparation method thereof. Background Art

[0002] In the field of building materials, dark ceramic tiles have poor transparency and color, and low wear resistance. In order to meet the problem of transparency and color of dark products, production solutions often lower the melting temperature of the glaze protective glaze layer, resulting in more molten glass phases, increasing transparency and color. The melting temperature of the protective glaze layer is low, and the wear resistance of the ceramic tile surface will also be reduced accordingly. The hardness is poor, and the glaze is easily scratched and worn. The design pattern will be blurred and white, affecting the appearance and decorative effect. The wear resistance of the dark ceramic tiles currently produced is basically level two at 600 revolutions, or even lower at level one at 150 revolutions. If the wear resistance of dark ceramic tile products is increased to level three at 1500 revolutions, the glaze will have crystallization and whitening, and the transparency and clarity will deteriorate. Lowering the glaze melting temperature to increase transparency and color will result in a decrease in wear resistance, especially in spaces with large traffic, which cannot meet the usage requirements of living scenarios.

[0003] At the same time, ceramic tiles are used in kitchens and bathrooms. In a humid environment, bacteria can easily breed and affect people's health.

[0004] How to improve the transparency and color of dark ceramic tile products while ensuring the wear resistance of the glaze, reducing glaze scratches, and having antibacterial properties has become a concern for many consumers and manufacturing companies. There is currently no better solution in the industry to solve the problem of dark ceramic tile products that can ensure the transparency and color of the glaze, antibacterial properties, good wear resistance, and solve the problem of glaze scratches and wear. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention provides a highly transparent, wear-resistant, antibacterial dry granule, a glaze, a ceramic tile, and a method for preparing the same. The glaze contains highly transparent, wear-resistant, antibacterial dry granules, and produces dark ceramic tiles with excellent translucency and color development, high wear resistance, few pores, and strong antibacterial properties, making them suitable for a wide range of applications.

[0006] After extensive research and testing, the present invention formulates high-temperature, high-transparency antibacterial materials, which are fired in a high-temperature frit furnace, melted and quenched into frit particles, which are then processed and crushed into small, transparent dry particles. The particles are added to the base protective glaze for use, so that dark-colored ceramic tile products have better translucency, color development, and antibacterial properties. At the same time, the highly translucent, wear-resistant, and antibacterial dry particle materials improve the wear resistance of the glaze, solving the problems of low wear resistance, poor translucency, and insufficient antibacterial properties of dark-colored ceramic tile products. The dark-colored ceramic tiles produced by the present invention can be used in residential areas and shopping malls with large traffic and frequent footfall, as well as in daily life areas, restaurant kitchens, exhibition halls, etc., to meet the different space design and use requirements of customers and solve the problems of glaze scratches and surface color wear that becomes lighter and white due to frequent footfall.

[0007] The technical solution adopted by the present invention to solve its technical problem is:

[0008] The present invention provides a high-transmittance, wear-resistant and antibacterial dry granule. The raw materials thereof include, by weight, 15-25 parts of potassium feldspar, 12-20 parts of lithium feldspar, 6-12 parts of dolomite, 4-12 parts of calcined clay, 2-10 parts of corundum, 0.2-1.0 parts of silver oxide, 0.2-1.0 parts of tungsten trioxide, 2-6 parts of zinc oxide, 20-30 parts of cubic boron nitride, and 5-15 parts of aluminum nitride.

[0009] The high-transmittance, wear-resistant and antibacterial dry particles are obtained by calcining raw materials at 1500-1600° C. and keeping the temperature for 30-60 minutes, and then quenching the raw materials. The water used for quenching the raw materials is circulating cooling water.

[0010] Preferably, the raw materials of the highly transparent, wear-resistant and antibacterial dry particles include, by mass, 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 0.8 parts of silver oxide, 0.8 parts of tungsten trioxide, 4 parts of zinc oxide, 25 parts of cubic boron nitride, and 10 parts of aluminum nitride;

[0011] Preferably, the sintering temperature is 900-1000°C and the sintering temperature is kept at 1500-1600°C for 20-30 minutes;

[0012] More preferably, the sintering is carried out at 950° C. and kept warm for 20-30 minutes, and then the sintering is carried out at 1520° C. and kept warm for 30-60 minutes.

[0013] Preferably, the temperature of the circulating cooling water is 10-30°C.

[0014] The present invention provides a method for preparing the above-mentioned highly permeable, wear-resistant and antibacterial dry particles, comprising the following steps:

[0015] S1. The raw materials of the highly transparent, wear-resistant and antibacterial dry particles are uniformly mixed according to a proportion, applied to a frit furnace for firing to obtain a frit slurry, and the frit slurry is placed in circulating cooling water for quenching;

[0016] S2. The granules obtained by the water quenching treatment are crushed and dried to obtain highly permeable, wear-resistant and antibacterial dry granules.

[0017] Preferably, the drying temperature is 200-250°C and the drying time is 1-2 hours;

[0018] Preferably, the crushed particles are 200-250 mesh;

[0019] Preferably, the firing temperature curve is from room temperature to 300-310℃, time 10-15min, 300-310℃ to 950-960℃, time 30-50min, 950-960℃ keeping warm for 20-30min, 950-960℃ to 1380-1390℃, time 60-90min, 1380-1390℃ to 1520-1530℃, time 80-120min, 1520-1530℃ keeping warm for 30-60min.

[0020] Further preferably, the firing temperature curve is from room temperature to 300°C for 10-15 minutes, from 300°C to 950°C for 30-50 minutes, kept at 950°C for 20-30 minutes, from 950°C to 1380°C for 60-90 minutes, from 1380°C to 1520°C for 80-120 minutes, and kept at 1520°C for 30-60 minutes.

[0021] The invention provides a high-transmittance, wear-resistant and antibacterial glaze. The raw materials of the glaze comprise, by mass, 10-20 parts of potassium feldspar, 6-16 parts of sodium feldspar, 8-12 parts of aluminum nitride, 1-5 parts of zinc oxide, 3-8 parts of corundum, 6-10 parts of kaolin, 30-40 parts of high-transmittance, wear-resistant and antibacterial dry particles, 5-10 parts of calcite, and 3-8 parts of calcite. The high-transmittance, wear-resistant and antibacterial dry particles are the above-mentioned high-transmittance, wear-resistant and antibacterial dry particles or the high-transmittance, wear-resistant and antibacterial dry particles prepared by the above-mentioned preparation method.

[0022] Preferably, the fineness requirement of the high-transparency, wear-resistant and antibacterial glaze is 325 mesh, with a sieve residue of 0.2-0.6%.

[0023] Preferably, the raw materials of the high-transmittance, wear-resistant and antibacterial glaze include, by mass, 15 parts of potassium feldspar, 11 parts of sodium feldspar, 10 parts of aluminum nitride, 4 parts of zinc oxide, 5 parts of corundum, 8 parts of kaolin, 35 parts of high-transmittance, wear-resistant and antibacterial dry particles, 7 parts of calcined talc, and 5 parts of calcite.

