Silver white metal dry granular glaze as well as preparation method and application thereof

Abstract

The invention relates to the technical field of architectural ceramics, in particular to silvery white metal dry granular glaze and a preparation method and application thereof, and the preparation method comprises the following steps: A, in an inert atmosphere, completely melting silicon elementary substances, aluminum elementary substances, iron elementary substances, chromium elementary substances, manganese elementary substances, vanadium elementary substances and nickel elementary substances, and crushing to obtain alloy liquid drops; under the natural environment, the alloy liquid drops are cooled, and alloy dry particles are obtained; b, uniformly mixing kaolin, quartz, calcite, dolomite, barium carbonate and zinc oxide, calcining, water-quenching, ball-milling and sieving to obtain a crystalline frit; and C, uniformly mixing the alloy dry granules, the crystalline frit and the suspending agent to obtain the silvery white metal dry granular glaze. According to the preparation method of the silvery white metal dry granular glaze, on the premise of ensuring that the silvery white metal texture effect is uniform, the silvery white metal dry granular glaze not only has excellent silvery white metal texture effect, transparency and antifouling property, but also has relatively high wear resistance and hardness.

Description

Technical Field

[0001] The invention relates to the technical field of building ceramics, in particular to a silvery-white metallic dry granular glaze and a preparation method and application thereof. Background Art

[0002] Metallic glaze is a special glaze. When applied to the surface of the body and fired at high temperature, the surface of the ceramic tile can present a metallic texture effect, and it is widely used in the building decoration industry. Existing metallic glazes are mainly composed of metal dry particles and frits, but the frits usually need to be added with fluxes such as lithium oxide (Li2O), boron oxide (B2O3), potassium oxide (K2O) and sodium oxide (Na2O) to lower their melting temperature. However, the chemical activity of the above-mentioned fluxes is extremely high, and they will gradually dissolve the metal oxides on the surface of the metal dry particles, forming pores and microcracks on the surface. Subsequently, the flux penetrates into the interior of the metal dry particles through the pores and cracks, reacting with them, and eventually causing the metal dry particles to completely corrode and discolor, losing their original metallic texture effect.

[0003] To prevent corrosion and discoloration of the metal particles, existing frits typically use feldspathic frits with a low flux content and a high silicon and aluminum content. Kaolin and quartz are the primary aluminum and silicon sources for these feldspathic frits. However, due to the high melting point of quartz and the relatively insufficient flux content, the proportion of unmelted quartz remaining in the frit is relatively high. 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 easily lead to a strong light scattering effect, thereby reducing the transparency of the glaze. As the content of unmelted quartz increases, the light scattering phenomenon intensifies, further affecting the transparency of the glaze.

[0004] At the same time, due to the insufficient flux content in the system, the aluminum oxide generated by the decomposition of kaolin at high temperatures (>950°C) is difficult to completely melt, and it will exist in the form of 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) are both significantly different from the refractive index of the glass phase (about 1.50), further exacerbating light scattering and further reducing the transparency of the glaze. The reduced transparency will cover the original pattern of the tile 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.

[0005] 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.

[0006] In summary, existing metal glazes not only fail to simultaneously achieve excellent metallic texture effects, transparency, and anti-fouling performance, but also fail to ensure the uniformity of the metallic texture effects. Summary of the Invention

[0007] The first purpose of the present invention is to propose a preparation method of a silvery-white metallic dry particle glaze. The preparation method is simple and easy to operate. On the premise of ensuring a uniform silvery-white metallic texture effect, the method not only has excellent silvery-white metallic texture effect, transparency and anti-fouling performance, but also has high wear resistance and hardness, thereby overcoming the shortcomings of the existing technology.

[0008] The second purpose of the present invention is to provide a silvery-white metallic dry granular glaze, which, while ensuring a uniform silvery-white metallic texture effect, not only has excellent silvery-white metallic texture effect, transparency and anti-fouling performance, but also has high wear resistance and hardness, thereby making the silvery-white metallic dry granular glaze both decorative and practical.

[0009] The third purpose of the present invention is to propose an application of a silvery-white metallic dry granular glaze, which is used to prepare silvery-white metallic texture tiles, ensuring that the obtained silvery-white metallic texture tiles can not only have excellent silvery-white metallic texture effects, transparency and anti-fouling performance, but also have high wear resistance and hardness, while achieving a uniform silvery-white metallic texture effect, so that the silvery-white metallic texture tiles are both decorative and practical.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] A method for preparing a silvery-white metallic dry granular glaze comprises the following steps:

[0012] A. 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 crushed to obtain alloy droplets;

[0013] The alloy droplets are cooled in a natural environment to obtain dry alloy particles;

[0014] B. uniformly mixing 30-40 parts of kaolin, 28-35 parts of quartz, 18-25 parts of calcite, 3-10 parts of dolomite, 2-10 parts of barium carbonate and 3-8 parts of zinc oxide, calcining, water quenching, ball milling and sieving to obtain a crystalline frit;

[0015] Wherein, the calcination temperature curve of the crystalline frit is:

[0016] It takes 1.5 to 3 hours to heat from room temperature to 300°C;

[0017] From 300℃ to 1530℃, it takes 1.5 to 2.5 hours;

[0018] 1530℃, keep warm for 0.5~1h;

[0019] C. Evenly mix the alloy dry particles, crystalline frit and suspending agent to obtain a silvery-white metallic dry particle glaze.

