Silvery-white metallic texture tile and preparation method thereof

Abstract

The present invention relates to the field of architectural ceramics, and in particular to a silvery-white metallic-textured ceramic tile and a method for preparing the same, comprising the following steps: A. preparing a ceramic blank, pressing the blank, and drying to obtain a body layer; B. applying a silvery-white metallic dry granular glaze to the surface of the body layer to obtain a silvery-white metallic dry granular glaze layer; and C. drying and calcining the ceramic tile at a temperature of 1180-1210°C, followed by polishing to obtain the silvery-white metallic-textured ceramic tile. The silvery-white metallic-textured ceramic tile and its preparation method, while ensuring a uniform silvery-white metallic texture, not only exhibits an excellent silvery-white metallic texture, transparency, and anti-fouling properties, but also has high wear resistance and hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of building ceramics, and in particular to a silvery-white metallic texture ceramic tile and a preparation method thereof. Background Art

[0002] In the vast ceramics market, consumer demands are becoming increasingly diverse and personalized. Consumers not only pursue practicality and durability but also have high expectations for artistic value and visual beauty. This shift in market demand is driving the ceramics industry to continuously innovate technology and develop products to meet these growing aesthetic and practical needs.

[0003] In the tile production process, the proper glaze formulation is crucial. The same base can produce varying glaze effects depending on the glaze. The varying tactile and visual qualities of the glazes also influence consumer choice. Metallic glazes are a special type of glaze. When applied to the base and fired at high temperatures, they impart a metallic texture to the tile surface and are widely used in the architectural decoration industry. Existing metallic glazes primarily consist of metal granules and frit. However, fluxing agents such as lithium oxide (Li2O), boron oxide (B2O3), potassium oxide (K2O), and sodium oxide (Na2O) are often added to the frit to lower its melting point. However, these fluxing agents are highly chemically active and gradually dissolve the metal oxides on the surface of the granules, creating pores and microcracks. The flux then penetrates through these pores and cracks into the granules, reacting with them and ultimately corroding and discoloring the granules, losing their original metallic texture.

[0004] To prevent corrosion and discoloration of the metal particles, existing frits typically utilize feldspathic frits with low flux content and high silicon and aluminum content. Kaolin and quartz serve as the primary aluminum and silicon sources in these frits. However, due to the high melting temperature of quartz and the relatively low flux content, the frit contains a high proportion of residual unmelted quartz. The refractive index of unmelted quartz (approximately 1.65) differs significantly from that of the glass phase (approximately 1.50). This refractive index mismatch can lead to strong light scattering, reducing the transparency of the glaze. As the unmelted quartz content increases, the light scattering phenomenon intensifies, further affecting the transparency of the glaze.

[0005] At the same time, due to insufficient flux in the system, the aluminum oxide produced by the decomposition of kaolin at high temperatures (>950°C) is difficult to completely melt. Instead, it exists as inert α-Al2O3 and mullite crystals. The refractive index of the inert α-Al2O3 (corundum phase, refractive index 1.76) and mullite crystals (refractive index 1.64) differs significantly from the refractive index of the glass phase (approximately 1.50), further exacerbating light scattering and reducing the transparency of the glaze. This reduced transparency can obscure the original pattern of the tile's decorative layer, affecting the overall decorative effect of the tile. In addition, due to the serious lack of flux content in the feldspar frit, the glass phase generated in the feldspar frit is seriously insufficient, and the generated glass phase is difficult to completely wrap the unmelted quartz, unmelted α-Al2O3 and mullite crystals, resulting in pores between the unmelted quartz, unmelted α-Al2O3 and mullite crystals. As a result, the porosity of the glaze surface of the metal glaze with added feldspar frit after calcination is high, pollutants are easily penetrated, and the anti-fouling performance is poor.

[0006] Since transparent glaze generally has high transparency and anti-fouling properties. Therefore, in order to effectively improve transparency and anti-fouling properties, the glaze surface formed after calcining the metal glaze with added feldspar frit has high anti-fouling performance without affecting the pattern effect of the original decorative layer of the tile. The existing technology attempts to add a large amount of transparent glaze to the metal glaze formula, but due to the large amount of transparent glaze added, the content of flux in the formula is also high, making the metal dry particles easily corroded completely, causing them to lose their original metallic texture effect. In addition, since transparent glaze generally contains a certain amount of water, the metal glaze obtained by compounding metal dry particles, feldspar frit and transparent glaze also contains water. Since the specific gravity of metal dry particles is very large, they are very easy to precipitate in the water-containing metal glaze obtained by the above compounding, resulting in poor distribution uniformity of the metal dry particles on the glaze surface after calcination, affecting the uniformity of the metallic texture effect.

[0007] In summary, existing ceramic tiles not only cannot simultaneously have excellent metallic texture effects, transparency and anti-fouling performance, but also cannot ensure the uniformity of the metallic texture effects. Summary of the Invention

[0008] The purpose of the present invention is to propose a silver-white metallic texture tile and a preparation method thereof. Under the premise of ensuring the uniform silver-white metallic texture effect, the silver-white metallic texture tile not only has excellent silver-white metallic texture effect, transparency and anti-fouling performance, but also has high wear resistance and hardness, so that the silver-white metallic texture tile has both decorative and practical properties, thereby overcoming the shortcomings of the existing technology.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] A method for preparing silvery-white metallic texture ceramic tiles comprises the following steps:

[0011] A. preparing a ceramic blank, pressing the ceramic blank, and drying it to obtain a green body layer;

[0012] B. applying a silvery-white metallic dry granular glaze to the surface of the green body layer to obtain a silvery-white metallic dry granular glaze layer;

[0013] C. After drying, calcining at a temperature of 1180-1210°C, and then polishing to obtain silvery white metallic texture tiles;

[0014] Wherein, in step B, the preparation method of the silvery white metallic dry particle glaze is:

[0015] B1. Under an inert atmosphere, 6 to 7 parts by mass of silicon, 0.1 to 0.2 parts by mass of aluminum, 60 to 65 parts by mass of iron, 25 to 30 parts by mass of chromium, 2 to 3 parts by mass of manganese, 0.1 to 0.5 parts by mass of vanadium, and 0.1 to 0.2 parts by mass of nickel are completely melted and crushed to obtain alloy droplets;

[0016] The alloy droplets are cooled in a natural environment to obtain dry alloy particles;

[0017] B2. 12 to 18 parts by mass 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 were mixed uniformly, calcined, water-quenched, ground and sieved to obtain a crystalline frit;

[0018] 10-18 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of sodium feldspar, 5-15 parts of calcite, 5-10 parts of calcined talc, 1-3 parts of zinc oxide, and 20-30 parts of crystalline frit are mixed uniformly by weight, and then sodium carboxymethyl cellulose, a water reducing agent, and water are added, and the mixture is ball-milled and sieved to obtain a transparent antifouling glaze slurry.

[0019] The transparent antifouling glaze slurry is dried, crushed and sieved to obtain the transparent antifouling glaze powder;

[0020] B3. Evenly mix the alloy dry particles, transparent antifouling glaze powder and suspending agent to obtain a silvery-white metallic dry particle glaze.