[0024] The present invention provides a method for preparing the above-mentioned high-transmittance, wear-resistant and antibacterial glaze, comprising the following steps:

[0025] The raw materials of the high-transmittance wear-resistant antibacterial glaze are added to printing paste and printing oil and ball-milled to obtain the high-transmittance wear-resistant antibacterial glaze; the mass ratio of the raw materials of the high-transmittance wear-resistant antibacterial glaze, printing paste and printing oil is 100:65-70:15-20.

[0026] The present invention provides a high-transmittance, wear-resistant and antibacterial ceramic tile, comprising a high-transmittance, wear-resistant and antibacterial glaze layer, which is obtained by firing the above-mentioned high-transmittance, wear-resistant and antibacterial glaze or the high-transmittance, wear-resistant and antibacterial glaze prepared by the above-mentioned preparation method.

[0027] Preferably, the firing temperature is 1200-1250°C.

[0028] Preferably, the firing is a roller kiln firing, which includes a preheating stage, an oxidation stage, a firing stage and a cooling stage, wherein the firing stage includes an early and late firing stage, and the bottom temperature is higher than the surface temperature during the firing process.

[0029] Further preferably, the firing stage includes an early firing stage and a late firing stage. The early firing stage includes four zones, with surface temperatures of 1160-1165°C, 1187-1192°C, 1205-1210°C, and 1212-1217°C, and corresponding bottom temperatures of 1175-1180°C, 1198-1210°C, 1210-1220°C, and 1216-1223°C, respectively. The time for each zone is 2-3 minutes; the late firing stage includes five zones (insulation zones), with surface temperatures of 1215-1220°C, and corresponding bottom temperatures of 1220-1225°C, and the time for each zone is 2-4 minutes.

[0030] The present invention provides a method for preparing the above-mentioned high-transmittance, wear-resistant and antibacterial ceramic tiles, comprising the following steps:

[0031] (1) Preparation of green body powder: add water to the raw materials of green body powder, ball mill, remove iron, sieve, spray granulate, control the moisture content to 6.5-7.5%, and let it age for later use;

[0032] (2) The green body powder is pressed into bricks and dried into green bricks;

[0033] (3) Spray water on the surface of the blank to moisten it and then glaze it;

[0034] (4) Inkjet printing;

[0035] (5) Screen printing of high-transparency, wear-resistant and antibacterial glaze, 100-120 mesh full-pass screen printing 2-3 times;

[0036] (6) Firing;

[0037] (7) Polishing and edge grinding to obtain highly transparent, wear-resistant and antibacterial ceramic tiles.

[0038] The wear-resistant glaze of the present invention is partially crushed into dry particles by firing the raw materials, thereby reducing the gas generated by the burning loss of organic matter and carbon-sulfur compounds in the raw glaze, effectively controlling the number of pores on the glaze surface, and improving the transparency of the wear-resistant glaze; the aluminum nitride and zinc oxide in the wear-resistant dry particles improve the transparency and color of the wear-resistant glaze, and are applied to the glaze layer of ceramic tiles, especially in dark products, which can better reflect the product surface clarity and glaze texture.

[0039] The wear-resistant dry particles of the present invention are introduced with high-hardness materials such as boron nitride and aluminum nitride, and are melted to form composite dry particles, which can reach a Mohs hardness of 9.0. The prepared wear-resistant glaze can reach a Mohs hardness of 8.0. The glaze has a high wear resistance level, and the wear resistance of the glaze surface of the dark product can reach level 4.

[0040] The catalyst / antibacterial agent of the present invention is introduced. Silver oxide and tungsten trioxide are added to the wear-resistant dry particles to react at high temperature to generate silver tungstate. Silver tungstate has a catalytic effect, which can accelerate the reaction rate of the material at high temperature. The frit slurry accelerates the reaction to be complete, reduces the melting temperature of the mixture, and improves the transparency and color of the glaze. Silver tungstate also has the function of inhibiting the activity of bacterial metabolic enzymes, causing metabolic disorders and being unfavorable for bacterial growth. Therefore, it has the function of inhibiting bacterial growth and antibacterial properties, providing a healthy living environment.

[0041] The present invention improves the dry granule firing system, performs heat preservation treatment at 950° C. and 1520° C. in two stages, fully discharges gas in the raw materials, and allows the raw materials to fully react. The present invention also improves the quenching process, improves the quenching flow rate control of the frit dry granule slurry, increases the number of openings, reduces the dry granule slurry flow rate, and lowers the circulating water temperature in the quenching environment. The quenching process requires circulating heat dissipation and cooling before use, uses circulating cooling water for quenching, increases the quenching rate, inhibits crystal nucleation and crystal growth, improves the transparency of the dry granules, increases the quenching temperature difference, and reduces the particle size of the frit particles formed after quenching, thereby reducing the frit crushing cost.

[0042] The present invention controls the amount of wear-resistant protective glaze, adjusts the glaze temperature and hardness, improves the wear resistance of the glaze surface, and uses a 100-mesh screen printing two-time process to control and reduce the thickness of the wear-resistant glaze layer. The thinning of the glaze layer enhances the transparency and color development of the glaze, while reducing the amount and saving costs.

[0043] The present invention improves the firing curve of the roller kiln. In the early stage of the firing stage, the surface temperature firing temperature is lowered and the bottom temperature firing temperature is increased, the oxidation exhaust zone is lengthened, and the oxidation exhaust of the body is completed before the glaze begins to melt. The number of pores on the glaze is reduced, the wear-resistant glaze has a good melting effect, and the structure is dense. In the wear resistance test of dark products, the whitening phenomenon of the wear layer glaze is significantly improved, and the anti-fouling performance and wear resistance level are improved.

[0044] The technical principles involved in the present invention are:

[0045] 1. The wear-resistant dry particles of the present invention are introduced with flux, boron nitride and aluminum nitride. The flux can quickly reduce the initial melting temperature of the mixed powder. The high-temperature firing melts the high-hardness material and the solvent into wear-resistant dry particles with good transparency and high hardness, thereby improving the transparency, color development and wear resistance of the wear-resistant glaze, especially on the surface of dark products, and significantly reducing the problem of scratches caused by stepping on.

[0046] 2. The catalyst / antibacterial agent of the present invention, silver oxide and tungsten trioxide are reacted by high-temperature firing to generate silver tungstate. Silver tungstate has a catalytic effect, which accelerates the reaction rate of the material at high temperature. The frit slurry accelerates the reaction to be complete, reduces the melting temperature of the mixture, and improves the transparency and color of the glaze. Dry particles containing silver tungstate are added to the wear-resistant glaze, and silver ions are introduced. On the surface of ceramic tiles, it has obvious bactericidal effect. Silver ions change the structure of bacteria, have a destructive effect on cell membranes and cell walls, inhibit the activity of bacterial metabolic enzymes, lead to metabolic disorders, and are not conducive to bacterial growth, thereby having a bactericidal effect and providing a healthy and safe living environment.

[0047] 3. The present invention pre-fires part of the glaze into dry granules, which can eliminate the gas components in the organic matter and carbon-sulfur compounds in the glaze. The dry granules account for no less than 25%. After high-temperature firing, the dry granules have fewer pores and less crystallization. High-temperature firing causes the high-temperature intolerant raw materials and flux to melt into a glass phase, reducing the impact of impurities and oxidizing reaction gases on the transparency of the wear-resistant glaze, and also improving the hardness and wear resistance of the glaze. This solves the problem that organic matter and carbon-sulfur compounds in ordinary glazes generate gas during firing, the exhaust is incomplete, and tiny pores remain on the glaze surface, affecting the transparency and color of the glaze, and causing dark products to turn white and have poor clarity.

