Silver white metal texture ceramic tile and preparation method thereof

Abstract

The invention relates to the technical field of building ceramics, in particular to a silver-white metal-texture ceramic tile and a preparation method thereof.The preparation method comprises the following steps that A, a ceramic blank is prepared, pressed and dried to obtain a blank layer; b, applying silver-white metal dry granular glaze to the surface of the green body layer to obtain a silver-white metal dry granular glaze layer; and C, after drying, calcining at the temperature of 1180-1210 DEG C, and polishing to obtain the silver-white ceramic tile with the metal texture. According to the silver-white metal texture ceramic tile and the preparation method thereof, on the premise that the silver-white metal texture effect is uniform, the silver-white metal texture ceramic tile not only has excellent silver-white metal texture effect, transparency and antifouling performance, but also has high wear resistance and hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of architectural ceramics, and particularly to a silver-white metallic texture tile and a preparation method thereof. Background Art

[0002] In the vast world of the ceramic market, consumers' demands are becoming increasingly diversified and personalized. They not only pursue the practicality and durability of ceramic products but also have extremely high expectations for their artistic value and visual beauty. This change in market demand has prompted the ceramic industry to continuously carry out technological innovation and product research and development to meet the growing aesthetic and practical needs.

[0003] In the production process of tiles, the formulation of glazes is extremely important. The same body will produce different glaze effects due to different glazes, and the tactile and visual sensations of different glazes will also affect the choices of consumers. Metallic glazes are a special type of glaze. When metallic glazes are applied to the surface of the body and fired at high temperatures, they can make the surface of the tile present a metallic texture effect and are widely used in the architectural decoration industry. Existing metallic glazes mainly consist of metallic dry particles and frit. However, the frit usually needs to add fluxes such as lithium oxide (Li2O), boron oxide (B2O3), potassium oxide (K2O), and sodium oxide (Na2O) to reduce its melting temperature. However, the chemical activity of the above fluxes is extremely high, and it will gradually dissolve the metal oxides on the surface of the metallic dry particles, forming pores and microcracks on their surfaces. Subsequently, the fluxes penetrate into the interior of the metallic dry particles through the pores and cracks and react with them, ultimately resulting in the complete corrosion and discoloration of the metallic dry particles and the loss of the original metallic texture effect.

[0004] In order to prevent the metallic dry particles from being corroded and discolored, existing frits usually adopt feldspathic frits with a low flux content and a high silicon-aluminum content, and the feldspathic frits use kaolin and quartz as the main aluminum source and silicon source. However, due to the relatively high melting temperature of quartz and the relatively insufficient flux content, the proportion of unmolten quartz remaining in the frit is relatively high. There is a significant difference in the refractive index between unmolten quartz (about 1.65) and the glass phase (about 1.50). The above refractive index mismatch easily causes a strong light scattering effect, thereby reducing the transparency of the glaze surface. As the content of unmolten quartz increases, the light scattering phenomenon intensifies, further affecting the transparency of the glaze surface.

[0005] Meanwhile, due to the insufficient content of flux in the system, the aluminum oxide generated by the decomposition of kaolin at high temperature (>950 °C) is difficult to be completely melted, and it will exist in the form of inert α-Al2O3 and mullite crystals. The refractive indices of inert α-Al2O3 (corundum phase, refractive index is 1.76) and mullite crystals (refractive index is 1.64) are quite different from the refractive index of the glass phase (about 1.50), which further exacerbates light scattering and thus further reduces the transparency of the glaze surface. The reduced transparency will cover the original pattern of the tile decorative layer and affect the overall decorative effect of the tile. In addition, due to the severely insufficient content of flux in the feldspathic frit, the glass phase formed in the feldspathic frit is severely insufficient, and the formed glass phase is difficult to completely wrap the unmolten quartz, unmolten α-Al2O3 and mullite crystals, resulting in pores between the unmolten quartz, unmolten α-Al2O3 and mullite crystals, leading to a relatively high porosity of the glaze surface after calcination of the metal glaze containing the feldspathic frit, easy infiltration of pollutants, and poor stain resistance.

[0006] Since transparent glaze generally has high transparency and stain resistance. Therefore, in order to effectively improve transparency and stain resistance, the glaze surface formed after calcination of the metal glaze containing the feldspathic frit has high stain resistance on the premise of not affecting the pattern effect of the original decorative layer of the tile. The prior art attempts to add a relatively large amount of transparent glaze to the metal glaze formula, but due to the relatively large addition amount of transparent glaze, the content of flux in the formula is also relatively large, making the metal dry particles easy to be completely corroded and losing 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, feldspathic frit and transparent glaze also contains water. Due to the extremely large specific gravity of the metal dry particles, they are very easy to precipitate in the above-mentioned compounded water-containing metal glaze, resulting in poor uniformity of the distribution of the metal dry particles on the glaze surface after calcination and affecting the uniformity of the metallic texture effect.

[0007] In summary, the existing tiles can neither simultaneously possess excellent metallic texture effect, transparency and stain resistance, nor ensure the uniformity of the metallic texture effect. Summary of the Invention

[0008] The purpose of the present invention is to provide a silver-white metallic texture tile and its preparation method. On the premise of ensuring the uniformity of the silver-white metallic texture effect, it can not only simultaneously have excellent silver-white metallic texture effect, transparency and stain resistance, but also have high wear resistance and hardness, so that the silver-white metallic texture tile combines decoration and practicability to overcome the deficiencies in the prior art.

[0009] To achieve this purpose, the present invention adopts the following technical solutions: A preparation method of a silver-white metallic texture tile, comprising the following steps: A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying. B. Apply a silver-white metallic dry granule glaze to the surface of the green body layer to obtain a silver-white metallic dry granule glaze layer. C. After drying, calcine at a temperature of 1180 - 1210 °C, and then obtain a silver-white metallic texture ceramic tile after polishing. Among them, in step B, the preparation method of the silver-white metallic dry granule glaze is as follows: B1. Under an inert atmosphere, completely melt 6 - 7 parts by mass of silicon, 0.1 - 0.2 parts by mass of aluminum, 60 - 65 parts by mass of iron, 25 - 30 parts by mass of chromium, 2 - 3 parts by mass of manganese, 0.1 - 0.5 parts by mass of vanadium, and 0.1 - 0.2 parts by mass of nickel, and obtain alloy droplets after liquid fragmentation. Cool the alloy droplets in a natural environment to obtain alloy dry granules. B2. Mix 12 - 18 parts by mass of quartz, 15 - 20 parts by mass of calcined aluminum oxide, 30 - 38 parts by mass of wollastonite, 8 - 12 parts by mass of zinc oxide, 18 - 22 parts by mass of strontium carbonate, and 1 - 5 parts by mass of barium carbonate evenly, and obtain a crystalline frit after calcination, water quenching, grinding, and sieving. Mix 10 - 18 parts by mass of calcined kaolin, 4 - 8 parts by mass of quartz, 20 - 30 parts by mass of potassium feldspar, 8 - 15 parts by mass of sodium feldspar, 5 - 15 parts by mass of calcite, 5 - 10 parts by mass of burnt talc, 1 - 3 parts by mass of zinc oxide, and 20 - 30 parts by mass of the crystalline frit evenly, then add sodium carboxymethyl cellulose, water reducing agent, and water, and obtain a transparent antifouling glaze slurry after ball milling and sieving. Dry, pulverize, and sieve the transparent antifouling glaze slurry to obtain transparent antifouling glaze powder. B3. Mix the alloy dry granules, transparent antifouling glaze powder, and suspending agent evenly to obtain a silver-white metallic dry granule glaze.