[0021] Furthermore, in step B1, the melting temperature is 1100-1200°C.

[0022] Furthermore, in step B1, the particle size distribution of the alloy dry particles is calculated according to mass percentage: the sieve residue of 100 mesh sieve is 0.1-0.5%, the sieve residue of 160 mesh sieve is 65-70%, the sieve residue of 200 mesh sieve is 83-87%, the sieve residue of 250 mesh sieve is 90-95%, and the sieve residue of 325 mesh sieve is 97-99%.

[0023] Furthermore, in step B2, the calcination temperature curve of the crystalline frit is:

[0024] It takes 1.5 to 3 hours to heat from room temperature to 300°C;

[0025] From 300℃ to 1530℃, it takes 2 to 3 hours;

[0026] 1530℃, keep warm for 0.5~1.5h.

[0027] Furthermore, in step B2, the particle size distribution of the crystalline frit is as follows: the sieve residue of 150 mesh is 0.1-0.5%, the sieve residue of 180 mesh is 40-50%, and the sieve residue of 200 mesh is 70-80%.

[0028] Furthermore, in step B2, the transparent antifouling glaze slurry, calculated by weight, includes 10 to 18 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 15 parts of calcite, 5 to 10 parts of calcined talc, 1 to 3 parts of zinc oxide, and 20 to 30 parts of crystalline frit, which are mixed evenly, and then 0.1 to 0.3 parts of sodium carboxymethyl cellulose, 0.15 to 0.35 parts of water reducer, and 30 to 40 parts of water, calculated by weight, are added.

[0029] Furthermore, in step B2, the transparent antifouling glaze powder is passed through a 100-mesh sieve, and the residue on the sieve is 0.1-0.3% by mass.

[0030] Furthermore, in step B3, the silvery-white metallic dry particle glaze is composed of 6 to 10 parts of alloy dry particles, 90 to 94 parts of transparent antifouling glaze powder and 180 to 200 parts of suspending agent, calculated by weight.

[0031] Furthermore, in step B, the glazing amount of the silvery white metallic dry granular glaze is 455-500 g / m 3 , specific gravity is 1.4~1.5.

[0032] A silvery-white metallic-textured ceramic tile is prepared by the above-mentioned method for preparing the silvery-white metallic-textured ceramic tile.

[0033] The technical solution provided by the present invention can have the following beneficial effects:

[0034] 1. This technical solution uses silicon (silicon is a metalloid), aluminum, iron, chromium, manganese, vanadium, and nickel as raw materials. These are melted and crushed under an inert atmosphere to form alloy droplets, which are then naturally cooled to produce alloy dry particles. During the natural cooling process, the surfaces of the alloy droplets exposed to air react with oxygen, forming a composite oxide protective film containing aluminum oxide, chromium oxide, and silicon dioxide. Ultimately, alloy dry particles with a "core-shell" structure are formed, with the core being a multi-element alloy matrix composed primarily of iron, chromium, and manganese, and the outer shell being the composite oxide protective film.

[0035] 2. During the calcination of the crystalline frit, wollastonite, a natural calcium silicate mineral (primarily composed of calcium silicate), decomposes under heat to form calcium oxide. Strontium carbonate decomposes under high temperature to form strontium oxide, while barium carbonate decomposes to form barium oxide. These calcium oxide, strontium oxide, and barium oxide react synergistically with the zinc oxide in the crystalline frit raw materials to form a calcium-strontium-zinc-barium composite flux. Because calcium, strontium, barium, and zinc ions all have low polarizability, large radii, and weak polarizability, they result in high lattice energy and strong bonding strength. This requires higher energies to disrupt the flux network, resulting in a relatively high onset melting point for this calcium-strontium-zinc-barium composite flux. Furthermore, a size-matching effect exists among the calcium, strontium, barium, and zinc ions (for example, the radius ratio of the barium ion to the zinc ion conforms to the Hume-Rothery rule), enabling the formation of a high-temperature finite solid solution. This solid solution destroys the necessary conditions for the formation of a low eutectic point through the mutual dissolution mechanism at the atomic level, resulting in a significant increase in the initial melting point of the calcium strontium zinc barium composite flux compared to a single flux.

[0036] 3. The anorthite and mullite crystals contained in the crystalline frit itself remain essentially stable and infusible, allowing these crystals to remain on the glaze surface of the golden metallic dry granule glaze after calcination. Combined with the anorthite and cordierite crystals generated during the calcination process from other raw materials in the transparent anti-fouling glaze powder, such as calcined kaolin, quartz, and calcite, the resulting glaze surface contains these three crystals after calcination. These crystals not only form a physical "armor" on the surface of the alloy dry particles, directly blocking the directional migration of alkali metal ions in the multi-component composite flux into the alloy dry particles, but the random distribution of these three crystals also transforms the diffusion path of the alkali metal ions in the multi-component composite flux from a linear one to a three-dimensional serrated one. This geometrically extends the diffusion barrier, strengthening the diffusion barrier and effectively inhibiting corrosion of the alloy dry particles by the alkali metal ions in the multi-component composite flux. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a glaze effect diagram of the silvery-white metallic texture ceramic tile obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0038] This technical solution provides a method for preparing silvery-white metallic texture tiles, comprising the following steps:

[0039] A. preparing a ceramic blank, pressing the ceramic blank, and drying it to obtain a green body layer;

[0040] B. applying a silvery-white metallic dry granular glaze to the surface of the green body layer to obtain a silvery-white metallic dry granular glaze layer;

[0041] C. After drying, calcining at a temperature of 1180-1210°C, and then polishing to obtain silvery white metallic texture tiles;

[0042] Wherein, in step B, the preparation method of the silvery white metallic dry particle glaze is:

[0043] B1. Under an inert atmosphere, 6 to 7 parts by mass of silicon, 0.1 to 0.2 parts by mass of aluminum, 60 to 65 parts by mass of iron, 25 to 30 parts by mass of chromium, 2 to 3 parts by mass of manganese, 0.1 to 0.5 parts by mass of vanadium, and 0.1 to 0.2 parts by mass of nickel are completely melted and crushed to obtain alloy droplets;

[0044] The alloy droplets are cooled in a natural environment to obtain dry alloy particles;

[0045] B2. 12 to 18 parts by mass 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 were mixed uniformly, calcined, water-quenched, ground and sieved to obtain a crystalline frit;

[0046] 10-18 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of sodium feldspar, 5-15 parts of calcite, 5-10 parts of calcined talc, 1-3 parts of zinc oxide, and 20-30 parts of crystalline frit are mixed uniformly by weight, and then sodium carboxymethyl cellulose, a water reducing agent, and water are added, and the mixture is ball-milled and sieved to obtain a transparent antifouling glaze slurry.

[0047] The transparent antifouling glaze slurry is dried, crushed and sieved to obtain the transparent antifouling glaze powder;

[0048] B3. Evenly mix the alloy dry particles, transparent antifouling glaze powder and suspending agent to obtain a silvery-white metallic dry particle glaze.