[0048] 4. Aluminum nitride is introduced into the wear-resistant glaze of the present invention. The structure of aluminum nitride does not change during high-temperature firing, and it can still maintain a high light transmittance, good transparency, hard porcelain, high wear resistance and chemical stability.

[0049] 5. The present invention controls the kiln firing curve. Before the glaze melts, it delays the temperature rise rate of the surface temperature of the kiln firing zone, increases the bottom temperature, increases the temperature difference between the bottom temperature and the surface temperature in the early stage, and fully completes the oxidation and exhaust of the green body. After the green body is completely exhausted, the kiln surface temperature is increased, the glaze melts, and the pores are closed, which can reduce the capillary pores of the ceramic tile glaze, make the glaze dense, and improve the anti-fouling performance and the wear-resistant glaze transparency and color.

[0050] 6. The firing temperature of the kiln of the present invention is 1200-1250°C, which is 20-50°C higher than the firing temperature of conventional ceramic tile products of 1180-1200°C. The wear-resistant glaze can be better melted into a transparent glass phase, improving the transparency and color.

[0051] The beneficial effects of the present invention are:

[0052] The glaze layer prepared by the high-transmittance, wear-resistant and antibacterial glaze with high-transmittance, wear-resistant and antibacterial dry particles is applied on the surface of dark-colored ceramic tiles, has good transparency and color development, high hardness and wear resistance, and antibacterial performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a physical picture of the wear resistance test of the ceramic tile (100*100mm) according to Example 6 of the present invention.

[0054] Figure 2 This is a comparison chart of the translucency and color development of dark ceramic tiles in Examples 1 and 3 of the present invention. The left side is the wear-resistant glaze (600*300mm) with good translucency and color development in Example 1, and the right side is the glaze (600*300mm) with poor translucency and color development in Example 3.

[0055] Figure 3 This is a pore test image of the ceramic tile of Comparative Example 4 of the present invention observed under a 200x magnifying glass (the diameter of the observation area is 5 mm). The capillary pores reflect light as white spots under the magnifying glass. DETAILED DESCRIPTION

[0056] The present invention is further described below with reference to the embodiments.

[0057] The following will clearly and completely describe the concept, specific scheme and technical effects of the present invention in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention. The various technical features in the invention can be combined interchangeably without conflicting with each other.

[0058] The present invention provides a method for preparing high-transmittance, wear-resistant and antibacterial dry particles, high-transmittance, wear-resistant and antibacterial glaze, and high-transmittance, wear-resistant and antibacterial ceramic tiles, comprising the following steps:

[0059] Step 1: Preparation of highly permeable, wear-resistant and antibacterial dry particles

[0060] The raw materials of high-transmittance, wear-resistant and antibacterial dry granules are as follows in parts by mass:

[0061] 15-25 parts of potassium feldspar, 12-20 parts of lithium feldspar, 6-12 parts of dolomite, 4-12 parts of calcined clay, 2-10 parts of corundum, 0.2-1.0 parts of silver oxide, 0.2-1.0 parts of tungsten trioxide, 2-6 parts of zinc oxide, 20-30 parts of cubic boron nitride, and 5-15 parts of aluminum nitride.

[0062] The raw materials used in the high-transmittance, wear-resistant and antibacterial dry particles of the present invention mainly include the following four parts: 1. High-hardness raw materials: mainly cubic boron nitride, corundum, and aluminum nitride; 2. High-temperature and high-transmittance materials: mainly aluminum nitride; 3. Catalyst / antibacterial agent: silver oxide, tungsten trioxide; 4. Flux: mainly including dolomite, zinc oxide, potassium feldspar, lithium feldspar, etc.

[0063] The high-transmittance, wear-resistant and antibacterial dry particles prepared by the above raw materials have a Mohs hardness of up to 9.0. They are used in high-transmittance, wear-resistant and antibacterial glazes to improve the transparency, color and hardness of the high-transmittance, wear-resistant glaze layer during the firing process of ceramic tiles. Since aluminum nitride is a hexagonal crystal system with a hardness of 7-8, corrosion resistance, high strength, and a high refractive index of 2.0-2.4, it improves the transparency, color and wear resistance of the ceramic tile glaze. Boron nitride is a cubic structure crystal, a wear-resistant material with a superhard structure, a Mohs hardness of 9.8, and a high refractive index of 2.0-2.4. Through the catalytic effect of fluxing agents such as dolomite, potassium feldspar, lithium feldspar and zinc oxide and catalyst silver tungstate, high-transmittance and high-wear-resistant materials such as aluminum nitride and boron nitride are fired at a high temperature of 1500-1600℃ to improve the hardness and transparency of the dry granular material. Silver oxide and tungsten trioxide react in a high-temperature furnace to form silver tungsten oxide, which has a catalytic effect, accelerating the rapid melting of aluminum nitride and boron nitride under the action of flux to form a new type of high-hardness, high-transmittance and antibacterial dry granular material, thereby improving the transparency, color development and wear resistance of dark-colored ceramic tile products.

[0064] The preparation steps of the above-mentioned highly permeable, wear-resistant and antibacterial dry particles include:

[0065] S1. The raw materials of the highly transparent, wear-resistant and antibacterial dry particles are mixed uniformly according to a ratio, and placed in a high-temperature frit furnace for calcination. The frit furnace calcination curve is as follows: from room temperature to 300°C, time 10-15min, 300 to 950°C, time 30-50min, 950°C insulation for 20-30min, 950 to 1380°C, time 60-90min, 1380 to 1520°C, time 80-120min, and 1520°C insulation for 30-60min to obtain a frit slurry. The frit slurry is passed through a slurry hole and placed in circulating cooling water for quenching treatment. The circulating cooling water temperature is maintained at 10-30°C, and the cooling water is recycled after heat dissipation treatment.

[0066] S2. The frit slurry is rapidly quenched by circulating cooling water, crushed twice into 200-250 mesh particles, and dried in an oven at 200-250° C. for 1-2 hours to obtain the highly transparent and wear-resistant dry particles.

[0067] The fineness of various raw materials used to prepare high-transparency, wear-resistant and antibacterial dry particles is controlled at 200-300 meshes, mixed evenly with a mixer according to the formula ratio, and spread in a high-temperature frit furnace, which can increase the reaction rate during high-temperature firing in the frit furnace and make the reaction more complete and uniform.