[0020] Furthermore, in step A, 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.

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

[0022] Furthermore, in step A, the particle size distribution of the alloy dry particles is calculated by mass percentage as follows: 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 B, the calcination temperature curve of the crystalline frit is:

[0024] It takes 2 hours to heat from room temperature to 300℃;

[0025] From 300℃ to 1530℃, it takes 2.5h;

[0026] 1530℃, keep warm for 1h.

[0027] Furthermore, in step B, calculated by weight, the raw materials of the crystalline frit include 35 parts of kaolin, 30 parts of quartz, 21 parts of calcite, 5 parts of dolomite, 5 parts of barium carbonate and 5 parts of zinc oxide.

[0028] Furthermore, in step B, 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%.

[0029] Furthermore, in step C, the silvery-white metallic dry particle glaze is composed of 7 to 10 parts of alloy dry particles, 90 to 93 parts of crystalline frits and 180 to 200 parts of suspending agent, calculated by weight.

[0030] A silvery-white metallic dry granular glaze is prepared by the above-mentioned preparation method of the silvery-white metallic dry granular glaze.

[0031] A silvery-white metallic dry granular glaze is used in the preparation of silvery-white metallic textured ceramic tiles. The silvery-white metallic dry granular glaze is used in the following application method: applying the silvery-white metallic dry granular glaze on the surface of a green body layer to form a silvery-white metallic dry granular glaze layer, drying the green body layer, calcining the green body layer at a temperature of 1100-1250°C, and polishing the green body layer to obtain the silvery-white metallic textured ceramic tiles.

[0032] The technical solution provided by the present invention can have the following beneficial effects:

[0033] The degree of quartz melting depends on factors such as the calcination curve of the crystalline frit and the total content of the quaternary composite flux (calcium oxide, magnesium oxide, barium oxide, and zinc oxide). Calcination temperatures below the temperature at which quartz completely melts (approximately 1700°C), insufficient calcination time, and especially insufficient total quaternary composite flux content will result in incomplete quartz melting. Insufficient quaternary composite flux content significantly raises the eutectic point of the crystalline frit formulation, while insufficient calcination temperature and time fail to provide sufficient thermodynamic driving force and kinetic conditions for the transition from quartz to a glassy phase. These factors work together to ultimately influence the degree of quartz melting. Therefore, the present technical solution optimizes the calcination temperature curve of the crystalline frit (wherein the highest calcination temperature of the calcination temperature curve is 1530°C, which is lower than the melting point of quartz 1700°C) and combines the design of "quartz supersaturation-quaternary composite flux under-proportioning" in the crystalline frit to prevent the quartz in the crystalline frit from being completely melted, thereby causing the crystalline frit to contain unmelted quartz.

[0034] 2. Since current architectural ceramic production lines generally use a high-temperature rapid firing process of 1100-1250°C, and the green body and glaze are fired simultaneously, the firing temperature of the silver-white metallic dry granular glaze is also 1100-1250°C. When a crystalline frit containing three types of crystals, namely unmelted quartz, anorthite crystals, and cordierite crystals, is added to the silver-white metallic dry granular glaze, at the calcination temperature of 1100-1250°C of the silver-white metallic dry granular glaze, the anorthite crystals and cordierite crystals in the crystalline frit are basically insoluble. Although the unmelted quartz can be further partially melted, it is still difficult to melt completely, resulting in the silver-white metallic dry granular glaze still containing unmelted quartz. Therefore, after firing, the silvery-white metallic dry granule glaze contains three types of crystals: anorthite, cordierite, and quartz. These three crystals not only form a physical "armor" on the surface of the alloy dry granules, thereby directly blocking the directional migration of alkali metal ions from the quaternary composite flux into the alloy dry granules, but also the random distribution of these three crystals transforms the diffusion path of the alkali metal ions in the quaternary composite flux from a linear one to a three-dimensional zigzag pattern. This geometrically extends the diffusion path, strengthening the diffusion barrier and effectively inhibiting the corrosion of the alloy dry granules by the alkali metal ions in the quaternary composite flux. In other words, these three crystals inhibit the corrosion of the alloy dry granules by the alkali metal ions in the quaternary composite flux by physically blocking and extending the diffusion path, which is beneficial for maintaining the stability of the alloy dry granule performance.