[0049] In order to overcome the technical defects of the existing technology, this technical solution proposes a method for preparing silvery-white metallic texture ceramic tiles. By optimizing the preparation method and raw materials, while ensuring the uniformity of the silvery-white metallic texture effect of the ceramic tiles, it can not only have excellent silvery-white metallic texture effect, transparency and anti-fouling performance, but also have high wear resistance and hardness to meet actual use requirements. It should be noted that the green body layer in this solution is made of conventional ceramic green bodies in the ceramic field after pressing and drying, and the ceramic green bodies are not further described here. In addition, the polishing process industry is also a commonly used polishing process in the field, which is not further described here.

[0050] Specifically, this technical solution uses silicon (a metalloid), aluminum, iron, chromium, manganese, vanadium, and nickel as raw materials. These are melted and liquid-fragmented under an inert atmosphere to form alloy droplets, which are then naturally cooled to produce dry alloy particles. During the natural cooling process, the surfaces of the alloy droplets, exposed to air, react with oxygen, forming a composite oxide protective film containing aluminum oxide, chromium oxide, and silicon dioxide. Ultimately, dry alloy particles with a "core-shell" structure are formed, with the core being a multi-element alloy matrix composed primarily of iron, chromium, and manganese, and the outer shell being the composite oxide protective film. It should be noted that metalloids, also known as semimetals, possess both metallic and non-metallic properties. Furthermore, liquid-fragmentation in this technical solution refers to the process of melting the alloy molten metal of silicon, aluminum, iron, chromium, manganese, vanadium, and nickel, which is accelerated by a high-pressure pump and then passed through a micro-orifice nozzle. The high-speed jet rubs against air or impacts a target plate, breaking the molten metal into alloy droplets.

[0051] The composite oxide protective film consists of two layers: an inner layer and an outer layer. The inner layer is composed of aluminum oxide, chromium oxide, and silicon dioxide. The aluminum oxide and chromium oxide work together to form a dense, continuous barrier layer that effectively blocks the intrusion of corrosive media such as flux. Silicon dioxide further enhances the film's density by filling grain boundary defects. Chromium oxide also imparts a favorable chemical passivation effect. The outer layer, composed of iron oxide, manganese dioxide, vanadium pentoxide, and nickel oxide, exhibits a porous structure and sacrificial protective properties, preferentially reacting with corrosive media such as flux to slow the erosion of the inner layer. This composite oxide protective film, through the synergistic protective mechanism of "dense inner layer barrier + porous outer layer buffer," ensures the reliability of the inner layer while also providing excellent corrosion resistance in the glaze environment through the sacrificial protection of the outer layer. This makes the composite oxide protective film less susceptible to corrosion by corrosive media such as flux, thereby maintaining the stability of the alloy dry particles.

[0052] Furthermore, the alloy dry particles of the present technical solution achieve excellent high-temperature stability through the following effects: (1) the high chromium content forms an iron-chromium solid solution matrix with the iron element, whose solidus temperature exceeds the threshold of 1300℃, thus constructing a high-temperature resistant crystal skeleton; (2) the silicon element and the chromium element in situ generate intermetallic compounds such as chromium trisilicon (high-temperature phase), and the above-mentioned high-temperature phase with a melting point exceeding 1500℃ permeates the grain boundary network in the form of dispersion strengthening, forming a three-dimensional support structure; (3) the addition of elemental silicon and elemental aluminum promotes the formation of a dense inner layer of aluminum oxide-chromium oxide-silicon dioxide, and the melting point of the inner layer can be as high as 2000℃, which is beneficial to improving the high-temperature stability of the alloy dry particles; (4) a trace amount of vanadium element can improve the high-temperature strength by refining the grains. Based on the high-temperature stability of the alloy dry particles, the alloy dry particles can be introduced into the glaze system, and the performance stability can be maintained after the glaze is calcined at high temperature.

[0053] Next, quartz, calcined aluminum oxide, wollastonite, zinc oxide, strontium carbonate, and barium carbonate are uniformly mixed, calcined, water-quenched, ground, and sieved to produce a crystalline frit. During the calcination of the crystalline frit, wollastonite, a natural calcium silicate mineral (primarily composed of calcium silicate), decomposes under heat to produce calcium oxide. Strontium carbonate decomposes under high temperature to produce strontium oxide, while barium carbonate decomposes to produce barium oxide. These calcium oxide, strontium oxide, and barium oxide interact synergistically with the zinc oxide in the crystalline frit raw materials to form a calcium-strontium-zinc-barium composite flux. Because calcium, strontium, barium, and zinc ions all have low polarizability, large radii, and weak polarizability, they exhibit high lattice energy and strong bonding strength. This requires a higher energy level to disrupt the flux network, resulting in a relatively high onset melting point for the calcium-strontium-zinc-barium composite flux. Furthermore, a size-matching effect exists between calcium, strontium, barium, and zinc ions (e.g., the radius ratio of barium to zinc ions conforms to the Hume-Rothery rule), allowing the formation of a high-temperature finite solid solution. This solid solution, through an atomic-level mutual solubility mechanism, destroys the necessary conditions for the formation of a eutectic point, resulting in a significantly higher onset melting point for the calcium-strontium-zinc-barium composite flux compared to single fluxes. In other words, the calcium-strontium-zinc-barium composite flux in this technical solution, through these multiple effects, results in a crystalline frit with a higher onset melting point.

[0054] Furthermore, under high temperature conditions, wollastonite decomposes to form calcium oxide and silicon dioxide, while quartz and calcined alumina in the formulation provide additional silicon dioxide and aluminum oxide, respectively. By precisely controlling the amounts of quartz, calcined alumina, and wollastonite added, the ratio of calcium oxide, aluminum oxide, and silicon dioxide introduced into the crystalline frit formulation is defined. Under these specific ratios, the aluminum oxide, silicon dioxide, and calcium oxide in the formulation react chemically with the formulation to form anorthite crystals (CaAl2Si2O8). The aluminum oxide and silicon dioxide then react to form mullite (3Al2O3·2SiO2). As a result, the crystalline frit contains both anorthite and mullite crystals, with the melting points of anorthite crystals at 1553°C and mullite crystals at 1850°C. These two crystals contribute to the high initial melting point of the crystalline frit.

[0055] In summary, this technical solution improves the initial melting point of the crystalline frit through the cooperation of the above-mentioned multiple effects.