[0068] According to the calcination curve above, the temperature is maintained at 950°C for 20-30 minutes to facilitate the oxidation reaction of the material and the oxidation and exhaust of organic matter and carbon and sulfur compounds. The temperature is raised to 1520°C and, under the catalysis of silver tungstate, maintained for 30-60 minutes to ensure sufficient material reaction and complete exhaust, thereby improving the transparency of the dry particles, promoting a stable crystal structure, and forming a composite wear-resistant frit slurry. The frit slurry is discharged into the quenching circulating water for quenching. The discharge flow rate is controlled and the opening flow rate is reduced. To maintain production, multiple discharge ports can be opened simultaneously to discharge the slurry. The purpose of controlling the discharge flow rate is to obtain smaller quenched frit particles, reduce subsequent crushing costs, and improve crushing efficiency. Using circulating cooling water and increasing the cooling rate of the frit slurry can reduce the growth rate of the frit crystal nucleus, inhibit the formation of crystallization, and increase the transparency of the wear-resistant dry particles. By improving the quenching environment, the cooling rate of the melt is accelerated. The faster the cooling, the less crystallization is generated, and the better the transparency of the high-transmittance, wear-resistant and antibacterial dry particles. The water temperature for quenching ordinary dry particles is 80-100℃ and the water used for cooling is fixed and not circulated. The quenching effect is reduced and the transmittance is only 70-75%. In order to improve the transparency of dry particles, circulating cooling water is used during the quenching process. The circulating water temperature is controlled at 10-30℃, which accelerates the cooling efficiency, reduces the crystal nucleus growth rate, and inhibits crystal growth. The transparency is significantly improved and the transmittance can reach 90%.

[0069] The raw material used for high-transmittance, wear-resistant and antibacterial dry particles is cubic boron nitride, a new type of superhard material with a Mohs hardness second only to diamond, with a hardness of 9.8. It can significantly improve the hardness of the wear-resistant dry particles, thereby improving the wear resistance of the wear-resistant glaze; the flux zinc oxide enhances the transparency and color of the dry particles, but if the dosage exceeds 5%, it will begin to become turbid and crystallize, and the transparency will gradually deteriorate; adding aluminum nitride can effectively improve the transparency of the wear-resistant glaze.

[0070] Silver oxide and tungsten trioxide are added to the high-transmittance, wear-resistant and antibacterial dry particles, and the high-temperature firing reaction generates silver tungstate. Silver tungstate has a catalytic effect, which can accelerate the reaction rate of the frit material, melt in a shorter time, react evenly, and form a high-transmittance, wear-resistant frit with a stable crystal structure, thereby improving the transparency of the wear-resistant glaze. Silver tungstate also has antibacterial properties. When used in ceramic tile glaze, the antibacterial agent can inhibit the activity of bacterial metabolic enzymes, leading to metabolic disorders, which is not conducive to bacterial growth, thereby having a bactericidal effect and providing a healthy and safe living environment.

[0071] Part of the raw materials in the highly transparent, wear-resistant and antibacterial glaze are prepared into dry particles to reduce the gas components produced by organic matter and carbon-sulfur compounds in the ceramic glaze, reduce gas generation during the firing process, complete decomposition, oxidation and chemical reactions under controlled conditions, reduce the number of pores on the glaze surface during the firing of ceramic tiles, form a stable silicate glass phase, and enhance the glaze surface's transparency, color development and anti-fouling properties.

[0072] Step 2: Preparation of high-transparency, wear-resistant and antibacterial glaze

[0073] The raw materials of high-transparency, wear-resistant and antibacterial glaze are as follows by mass:

[0074] Potassium feldspar 10-20, sodium feldspar 6-16, aluminum nitride 8-12, zinc oxide 1-5, corundum 3-8, kaolin 6-10, high-transparency, wear-resistant and antibacterial dry particles 25-40, burned talc 5-10, calcite 3-8.

[0075] The proportion of high-transmittance, wear-resistant dry particles in the high-transmittance, wear-resistant and antibacterial glaze is no less than 25%. Some raw materials are introduced as dry particles to reduce the oxidation of organic carbon and sulfur compounds to produce gas during the firing of the wear-resistant glaze, reduce the pores of the glaze, increase the density of the glaze, and improve the anti-fouling performance and transparent color of the glaze.

[0076] The fineness of each chemical raw material of the high-transparency, wear-resistant and antibacterial glaze is 200-300 meshes. The finer the raw materials, the more uniform the ball milling mixing, which improves the ball milling efficiency and the stability of the glaze performance.

[0077] The higher the proportion of wear-resistant dry particles in high-transmittance, wear-resistant and antibacterial glaze, the better the transparency and color. The lower the proportion of dry particles, especially the surface of darker products will turn white and the transparency and color will deteriorate. The higher the proportion of wear-resistant dry particles, the better the wear resistance of the glaze. The wear resistance level of darker products can reach level 4 2100 revolutions. However, if the proportion of wear-resistant dry particles is too high, the transparency and color will be reduced. After use, the glaze of dark products will turn white and the effect will be poor.

[0078] Aluminum nitride is added to the high-transmittance, wear-resistant and antibacterial glaze. Aluminum nitride has a high refractive index of 2.0-2.4, which improves the high-temperature light transmittance of the high-temperature glaze and the transparency and color of the dark ceramic tile glaze, with a light transmittance of up to 90%.

[0079] The preparation steps of the above-mentioned high-transparency, wear-resistant and antibacterial glaze include:

[0080] The raw materials of high-transparency, wear-resistant and antibacterial glaze, printing paste and printing oil are put into a ball mill according to the proportion, and the ball milling fineness of the glaze is required to be 325 mesh sieve with 0.2-0.6% residue on the sieve.

[0081] High-transparency, wear-resistant and antibacterial glaze fineness: The finer the ball milling fineness, the lower the temperature, the lower the glaze hardness and wear resistance. Reasonable glaze fineness is conducive to controlling the wear resistance stability of the glaze surface. The ball milling glaze fineness is controlled to be 0.2-0.6% of the 325 mesh sieve residue.

[0082] Step 3: Preparation of highly transparent, wear-resistant and antibacterial ceramic tiles

[0083] (1) Preparation of green body powder, ball milling, iron removal, sieving, spray tower granulation, moisture control 6.5-7.5%, aging for later use;

[0084] (2) The green body powder is pressed into bricks using a Henglitai YP5009 hydraulic press and then dried in a drying kiln at 150-250℃ to form green bricks;

[0085] (3) Spray water on the surface of the blank to moisten it, then pour glaze on it. The specific gravity is 1.80-1.88g / ml and the amount of glaze is 420-550g / m 2 ;

[0086] (4) After the glaze layer is applied, the inkjet design is printed using a new Jingtai digital inkjet printer to create a colorful marble pattern;

[0087] (5) Screen printing wear-resistant protective glaze, 100 mesh full-pass screen printing twice;

[0088] (6) Roller kiln firing, firing temperature 1200-1250 degrees, kiln firing cycle 70-90 minutes, high temperature zone holding time 10-20 minutes;

[0089] (7) Semi-finished product polishing: use medium light module polishing, the glossiness after polishing is 90-97 degrees, and the edges are ground to obtain highly transparent, wear-resistant and antibacterial ceramic tiles.

[0090] The raw materials in the green body powder are as follows: 22 parts Fengze stone powder, 14 parts kaolin, 12 parts pressed mud, 6 parts sodium stone powder, 11 parts Guangdong black mud, 4 parts black talc, 8 parts potassium stone powder, 7 parts pyrophyllite, and 16 parts Guangrun sand. The chemical composition of the green body powder includes: SiO2 65.88%, Al2O3 20.32%, Fe2O3 0.7%, TiO2 0.16%, CaO 0.51%, MgO 0.91%, K2O 3.73%, Na2O 2.65%, and loss on ignition 4.83%.