[0035] 3. The glass phase in the crystalline frit completely enters the liquid molten state, and promotes the partial melting of the unmelted quartz particles through the melting effect. The molten glass phase and the melted quartz components penetrate each other and diffuse evenly at high temperature, eventually forming a continuous and dense glaze glass phase; the above-mentioned glaze glass phase significantly reduces the glaze porosity by wrapping the alloy dry particles and unmelted quartz, filling the grain boundary voids and strengthening the bonding of crystal particles, thereby blocking the stain penetration channel, and giving the silver-white metal dry particle glaze excellent anti-fouling properties. It should be noted that although the total content of the quaternary composite flux is not enough to completely melt the quartz, its total content can ensure that the amount of glaze glass phase generated is sufficient to achieve the multiple functions of alloy dry particle wrapping, grain boundary filling and particle bonding, and maintain its anti-fouling properties while ensuring the dense structure of the glaze. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a glaze effect diagram of a silvery-white metallic textured tile made using the silvery-white metallic dry granular glaze in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] The present invention provides a method for preparing a silvery-white metallic dry granular glaze, comprising the following steps:

[0038] A. 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 crushed to obtain alloy droplets;

[0039] The alloy droplets are cooled in a natural environment to obtain alloy dry particles;

[0040] B. uniformly mixing 30-40 parts of kaolin, 28-35 parts of quartz, 18-25 parts of calcite, 3-10 parts of dolomite, 2-10 parts of barium carbonate and 3-8 parts of zinc oxide, calcining, water quenching, ball milling and sieving to obtain a crystalline frit;

[0041] Wherein, the calcination temperature curve of the crystalline frit is:

[0042] It takes 1.5 to 3 hours to heat from room temperature to 300°C;

[0043] From 300℃ to 1530℃, it takes 1.5 to 2.5 hours;

[0044] 1530℃, keep warm for 0.5~1h;

[0045] C. Evenly mix the alloy dry particles, crystalline frit and suspending agent to obtain a silvery-white metallic dry particle glaze.

[0046] In order to overcome the technical defects of the existing technology, this technical solution proposes a preparation method of a silver-white metallic dry particle glaze. By optimizing the preparation method and raw materials, it is beneficial to ensure the uniformity of the silver-white metallic texture effect, while not only having excellent silver-white metallic texture effect, transparency and anti-fouling performance, but also having high wear resistance and hardness to meet actual usage needs.

[0047] Specifically, this technical solution uses silicon (silicon is a metalloid), aluminum, iron, chromium, manganese, vanadium, and nickel as raw materials. After melting and liquid fragmentation under an inert atmosphere to form alloy droplets, the 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 forms a composite oxide protective film containing components such as aluminum oxide, chromium oxide, and silicon dioxide, ultimately forming alloy dry particles with a "core-shell" structure, with the core being a multi-element alloy matrix mainly composed of iron, chromium, and manganese, and the shell being a composite oxide protective film. It should be noted that metalloids, also known as semimetals, have both metallic and non-metallic properties. In addition, the liquid fragmentation of this technical solution refers to the alloy melt obtained by melting silicon, aluminum, iron, chromium, manganese, vanadium, and nickel, which is accelerated by a high-pressure pump and passed through a microporous nozzle. The high-speed jet rubs with the air or hits the target plate to fragment the metal melt into alloy droplets.

[0048] 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.

[0049] 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 iron, whose solidus temperature exceeds the threshold of 1300°C, constructing a high-temperature resistant crystal skeleton; (2) Silicon and chromium form in situ intermetallic compounds such as chromium trisilicon (high-temperature phases), and the above-mentioned 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 of aluminum oxide-chromium oxide-silicon dioxide, and the melting point of the inner layer can reach 2000°C, which is beneficial to improving the high-temperature stability of the alloy dry particles; (4) The trace amount of vanadium 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.

[0050] Secondly, kaolin, quartz, calcite, dolomite, barium carbonate and zinc oxide are uniformly mixed and obtained after calcination, water quenching, ball milling and sieving. First, during the calcination of the crystalline frit, calcite (mainly composed of calcium carbonate) and dolomite (mainly composed of calcium magnesium carbonate double salt) are heated and decomposed to generate calcium oxide, dolomite is heated and can also decompose to generate magnesium oxide, and barium carbonate decomposes to generate barium oxide at high temperatures. Calcium oxide, magnesium oxide, barium oxide and the raw material zinc oxide in the crystalline frit cooperate with each other to form a quaternary composite flux of calcium oxide-magnesium oxide-barium oxide-zinc oxide. Because calcium ions, magnesium ions, barium ions and zinc ions are all low-polarizability ions, their radii are large and their polarizability is weak, resulting in high lattice energy and large bonding strength. Higher energy is required to destroy the flux network structure, making the initial melting point of the above-mentioned quaternary composite flux relatively high. Furthermore, a size-matching effect exists among the calcium, magnesium, barium, and zinc ions (e.g., the radius ratio of the barium ion to the zinc ion conforms to the Hume-Rothery rule), allowing the formation of a high-temperature finite solid solution. This solid solution disrupts the conditions for eutectic formation through atomic-level mutual dissolution, resulting in a quaternary composite flux with an onset melting point higher than that of a single flux. In other words, the quaternary composite flux in this technical solution, through these multiple effects, imparts a higher onset melting point to the crystalline frit.