[0010] Furthermore, in step B1, the melting temperature of the melting is 1100 - 1200 °C.

[0011] Furthermore, in step B1, calculated by mass percentage, the particle size distribution of the alloy dry granules is: the residue on a 100 - mesh sieve is 0.1 - 0.5%, the residue on a 160 - mesh sieve is 65 - 70%, the residue on a 200 - mesh sieve is 83 - 87%, the residue on a 250 - mesh sieve is 90 - 95%, and the residue on a 325 - mesh sieve is 97 - 99%.

[0012] Furthermore, in step B2, the calcination temperature curve of the crystalline frit is as follows: Rise from room temperature to 300 °C, taking 1.5 - 3 h; Rise from 300 °C to 1530 °C, taking 2 - 3 h; 1530 °C, keep warm for 0.5 - 1.5 h.

[0013] Further, in step B2, the particle size distribution of the crystalline frit is as follows: the residue on a 150 - mesh sieve is 0.1 - 0.5%, the residue on a 180 - mesh sieve is 40 - 50%, and the residue on a 200 - mesh sieve is 70 - 80%.

[0014] Further, in step B2, calculated by mass fraction, the transparent antifouling glaze slurry 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 calcined talc, 1 - 3 parts of zinc oxide, and 20 - 30 parts of crystalline frit. After mixing evenly, 0.1 - 0.3 parts of sodium carboxymethyl cellulose, 0.15 - 0.35 parts of water - reducing agent, and 30 - 40 parts of water are added by mass fraction.

[0015] Further, in step B2, calculated by mass percentage, the transparent antifouling glaze powder passes through a 100 - mesh sieve, and the residue is 0.1 - 0.3%.

[0016] Further, in step B3, calculated by mass fraction, the silver - white metallic dry - granule glaze is composed of 6 - 10 parts of alloy dry - granules, 90 - 94 parts of transparent antifouling glaze powder, and 180 - 200 parts of suspending agent.

[0017] Further, in step B, the application amount of the silver - white metallic dry - granule glaze is 455 - 500 g / m 3 , and the specific gravity is 1.4 - 1.5.

[0018] A silver - white metallic texture ceramic tile is prepared by the preparation method of the above - mentioned silver - white metallic texture ceramic tile.

[0019] The technical solution provided by the present invention may include the following beneficial effects: 1. This technical solution uses silicon (silicon is a metalloid), aluminum, iron, chromium, manganese, vanadium, and nickel as raw materials. After melting and liquid - crushing in an inert atmosphere to form alloy droplets, alloy dry - granules are prepared by natural cooling. During the natural cooling process, the surface of the alloy droplets exposed to air reacts with oxygen and forms a composite oxide protective film containing components such as aluminum oxide, chromium oxide, and silicon dioxide, finally forming alloy dry - granules with a "core - shell" structure, where the core is a multi - element alloy matrix mainly composed of iron, chromium, and manganese, and the shell is a composite oxide protective film.

[0020] 2. During the calcination of crystalline frit, wollastonite, as a natural calcium silicate mineral (with a main chemical composition of calcium silicate), decomposes upon heating to form calcium oxide; strontium carbonate decomposes into strontium oxide under high-temperature conditions, and barium carbonate decomposes to form barium oxide. The calcium oxide, strontium oxide, and barium oxide thus formed synergistically interact with zinc oxide in the crystalline frit raw material to jointly constitute a calcium-strontium-zinc-barium composite flux. Since calcium ions, strontium ions, barium ions, and zinc ions are all low-polarizability ions with relatively large radii and weak polarization abilities, they result in a high lattice energy and strong bonding strength, requiring higher energy to break the flux network structure, making the initial melting point of the above-mentioned calcium-strontium-zinc-barium composite flux relatively high. Additionally, there is a size-matching effect among calcium ions, strontium ions, barium ions, and zinc ions (such as the radius ratio of barium ions to zinc ions conforming to the Hume-Rothery rule), which can form a high-temperature limited solid solution. This solid solution, through the atomic-level mutual solubility mechanism, disrupts the necessary conditions for the formation of the eutectic point, resulting in a significant increase in the initial melting point of the calcium-strontium-zinc-barium composite flux compared to single fluxes.