[0091] The glaze contains the following raw materials by weight: 25 parts potassium feldspar, 18 parts sodium feldspar, 8 parts kaolin, 8 parts calcined clay, 6 parts talc, 5 parts wollastonite, 20 parts quartz, and 10 parts zirconium silicate. The glaze's chemical composition includes: 49.32% SiO₂, 20.53% Al₂O₃, 0.15% Fe₂O₃, 0.08% TiO₂, 2.32% ZnO, 4.21% CaO, 3.65% MgO, 3.53% K₂O, 2.76% Na₂O, 3.24% BaO, 5.74% ZrO₂, and a loss on ignition of 4.36%.

[0092] Xinjingtai digital inkjet printer uses inks in the following colors: blue, brown, beige, black, bright red, bright yellow and other colors. By inputting the inkjet design pattern, it prints out colorful marble design effects on the surface of ceramic tiles.

[0093] High-transparency, wear-resistant glazes are printed twice with a 100-mesh screen, ensuring uniform surface application. Fewer prints can produce yellow edges, while more prints can reduce the transparency of the glaze. To ensure the transparency and color development of dark products, the wear-resistant glaze's own light transmission properties and the number of glaze layer prints must be controlled. This increases the wear-resistant glaze's temperature, improves the glaze's wear resistance, and reduces the likelihood of scratches from foot traffic, which can affect the product's aesthetics.

[0094] Roller kiln firing includes preheating stage, oxidation stage, firing stage and cooling stage. The firing temperature is 1225℃. In the early stage of firing, the surface temperature of the kiln firing curve is controlled to 1160℃, 1187℃, 1210℃, 1217℃, and the bottom temperature is 1180℃, 1210℃, 1220℃, 1223℃; the surface temperature of the insulation zone is 1220℃×5 zones, and the bottom temperature is 1225℃×5 zones; the purpose of delaying the temperature rise rate of the surface temperature in the firing stage is to quickly oxidize and decompose the body before the glaze melts, and the oxidizing gas of the body is discharged. After the exhaust is complete, the kiln surface temperature is increased, the glaze layer is melted, and the pores are closed, which can reduce the pores on the glaze of ceramic tiles, make the glaze dense, and improve the anti-fouling performance and the wear-resistant glaze transparency and color.

[0095] The firing process increases the firing temperature and holding time of the high-temperature zone of the roller kiln. The wide-body roller kiln of 1200-1250℃ increases the firing temperature of the kiln, which can correspondingly increase the proportion of the wear-resistant glaze melted into the glass phase and its own sintering temperature, increase the proportion of wear-resistant dry particles in the wear-resistant glaze, and improve the light transmittance and wear resistance of the glaze accordingly, which can not only meet the glaze's translucency and color, but also improve the hardness and wear resistance of the wear-resistant glaze, and solve the problems of poor translucency and color development and low wear resistance of dark ceramic tile products.

[0096] The raw materials used in the green powders in the following examples and comparative examples are as follows: 22 parts Fengze stone powder, 14 parts kaolin, 12 parts pressed mud, 6 parts sodium stone powder, 11 parts Guangdong black mud, 4 parts black talc, 8 parts potassium stone powder, 7 parts pyrophyllite, and 16 parts Guangrun sand. The green powder has a chemical composition of 65.88% SiO₂, 20.32% Al₂O₃, 0.7% Fe₂O₃, 0.16% TiO₂, 0.51% CaO, 0.91% MgO, 3.73% K₂O, 2.65% Na₂O, and a loss on ignition of 4.83%.

[0097] The following examples and comparative examples contain the following raw materials in the following weight percentages: 25 parts potassium feldspar, 18 parts sodium feldspar, 8 parts kaolin, 8 parts calcined clay, 6 parts talc, 5 parts wollastonite, 20 parts quartz, and 10 parts zirconium silicate. The chemical composition of the glaze includes: 49.32% SiO₂, 20.53% Al₂O₃, 0.15% Fe₂O₃, 0.08% TiO₂, 2.32% ZnO, 4.21% CaO, 3.65% MgO, 3.53% K₂O, 2.76% Na₂O, 3.24% BaO, 5.74% ZrO₂, and a loss on ignition of 4.36%.

[0098] Example 1

[0099] A method for preparing high-transmittance, wear-resistant and antibacterial dry particles, high-transmittance, wear-resistant and antibacterial glaze, and high-transmittance, wear-resistant and antibacterial ceramic tiles, comprising the following steps:

[0100] Step 1: Preparation of highly permeable, wear-resistant and antibacterial dry particles

[0101] The mass proportions of various raw materials are: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 0.5 parts of silver oxide, 0.5 parts of tungsten trioxide, 4 parts of zinc oxide, 20 parts of cubic boron nitride, and 8 parts of aluminum nitride.

[0102] The raw materials of the high-transmittance, wear-resistant and antibacterial dry particles are uniformly mixed according to a proportion, and applied to a high-temperature frit furnace for calcination. The frit furnace calcination curve is as follows: from room temperature to 300°C for 15 minutes, from 300°C to 950°C for 40 minutes, and kept at 950°C for 30 minutes, from 950°C to 1380°C for 90 minutes, from 1380°C to 1520°C for 120 minutes, and kept at 1520°C for 40 minutes to obtain a frit slurry. The frit slurry is passed through a slurry discharge hole and placed in circulating cooling water for quenching treatment. The circulating cooling water temperature is maintained at 10-30°C. The frit is crushed twice into 200-250 mesh particles and dried to prepare the high-transmittance, wear-resistant and antibacterial dry particles.

[0103] Step 2: Preparation of high-transparency, wear-resistant and antibacterial glaze

[0104] The mass proportions of the raw materials are: 15 parts of potassium feldspar, 11 parts of sodium feldspar, 10 parts of aluminum nitride, 4 parts of zinc oxide, 5 parts of corundum, 8 parts of kaolin, 35 parts of high-transmittance, wear-resistant and antibacterial dry particles, 7 parts of calcined talc and 5 parts of calcite.

[0105] The raw materials of high-transparency, wear-resistant and antibacterial glaze are put into a ball mill for ball milling. The milling parameters of a 3-ton ball mill are as follows: 100 parts of wear-resistant glaze dry powder, 65 parts of printing paste, and 15 parts of printing oil. The ball milling is carried out for 5 hours. The fineness after ball milling is required to be controlled to 325 mesh sieve, and the sieve residue is 0.2-0.6%.

[0106] Step 3: Preparation of highly transparent, wear-resistant and antibacterial ceramic tiles

[0107] (1) Preparation of green body powder: add water to the raw materials of green body powder and ball mill, remove iron, sieve, granulate in spray tower, control the moisture content to 6.5-7.5%, and let it stand for use.