[0056] Furthermore, the transparent antifouling glaze slurry of the present technical solution includes raw materials such as crystalline frit, calcined kaolin, quartz, potassium feldspar, sodium feldspar, calcite, burnt talc and zinc oxide, and the transparent antifouling glaze powder includes raw materials such as crystalline frit, calcined kaolin, quartz, potassium feldspar, sodium feldspar, calcite, burnt talc and zinc oxide. During the formulation design process, the addition amount of low-temperature flux potassium feldspar and sodium feldspar is limited to ensure that the sum of the two addition amounts is less than the addition amount of low-temperature flux in existing common glazes. The reduction in the content of low-temperature flux is conducive to improving the initial melting point of the transparent antifouling glaze powder. Combined with the effect of improving the initial melting point of the crystalline frit itself, it is conducive to the initial melting point of the transparent antifouling glaze powder, thereby improving the melting threshold of the golden metal dry granular glaze as a whole. At the same time, during the high-temperature firing stage, potassium feldspar decomposes to form potassium oxide, sodium feldspar decomposes to form sodium oxide, calcite decomposes to form calcium oxide, and burnt talc decomposes to form magnesium oxide. The aforementioned oxides, along with a calcium, strontium, zinc, and barium composite flux, form a multi-component composite flux. Because the silvery-white metallic dry granule glaze has a high melting threshold, it significantly shortens the contact time between the multi-component composite flux (i.e., flux) and the alloy dry granules during the high-temperature firing stage, effectively inhibiting the flux's corrosive effects on the alloy dry granules and helping to maintain the stability of the alloy dry granule's performance.

[0057] It should be noted that the increase in the melting threshold of the silver-white metal dry particle glaze in this technical solution can enable it to maintain a higher viscosity in the initial stage of rapid firing, delay the closure of the silver-white metal dry particle glaze layer to facilitate exhaust, and avoid the gas being trapped inside the silver-white metal dry particle glaze layer to form pinholes or bubbles, thereby ensuring the quality of the obtained tiles.

[0058] Thirdly, during the high-temperature firing process, the raw materials in the transparent antifouling glaze powder of the present technical solution undergo the following reactions: calcined kaolin decomposes to form aluminum oxide and silicon dioxide, quartz provides additional silicon dioxide, calcite decomposes to produce calcium oxide, calcium oxide reacts with aluminum oxide and silicon dioxide to form anorthite crystals (CaAl2Si2O8); calcined talc decomposes to form magnesium oxide, magnesium oxide reacts with aluminum oxide and silicon dioxide in the system to form cordierite crystals (Mg2Al2Si2O8). 18 At the same time, the anorthite and mullite crystals contained in the crystalline frit remain essentially stable and infusible at a calcination temperature of 1180-1210°C, allowing the golden metallic dry granule glaze to retain these crystals on its surface after calcination. Combined with the anorthite and cordierite crystals formed during the calcination process by other raw materials in the transparent anti-fouling glaze powder, such as calcined kaolin, quartz, and calcite, the resulting golden metallic dry granule glaze contains these three crystals after calcination. These crystals not only form a physical "armor" on the surface of the alloy dry particles, directly blocking the directional migration of alkali metal ions in the multi-component composite flux into the alloy dry particles, but also the random distribution of these three crystals transforms the diffusion path of the alkali metal ions in the multi-component composite flux from a linear one to a three-dimensional zigzag pattern. This geometrically extends the diffusion barrier, strengthening the diffusion barrier and effectively inhibiting corrosion of the alloy dry particles by the alkali metal ions in the multi-component composite flux. That is, the above-mentioned various crystals inhibit the corrosion of the alloy dry particles by the alkali metal ions in the multi-component composite flux by physically blocking and extending the diffusion path, which is beneficial to maintaining the stability of the performance of the alloy dry particles.

[0059] In summary, this technical solution prevents the corrosion of the alloy dry particles and maintains the stability of their performance through the mutual cooperation of the above-mentioned multiple effects. When the silvery-white metallic dry particle glaze is applied to the surface of the body layer, it only needs to be polished after calcination to remove the composite oxide protective film on the surface of the alloy dry particles. The multi-component alloy matrix (the color of the multi-component alloy matrix is silvery-white) mainly composed of iron, chromium and manganese inside the alloy dry particles can be exposed, thereby presenting a silvery-white metallic texture effect.

[0060] It should be noted that since the glaze surface of the silvery-white metallic dry granular glaze after calcination contains three types of crystals, namely, anorthite crystals, mullite and cordierite crystals, and the above three crystals have high hardness and wear resistance, they give the tiles higher hardness and wear resistance.

[0061] Furthermore, the quartz in the crystalline frit not only participates in the formation of anorthite and mullite crystals, but also forms a silicate glass network with the calcium, strontium, zinc, and barium composite flux and calcined aluminum oxide, forming the glass phase of the crystalline frit. When the crystalline frit is added to a transparent antifouling glaze powder, which is then added to the silvery-white metal dry particles and fired within a calcination temperature range of 1180-1210°C, the high-melting-point anorthite crystals (melting point 1553°C) and mullite crystals (melting point 1850°C) in the crystalline frit serve as a rigid skeleton supporting the glaze surface. At this point, the glass phase within the crystalline frit melts into a liquid state. This serves as a prefabricated glass phase precursor, initially fusing with the silica and aluminum oxide decomposed from the kaolin in the formulation to form a low-viscosity silicate glass matrix. At the same time, the raw materials in the formula system, such as potassium feldspar, sodium feldspar, calcite, calcite, and zinc oxide, melt into an alkali metal aluminum silicate liquid phase, which fuses with the low-viscosity silicate glass matrix, eroding the quartz particles and promoting their melting. The various components diffuse and fuse with each other, ultimately forming a continuous and dense glaze glass phase. This glaze glass phase significantly reduces the glaze porosity by encapsulating the alloy particles, filling the grain boundary voids, and strengthening the bonding of crystal particles, blocking the penetration channels of stains, thereby giving the tile excellent anti-fouling properties.

[0062] Furthermore, since the amount of strontium carbonate added to the crystalline frit is 18 to 22 parts, after calcination and decomposition, the crystalline frit has a high strontium oxide content. When this high-strontium oxide crystalline frit is introduced into a transparent anti-fouling glaze powder and then added to a silvery-white metal dry particle system, the strontium oxide not only reduces the connection of silicon-oxygen tetrahedra in the melt that forms the glaze glass phase, reducing the melt's viscosity at high temperatures, thereby enhancing the fluidity of the silvery-white metal dry particles during firing, allowing for more uniform spreading and avoiding localized accumulation or incomplete coverage, but also reduces the surface tension of the glaze glass phase melt, thereby reducing defects such as shrinkage cavities and pinholes caused by uneven surface tension during cooling of the glaze layer, making the glaze surface smoother and more even, thus endowing the tile with excellent anti-fouling properties.

[0063] In summary, this technical solution ensures that the tiles have excellent anti-fouling performance through the above-mentioned multiple effects.