[0051] Furthermore, kaolin decomposes at high temperature to produce aluminum oxide and silicon dioxide. Quartz can also provide silicon dioxide. Calcium oxide produced by thermal decomposition of calcite and dolomite reacts with aluminum oxide and silicon dioxide in the formula system to form anorthite crystals (CaAl2Si2O8). At the same time, magnesium oxide produced by thermal decomposition of calcite and dolomite reacts with aluminum oxide and silicon dioxide in the formula system to form cordierite crystals (Mg2Al2Si2O8). 18 ).

[0052] The degree of quartz melting is also related to factors such as the calcination curve of the crystalline frit and the total content of the quaternary composite flux (calcium oxide, magnesium oxide, barium oxide, and zinc oxide). Calcination temperatures below the temperature at which quartz completely melts (approximately 1700°C), insufficient calcination time, and, particularly, insufficient total quaternary composite flux content, will result in incomplete quartz melting. Insufficient quaternary composite flux content significantly raises the eutectic point of the crystalline frit formulation, while insufficient calcination temperature and time fail to provide sufficient thermodynamic driving force and kinetic conditions for the transition from quartz to a glassy phase. These factors, combined, ultimately influence the degree of quartz melting. Therefore, the present technical solution optimizes the calcination temperature curve of the crystalline frit (wherein the highest calcination temperature of the calcination temperature curve is 1530°C, which is lower than the melting point of quartz 1700°C) and combines the design of "quartz supersaturation-quaternary composite flux under-proportioning" in the crystalline frit to prevent the quartz in the crystalline frit from being completely melted, thereby causing the crystalline frit to contain unmelted quartz.

[0053] In summary, the crystalline frit of the present technical solution includes three types of crystals: anorthite crystals, cordierite crystals and unmelted quartz. The melting point of anorthite crystals is 1553°C, the melting point of cordierite crystals is 1760°C, and the melting point of quartz is 1700°C. The above three crystals make the crystalline frit have a higher melting point.

[0054] Therefore, the technical solution improves the initial melting temperature of the crystalline frit through the cooperation of the above-mentioned multiple effects, thereby improving the melting threshold of the silver-white metal dry particle glaze as a whole, and significantly shortening the contact time between the quaternary composite flux (i.e., flux) and the alloy dry particles during the high-temperature firing stage, thereby effectively inhibiting the corrosion of the flux on the alloy dry particles, which is beneficial to maintaining the stability of the performance of the alloy dry particles.

[0055] Furthermore, because current architectural ceramic production lines generally use a high-temperature rapid firing process of 1100-1250°C, and the green body and glaze are fired simultaneously, the firing temperature of the silvery-white metallic dry granular glaze is also 1100-1250°C. When a crystalline frit containing three types of crystals, namely unmelted quartz, anorthite crystals, and cordierite crystals, is added to the silvery-white metallic dry granular glaze, at the calcination temperature of 1100-1250°C of the silvery-white metallic dry granular glaze, the anorthite crystals and cordierite crystals in the crystalline frit are essentially insoluble. While the unmelted quartz can further melt partially, it is still difficult to melt completely, resulting in the silvery-white metallic dry granular glaze still containing unmelted quartz. Therefore, after firing, the silvery-white metallic dry granule glaze contains three types of crystals: anorthite, cordierite, and quartz. These three crystals not only form a physical "armor" on the surface of the alloy dry granules, thereby directly blocking the directional migration of alkali metal ions from the quaternary composite flux into the alloy dry granules, but also the random distribution of these three crystals transforms the diffusion path of the alkali metal ions in the quaternary composite flux from a linear one to a three-dimensional zigzag pattern. This geometrically extends the diffusion path, strengthening the diffusion barrier and effectively inhibiting the corrosion of the alloy dry granules by the alkali metal ions in the quaternary composite flux. In other words, these three crystals inhibit the corrosion of the alloy dry granules by the alkali metal ions in the quaternary composite flux by physically blocking and extending the diffusion path, which is beneficial for maintaining the stability of the alloy dry granule performance.

[0056] In summary, the present 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 blank, it only needs to be polished 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.

[0057] 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, cordierite crystals and unmelted quartz, and the above three crystals have high hardness and wear resistance, the silvery-white metallic dry granular glaze has high hardness and wear resistance.