[0021] 3. The anorthite crystals and mullite crystals contained in the crystalline frit itself basically remain stable and do not melt, such that the above-mentioned crystals are retained in the glaze surface after the calcination of the golden metallic dry glaze. Combining with the anorthite crystals and cordierite crystals generated during the calcination of other raw materials such as calcined kaolin, quartz, and calcite in the transparent antifouling glaze powder, the glaze surface obtained after the calcination of the golden metallic dry glaze contains three types of crystals: anorthite crystals, mullite crystals, and cordierite crystals. The above-mentioned crystals can not only form a physical "armor" on the surface of the alloy dry granules, thereby directly blocking the directional migration of alkali metal ions in the multi-component composite flux towards the alloy dry granules, but also the random distribution of the above three types of crystals transforms the diffusion path of alkali metal ions in the multi-component composite flux from linear to three-dimensional zigzag, strengthening the diffusion barrier through geometric path extension and effectively inhibiting the corrosion of alloy dry granules by alkali metal ions in the multi-component composite flux. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is the effect diagram of the glaze surface of the silver-white metallic texture ceramic tile obtained in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0023] The present technical solution provides a method for preparing a silver-white metallic texture ceramic tile, comprising the following steps: A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying; B. Apply the silver-white metallic dry glaze to the surface of the green body layer to obtain a silver-white metallic dry glaze layer; C. After drying, calcine at a temperature of 1180 - 1210 °C, and then obtain a silver-white metallic texture ceramic tile after polishing; Among them, in step B, the preparation method of the silver-white metallic dry glaze is as follows: B1. Under an inert atmosphere, 6 - 7 parts by mass of silicon, 0.1 - 0.2 parts by mass of aluminum, 60 - 65 parts by mass of iron, 25 - 30 parts by mass of chromium, 2 - 3 parts by mass of manganese, 0.1 - 0.5 parts by mass of vanadium, and 0.1 - 0.2 parts by mass of nickel are completely melted, and after liquid fragmentation, alloy droplets are obtained; Under natural environment, the alloy droplets are cooled to obtain alloy dry grains; B2. 12 - 18 parts by mass of quartz, 15 - 20 parts by mass of calcined aluminum oxide, 30 - 38 parts by mass of wollastonite, 8 - 12 parts by mass of zinc oxide, 18 - 22 parts by mass of strontium carbonate, and 1 - 5 parts by mass of barium carbonate are mixed evenly, and after calcination, water quenching, grinding, and sieving, a crystalline frit is obtained; 10 - 18 parts by mass of calcined kaolin, 4 - 8 parts by mass of quartz, 20 - 30 parts by mass of potassium feldspar, 8 - 15 parts by mass of sodium feldspar, 5 - 15 parts by mass of calcite, 5 - 10 parts by mass of burnt talc, 1 - 3 parts by mass of zinc oxide, and 20 - 30 parts by mass of the crystalline frit are mixed evenly, then carboxymethyl cellulose sodium, water reducing agent, and water are added, and after ball milling and sieving, a transparent antifouling glaze slurry is obtained; The transparent antifouling glaze slurry is dried, pulverized, and sieved to obtain transparent antifouling glaze powder; B3. The alloy dry grains, transparent antifouling glaze powder, and suspending agent are mixed evenly to obtain a silver - white metallic dry - grain glaze.

[0024] In order to overcome the technical defects existing in the prior art, this technical solution proposes a preparation method of silver - white metallic texture tiles. By optimizing the preparation method and raw materials, on the premise of ensuring the uniformity of the silver - white metallic texture effect of the tiles, it not only has excellent silver - white metallic texture effect, transparency, and antifouling performance, but also has high wear resistance and hardness to meet the actual use requirements. It should be noted that the green body layer in this solution is formed by pressing and drying the conventional ceramic blank in the ceramic field, and no further description of the ceramic blank is made here. In addition, the polishing treatment industry also uses the commonly used polishing process in the field, and no further description of it is made here.

[0025] Specifically, this technical solution uses silicon (silicon is a metalloid), aluminum, iron, chromium, manganese, vanadium, and nickel as raw materials. After melting and liquid atomization in an inert atmosphere to form alloy droplets, alloy dry particles are prepared by natural cooling. During the natural cooling process, the surface of the alloy droplets exposed to air reacts with oxygen, and a composite oxide protective film containing components such as aluminum oxide, chromium oxide, and silicon dioxide is formed. Eventually, alloy dry particles with a "core-shell" structure are formed, where the core is a multi-element alloy matrix mainly composed of iron, chromium, and manganese, and the shell is the composite oxide protective film. It should be noted that a metalloid, also known as a semimetal, has both metallic and non-metallic properties. In addition, the liquid atomization in this technical solution means that the alloy melt obtained by melting silicon, aluminum, iron, chromium, manganese, vanadium, and nickel is accelerated by a high-pressure pump and then passes through a microporous nozzle. The high-speed jet frictions with air or impacts a target plate to break the metal melt into alloy droplets.

[0026] 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 combined action of aluminum oxide and chromium oxide forms a dense and continuous barrier layer, which can effectively block the intrusion of corrosive media such as fluxes; silicon dioxide further enhances the denseness of the film layer by filling grain boundary defects; at the same time, chromium oxide also imparts good chemical passivation effect to the material. The outer layer is composed of iron oxide, manganese dioxide, vanadium pentoxide, and nickel oxide, presenting a porous structure and having sacrificial protection characteristics. It can preferentially react with corrosive media such as fluxes to delay the erosion process of the inner layer. That is, through the above "dense inner layer barrier + porous outer layer buffering" synergistic protection mechanism of the composite oxide protective film in this technical solution, not only the reliability of the inner layer film is ensured, but also through the sacrificial protection of the outer layer film, the composite oxide protective film has excellent corrosion resistance in the glaze environment, making it not easily corroded by corrosive media such as fluxes, thus being conducive to maintaining the stability of the properties of the alloy dry particles.

[0027] Furthermore, the alloy dry granules of this technical solution achieve excellent high-temperature stability through the following effects: (1) The high chromium content forms an iron-chromium solid solution matrix with elemental iron, and its solidus temperature breaks through the 1300 °C threshold, constructing a high-temperature-resistant crystal skeleton; (2) Elemental silicon and elemental chromium in-situ generate intermetallic compounds (high-temperature phases) such as chromium trisilicide. The high-temperature phases with a melting point exceeding 1500 °C penetrate 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 film of aluminum oxide-chromium oxide-silicon dioxide, and the melting point of the inner layer film can be as high as 2000 °C, which is beneficial to improving the high-temperature stability of the alloy dry granules; (4) Trace amounts of elemental vanadium can improve the high-temperature strength by refining the grains. Based on the high-temperature stability of the alloy dry granules, when the alloy dry granules are introduced into the glaze system, their performance stability can still be maintained after high-temperature calcination of the glaze.

[0028] Secondly, quartz, calcined alumina, wollastonite, zinc oxide, strontium carbonate, and barium carbonate are mixed evenly and then obtained crystalline frit after calcination, water quenching, grinding, and sieving. First, during the calcination of the crystalline frit, wollastonite, as a natural calcium silicate mineral (mainly with a chemical composition of calcium silicate), decomposes upon heating to generate calcium oxide; strontium carbonate decomposes into strontium oxide under high-temperature conditions, and barium carbonate decomposes into barium oxide. The generated calcium oxide, strontium oxide, and barium oxide synergistically act with zinc oxide in the crystalline frit raw materials to jointly form a calcium-strontium-zinc-barium composite flux. Since calcium ions, strontium ions, barium ions, and zinc ions are all ions with low polarizability, relatively large radii, and weak polarization ability, resulting in high lattice energy and strong bonding strength, higher energy is required to break the flux network structure, making the initial melting point of the above calcium-strontium-zinc-barium composite flux relatively high. In addition, there is a size matching effect among calcium ions, strontium ions, barium ions, and zinc ions (for example, the radius ratio of barium ions to zinc ions conforms to the Hume-Rothery rule), which can form a high-temperature limited solid solution. This solid solution, through the atomic-level mutual solubility mechanism, destroys the necessary conditions for the formation of the eutectic point, resulting in a significant increase in the initial melting point of the calcium-strontium-zinc-barium composite flux compared to a single flux. That is, the calcium-strontium-zinc-barium composite flux in this technical solution enables the crystalline frit to have a relatively high initial melting point through the above-mentioned various effects.