[0108] (2) The green body powder is pressed into green body by hydraulic press and dried in a drying kiln at 150-250℃ to form green body;

[0109] (3) Spray water on the surface of the blank to moisten it, then apply glaze. The specific gravity of the glaze is 1.75-1.88g / ml, and the amount of glaze is 420-550g / m 2 ;

[0110] (4) The glaze surface is printed with an inkjet design using a digital inkjet machine to form a colorful marble pattern;

[0111] (5) Screen printing of high-transparency, wear-resistant and antibacterial glaze, 100 mesh full-pass screen printing twice;

[0112] (6) Roller kiln firing, firing temperature 1220℃, including preheating stage, oxidation stage, firing stage and cooling stage, among which, the preheating stage is from room temperature to 800℃, time is 15min; the oxidation stage is from 800℃ to 1150℃, time is 25min. In the early stage of firing stage, the surface temperature of the four zones of the kiln firing curve is controlled to be 1165℃, 1192℃, 1205℃, and 1212℃ respectively, and the bottom temperature is 1175℃, 1198℃, 1210℃, and 1216℃ respectively, and the time for each zone is 2min; the surface temperature of the insulation zone is 1215℃×5 zones, and the bottom temperature is 1220℃×5 zones, and the insulation time of the high temperature zone is 10min in total; the cooling stage is from 1220℃ to room temperature, time is 15min.

[0113] (7) Polishing of semi-finished products: Use medium light module to polish, the glossiness after polishing is 90-97 degrees, and grind the edges to obtain highly transparent, wear-resistant and antibacterial ceramic tiles.

[0114] Example 2

[0115] Same as Example 1, except that in step 1, the highly permeable, wear-resistant and antibacterial dry particles are prepared

[0116] Step 1: Preparation of highly permeable, wear-resistant and antibacterial dry particles

[0117] The mass proportions of various raw materials are reduced to reduce the ratio of cubic boron nitride, aluminum nitride and zinc oxide: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 0.5 parts of silver oxide, 0.5 parts of tungsten trioxide, 2 parts of zinc oxide, 16 parts of cubic boron nitride, and 4 parts of aluminum nitride.

[0118] Example 3

[0119] Same as Example 1, except that in step 2, the preparation of the highly transparent, wear-resistant and antibacterial glaze is

[0120] Step 2: Preparation of high-transparency, wear-resistant and antibacterial glaze

[0121] The mass proportions of raw materials are reduced to: 15 parts of potassium feldspar, 11 parts of sodium feldspar, 6 parts of aluminum nitride, 4 parts of zinc oxide, 5 parts of corundum, 8 parts of kaolin, 25 parts of high-transmittance, wear-resistant and antibacterial dry particles, 7 parts of calcined talc, and 5 parts of calcite.

[0122] Example 4

[0123] Same as Example 1, except that in step 1, the highly permeable, wear-resistant and antibacterial dry particles are prepared

[0124] Step 1: Preparation of highly permeable, wear-resistant and antibacterial dry particles

[0125] The mass proportions of various raw materials are used to increase the ratio of silver oxide and tungsten trioxide: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 0.8 parts of silver oxide, 0.8 parts of tungsten trioxide, 4 parts of zinc oxide, 20 parts of cubic boron nitride, and 8 parts of aluminum nitride.

[0126] Comparative Example 1

[0127] The same as Example 1, except that in the preparation of highly transparent, wear-resistant and antibacterial dry particles in step 1, there is no cubic boron nitride in the raw material ratio of the wear-resistant dry particles, and the mass parts of various raw materials are: 30 parts of potassium feldspar, 20 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined soil, 6 parts of corundum, 0.5 parts of silver oxide, 0.5 parts of tungsten trioxide, 5 parts of zinc oxide, and 10 parts of aluminum nitride.

[0128] Comparative Example 2

[0129] Same as Example 1, except that in step 1, high-transmittance, wear-resistant and antibacterial dry particles are prepared, and the holding time of the wear-resistant dry particles at 950° C. and 1520° C. is 0 min.

[0130] Comparative Example 3

[0131] The same as Example 1, except that in step 1, the highly transparent, wear-resistant and antibacterial dry particles are prepared. After the wear-resistant dry particles are fired, no circulating cooling water is used for quenching, and the water temperature is 80-100°C.

[0132] Comparative Example 4

[0133] The same as Example 1, except that in the preparation of high-transmittance, wear-resistant and antibacterial dry particles in step 1, the wear-resistant dry particle raw materials are not pre-fired into dry particles, and the dry particle powder raw materials are directly added to the wear-resistant glaze powder raw materials in proportion, and the wear-resistant glaze is obtained by ball milling.

[0134] Comparative Example 5

[0135] The same as Example 1, except that in step 1, the preparation of highly transparent, wear-resistant and antibacterial dry particles, the ratio of raw materials for wear-resistant dry particles, no silver oxide and tungsten trioxide, and the mass fractions of various raw materials are: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined soil, 6 parts of corundum, 4 parts of zinc oxide, 20 parts of cubic boron nitride, and 8 parts of aluminum nitride.

[0136] Comparative Example 6

[0137] Same as Example 1, except that in step 3, the preparation of high-transmittance, wear-resistant and antibacterial ceramic tiles is

[0138] (6) Roller kiln firing, the kiln firing curve is different, the firing temperature is 1225℃, including preheating stage, oxidation stage, firing stage and cooling stage, among which, the preheating stage is from room temperature to 800℃, the time is 15min; the oxidation stage is from 800℃ to 1150℃, the time is 25min, in the early stage of the firing stage, the kiln firing curve is controlled, the surface temperatures of the four zones are 1175℃, 1207℃, 1214℃, and 1218℃, and the bottom temperatures are 1175℃, 1207℃, 1218℃, and 1222℃, respectively, and the time for each zone is 2min; the surface temperature of the insulation zone is 1222℃×5 zones, and the bottom temperature is 1225℃×5 zones, and the insulation time of the high temperature zone is 10min in total; the cooling stage is from 1225℃ to room temperature, the time is 15min.

[0139] The high-transmittance, wear-resistant and antibacterial ceramic tiles prepared in the above examples and comparative examples were tested:

[0140] Wear-resistant glaze transmittance test: The percentage of the luminous flux passing through a transparent or translucent body to the incident luminous flux is the transmittance. The wear-resistant glaze is beaten into a cake and fired in a kiln under the same conditions. It is then polished into a 2mm thick sheet. The percentage of the luminous flux passing through the sheet to the incident luminous flux is tested.

[0141] Number of pores: Observe the fired sample bricks with a 200x magnifying glass and connect to a computer for data statistics, the number of pores per square centimeter;

[0142] Abrasion loss: Under the same conditions, cut the test brick into 100×100mm small pieces, place them on the wear tester, grind them for 6000 revolutions, and weigh them to calculate the weight loss of the bricks, which is the abrasion loss.

[0143] Mohs hardness test: The test is carried out on the fired sample bricks in accordance with the JC / T 908-2013 "Artificial Stone" standard;

[0144] Wear resistance test: The test is carried out on fired samples in accordance with GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of surface resistance of glazed tiles";

[0145] Antibacterial test: The antibacterial performance of fired samples is tested according to the standard JC / T 897-2014 "Antibacterial Performance of Antibacterial Ceramic Products";

[0146] Color saturation test: The color saturation of fired bricks was tested using a Triumph spectrophotometer. The spectral data reflected by the object was measured to calculate the color saturation (C). The larger the value, the darker and more vivid the color.