[0064] Finally, the calcium feldspar crystals generated by this technical solution belong to the triclinic system and have a dense crystal structure. Their refractive index is similar to that of the glaze glass phase, and there are no significant light scattering centers. Therefore, the calcium feldspar crystals have extremely high transparency. Therefore, in order to improve the transparency of tiles coated with silver-white metallic dry granular glaze, this technical solution limits the amount of raw materials added in the transparent anti-fouling glaze powder, such as crystalline frit, calcined kaolin, quartz, calcite, and calcined talc, to ensure that the transparent anti-fouling glaze powder is mainly composed of calcium feldspar crystals after calcination, giving the silver-white metallic dry granular glaze with the added transparent anti-fouling glaze powder high transparency, thereby improving the transparency of the tile glaze surface. At the same time, this technical solution limits the amount of raw materials added in the transparent anti-fouling glaze powder, such as crystalline frit, potassium feldspar, sodium feldspar, calcite, calcined talc, and zinc oxide, to avoid excessive content of the multi-component composite flux, and appropriately increases its amount to promote the formation of more glaze glass phase. The increase in the glass phase content helps to further enhance the high transparency of the silver-white metallic dry granular glaze to which the transparent anti-fouling glaze powder is added, thereby improving the transparency of the ceramic tile glaze. In addition, the transparent anti-fouling glaze powder and the zinc oxide in the crystalline frit act as a nucleus former, which reduces the crystallization activation energy and the crystallization peak temperature, and is beneficial to the crystallization of calcium feldspar crystals, thereby further improving the transparency of the silver-white metallic dry granular glaze. That is, the present technical solution effectively improves the transparency of ceramic tiles through the above-mentioned multiple effects. It should be noted that although the glaze surface obtained by calcining the silver-white metallic dry granular glaze in the present technical solution contains mullite crystals and cordierite crystals with low transparency, the amount of mullite crystals and cordierite crystals is limited and is not enough to affect the transparency of the glaze surface, so that the glaze surface still has a high transparency, thereby making the ceramic tile have high transparency.

[0065] At the same time, this technical solution uses a suspending agent to achieve water-free dispersion of alloy dry particles, solving the technical problem that alloy dry particles are easy to settle in glaze containing water, so that the alloy dry particles can be evenly dispersed in the glaze, so that the glaze surface of the ceramic tile coated with silver-white metallic dry particle glaze presents a uniform and strong metallic texture effect after calcination.

[0066] It should be noted that the manufacturer of the suspending agent is Jiangxi Qiantao New Materials Co., Ltd., and the model number is 6122A. It should be further noted that the inert atmosphere can be argon, nitrogen, etc., and the specific type is not limited here.

[0067] Preferably, in step B1, calculated by weight, the raw materials of the alloy dry particles include 6.4 parts of silicon, 0.11 parts of aluminum, 62.59 parts of iron, 27.77 parts of chromium, 2.54 parts of manganese, 0.24 parts of vanadium and 0.11 parts of nickel.

[0068] By optimizing the ratio of the raw materials of the alloy dry particles, the thickness ratio of the multi-element alloy matrix and the composite oxide protective film is precisely controlled. Under the premise that the composite oxide protective film is sufficient to prevent the alloy dry particles from being corroded, after polishing and removing the composite oxide protective film on the surface of the alloy dry particles, the multi-element alloy matrix retains a larger volume, forming a continuous, highly exposed metal phase, thereby improving the metallic texture effect of the glaze.

[0069] To further illustrate, in step B1, the melting temperature is 1100-1200°C.

[0070] By limiting the melting temperature, silicon, aluminum, iron, chromium, manganese, vanadium, and nickel are completely melted and intermixed, thereby ensuring the properties of the resulting alloy dry particles. It should be noted that although the melting points of silicon, aluminum, iron, chromium, manganese, vanadium, and nickel are 1410-1414°C, 660°C, 1538-1539°C, 1907°C, 1907°C, 1244°C, and 1917°C, the melting of these elements triggers a low-melting-point eutectic reaction, allowing them to completely melt and achieve compositional homogenization at temperatures of 1100-1200°C through eutectic dissolution and atomic diffusion. In addition, the obtained alloy dry particles can maintain the solid lattice structure and surface integrity even if the calcination temperature of the glaze to which the alloy dry particles are added is higher than the melting temperature due to the formation of high-melting-point intermetallic compounds (such as iron-solid solution, chromium trisilicon, etc.) inside the alloy and the film layer formed by the oxide on the surface, thereby avoiding the performance degradation of the alloy dry particles caused by high-temperature melting.

[0071] Further explanation, in step B1, the particle size distribution of the alloy dry particles is calculated according to mass percentage: the sieve residue of 100 mesh sieve is 0.1-0.5%, the sieve residue of 160 mesh sieve is 65-70%, the sieve residue of 200 mesh sieve is 83-87%, the sieve residue of 250 mesh sieve is 90-95%, and the sieve residue of 325 mesh sieve is 97-99%.

[0072] By optimizing the particle grading of the alloy dry particles, it is not only beneficial to improve its suspension stability, thereby improving the uniformity of the metallic texture effect, but also beneficial to improve the fluidity of the silver-white metallic dry particle glaze after high-temperature calcination, ensuring the smoothness of the glaze surface obtained after calcination of the silver-white metallic dry particle glaze, thereby improving the anti-fouling property.

[0073] Preferably, calculated by mass percentage, the particle size distribution of the alloy dry particles is: the sieve residue on the 100-mesh sieve is 0.1%, the sieve residue on the 160-mesh sieve is 70%, the sieve residue on the 200-mesh sieve is 86.2%, the sieve residue on the 250-mesh sieve is 92.6%, and the sieve residue on the 325-mesh sieve is 98%.

[0074] Further explanation, in step B2, the calcination temperature curve of the crystalline frit is:

[0075] It takes 1.5 to 3 hours to heat from room temperature to 300°C;

[0076] From 300℃ to 1530℃, it takes 2 to 3 hours;

[0077] 1530℃, keep warm for 0.5~1.5h.

[0078] This technical solution helps to ensure the relevant performance of the crystalline frit by optimizing the calcination temperature curve.

[0079] Further, in step B2, the particle size distribution of the crystalline frit is as follows: the sieve residue of 150 mesh is 0.1-0.5%, the sieve residue of 180 mesh is 40-50%, and the sieve residue of 200 mesh is 70-80%.

[0080] By optimizing the particle grading of the crystalline frit, not only can the silver-white metallic dry granular glaze have good fluidity during the glazing process and be evenly spread on the surface of the body layer, avoiding defects such as uneven glaze flow, glaze piling or bottom exposure, and ensuring uniform thickness of the glaze layer, but also the crystalline frit can be fully melted during the calcination process of the silver-white metallic dry granular glaze, so that the glaze layer obtained after calcination has a higher density, which is beneficial to improving the anti-fouling performance.

[0081] Further explanation, in step B2, the transparent antifouling glaze slurry includes, calculated by mass, 10-18 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of sodium feldspar, 5-15 parts of calcite, 5-10 parts of burnt talc, 1-3 parts of zinc oxide, and 20-30 parts of crystalline frit, which are mixed evenly, and then 0.1-0.3 parts of sodium carboxymethyl cellulose, 0.15-0.35 parts of water reducer and 30-40 parts of water are added, calculated by mass.

[0082] By limiting the addition amounts of sodium carboxymethyl cellulose, water reducing agent and water in the transparent antifouling glaze slurry, it is helpful to ensure the performance of the transparent glaze slurry, and further to ensure the performance of the transparent antifouling glaze powder obtained after the transparent antifouling glaze slurry is dried, crushed and sieved.