[0029] Furthermore, at high temperatures, wollastonite decomposes to form calcium oxide and silicon dioxide. Meanwhile, quartz and calcined alumina in the formula provide additional silicon dioxide and aluminum oxide respectively. By precisely controlling the addition amounts of quartz, calcined aluminum oxide, and wollastonite, the ratios of calcium oxide, aluminum oxide, and silicon dioxide introduced into the crystalline frit formula system are defined. Under these specific ratio conditions, aluminum oxide, silicon dioxide, and calcium oxide in the formula system undergo chemical reactions to form anorthite crystals (CaAl2Si2O8), and aluminum oxide and silicon dioxide can react to form mullite (3Al2O3·2SiO2). Therefore, the crystalline frit contains two types of crystals, anorthite crystals and mullite crystals. The melting point of anorthite crystals is 1553 °C, and the melting point of mullite crystals is 1850 °C. These two types of crystals endow the crystalline frit with a relatively high initial melting point.

[0030] In summary, through the mutual cooperation of the above-mentioned various effects, the initial melting point of the crystalline frit is improved in this technical solution.

[0031] Furthermore, the transparent antifouling glaze slurry of this technical solution includes raw materials such as crystalline frit, calcined kaolin, quartz, potassium feldspar, sodium feldspar, calcite, burnt talc, and zinc oxide. Thus, 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 amounts of the low-temperature fluxes potassium feldspar and sodium feldspar are limited to ensure that the sum of their addition amounts is less than that of the low-temperature fluxes in common existing glazes. The reduction of the content of the low-temperature flux is beneficial to increasing the initial melting point of the transparent antifouling glaze powder. Combining with the function of the crystalline frit itself in increasing the initial melting point, it is beneficial to the initial melting point of the transparent antifouling glaze powder, and thus the melting threshold of the golden metallic dry granule glaze is increased as a whole. Meanwhile, 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. These oxides and the calcium strontium zinc barium composite flux together constitute a multi-component composite flux. Since the silver-white metallic dry granule glaze has a relatively high melting threshold, the contact time between the multi-component composite flux (i.e., the flux) and the alloy dry granules during the high-temperature firing stage is significantly shortened, thereby effectively inhibiting the corrosive effect of the flux on the alloy dry granules and being beneficial to maintaining the stability of the alloy dry granule performance.

[0032] It should be noted that the increase in the melting threshold of the silver-white metallic dry granule glaze in this technical solution enables it to maintain a relatively high viscosity at the initial stage of fast firing, delaying the sealing of the silver-white metallic dry granule glaze layer to facilitate gas exhaust, and avoiding the formation of pinholes or bubbles due to gas being trapped inside the silver-white metallic dry granule glaze layer, thereby ensuring the quality of the resulting ceramic tiles.

[0033] Again, during the high-temperature firing process of the raw materials in the transparent antifouling glaze powder of this technical solution, the following reactions occur among the raw materials: Calcined kaolin decomposes to form aluminum oxide and silicon dioxide, quartz provides additional silicon dioxide, calcite decomposes to produce calcium oxide, and calcium oxide reacts with aluminum oxide and silicon dioxide to form anorthite crystals (CaAl2Si2O8); burnt talc decomposes to form magnesium oxide, and magnesium oxide reacts with aluminum oxide and silicon dioxide in the system to form cordierite crystals (Mg2Al2Si2O 18 ). At the same time, the anorthite crystals and mullite crystals contained in the crystalline frit itself basically remain stable and do not melt at the firing temperature of 1180-1210 °C, so that the above crystals are retained in the glaze surface after the golden metallic dry glaze is fired. Combined with the anorthite crystals and cordierite crystals generated by other raw materials such as calcined kaolin, quartz, and calcite in the transparent antifouling glaze powder during the firing process, the glaze surface obtained after the golden metallic dry glaze is fired contains three kinds of crystals: anorthite crystals, mullite crystals, and cordierite crystals. The above crystals can not only form a physical "armor" on the surface of the alloy dry particles, thereby directly blocking the directional migration of alkali metal ions in the multi-component composite flux to the alloy dry particles, but also the random distribution of the above three kinds of crystals converts the diffusion path of alkali metal ions in the multi-component composite flux from linear to three-dimensional zigzag, and strengthens the diffusion barrier by extending the geometric path, effectively inhibiting the corrosion of alloy dry particles by alkali metal ions in the multi-component composite flux. That is, the above-mentioned various crystals inhibit the corrosion of alloy dry particles by alkali metal ions in the multi-component composite flux by means of physical barrier and extending the diffusion path, which is beneficial to maintaining the stability of the performance of alloy dry particles.

[0034] In summary, through the mutual cooperation of the above-mentioned various functions of this technical solution, the alloy dry particles are prevented from being corroded and the stability of their performance is maintained. When the silver-white metallic dry glaze is applied to the surface of the green body layer, only after firing and polishing to remove the composite oxide protective film on the surface of the alloy dry particles, the multi-component alloy matrix mainly composed of iron, chromium, and manganese (the color of the multi-component alloy matrix is silver-white) inside the alloy dry particles can be exposed, thus presenting a silver-white metallic texture effect.

[0035] It should be noted that since the glaze surface after the silver-white metallic dry glaze is fired contains three kinds of crystals: anorthite crystals, mullite, and cordierite crystals, and the above three kinds of crystals have high hardness and wear resistance, the tiles are given high hardness and wear resistance.

[0036] Again, in addition to participating in the formation of anorthite crystals and mullite crystals, the quartz in the crystalline frit can also form a silicate glass network with the calcium strontium zinc barium composite flux and calcined alumina to form the glass phase of the crystalline frit. When the crystalline frit is added to the transparent antifouling glaze powder and then the transparent antifouling glaze powder is added to the silver-white metal dry granules for firing, within the firing 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 structure to support the glaze surface. At this time, the glass phase in the crystalline frit melts into a liquid state, which, as a precursor of the prefabricated glass phase, first melts with the silica and alumina decomposed from kaolin in the formulation system to form a low-viscosity silicate glass matrix. At the same time, raw materials such as potassium feldspar, sodium feldspar, calcite, burnt talc, and zinc oxide in the formulation system melt into an alkali metal aluminosilicate liquid phase, fuse with the low-viscosity silicate glass matrix, erode the quartz particles and promote their melting, and each component diffuses and fuses with each other, ultimately forming a continuous and dense glaze glass phase. The above-mentioned glaze glass phase significantly reduces the porosity of the glaze by wrapping the alloy dry granules, filling the grain boundary voids, and strengthening the bonding of crystal particles, blocking the stain penetration channels, thereby endowing the ceramic tile with excellent antifouling performance.