[0058] Furthermore, the quartz in the crystalline frit not only participates in the formation of anorthite and cordierite crystals, while some quartz remains unmelted, but also forms a silicate glass network with the quaternary composite flux and the decomposition products of kaolin, forming the glass phase of the crystalline frit. When the crystalline frit is introduced into the silvery-white metallic dry granular glaze system, within the calcination temperature range of 1100-1250°C, the high-melting-point anorthite crystals (melting point 1553°C) and cordierite crystals (melting point 1760°C) in the crystalline frit maintain a stable rigid skeleton structure. At this point, the glass phase within the crystalline frit fully enters a liquid, molten state, and through dissolution, it promotes the partial melting of unmelted quartz particles. At high temperatures, the molten glass phase and the melted quartz components interpenetrate and diffuse evenly, ultimately forming a continuous, dense glaze glass phase. This glaze glass phase significantly reduces the glaze porosity by encapsulating the alloy dry particles and unmelted quartz, filling grain boundary voids, and strengthening the bonding of crystal particles, thereby blocking the channels for stain penetration and imparting excellent anti-fouling properties to the silvery-white metallic dry particle glaze. It should be noted that although the total content of the quaternary composite flux is insufficient to completely melt the quartz, its total content ensures that the amount of glaze glass phase generated is sufficient to achieve the multiple functions of alloy dry particle encapsulation, grain boundary filling, and particle bonding, maintaining its anti-fouling properties while ensuring a dense glaze structure.

[0059] Furthermore, the anorthite crystals produced by this technical solution are triclinic, dense, and have a refractive index close to that of the glass phase, resulting in no significant light scattering centers and extremely high transparency. Therefore, this technical solution, by regulating the addition amounts of kaolin, calcite, and dolomite to the crystalline frit, induces the production of a high content of anorthite crystals, imparting high transparency to the crystalline frit. Adding this crystalline frit to a silvery-white metallic dry granular glaze can help improve the transparency of the silvery-white metallic dry granular glaze.

[0060] In addition, the raw material zinc oxide in the crystalline frit can not only act as a flux, but also as a crystal nucleation agent, reducing the crystallization activation energy and crystallization peak temperature, which is beneficial to the crystallization of calcium feldspar crystals, thereby further improving the transparency of the silvery-white metallic dry granular glaze.

[0061] Therefore, through the above two effects, this technical solution makes the glaze surface obtained by calcining the silvery-white metallic dry granular glaze have a high transparency. It should be noted that although the glaze surface obtained by calcining the silvery-white metallic dry granular glaze in this technical solution contains unfused quartz with low transparency, the amount of unfused quartz is limited and is not sufficient to affect the transparency of the glaze surface, so the glaze surface still has a high transparency.

[0062] Furthermore, due to the significant content of anorthite crystals in the calcined crystalline frit, when this high-anorthite content is introduced into the silvery-white metallic dry granular glaze system, the anorthite crystals form a rigid skeleton uniformly distributed throughout the glaze layer. This skeleton structure physically constrains the glass phase's high-temperature softening rate, effectively slowing the fluidity of the silvery-white metallic dry granular glaze during high-temperature firing, thereby broadening the calcination temperature range of the silvery-white metallic dry granular glaze.

[0063] Finally, 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 silver-white metallic dry particle glaze, thereby making the silver-white metallic dry particle glaze have a glaze surface with a high uniformity of metallic texture effect.

[0064] 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.

[0065] Further explanation, in step A, calculated by mass, 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.

[0066] 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.

[0067] Further description, in step A, the melting temperature of the melting is 1100-1200°C.

[0068] By limiting the melting temperature, silicon, aluminum, iron, chromium, manganese, vanadium, and nickel are completely melted and intermixed, thereby ensuring the properties of the final 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 can trigger a low-melting-point eutectic reaction, allowing them to completely melt and achieve compositional homogenization at a temperature 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.

[0069] Further explanation, in step A, calculated according to mass percentage, the particle size distribution of the alloy dry particles is: 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%.

[0070] 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.

[0071] Calculated by mass percentage, the particle size distribution of the alloy dry particles is as follows: 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%.

[0072] Further explanation, in step B, the calcination temperature curve of the crystalline frit is:

[0073] It takes 2 hours to heat from room temperature to 300℃;

[0074] From 300℃ to 1530℃, it takes 2.5h;

[0075] 1530℃, keep warm for 1h.

[0076] This technical solution further optimizes the calcination temperature curve of the crystalline frit, so that the calcination temperature curve reaches the optimal value, which is conducive to ensuring that the performance of the crystalline frit reaches the best.

[0077] Further explanation, in step B, calculated by weight, the raw materials of the crystalline frit include 35 parts of kaolin, 30 parts of quartz, 21 parts of calcite, 5 parts of dolomite, 5 parts of barium carbonate and 5 parts of zinc oxide.

[0078] By further optimizing the ratio of the raw materials of the crystalline frit, it is more conducive to ensuring the performance of the silvery-white metallic dry granular glaze.