[0083] It should be noted that the water reducing agent may be sodium tripolyphosphate, and the specific type is not limited here.

[0084] Further, in step B2, the transparent antifouling glaze powder is passed through a 100-mesh sieve, and the residue on the sieve is 0.1-0.3% by mass.

[0085] By controlling the fineness of the transparent anti-fouling glaze powder, it is not only beneficial to make the glaze glass phase formed by the silver-white metallic dry granular glaze with the transparent anti-fouling glaze powder added during the calcination process denser and with lower porosity, thereby improving the anti-fouling property of the ceramic tile, but also to promote the suspension stability and uniformity of the transparent anti-fouling glaze powder in the silver-white metallic dry granular glaze, thereby making the metallic texture effect of the ceramic tile more uniform.

[0086] Further description, in step B3, the silvery-white metallic dry particle glaze is composed of 6 to 10 parts of alloy dry particles, 90 to 94 parts of transparent antifouling glaze powder and 180 to 200 parts of suspending agent, calculated by weight.

[0087] 6-10 parts of dry alloy particles ensure a rich metallic texture on the glaze while avoiding the loosening of the glaze structure caused by excessive addition. 90-94 parts of transparent anti-fouling glaze powder, as the base glass phase, not only fully encapsulates the dry alloy particles to form a stable bond but also maintains sufficient fluidity for a smooth glaze surface. 180-200 parts of suspending agent impart ideal rheological properties to the glaze, preventing the heavier dry alloy particles from settling and ensuring uniform coating during glazing. Therefore, by limiting the addition amounts of dry alloy particles, crystalline frit, and suspending agent, this technical solution helps achieve optimal product performance, thereby improving product quality and stability.

[0088] Preferably, in step B3, the silvery-white metallic dry particle glaze is composed of 10 parts of alloy dry particles, 90 parts of transparent antifouling glaze powder and 200 parts of suspending agent, calculated by weight.

[0089] By further limiting the added amounts of alloy dry particles, transparent antifouling glaze powder and suspending agent, the performance of the silvery-white metallic dry particle glaze is optimized, thereby improving the quality and stability of the product.

[0090] Further description, in step B, the glaze amount of the silvery white metallic dry granular glaze is 455-500 g / m 3 , specific gravity is 1.4~1.5.

[0091] In order to obtain a better metallic texture effect, this technical solution adjusts the glaze amount and specific gravity of the silver-white metallic dry granular glaze, so that the tiles coated with the silver-white metallic dry granular glaze have a better metallic texture effect after calcination and polishing, thereby improving the quality and stability of the tiles.

[0092] A silvery-white metallic-textured ceramic tile is prepared by the above-mentioned method for preparing the silvery-white metallic-textured ceramic tile.

[0093] This proposal also proposes a silver-white metallic texture tile, which, while ensuring the uniformity of the silver-white metallic texture effect, not only has excellent silver-white metallic texture effect, transparency and anti-fouling performance, but also has high wear resistance and hardness, thereby making the silver-white metallic texture tile both decorative and practical.

[0094] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0095] The manufacturer of the suspending agents in the examples and comparative examples of the present invention is Jiangxi Qiantao New Materials Co., Ltd., and the model number is 6122A.

[0096] Example 1

[0097] A. preparing a ceramic blank, pressing the ceramic blank, and drying it to obtain a green body layer;

[0098] B. Applying silvery white metallic dry granular glaze to the surface of the body layer to obtain a silvery white metallic dry granular glaze layer; wherein the amount of the silvery white metallic dry granular glaze applied is 489 g / m 3 , specific gravity is 1.4;

[0099] C. After drying, calcining at 1180℃ and then polishing to obtain silvery white metallic texture tiles;

[0100] Wherein, in step B, the preparation method of the silvery white metallic dry granular glaze is:

[0101] B1. Under an argon atmosphere, 6.4 parts of silicon, 0.11 parts of aluminum, 62.59 parts of iron, 27.77 parts of chromium, 2.54 parts of manganese, 0.24 parts of vanadium, and 0.11 parts of nickel, calculated by weight, were completely melted at a temperature of 1100-1200°C, and the liquid was crushed to obtain alloy droplets; the alloy droplets were cooled under natural conditions to obtain alloy dry particles; wherein, the particle size distribution of the alloy dry particles, calculated by weight percentage, was as follows: 0.1% on a 100-mesh sieve, 70% on a 160-mesh sieve, 86.2% on a 200-mesh sieve, 92.6% on a 250-mesh sieve, and 98% on a 325-mesh sieve;

[0102] B2. 15 parts quartz, 18 parts calcined alumina, 35 parts wollastonite, 10 parts zinc oxide, 20 parts strontium carbonate, and 2 parts barium carbonate (by weight) were mixed uniformly. The mixture was calcined, water-quenched, ground, and sieved to obtain a crystalline frit. The temperature was raised from room temperature to 300°C for 2 hours, from 300°C to 1530°C for 2.5 hours, and then held at 1530°C for 1 hour. The particle size distribution of the crystalline frit was as follows: 0.2% on a 150-mesh sieve, 40% on a 180-mesh sieve, and 75% on a 200-mesh sieve.

[0103] 14 parts of calcined kaolin, 5 parts of quartz, 25 parts of potassium feldspar, 10 parts of sodium feldspar, 11 parts of calcite, 8 parts of calcined talc, 2 parts of zinc oxide, and 25 parts of crystalline frit are mixed uniformly, and then 0.1 parts of sodium carboxymethyl cellulose, 0.25 parts of sodium tripolyphosphate, and 40 parts of water are added, and the mixture is ball-milled and sieved to obtain a transparent antifouling glaze slurry;

[0104] The transparent antifouling glaze slurry is dried, crushed and sieved to obtain a transparent antifouling glaze powder; wherein, according to the mass percentage, the transparent antifouling glaze powder passes through a 100-mesh sieve, and the sieve residue is 0.2%;

[0105] B3. 10 parts of alloy dry particles, 90 parts of transparent antifouling glaze powder and 200 parts of suspending agent were mixed to obtain a silvery white metallic dry particle glaze.

[0106] The glaze effect of the silvery white metallic texture tile obtained in Example 1 is shown in the figure below: Figure 1 As shown, it can be seen that its glaze can present a strong and uniform silver-white metallic texture effect under light conditions.

[0107] Example 2

[0108] A. preparing a ceramic blank, pressing the ceramic blank, and drying it to obtain a green body layer;

[0109] B. Applying silvery white metallic dry granular glaze to the surface of the body layer to obtain a silvery white metallic dry granular glaze layer; wherein the amount of the silvery white metallic dry granular glaze applied is 470 g / m 3 , specific gravity is 1.45;

[0110] C. After drying, calcining at 1210℃ and then polishing to obtain silvery white metallic texture tiles;

[0111] Wherein, in step B, the preparation method of the silvery white metallic dry granular glaze is:

[0112] B1. Under a nitrogen atmosphere, 6.6 parts of silicon, 0.1 parts of aluminum, 62.3 parts of iron, 27.5 parts of chromium, 2 parts of manganese, 0.2 parts of vanadium, and 0.18 parts of nickel, calculated by weight, were completely melted at 1150°C and crushed to obtain alloy droplets. The alloy droplets were cooled in a natural environment to obtain dry alloy particles. The particle size distribution of the dry alloy particles, calculated by weight percentage, was as follows: 0.3% on a 100-mesh sieve, 66.8% on a 160-mesh sieve, 85.5% on a 200-mesh sieve, 92.5% on a 250-mesh sieve, and 97.8% on a 325-mesh sieve.