[0037] Furthermore, since the addition amount of strontium carbonate in the crystalline frit is 18 - 22 parts, after calcination and decomposition, the content of strontium oxide in the crystalline frit is relatively high. When the crystalline frit with a high strontium oxide content is introduced into the transparent antifouling glaze powder and then added to the silver-white metal dry granule system, strontium oxide can not only reduce the connection of silicon-oxygen tetrahedrons in the melt for forming the glaze glass phase, lower the viscosity of the melt at high temperatures, so that during the firing process, the fluidity of the silver-white metal dry granules is enhanced, and they can spread more evenly, avoiding local accumulation or incomplete coverage, but also strontium oxide can reduce the surface tension of the glaze glass phase melt, thereby reducing defects such as shrinkage pores and pinholes generated due to uneven surface tension during the cooling process of the glaze layer, making the glaze surface smoother and flatter, and thus endowing the ceramic tile with excellent antifouling performance.

[0038] In summary, the technical solution ensures that the ceramic tile has excellent antifouling performance through the above-mentioned multiple aspects.

[0039] Finally, the calcium feldspar crystals generated by this technical solution belong to the triclinic system, with a dense crystal structure, and its refractive index is close to that of the glazed glass phase. There is no significant light scattering center, so the calcium feldspar crystals have extremely high transparency. Therefore, in order to improve the transparency of the ceramic tile with the silver-white metal dry granular glaze, this technical solution limits the amount of raw material crystalline frit, calcined kaolin, quartz, calcite and talc added in the transparent antifouling glaze powder to ensure that the transparent antifouling glaze powder is mainly composed of calcium feldspar crystals after calcination, giving the silver-white metal dry granular glaze with the transparent antifouling glaze powder high transparency, thereby improving the transparency of the ceramic tile glaze; at the same time, this technical solution limits the amount of raw materials such as crystalline frit, potassium feldspar, sodium feldspar, calcite, talc and zinc oxide added to form the multi-component composite flux in the transparent antifouling glaze powder, and appropriately increases its amount under the premise of avoiding excessive content of the multi-component composite flux, so as to promote the generation of more glazed glass phases. The increase in the glass phase content helps to further enhance the high transparency of the silver-white metal dry granular glaze to which the transparent anti-fouling glaze powder is added, thereby improving the transparency of the tile glaze. In addition, the zinc oxide in the transparent anti-fouling glaze powder and the crystalline frit acts 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 metal dry granular glaze. That is, the present technical solution effectively improves the transparency of the ceramic tile through the above-mentioned multi-faceted effects. It should be noted that although the glaze surface obtained by calcining the silver-white metal 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, which 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.

[0040] At the same time, the technical solution adopts a suspending agent to achieve waterless dispersion of alloy dry particles, which solves 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 metal dry particle glaze after calcination presents a uniform and strong metallic texture effect.

[0041] It should be noted that the manufacturer of the suspending agent is Jiangxi Qiantao New Material Co., Ltd., and the model is 6122A. It should be further noted that the inert atmosphere can be argon gas, nitrogen gas, etc., and the specific type is not limited here.

[0042] 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.

[0043] By optimizing the proportion of raw materials of the alloy dry particles, the thickness ratio of the multi - element alloy matrix and the composite oxide protective film is precisely regulated. On the premise that the composite oxide protective film is sufficient to prevent the alloy dry particles from being corroded, after polishing to remove the composite oxide protective film on the surface of the alloy dry particles, a relatively large volume of the multi - element alloy matrix is retained, forming a continuous and highly exposed metal phase, enhancing the metallic texture effect of the glaze surface.

[0044] Further explanation, in step B1, the melting temperature of the melting is 1100 - 1200 °C.

[0045] By limiting the melting temperature, silicon, aluminum, iron, chromium, manganese, vanadium and nickel are completely melted and doped with each other, which is beneficial to ensuring the performance of the finally obtained alloy dry particles. It should be noted that although the melting point of silicon is 1410 - 1414 °C, the melting point of aluminum is 660 °C, the melting point of iron is 1538 - 1539 °C, the melting point of chromium is 1907 °C, the melting point of manganese is 1907 °C, the melting point of vanadium is 1244 °C, and the melting point of nickel is 1917 °C), but the above - mentioned elements can trigger eutectic reactions during melting, enabling the above - mentioned elements to achieve complete melting and compositional homogenization through eutectic dissolution and atomic diffusion at a temperature of 1100 - 1200 °C. In addition, due to the formation of high - melting - point intermetallic compounds (such as iron - solid solution, chromium trisilicide, etc.) inside the alloy and the film layer formed by surface oxides in the obtained alloy dry particles, even if the calcination temperature of the glaze added with alloy dry particles is higher than the melting temperature, the alloy dry particles can still maintain a solid lattice structure and surface integrity, thus avoiding the deterioration of the performance of alloy dry particles caused by high - temperature melting.

[0046] Further explanation, in step B1, calculated by mass percentage, the particle size distribution of the alloy dry particles is as follows: the residue on a 100 - mesh sieve is 0.1 - 0.5%, the residue on a 160 - mesh sieve is 65 - 70%, the residue on a 200 - mesh sieve is 83 - 87%, the residue on a 250 - mesh sieve is 90 - 95%, and the residue on a 325 - mesh sieve is 97 - 99%.

[0047] By optimizing the particle size distribution 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 enhancing the fluidity of the silver - white metallic dry particle glaze after high - temperature calcination, ensuring the flatness of the glaze surface obtained after calcination of the silver - white metallic dry particle glaze, and thus improving the stain resistance.

[0048] Preferably, calculated by mass percentage, the particle size distribution of the alloy dry particles is as follows: the residue on a 100 - mesh sieve is 0.1%, the residue on a 160 - mesh sieve is 70%, the residue on a 200 - mesh sieve is 86.2%, the residue on a 250 - mesh sieve is 92.6%, and the residue on a 325 - mesh sieve is 98%.

[0049] Further explanation: In step B2, the calcination temperature curve of the crystalline frit is as follows: Rise from room temperature to 300 °C, taking 1.5 to 3 hours; Rise from 300 °C to 1530 °C, taking 2 to 3 hours; At 1530 °C, keep warm for 0.5 to 1.5 hours.

[0050] By optimizing the calcination temperature curve of the crystalline frit, it is beneficial to ensure its related properties.