[0079] Further, in step B, 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 silvery-white metallic dry particle glaze obtained by mixing the crystalline frit with the suspending agent and the alloy dry particles have higher fluidity, ensuring the smoothness of the glaze surface obtained after the silvery-white metallic dry particle glaze is calcined, but also the crystalline frit can be fully melted during the calcination process of the silvery-white metallic dry particle glaze, thereby making the glaze surface obtained after the silvery-white metallic dry particle glaze calcined have a higher density, which is beneficial to improving the anti-fouling performance.

[0081] Further description, in step C, calculated by weight, the silvery-white metallic dry particle glaze is composed of 7 to 10 parts of alloy dry particles, 90 to 93 parts of crystalline frits and 180 to 200 parts of suspending agent.

[0082] 7-10 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; 90-93 parts of crystalline frit, as the base glass phase, not only fully encapsulates the dry alloy particles to form a stable bond, but also maintains sufficient fluidity to achieve 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, this technical solution, by limiting the addition amounts of dry alloy particles, crystalline frit, and suspending agent, is conducive to achieving optimal product performance, thereby improving product quality and stability.

[0083] Preferably, in step C, the silvery-white metallic dry particle glaze is composed of 10 parts of alloy dry particles, 90 parts of crystalline frits and 200 parts of suspending agent, calculated by weight.

[0084] By further limiting the addition amounts of alloy dry particles, crystalline frits and suspending agents, the performance of the silvery-white metallic dry particle glaze is optimized, thereby improving the quality and stability of the product.

[0085] A silvery-white metallic dry granular glaze is prepared by the above-mentioned method for preparing the silvery-white metallic dry granular glaze.

[0086] This proposal also proposes a silver-white metallic dry particle glaze, 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, so as to overcome the shortcomings of the existing technology.

[0087] A silvery-white metallic dry granular glaze is used in the preparation of silvery-white metallic textured ceramic tiles. The silvery-white metallic dry granular glaze is used in the following application method: applying the silvery-white metallic dry granular glaze on the surface of a green body layer to form a silvery-white metallic dry granular glaze layer, drying the green body layer, calcining the green body layer at a temperature of 1100-1250°C, and polishing the green body layer to obtain the silvery-white metallic textured ceramic tiles.

[0088] This technical solution also proposes the application of a silvery-white metallic dry granular glaze, which is used to prepare silvery-white metallic texture tiles, ensuring that the obtained silvery-white metallic texture tiles can not only have excellent silvery-white metallic texture effects, transparency and anti-fouling properties, but also have high wear resistance and hardness, while achieving a uniform silvery-white metallic texture effect. This allows the silvery-white metallic texture tiles to be both decorative and practical. It should be noted that the green body layer in this solution is formed by pressing and drying conventional ceramic green bodies in the ceramic field, 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, and it is not further described here.

[0089] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0090] 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.

[0091] Example 1

[0092] A. 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, are completely melted at a temperature of 1100 to 1200° C., and the liquid is crushed to obtain alloy droplets; the alloy droplets are cooled under a natural environment to obtain alloy dry particles; wherein, the particle size distribution of the alloy dry particles, calculated by weight percentage, is as follows: the sieve residue on a 100-mesh sieve is 0.1%, the sieve residue on a 160-mesh sieve is 70%, the sieve residue on a 200-mesh sieve is 86.2%, the sieve residue on a 250-mesh sieve is 92.6%, and the sieve residue on a 325-mesh sieve is 98%;

[0093] B. 35 parts of kaolin, 30 parts of quartz, 21 parts of calcite, 5 parts of dolomite, 5 parts of barium carbonate, and 5 parts of zinc oxide, calculated by weight, were uniformly mixed, calcined, water-quenched, ball-milled, and sieved to obtain a crystalline frit; wherein the calcination temperature curve of the crystalline frit was as follows: from room temperature to 300° C., taking 2 hours; from 300° C. to 1530° C., taking 2.5 hours; and holding at 1530° C. for 1 hour; the particle size distribution of the crystalline frit was as follows: the sieve residue on a 150-mesh sieve was 0.3%, the sieve residue on a 180-mesh sieve was 44.6%, and the sieve residue on a 200-mesh sieve was 75.3%;

[0094] C. Evenly mix the silvery-white metallic dry particle glaze, which includes 10 parts of alloy dry particles, 90 parts of crystalline frits and 200 parts of suspending agent, calculated by weight, to obtain the silvery-white metallic dry particle glaze.

[0095] The silvery white metallic dry granular glaze obtained in Example 1 is applied on the surface of the green body layer to form a silvery white metallic dry granular glaze layer, which is then dried and calcined at 1180°C, and then fully polished to obtain a silvery white metallic textured tile. The glaze effect is shown in the figure below. Figure 1 As shown. Figure 1 It can be seen that its glaze can present a strong and uniform silver-white metallic texture effect under lighting conditions.