[0113] B2. 16 parts of quartz, 18 parts of calcined alumina, 32 parts of wollastonite, 19 parts of zinc oxide, 18 parts of strontium carbonate, and 3 parts of barium carbonate were mixed uniformly by weight. The mixture was calcined, water-quenched, ground, and sieved to obtain a crystalline frit. The calcination temperature profile of the crystalline frit was as follows: from room temperature to 300°C for 2 hours; from 300°C to 1530°C for 3 hours; and then held at 1530°C for 0.8 hours. The particle size distribution of the crystalline frit was as follows: 0.1% on a 150-mesh sieve, 50% on a 180-mesh sieve, and 78% on a 200-mesh sieve.

[0114] 16 parts of calcined kaolin, 6 parts of quartz, 25 parts of potassium feldspar, 8 parts of sodium feldspar, 12 parts of calcite, 15 parts of calcined talc, 2 parts of zinc oxide, and 25 parts of crystalline frit are mixed uniformly, and then 0.2 parts of sodium carboxymethyl cellulose, 0.2 parts of sodium tripolyphosphate, and 30 parts of water are added, and a transparent antifouling glaze slurry is obtained after ball milling and sieving.

[0115] The transparent antifouling glaze slurry is dried, crushed and sieved to obtain a transparent antifouling glaze powder; wherein, according to the mass percentage, the transparent antifouling glaze powder passes through a 100-mesh sieve, and the sieve residue is 0.2%;

[0116] B3. Mix 7 parts of alloy dry particles, 92 parts of transparent antifouling glaze powder and 180 parts of suspending agent to obtain a silvery white metallic dry particle glaze.

[0117] Example 3

[0118] A. preparing a ceramic blank, pressing the ceramic blank, and drying it to obtain a green body layer;

[0119] B. Applying silvery white metallic dry granular glaze to the surface of the body layer to obtain a silvery white metallic dry granular glaze layer; wherein the glazing amount of the silvery white metallic dry granular glaze is 490 g / m 3 , specific gravity is 1.5;

[0120] C. After drying, calcining at 1200℃ and then polishing to obtain silvery white metallic texture tiles;

[0121] Wherein, in step B, the preparation method of the silvery white metallic dry granular glaze is:

[0122] B1. Under an argon atmosphere, 7 parts by mass of silicon, 0.2 parts by mass of aluminum, 64.2 parts by mass of iron, 28.1 parts by mass of chromium, 2.7 parts by mass of manganese, 0.33 parts by mass of vanadium, and 0.18 parts by mass of nickel were completely melted at 1200°C and crushed to obtain alloy droplets. The alloy droplets were then cooled in a natural environment to obtain dry alloy particles. The particle size distribution of the dry alloy particles, calculated by mass percentage, was as follows: 0.3% on a 100-mesh sieve, 70% on a 160-mesh sieve, 85% on a 200-mesh sieve, 92% on a 250-mesh sieve, and 98% on a 325-mesh sieve.

[0123] B2. 18 parts of quartz, 20 parts of calcined alumina, 35 parts of wollastonite, 8 parts of zinc oxide, 22 parts of strontium carbonate, and 3 parts of barium carbonate (by weight) were mixed uniformly. The mixture was calcined, water-quenched, ground, and sieved to obtain a crystalline frit. The calcination temperature profile of the crystalline frit was as follows: from room temperature to 300°C for 2 hours; from 300°C to 1530°C for 2 hours; and then held at 1530°C for 1.5 hours. The particle size distribution of the crystalline frit was as follows: 0.5% on a 150-mesh sieve, 48% on a 180-mesh sieve, and 75% on a 200-mesh sieve.

[0124] 12 parts of calcined kaolin, 8 parts of quartz, 25 parts of potassium feldspar, 12 parts of sodium feldspar, 12 parts of calcite, 10 parts of calcined talc, 3 parts of zinc oxide, and 25 parts of crystalline frit are mixed uniformly, and then 0.2 parts of sodium carboxymethyl cellulose, 0.35 parts of sodium tripolyphosphate, and 35 parts of water are added, and the mixture is ball-milled and sieved to obtain a transparent antifouling glaze slurry;

[0125] The transparent antifouling glaze slurry is dried, crushed and sieved to obtain a transparent antifouling glaze powder; wherein, according to the mass percentage, the transparent antifouling glaze powder passes through a 100-mesh sieve, and the sieve residue is 0.2%;

[0126] B3. Mix 6 parts of alloy dry particles, 90 parts of transparent antifouling glaze powder and 180 parts of suspending agent to obtain a silvery white metallic dry particle glaze.

[0127] Comparative Example 1

[0128] The preparation method and raw materials of Comparative Example 1 are the same as those of Example 1, except that the alloy dry particles of Comparative Example 1 only include iron, chromium and manganese, and no silicon, aluminum, vanadium and nickel are added.

[0129] Comparative Example 2

[0130] The preparation method and raw materials of Comparative Example 2 are the same as those of Example 1, except that no crystalline frit is added to the transparent antifouling glaze powder of Comparative Example 2.

[0131] Comparative Example 3

[0132] The preparation method and raw materials of Comparative Example 3 are the same as those of Example 1, except that calcite is not added to the transparent antifouling glaze powder of Comparative Example 3.

[0133] The surface effects of the silvery-white metallic texture tiles prepared in the examples and comparative examples were observed, and the obtained silvery-white metallic texture tiles were subjected to conventional glossiness tests, hardness tests, and antifouling grade tests in the field of architectural ceramics. The results are shown in Table 1 below:

[0134] Table 1 Performance test results of tiles of Examples and Comparative Examples

[0135]

[0136] It can be seen from the performance test results in Table 1 that the prepared silver-white metallic texture tiles not only have excellent silver-white metallic texture effects, transparency and anti-fouling performance, but also have high wear resistance and hardness, while ensuring the uniformity of the silver-white metallic texture effect. It is both decorative and practical, and is more conducive to meeting the use needs of consumers.

[0137] In Comparative Example 1, since the raw materials in the alloy dry particles only include iron, chromium and manganese, and no silicon, aluminum, vanadium and nickel are added, the system can only rely on the oxides formed by the oxidation of iron, chromium and manganese in air as a composite oxide protective layer. The structural density of the composite oxide protective layer is insufficient and the corrosion resistance is limited. Not only does it lead to a limited metallic texture effect of the tiles obtained in Comparative Example 1, but it also causes a certain degree of corrosion of the alloy dry particles, introducing impurity colors on the surface of the tiles.