[0051] Further explanation: In step B2, the particle size distribution of the crystalline frit is as follows: the residue on a 150-mesh sieve is 0.1 to 0.5%, the residue on an 180-mesh sieve is 40 to 50%, and the residue on a 200-mesh sieve is 70 to 80%.

[0052] By optimizing the particle size distribution of the crystalline frit, not only can the silver-white metallic dry granule glaze have good fluidity during the glazing process, be able to spread evenly on the surface of the green body layer, avoid defects such as uneven glaze flow, piled glaze or exposed bottom, ensure the uniform thickness of the glaze layer, but also can make the crystalline frit fully melt during the calcination of the silver-white metallic dry granule glaze, so that the glaze layer obtained after calcination of the silver-white metallic dry granule glaze has a high density, which is beneficial to improving the antifouling performance.

[0053] Further explanation: In step B2, calculated by mass fraction, the transparent antifouling glaze slurry 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. After mixing evenly, 0.1 to 0.3 parts of sodium carboxymethyl cellulose, 0.15 to 0.35 parts of water reducing agent and 30 to 40 parts of water are added according to mass fraction.

[0054] By limiting the addition amounts of sodium carboxymethyl cellulose, water reducing agent and water in the transparent antifouling glaze slurry, it is beneficial to ensure the performance of the transparent glaze slurry, and further beneficial to ensure the performance of the transparent antifouling glaze powder obtained after drying, pulverizing and sieving the transparent antifouling glaze slurry.

[0055] It should be noted that the water reducing agent can be sodium tripolyphosphate, and the specific type is not limited here.

[0056] Further explanation: In step B2, by mass percentage, the transparent antifouling glaze powder passes through a 100-mesh sieve, and the residue is 0.1 to 0.3%.

[0057] By controlling the fineness of the transparent antifouling glaze powder, it is not only beneficial to make the glaze glass phase formed by the silver-white metal dry particle glaze with the transparent antifouling glaze powder added during the calcination process denser and with lower porosity, thereby improving the antifouling property of the tile, but also to promote the suspension stability and uniformity of the transparent antifouling glaze powder in the silver-white metal dry particle glaze, thereby making the metallic texture effect of the tile more uniform.

[0058] Further, 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.

[0059] 6 to 10 parts of alloy dry particles can ensure that the glaze presents a full metallic texture effect, while avoiding the loose glaze structure caused by excessive addition; 90 to 94 parts of transparent anti-fouling glaze powder as the basic glass phase can not only fully wrap the alloy dry particles to form a stable combination, but also maintain sufficient fluidity to achieve a smooth glaze surface; 180 to 200 parts of suspending agent give the glaze ideal rheological properties, which can not only prevent the sedimentation of alloy dry particles with a large specific gravity, but also ensure uniform coating during glazing. Therefore, this technical solution is conducive to achieving better performance of the product by limiting the addition amount of alloy dry particles, crystalline frits and suspending agents, thereby improving the quality and stability of the product.

[0060] 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.

[0061] 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 can be optimized, thereby improving the quality and stability of the product.

[0062] Further, 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.

[0063] In order to obtain a better metallic texture effect, this technical solution adjusts the glazing 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.

[0064] A silvery-white metallic texture ceramic tile is prepared by the above-mentioned method for preparing the silvery-white metallic texture ceramic tile.

[0065] The present solution also proposes a silver-white metallic texture tile, which, on the premise of ensuring a uniform silver-white metallic texture effect, not only can simultaneously have excellent silver-white metallic texture effect, transparency and stain resistance, but also has high wear resistance and hardness, so that the silver-white metallic texture tile combines decoration and practicality.

[0066] The technical solution of the present invention will be further described below through specific embodiments.

[0067] In the examples and comparative examples of the present invention, the manufacturer of the suspending agent is Jiangxi Qiantao New Materials Co., Ltd., and the model is 6122A.

[0068] Example 1 A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying. B. Apply a silver-white metallic dry glaze on the surface of the green body layer to obtain a silver-white metallic dry glaze layer; wherein, the glazing amount of the silver-white metallic dry glaze is 489 g / m 3 , and the specific gravity is 1.4. C. After drying, calcine at a temperature of 1180 °C, and then obtain a silver-white metallic texture tile after polishing. Among them, in step B, the preparation method of the silver-white metallic dry glaze is as follows: B1. Under an argon atmosphere, 6.4 parts by mass of silicon, 0.11 parts by mass of aluminum, 62.59 parts by mass of iron, 27.77 parts by mass of chromium, 2.54 parts by mass of manganese, 0.24 parts by mass of vanadium and 0.11 parts by mass of nickel are completely melted at a temperature of 1100-1200 °C, and alloy droplets are obtained after liquid fragmentation; in the natural environment, the alloy droplets are cooled to obtain alloy dry grains; wherein, calculated by mass percentage, the particle size distribution of the alloy dry grains is: the residue on a 100-mesh sieve is 0.1%, the residue on a 160-mesh sieve is 70%, the residue on a 200-mesh sieve is 86.2%, the residue on a 250-mesh sieve is 92.6%, and the residue on a 325-mesh sieve is 98%. B2. Mix 15 parts by mass of quartz, 18 parts by mass of calcined aluminum oxide, 35 parts by mass of wollastonite, 10 parts by mass of zinc oxide, 20 parts by mass of strontium carbonate and 2 parts by mass of barium carbonate evenly, and obtain a crystalline frit after calcination, water quenching, grinding and sieving; among them, it takes 2 h to rise from room temperature to 300 °C; it takes 2.5 h to rise from 300 °C to 1530 °C; keep the temperature at 1530 °C for 1 h; the particle size distribution of the crystalline frit is: the residue on a 150-mesh sieve is 0.2%, the residue on an 180-mesh sieve is 40%, and the residue on a 200-mesh sieve is 75%. Mix 14 parts of calcined kaolin, 5 parts of quartz, 25 parts of potassium feldspar, 10 parts of albite, 11 parts of calcite, 8 parts of calcined talc, 2 parts of zinc oxide, and 25 parts of crystalline frit by mass fraction. After mixing evenly, add 0.1 part of sodium carboxymethyl cellulose, 0.25 part of sodium tripolyphosphate, and 40 parts of water by mass fraction. After ball milling and sieving, a transparent antifouling glaze slurry is obtained. Dry, pulverize, and sieve the transparent antifouling glaze slurry to obtain transparent antifouling glaze powder. Among them, by mass percentage, the transparent antifouling glaze powder passes through a 100-mesh sieve, and the sieve residue is 0.2%. B3. Mix 10 parts of alloy dry granules, 90 parts of transparent antifouling glaze powder, and 200 parts of suspending agent evenly to obtain a silver-white metallic dry granule glaze.