[0096] Example 2

[0097] A. 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, are completely melted at a temperature of 1150° C., and the liquid is crushed to obtain alloy droplets; the alloy droplets are cooled under a natural environment to obtain alloy dry particles; wherein, the particle size distribution of the alloy dry particles, calculated by weight percentage, is as follows: the sieve residue on a 100-mesh sieve is 0.3%, the sieve residue on a 160-mesh sieve is 66.8%, the sieve residue on a 200-mesh sieve is 85.5%, the sieve residue on a 250-mesh sieve is 92.5%, and the sieve residue on a 325-mesh sieve is 97.8%;

[0098] B. 35 parts of kaolin, 30 parts of quartz, 22 parts of calcite, 5 parts of dolomite, 6 parts of barium carbonate, and 5 parts of zinc oxide, calculated by weight, were uniformly mixed, calcined, water-quenched, ball-milled, and sieved to obtain a crystalline frit; wherein the calcination temperature curve of the crystalline frit was as follows: from room temperature to 300° C., taking 2 hours; from 300° C. to 1530° C., taking 1.8 hours; and holding at 1530° C. for 0.8 hours; the particle size distribution of the crystalline frit was as follows: the sieve residue on a 150-mesh sieve was 0.3%, the sieve residue on a 180-mesh sieve was 48.2%, and the sieve residue on a 200-mesh sieve was 73.5%;

[0099] C. Evenly mix 8 parts of alloy dry particles, 93 parts of crystalline frits and 180 parts of suspending agent calculated by mass to obtain a silvery white metallic dry particle glaze.

[0100] Example 3

[0101] A. Under an argon atmosphere, 7 parts 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, calculated by weight, are completely melted at a temperature of 1200° C., and the liquid is crushed to obtain alloy droplets; the alloy droplets are cooled under a natural environment to obtain alloy dry particles; wherein, the particle size distribution of the alloy dry particles, calculated by weight percentage, is as follows: the sieve residue on a 100-mesh sieve is 0.3%, the sieve residue on a 160-mesh sieve is 70%, the sieve residue on a 200-mesh sieve is 85%, the sieve residue on a 250-mesh sieve is 92%, and the sieve residue on a 325-mesh sieve is 98%;

[0102] B. 35 parts of kaolin, 32 parts of quartz, 21 parts of calcite, 8 parts of dolomite, 6 parts of barium carbonate, and 5 parts of zinc oxide, calculated by weight, were uniformly mixed, calcined, water-quenched, ball-milled, and sieved to obtain a crystalline frit; wherein the calcination temperature curve of the crystalline frit was as follows: from room temperature to 300° C., taking 3 hours; from 300° C. to 1530° C., taking 1.5 hours; and holding at 1530° C. for 1 hour; the particle size distribution of the crystalline frit was as follows: the sieve residue on a 150-mesh sieve was 0.3%, the sieve residue on a 180-mesh sieve was 45.8%, and the sieve residue on a 200-mesh sieve was 75.4%;

[0103] C. Evenly mix 8 parts of alloy dry particles, 92 parts of crystalline frits and 190 parts of suspending agent calculated by mass to obtain a silvery white metallic dry particle glaze.

[0104] Comparative Example 1

[0105] The preparation method and raw materials of Comparative Example 1 are the same as those of Example 1, except that the raw materials in the alloy dry particles of Comparative Example 1 only include iron, chromium and manganese, and no silicon, aluminum, vanadium and nickel are added.

[0106] Comparative Example 2

[0107] The preparation method and raw materials of Comparative Example 2 are the same as those of Example 1, except that quartz is not added to the crystalline frit of Comparative Example 2.

[0108] Comparative Example 3

[0109] 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 crystalline frit of Comparative Example 3.

[0110] Comparative Example 4

[0111] The preparation method and raw materials of Comparative Example 4 are the same as those of Example 1, except that dolomite is not added to the crystalline frit of Comparative Example 4.

[0112] The silvery-white metallic dry granular glaze prepared in the examples and comparative examples was applied to the surface of the green body layer to form a silvery-white metallic dry granular glaze layer. After drying, the glaze layer was calcined at 1180°C and then fully polished to obtain a silvery-white metallic textured ceramic tile. The surface effects of the silvery-white metallic dry granular glazes prepared in the examples and comparative examples were observed, and the obtained silvery-white metallic textured ceramic tiles were subjected to conventional gloss, hardness, and anti-fouling tests in the field of architectural ceramics. The results are shown in Table 1 below:

[0113] Table 1 Performance test results of tiles of embodiment and comparative example

[0114]

[0115] It can be seen from the performance test results in Table 1 that the silver-white metallic texture tiles made from the silver-white metallic dry granular glaze of the present technical solution not only have excellent silver-white metallic texture effects, transparency and anti-fouling performance, but also have high wear resistance and hardness, while ensuring uniform silver-white metallic texture effects, and are both decorative and practical, which is more conducive to meeting the use needs of consumers.