[0138] In Comparative Example 2, since no crystalline frit is added to the transparent antifouling glaze powder, the following effects will occur: (1) the crystalline frit cannot be used in Comparative Example 2 to inhibit the corrosion of the alkali metal ions in the multi-component composite flux on the alloy dry particles, thereby reducing the metallic texture effect of the tile and causing the obtained tile to have impurity color. (2) the amount of mullite crystals and anorthite crystals in the glaze surface of the silvery-white metallic dry particle glaze after calcination is reduced, resulting in a decrease in the hardness and wear resistance of the tile obtained in Comparative Example 2. (3) the crystalline frit cannot be used to improve the antifouling performance, thereby reducing the antifouling performance of the tile. It should be noted that the crystalline frit simultaneously generates anorthite crystals with high transparency and mullite crystals with poor transparency, and the amount of glass phase generated in the crystalline frit is not high, making the transparency of the crystalline frit relatively poor. Therefore, when no crystalline frit is added in Comparative Example 2, the transparency of the tile obtained in Comparative Example 2 tends to be improved, and has a higher transparency.

[0139] In Comparative Example 3, since calcite is not added to the transparent antifouling glaze powder, the following effects will occur: (1) The amount of calcium feldspar crystals precipitated during calcination of the silvery-white metallic dry granular glaze is reduced, and the characteristics of calcium feldspar crystals in increasing hardness and wear resistance cannot be utilized, thereby reducing the hardness and wear resistance of the tiles obtained using Comparative Example 3; (2) The total content of the multi-component composite flux in the silvery-white metallic dry granular glaze is reduced, and the amount of glaze glass phase generated after calcination is reduced, which not only reduces the degree to which the glaze glass phase increases the transparency of the tiles, but also reduces the encapsulation of the glaze glass relative to the calcium feldspar crystals, mullite crystals and cordierite crystals, making it easy for pores to exist between the calcium feldspar crystals, mullite crystals and cordierite crystals, resulting in a decrease in the antifouling performance of the glaze; (3) The amount of calcium feldspar crystals precipitated after calcination of the silvery-white metallic dry granular glaze is reduced, resulting in a decrease in the transparency of the glaze. It should be noted that, although the amount of anorthite crystals generated in Comparative Example 3 is reduced and the anorthite crystals cannot play the role of inhibiting the corrosion of the alloy dry particles by the alkali metal ions in the multi-component composite flux, the total content of the multi-component composite flux in the silvery-white metallic dry particle glaze is reduced, thereby reducing the tendency of the alkali metal ions in the quaternary composite flux to corrode the alloy dry particles.

[0140] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are intended solely to illustrate the principles of the present invention and are not to be construed in any way as limiting the scope of protection of the present invention. Based on the explanations herein, those skilled in the art will readily conceive of other specific embodiments of the present invention without inventive effort, and such embodiments will fall within the scope of protection of the present invention.

Claims

1. A method for preparing silvery-white metallic texture tiles, characterized in that: The following steps are involved: A. preparing a ceramic blank, pressing the ceramic blank, and drying it to obtain a green body layer; B. applying a silvery-white metallic dry granular glaze to the surface of the green body layer to obtain a silvery-white metallic dry granular glaze layer; C. After drying, calcining at a temperature of 1180-1210°C, and then polishing to obtain silvery white metallic texture tiles; Wherein, in step B, the preparation method of the silvery white metallic dry particle glaze is: B1. Under an inert atmosphere, 6 to 7 parts by mass of silicon, 0.1 to 0.2 parts by mass of aluminum, 60 to 65 parts by mass of iron, 25 to 30 parts by mass of chromium, 2 to 3 parts by mass of manganese, 0.1 to 0.5 parts by mass of vanadium, and 0.1 to 0.2 parts by mass of nickel are completely melted and crushed to obtain alloy droplets; The alloy droplets are cooled in a natural environment to obtain alloy dry particles; The liquid fragmentation method specifically comprises: melting silicon, aluminum, iron, chromium, manganese, vanadium and nickel to obtain an alloy melt, accelerating it through a high-pressure pump and passing it through a micro-hole nozzle, where the high-speed jet rubs with air or hits a target plate to fragment the metal melt into alloy droplets; B2. 12 to 18 parts by mass 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 were mixed uniformly, calcined, water-quenched, ground and sieved to obtain a crystalline frit; 10-18 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of sodium feldspar, 5-15 parts of calcite, 5-10 parts of calcined talc, 1-3 parts of zinc oxide, and 20-30 parts of crystalline frit are mixed uniformly by weight, and then sodium carboxymethyl cellulose, a water reducing agent, and water are added, and the mixture is ball-milled and sieved to obtain a transparent antifouling glaze slurry. The transparent antifouling glaze slurry is dried, crushed and sieved to obtain the transparent antifouling glaze powder; B3. Evenly mix the alloy dry particles, transparent antifouling glaze powder and suspending agent to obtain a silvery-white metallic dry particle glaze.

2. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B1, the melting temperature is 1100-1200°C.

3. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B1, the particle size distribution of the dry alloy particles is calculated according to mass percentage: the sieve residue of the 100-mesh sieve is 0.1-0.5%, the sieve residue of the 160-mesh sieve is 65-70%, the sieve residue of the 200-mesh sieve is 83-87%, the sieve residue of the 250-mesh sieve is 90-95%, and the sieve residue of the 325-mesh sieve is 97-99%.

4. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B2, the calcination temperature curve of the crystalline frit is: It takes 1.5 to 3 hours to heat from room temperature to 300°C; From 300℃ to 1530℃, it takes 2 to 3 hours; 1530℃, keep warm for 0.5~1.5h.

5. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B2, the particle size distribution of the crystalline frit is as follows: the sieve residue of 150 mesh is 0.1-0.5%, the sieve residue of 180 mesh is 40-50%, and the sieve residue of 200 mesh is 70-80%.

6. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B2, the transparent antifouling glaze slurry, calculated by mass, includes 10-18 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of sodium feldspar, 5-15 parts of calcite, 5-10 parts of burnt talc, 1-3 parts of zinc oxide, and 20-30 parts of crystalline frit, which are mixed evenly, and then 0.1-0.3 parts of sodium carboxymethyl cellulose, 0.15-0.35 parts of water reducer and 30-40 parts of water, calculated by mass, are added.

7. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B2, the transparent antifouling glaze powder is passed through a 100-mesh sieve, and the residue on the sieve is 0.1-0.3% by mass.

8. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B3, the silvery-white metallic dry particle glaze is composed of 6 to 10 parts of alloy dry particles, 90 to 94 parts of transparent antifouling glaze powder and 180 to 200 parts of suspending agent, calculated by weight.

9. The method for preparing a silvery-white metallic texture tile according to claim 1, characterized in that: In step B, the glaze amount of the silvery white metallic dry granular glaze is 455-500 g / m 3 , specific gravity is 1.4~1.

5.

10. A silvery white metallic texture tile, characterized in that: The ceramic tile is prepared by the preparation method of the silvery-white metallic texture ceramic tile according to any one of claims 1 to 9.

Images