[0069] The glaze surface effect diagram of the silver-white metallic texture ceramic tile obtained in Example 1 is as Figure 1 shown. It can be seen that its glaze surface can present a strong and uniform silver-white metallic texture effect under the condition of light.

[0070] Example 2 A. Prepare a ceramic blank, press the ceramic blank, and obtain a blank layer after drying. B. Apply the silver-white metallic dry granule glaze on the surface of the blank layer to obtain a silver-white metallic dry granule glaze layer. Among them, the glaze application amount of the silver-white metallic dry granule glaze is 470 g / m 3 , and the specific gravity is 1.45. C. After drying, calcine at a temperature of 1210 °C, and then obtain a silver-white metallic texture ceramic tile after polishing treatment. Among them, in step B, the preparation method of the silver-white metallic dry granule glaze is as follows: B1. Under a nitrogen atmosphere, completely melt 6.6 parts of silicon, 0.1 part of aluminum, 62.3 parts of iron, 27.5 parts of chromium, 2 parts of manganese, 0.2 part of vanadium, and 0.18 part of nickel by mass fraction at a temperature of 1150 °C, and obtain alloy droplets after liquid fragmentation. Cool the alloy droplets in a natural environment to obtain alloy dry granules. Among them, by mass percentage, the particle size distribution of the alloy dry granules is: the sieve residue of a 100-mesh sieve is 0.3%, the sieve residue of a 160-mesh sieve is 66.8%, the sieve residue of a 200-mesh sieve is 85.5%, the sieve residue of a 250-mesh sieve is 92.5%, and the sieve residue of a 325-mesh sieve is 97.8%. B2. Mix 16 parts by mass of quartz, 18 parts of calcined aluminum oxide, 32 parts of wollastonite, 19 parts of zinc oxide, 18 parts of strontium carbonate, and 3 parts of barium carbonate evenly, and obtain a crystalline frit after calcination, water quenching, grinding, and sieving. Among them, the calcination temperature curve of the crystalline frit is as follows: rising from room temperature to 300 °C takes 2 hours; rising from 300 °C to 1530 °C takes 3 hours; maintaining at 1530 °C for 0.8 hours. The particle size distribution of the crystalline frit is as follows: the residue on a 150-mesh sieve is 0.1%, the residue on a 180-mesh sieve is 50%, and the residue on a 200-mesh sieve is 78%. Mix 16 parts by mass of calcined kaolin, 6 parts of quartz, 25 parts of potassium feldspar, 8 parts of sodium feldspar, 12 parts of calcite, 15 parts of burnt talc, 2 parts of zinc oxide, and 25 parts of the crystalline frit evenly, then add 0.2 parts of sodium carboxymethyl cellulose, 0.2 parts of sodium tripolyphosphate, and 30 parts of water by mass, and obtain a transparent antifouling glaze slurry after ball milling and sieving. Dry, pulverize, and sieve the transparent antifouling glaze slurry to obtain transparent antifouling glaze powder. Among them, by mass percentage, the residue on a 100-mesh sieve of the transparent antifouling glaze powder is 0.2%. B3. Mix 7 parts of alloy dry particles, 92 parts of transparent antifouling glaze powder, and 180 parts of suspending agent evenly to obtain a silver-white metallic dry particle glaze.

[0071] Example 3 A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying. B. Apply the silver-white metallic dry particle glaze to the surface of the green body layer to obtain a silver-white metallic dry particle glaze layer. Among them, the glazing amount of the silver-white metallic dry particle glaze is 490 g / m 3 , and the specific gravity is 1.5. C. After drying, calcine at a temperature of 1200 °C, and then obtain a silver-white metallic texture ceramic tile after polishing. Among them, in step B, the preparation method of the silver-white metallic dry particle glaze is as follows: B1. Under an argon atmosphere, completely melt 7 parts by mass of silicon, 0.2 parts of aluminum, 64.2 parts of iron, 28.1 parts of chromium, 2.7 parts of manganese, 0.33 parts of vanadium, and 0.18 parts of nickel at a temperature of 1200 °C, and obtain alloy droplets after liquid fragmentation. Cool the alloy droplets in a natural environment to obtain alloy dry particles. Among them, by mass percentage, the particle size distribution of the alloy dry particles is as follows: the residue on a 100-mesh sieve is 0.3%, the residue on a 160-mesh sieve is 70%, the residue on a 200-mesh sieve is 85%, the residue on a 250-mesh sieve is 92%, and the residue on a 325-mesh sieve is 98%. B2. Mix 18 parts by mass of feldspar, 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 evenly, and obtain a crystalline frit after calcination, water quenching, grinding, and sieving; among them, the calcination temperature curve of the crystalline frit is: rising from room temperature to 300 °C, taking 2 h; rising from 300 °C to 1530 °C, taking 2 h; at 1530 °C, holding for 1.5 h; the particle size distribution of the crystalline frit is: the residue on a 150-mesh sieve is 0.5%, the residue on a 180-mesh sieve is 48%, and the residue on a 200-mesh sieve is 75%; Mix 12 parts of calcined kaolin, 8 parts of quartz, 25 parts of potassium feldspar, 12 parts of albite, 12 parts of calcite, 10 parts of burnt talc, 3 parts of zinc oxide, and 25 parts of crystalline frit evenly by mass, then add 0.2 parts of sodium carboxymethyl cellulose, 0.35 parts of sodium tripolyphosphate, and 35 parts of water by mass, and obtain a transparent antifouling glaze slurry after ball milling and sieving; Obtain transparent antifouling glaze powder after drying, pulverizing, and sieving the transparent antifouling glaze slurry; among them, by mass percentage, the residue on a 100-mesh sieve of the transparent antifouling glaze powder is 0.2%; B3. Mix 6 parts of alloy dry particles, 90 parts of transparent antifouling glaze powder, and 180 parts of suspending agent evenly to obtain a silver-white metallic dry particle glaze.

[0072] Comparative Example 1 The preparation method and raw materials of Comparative Example 1 are the same as those of Example 1, except that the alloy dry particles in Comparative Example 1 only include iron, chromium, and manganese, and do not add silicon, aluminum, vanadium, and nickel.

[0073] Comparative Example 2 The preparation method and raw materials of Comparative Example 2 are the same as those of Example 1, except that the crystalline frit is not added to the transparent antifouling glaze powder in Comparative Example 2.

[0074] Comparative Example 3 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 in Comparative Example 3.