[0147] The test results are shown in Table 1 below:

[0148] Table 1

[0149]

[0150] In Examples 1-4, aluminum nitride, boron nitride, silver oxide and tungsten trioxide are adjusted, and the transmittance, color development and wear resistance of dark ceramic tiles change. The proportion of aluminum nitride is increased, and the light transmittance is significantly improved, especially when the ceramic tile pattern design color is darker, the effect is more obvious. In Examples 2 and 3, aluminum nitride and boron nitride are reduced, and the transmittance and wear resistance of the glaze are reduced; in Example 4, silver oxide and tungsten trioxide in the dry particles react in a high-temperature frit furnace to generate silver tungstate, which has a catalytic effect and can promote the reaction rate of the material at high temperature. The frit slurry accelerates the reaction to complete, reduces the melting temperature of the mixture, improves the transmittance and color development of the glaze, and also has good antibacterial properties.

[0151] The contrast of the dark ceramic tiles' translucent colors of Examples 1 and 3 is shown in the figure below. Figure 2 It can be seen that the dark ceramic tiles in Example 1 have better transparency and color.

[0152] In comparative example 1, there is no cubic boron nitride in the high-transmittance, wear-resistant and antibacterial dry particles, and the hardness and wear resistance level of the wear-resistant glaze are reduced, directly to level 1 150 turns, the glaze wear increases, and glaze surface abrasion and scratches are easily generated, affecting the use function and aesthetic value of the ceramic tiles.

[0153] Comparative Example 2: In the firing process of highly transparent, wear-resistant and antibacterial dry particles, it is necessary to reasonably control the holding time of the raw material oxidation and decomposition stage and the catalytic holding time of the heating curve. Different firing curves for the same raw materials affect the porosity, hardness and wear resistance of the glaze, and affect the transparency and color of the dark product wear-resistant glaze. If the curve is not formulated reasonably, the glaze surface will turn white.

[0154] Comparative Example 3 illustrates the quenching process of dry particles. Circulating cooling water affects the quenching rate, inhibits nucleation and crystal growth, and improves the transparency and color saturation of the wear-resistant dry particles.

[0155] Comparative Example 4: The dry granular raw materials were not pre-fired and were directly used. The pores on the glaze increased (e.g. Figure 3 ), the glaze's transparency and color are poor, and its hardness and wear resistance are reduced.

[0156] Comparative Example 5 shows that silver oxide and tungsten trioxide in the wear-resistant dry particles act as catalysts and antibacterial agents. If they are cancelled, the antibacterial function will be significantly weakened, the pores will increase, and the glaze transparency and color will deteriorate.

[0157] Comparative Example 6, the early firing curve of the kiln firing stage is adjusted. When the bottom temperature and surface temperature are consistent, it is difficult to exhaust the body, the wear-resistant glaze has more pores, and the glaze surface has poor transparency and color. It is necessary to further increase the temperature difference between the bottom temperature and the surface temperature, which is conducive to oxidation and exhaust of the body, reducing the glaze surface pores and the whitening of the dark product surface, and helping to improve the glaze surface transparency and color.

[0158] Through testing of Examples 1-4 and Comparative Examples 1-6, the wear-resistant dry particles and wear-resistant glaze were adjusted to a reasonable ratio, and the roller kiln firing curve was optimized. The green body was fully oxidized before sintering to reduce the formation of capillary pores on the glaze surface. Based on Example 4, the ratio of wear-resistant dry particles and glaze was further optimized and tested in the following examples.

[0159] Example 5

[0160] Same as Example 4, except that step 1 and step 2 are different

[0161] Step 1: Preparation of highly permeable, wear-resistant and antibacterial dry particles

[0162] The mass proportions of various raw materials are adjusted to: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 1.0 part of silver oxide, 1.0 part of tungsten trioxide, 5 parts of zinc oxide, 28 parts of cubic boron nitride, and 12 parts of aluminum nitride.

[0163] Step 2: Preparation of high-transparency, wear-resistant and antibacterial glaze

[0164] The mass proportions of the raw materials are adjusted to: 15 parts of potassium feldspar, 11 parts of sodium feldspar, 12 parts of aluminum nitride, 5 parts of zinc oxide, 5 parts of corundum, 8 parts of kaolin, 40 parts of high-transmittance, wear-resistant and antibacterial dry particles, 7 parts of calcined talc, and 5 parts of calcite.

[0165] Example 6

[0166] Same as Example 4, except that (6) roller kiln firing in the preparation of high-transmittance, wear-resistant and antibacterial ceramic tiles in step 1 and step 3, the difference in kiln firing curves

[0167] Step 1: Preparation of highly permeable, wear-resistant and antibacterial dry particles

[0168] The mass proportions of various raw materials are adjusted to: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 0.8 parts of silver oxide, 0.8 parts of tungsten trioxide, 4 parts of zinc oxide, 25 parts of cubic boron nitride, and 10 parts of aluminum nitride.

[0169] Step 3 Preparation of highly transparent, wear-resistant and antibacterial ceramic tiles

[0170] (6) Roller kiln firing, firing temperature 1225℃, including preheating stage, oxidation stage, firing stage and cooling stage, among which, the preheating stage is from room temperature to 800℃, time is 15min; the oxidation stage is from 800℃ to 1150℃, time is 25min. In the early stage of firing stage, the surface temperature of the four zones of the kiln firing curve is controlled to be 1160℃, 1187℃, 1210℃, and 1217℃ respectively, and the bottom temperature is 1180℃, 1210℃, 1220℃, and 1223℃ respectively, and the time for each zone is 2min; the surface temperature of the insulation zone is 1220℃×5 zones, and the bottom temperature is 1225℃×5 zones. The insulation time of the high temperature zone is 12min in total; the cooling stage is from 1225℃ to room temperature, time is 15min.

[0171] The test results of Example 5 and Example 6 are shown in Table 2 below:

[0172] Table 2

[0173]

[0174] After testing, in Example 5, due to the high melting point of boron nitride, aluminum nitride and high-transmittance, wear-resistant and antibacterial dry granular materials, if used in excess, the melting point of the high-transmittance, wear-resistant and antibacterial glaze will also be too high, the kiln firing temperature cannot meet the glaze melting temperature requirement, the glaze cannot be well melted into a glass phase, the molten glass phase is reduced, the light transmittance deteriorates, and the wear-resistant glaze layer on the surface has a whitening phenomenon; although the hardness and wear resistance of the glaze are improved, the transmittance and color are reduced, and the effect is not good; in Example 6, the number of pores on the glaze is small, the light transmittance and glaze color saturation reach the optimal value, and the antibacterial performance reaches 95%; the wear resistance test (such as Figure 1 As shown), the glaze has low wear and tear and can be wear-resistant up to level 4 (2100 revolutions). It can solve the problem of transparent color of most dark products and the problem of glaze wear and scratches caused by trampling, so you can use it with confidence.