[0116] 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.

[0117] In Comparative Example 2, because quartz was not added to the crystalline frit, the unfused quartz could not be used to inhibit the corrosion of the alloy dry particles by the alkali metal ions in the quaternary composite flux. This reduced the metallic texture of the tile and resulted in the presence of impurities. Furthermore, the lack of quartz in the crystalline frit in Comparative Example 2 also resulted in the absence of unfused quartz on the glaze surface after firing of the silvery-white metallic dry particle glaze. This prevented the unfused quartz from increasing the hardness and wear resistance, resulting in reduced hardness and wear resistance of the tile produced in Comparative Example 2.

[0118] Since no calcite is added to the crystalline frit in Comparative Example 3, the following effects will occur: (1) the amount of anorthite crystals precipitated during calcination of the silvery-white metallic dry granular glaze is reduced, and the characteristic of anorthite 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 quaternary composite flux in the silvery-white metallic dry granular glaze is reduced, and the amount of glass phase generated after calcination is reduced, and it is difficult for the glass phase to completely wrap the unmelted quartz, anorthite crystals and cordierite crystals, resulting in pores between the unmelted quartz, anorthite crystals and cordierite crystals, resulting in a decrease in the anti-fouling performance of the glaze; (3) the amount of anorthite 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 quaternary composite flux, the total content of the quaternary 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.

[0119] Since no dolomite is added to the crystalline frit in Comparative Example 4, the following effects will occur: (1) the amount of anorthite crystals and cordierite crystals precipitated during calcination of the silvery-white metallic dry granular glaze is reduced, and the characteristics of anorthite crystals and cordierite crystals in increasing hardness and wear resistance cannot be utilized, thereby reducing the hardness and wear resistance of the tiles obtained using Comparative Examples 3 and 4; (2) the total content of the quaternary composite flux in the silvery-white metallic dry granular glaze is reduced, and the amount of the glass phase generated after calcination is reduced. It is difficult for the glass phase to completely wrap the unmelted quartz and anorthite crystals, resulting in pores between the unmelted quartz and anorthite crystals, resulting in a decrease in the anti-fouling performance of the glaze; (3) the amount of anorthite 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 and cordierite crystals generated in Comparative Example 4 is reduced, and the anorthite crystals and cordierite crystals cannot play the role of inhibiting the corrosion of the alloy dry particles by the alkali metal ions in the quaternary composite flux, the total content of the quaternary 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.

[0120] 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 a silvery-white metallic dry granular glaze, characterized in that: The following steps are involved: A. 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 crushed to obtain alloy droplets; The alloy droplets are cooled in a natural environment to obtain dry alloy particles; B. uniformly mixing 30-40 parts of kaolin, 28-35 parts of quartz, 18-25 parts of calcite, 3-10 parts of dolomite, 2-10 parts of barium carbonate and 3-8 parts of zinc oxide, calcining, water quenching, ball milling and sieving to obtain a crystalline frit; Wherein, 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 1.5 to 2.5 hours; 1530℃, keep warm for 0.5~1h; C. Evenly mix the alloy dry particles, crystalline frit and suspending agent to obtain a silvery-white metallic dry particle glaze.

2. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step A, 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, calculated by weight.

3. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step A, the melting temperature is 1100-1200°C.

4. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step A, the particle size distribution of the alloy dry particles is calculated by mass percentage as follows: 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%.

5. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step B, the calcination temperature curve of the crystalline frit is: It takes 2 hours to heat from room temperature to 300℃; From 300℃ to 1530℃, it takes 2.5h; 1530℃, keep warm for 1h.

6. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step B, the raw materials of the crystalline frit include 35 parts of kaolin, 30 parts of quartz, 21 parts of calcite, 5 parts of dolomite, 5 parts of barium carbonate and 5 parts of zinc oxide, calculated by weight.

7. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step B, 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%.

8. The method for preparing a silvery-white metallic dry granular glaze according to claim 1, characterized in that: In step C, the silvery-white metallic dry particle glaze is composed of 7 to 10 parts of alloy dry particles, 90 to 93 parts of crystalline frits and 180 to 200 parts of suspending agent, calculated by weight.

9. A silvery white metallic dry granular glaze, characterized in that: The silvery-white metallic dry particle glaze is prepared by the preparation method of any one of claims 1 to 8.

10. Application of a silvery-white metallic dry granular glaze in preparing silvery-white metallic texture tiles, characterized in that: The silvery-white metallic dry granular glaze as described in claim 9 is used in the following application method: applying the silvery-white metallic dry granular glaze on the surface of the green body layer to form a silvery-white metallic dry granular glaze layer, drying and calcining at a temperature of 1100-1250° C., and then polishing to obtain silvery-white metallic textured tiles.

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