[0075] Observe the surface effects of the silver-white metallic texture tiles prepared in the examples and comparative examples, and conduct conventional glossiness tests, hardness, and antifouling grade tests on the obtained silver-white metallic texture tiles in the field of building ceramics technology. The results are shown in Table 1 below: Table 1 Performance test results of the tiles in the examples and comparative examples

[0076] As can be seen from the performance test results in Table 1, the prepared silver-white metallic texture tiles can not only have excellent silver-white metallic texture effects, transparency, and stain resistance while ensuring uniform silver-white metallic texture effects, but also have high wear resistance and hardness, combining decoration and practicality, and are more conducive to meeting the usage requirements of consumers.

[0077] In Comparative Example 1, since the raw materials in the alloy dry granules only include iron, chromium, and manganese, and silicon, aluminum, vanadium, and nickel are not added, only the oxides formed by the oxidation of iron, chromium, and manganese in the air can be used as the composite oxide protective layer in the system. The structural compactness of this composite oxide protective layer is insufficient, and the anti-corrosion ability is limited. This not only results in limited metallic texture effects of the tiles obtained in Comparative Example 1 but also causes a certain degree of corrosion of the alloy dry granules, introducing impurity colors on the tile surface.

[0078] In Comparative Example 2, since crystalline frit is not added to the transparent stain-resistant glaze powder, the following effects will occur: (1) It is impossible to utilize the role of crystalline frit to inhibit the corrosion of alloy dry granules by alkali metal ions in the multi-component composite flux in Comparative Example 2, resulting in a reduction in the metallic texture effect of the tiles, and impurity colors existing in the obtained tiles. (2) The amounts of mullite crystals and anorthite crystals in the glaze surface after the calcination of the silver-white metallic dry granule glaze are reduced, leading to a decrease in the hardness and wear resistance of the tiles prepared in Comparative Example 2. (3) It is impossible to utilize the crystalline frit to improve the stain resistance performance, resulting in a decline in the stain resistance of the tiles. It should be noted that the crystalline frit simultaneously generates a high amount of anorthite crystals with high transparency and a low amount of mullite crystals with poor transparency, and the amount of the glass phase formed in the crystalline frit is not high, making the transparency of the crystalline frit relatively poor. Therefore, when crystalline frit is not added in Comparative Example 2, the transparency of the tiles obtained in Comparative Example 2 has a tendency to increase and has relatively high transparency.

[0079] 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 glazed glass phase generated after calcination is reduced, which not only reduces the degree to which the glazed glass phase increases the transparency of the tiles, but also reduces the encapsulation of the glazed glass relative to 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 calcium feldspar crystals generated in Comparative Example 3 is reduced and the calcium feldspar 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 metal 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.

[0080] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A method for preparing a silver-white metallic texture tile, characterized in that, It includes the following steps: A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying; B. Apply a silver-white metallic dry glaze on the surface of the green body layer to obtain a silver-white metallic dry glaze layer; C. After drying, calcine at a temperature of 1180 - 1210 °C, and then obtain a silver-white metallic texture ceramic tile after polishing; Among them, in step B, the preparation method of the silver-white metallic dry glaze is as follows: B1. Under an inert atmosphere, completely melt 6 - 7 parts by mass of silicon, 0.1 - 0.2 parts by mass of aluminum, 60 - 65 parts by mass of iron, 25 - 30 parts by mass of chromium, 2 - 3 parts by mass of manganese, 0.1 - 0.5 parts by mass of vanadium, and 0.1 - 0.2 parts by mass of nickel, and obtain alloy droplets after liquid fragmentation; Cool the alloy droplets in a natural environment to obtain alloy dry grains; B2. Mix 12 - 18 parts by mass of quartz, 15 - 20 parts by mass of calcined alumina, 30 - 38 parts by mass of wollastonite, 8 - 12 parts by mass of zinc oxide, 18 - 22 parts by mass of strontium carbonate, and 1 - 5 parts by mass of barium carbonate evenly, and obtain a crystalline frit after calcination, water quenching, grinding, and sieving; Mix 10 - 18 parts by mass of calcined kaolin, 4 - 8 parts by mass of quartz, 20 - 30 parts by mass of potassium feldspar, 8 - 15 parts by mass of sodium feldspar, 5 - 15 parts by mass of calcite, 5 - 10 parts by mass of burnt talc, 1 - 3 parts by mass of zinc oxide, and 20 - 30 parts by mass of the crystalline frit evenly, then add sodium carboxymethyl cellulose, water reducing agent, and water, and obtain a transparent antifouling glaze slurry after ball milling and sieving; Dry the transparent antifouling glaze slurry, pulverize it, and sieve it to obtain a transparent antifouling glaze powder; B3. Mix the alloy dry grains, the transparent antifouling glaze powder, and a suspending agent evenly to obtain a silver-white metallic dry glaze.

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

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

4. The preparation method of a silver-white metallic texture tile according to claim 1, characterized in that In step B2, the calcination temperature curve of the crystalline frit is as follows: Rise from room temperature to 300 °C, taking 1.5 - 3 h; Rise from 300 °C to 1530 °C, taking 2 - 3 h; At 1530 °C, keep the temperature for 0.5 - 1.5 h.

5. The preparation method of a silver-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 residue on a 150 - mesh sieve is 0.1 - 0.5%, the residue on a 180 - mesh sieve is 40 - 50%, and the residue on a 200 - mesh sieve is 70 - 80%.

6. The preparation method of a silver-white metallic texture tile according to claim 1, characterized in that, In step B2, after mixing 10 - 18 parts by mass of calcined kaolin, 4 - 8 parts by mass of quartz, 20 - 30 parts by mass of potassium feldspar, 8 - 15 parts by mass of sodium feldspar, 5 - 15 parts by mass of calcite, 5 - 10 parts by mass of burnt talc, 1 - 3 parts by mass of zinc oxide, and 20 - 30 parts by mass of the crystalline frit evenly, then add 0.1 - 0.3 parts by mass of sodium carboxymethyl cellulose, 0.15 - 0.35 parts by mass of water reducing agent, and 30 - 40 parts by mass of water according to the mass parts.

7. The preparation method of a silver-white metallic texture tile according to claim 1, characterized in that, In step B2, by mass percentage, the transparent antifouling glaze powder is screened through a 100-mesh sieve, and the sieve residue is 0.1-0.3%.

8. The preparation method of a silver-white metallic texture tile according to claim 1, characterized in that, In step B3, calculated by mass parts, the silver-white metallic dry granule glaze is composed of 6-10 parts of alloy dry granules, 90-94 parts of transparent antifouling glaze powder, and 180-200 parts of suspending agent.

9. The preparation method of a silver-white metallic texture tile according to claim 1, characterized in that, In step B, the application amount of the silver-white metallic dry granule glaze is 455-500 g / m 3 , and the specific gravity is 1.4-1.

5.

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

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