[0175] The high-transparency, wear-resistant and antibacterial ceramic tiles of the present invention are calcined at a high temperature of 1200-1250 degrees. The surface glaze layer has high hardness, good translucency and color development, and has the characteristics of fire resistance, high temperature resistance, acid and alkali corrosion resistance, etc.; batch production can be achieved, especially dark-colored ceramic tile products, which can be used in residential areas and shopping malls with frequent pedestrian traffic, restaurant kitchens, exhibition halls, etc., to meet customers' different space design and use needs. The dark-colored ceramic tiles produced by the present invention can be used in shopping malls and living areas with large traffic and frequent footsteps. The glaze has high wear resistance and will not cause glaze scratches and surface color wear and lightening due to frequent footsteps. Antibacterial agents are introduced into the glaze of wear-resistant ceramic tiles and applied to the glaze of ceramic tiles. The antibacterial agents can inhibit the activity of bacterial metabolic enzymes, leading to metabolic disorders, which are not conducive to bacterial growth, thereby having a bactericidal effect and providing a healthy and safe living environment.

[0176] The above is a specific description of the preferred implementation of the present invention, but the invention is not limited to the embodiments. Those skilled in the art can make various equivalent modifications or substitutions without violating the spirit of the present invention. These equivalent modifications or substitutions are all included in the scope defined by the claims of the present invention.

Claims

1. A highly permeable, wear-resistant and antibacterial dry granule, characterized in that: The raw materials are composed of the following components by mass: 15-25 parts of potassium feldspar, 12-20 parts of lithium feldspar, 6-12 parts of dolomite, 4-12 parts of calcined clay, 2-10 parts of corundum, 0.5-1.0 parts of silver oxide, 0.5-1.0 parts of tungsten trioxide, 4-6 parts of zinc oxide, 20-30 parts of cubic boron nitride, and 8-15 parts of aluminum nitride; The high-transmittance, wear-resistant and antibacterial dry particles are obtained by calcining raw materials at 1500-1600° C. and keeping the temperature for 30-60 minutes, and then quenching the raw materials. The water used for quenching is circulating cooling water, and the temperature of the circulating cooling water is 10-30° C.

2. The highly permeable, wear-resistant and antibacterial dry granules according to claim 1, characterized in that The raw materials of the high-transmittance, wear-resistant and antibacterial dry particles are composed of the following components in parts by mass: 20 parts of potassium feldspar, 16 parts of lithium feldspar, 9 parts of dolomite, 8 parts of calcined clay, 6 parts of corundum, 0.8 parts of silver oxide, 0.8 parts of tungsten trioxide, 4 parts of zinc oxide, 25 parts of cubic boron nitride, and 10 parts of aluminum nitride; Before firing and holding at 1500-1600℃, fire and hold at 900-1000℃ for 20-30min.

3. The method for preparing the highly permeable, wear-resistant and antibacterial dry granules according to any one of claims 1 to 2, wherein: The following steps are involved: S1. The raw materials of the highly transparent, wear-resistant and antibacterial dry particles are uniformly mixed according to a proportion, applied to a frit furnace for firing to obtain a frit slurry, and the frit slurry is placed in circulating cooling water for quenching; S2. The granules obtained by the water quenching treatment are crushed and dried to obtain highly permeable, wear-resistant and antibacterial dry granules.

4. The preparation method according to claim 3, characterized in that The particles after crushing are 200-250 mesh; The temperature curve of firing in the frit furnace is from room temperature to 300-310℃, time 10-15min, 300-310℃ to 950-960℃, time 30-50min, keeping at 950-960℃ for 20-30min, 950-960℃ to 1380-1390℃, time 60-90min, 1380-1390℃ to 1520-1530℃, time 80-120min, and keeping at 1520-1530℃ for 30-60min.

5. A highly transparent, wear-resistant and antibacterial glaze, characterized in that: The raw materials include, by mass, 10-20 parts of potassium feldspar, 6-16 parts of sodium feldspar, 10-12 parts of aluminum nitride, 1-5 parts of zinc oxide, 3-8 parts of corundum, 6-10 parts of kaolin, 35-40 parts of high-permeability, wear-resistant and antibacterial dry particles, 5-10 parts of calcite, and 3-8 parts of calcite; the high-permeability, wear-resistant and antibacterial dry particles are the high-permeability, wear-resistant and antibacterial dry particles described in any one of claims 1-2 or the high-permeability, wear-resistant and antibacterial dry particles prepared by the preparation method described in any one of claims 3-4.

6. The high-transmittance, wear-resistant and antibacterial glaze according to claim 5, characterized in that: The raw materials of the high-transmittance, wear-resistant and antibacterial glaze include, by mass, 15 parts of potassium feldspar, 11 parts of sodium feldspar, 10 parts of aluminum nitride, 4 parts of zinc oxide, 5 parts of corundum, 8 parts of kaolin, 35 parts of high-transmittance, wear-resistant and antibacterial dry particles, 7 parts of calcined talc, and 5 parts of calcite; The fineness requirement of the high-transparency, wear-resistant and antibacterial glaze is 325 mesh, with a sieve residue of 0.2-0.6%.

7. The method for preparing the highly transparent, wear-resistant and antibacterial glaze according to any one of claims 5 to 6, characterized in that: The following steps are involved: The raw materials of the high-transmittance wear-resistant antibacterial glaze are added to printing paste and printing oil and ball-milled to obtain the high-transmittance wear-resistant antibacterial glaze; the mass ratio of the raw materials of the high-transmittance wear-resistant antibacterial glaze, printing paste and printing oil is 100:65-70:15-20.

8. A highly transparent, wear-resistant and antibacterial ceramic tile, characterized in that: The invention comprises a high-transmittance, wear-resistant and antibacterial glaze layer, which is obtained by firing the high-transmittance, wear-resistant and antibacterial glaze according to any one of claims 5 to 6 or the high-transmittance, wear-resistant and antibacterial glaze prepared by the preparation method of the high-transmittance, wear-resistant and antibacterial glaze according to claim 7.

9. The highly transparent, wear-resistant and antibacterial ceramic tile according to claim 8, characterized in that: The high-transparency, wear-resistant and antibacterial glaze layer is fired in a roller kiln, and the firing process includes a preheating stage, an oxidation stage, a firing stage and a cooling stage. The firing stage includes an early firing stage and a late firing stage. The early firing stage includes four zones, and the surface temperatures are 1160-1165°C, 1187-1192°C, 1205-1210°C, and 1212-1217°C, respectively. The corresponding bottom temperatures are 1175-1180°C, 1198-1210°C, 1210-1220°C, and 1216-1223°C, respectively. The time for each zone is 2-3 minutes. The late firing stage includes five zones, and the surface temperatures are all 1215-1220°C, and the corresponding bottom temperatures are all 1220-1225°C. The time for each zone is 2-4 minutes.

10. The method for preparing a highly transparent, wear-resistant and antibacterial ceramic tile according to any one of claims 8 to 9, characterized in that: The following steps are involved: (1) Preparation of green body powder: add water to the raw materials of green body powder, ball mill, remove iron, sieve, spray granulate, control the moisture content to 6.5-7.5%, and let it age for later use; (2) The green body powder is pressed into bricks and dried into green bricks; (3) Spray water on the surface of the blank to moisten it and then glaze it; (4) Inkjet printing; (5) Screen printing of high-transparency, wear-resistant and antibacterial glaze, 100-120 mesh full-pass screen printing 2-3 times; (6) Firing; (7) Polishing and edge grinding to obtain highly transparent, wear-resistant and antibacterial ceramic tiles.

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