Golden yellow 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 golden yellow metal dry granular glaze and a preparation method and application thereof.The preparation method comprises the following steps that A, under the inert atmosphere, copper simple substances, aluminum simple substances, zinc simple substances, tin simple substances, chromium simple substances and terbium simple substances are completely molten, and copper alloy liquid drops are obtained after liquid breaking; cooling the copper alloy liquid drops in a natural environment to obtain copper alloy dry particles; b, uniformly mixing kaolin, quartz, calcite, dolomite, barium carbonate and zinc oxide, calcining, quenching with water, grinding and sieving to obtain a crystalline frit; and C, uniformly mixing the copper alloy dry granules, the crystalline frit and the suspending agent to obtain the golden yellow metal dry granular glaze. The preparation method of the golden yellow metal dry granular glaze is high in operability, and on the premise that the golden yellow metal texture effect is uniform, the golden yellow metal dry granular glaze can have the excellent golden yellow metal texture effect, transparency and antifouling performance at the same time and also has high abrasion resistance and hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of architectural ceramics, and particularly to a golden metallic dry granule glaze, its preparation method and application. Background Art

[0002] Metal glazes are a special type of glaze. When metal glazes are applied to the surface of a green body and fired at high temperature, they can give the surface of the ceramic tile a metallic texture effect and are widely used in the architectural decoration industry. Existing metal glazes mainly consist of metal dry granules 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 they will gradually dissolve the metal oxides on the surface of the metal dry granules, forming pores and microcracks on their surface. Subsequently, the fluxes penetrate into the interior of the metal dry granules through the pores and cracks and react with them, ultimately resulting in the complete corrosion and discoloration of the metal dry granules, losing their original metallic texture effect.

[0003] In order to prevent the metal dry granules from being corroded and discolored, existing frits usually adopt feldspathic frits with a relatively low flux content and a relatively high silicon-aluminum content, and this feldspathic frit uses 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. The refractive index of unmolten quartz (about 1.65) is significantly different from that of 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.

[0004] At the same time, due to the insufficient content of fluxes in the system, the aluminum oxide generated by the decomposition of kaolin at high temperature (>950 °C) is difficult to be completely melted and will exist in the form of inert α-Al2O3 and mullite crystals. The refractive indices of inert α-Al2O3 (corundum phase, refractive index 1.76) and mullite crystals (refractive index 1.64) are both quite different from that of the glass phase (about 1.50), further intensifying the light scattering and thus further reducing the transparency of the glaze surface. The reduction in transparency will cover the original pattern of the ceramic tile decorative layer and affect the overall decorative effect of the ceramic tile. In addition, due to the serious shortage of fluxes in the feldspathic frit, the amount of glass phase generated in the feldspathic frit is seriously insufficient, and the generated 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, and causing a relatively high porosity of the glaze surface after calcination of the metal glaze containing the feldspathic frit, and pollutants are easily infiltrated, and the antifouling performance is poor.

[0005] 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 calcining the metal glaze added with feldspathic frit has high stain resistance without affecting the pattern effect of the original decorative layer of the ceramic tile. The prior art attempts to add a relatively large amount of transparent glaze to the metal glaze formula. However, due to the relatively large addition amount of transparent glaze, the content of the flux in the formula is also relatively large, making the metal dry particles easily completely corroded and losing their original metallic texture effect. In addition, since transparent glaze generally contains a certain amount of moisture, the metal glaze obtained by compounding metal dry particles, feldspathic frit and transparent glaze also contains moisture. 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.

[0006] In summary, the existing metal glazes 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

[0007] The first object of the present invention is to provide a method for preparing a golden metallic dry particle glaze, which has a simple preparation method and strong operability. On the premise of ensuring the uniformity of the golden metallic texture effect, it can not only simultaneously have excellent golden metallic texture effect, transparency and stain resistance, but also have high wear resistance and hardness, so as to overcome the deficiencies of the prior art.

[0008] The second object of the present invention is to provide a golden metallic dry particle glaze, which on the premise of ensuring the uniformity of the golden metallic texture effect, can not only simultaneously have excellent golden metallic texture effect, transparency and stain resistance, but also have high wear resistance and hardness, so that the golden metallic dry particle glaze combines decoration and practicality.

[0009] The third object of the present invention is to provide an application of a golden metallic dry particle glaze, which is applied to the preparation of golden metallic texture ceramic tiles. On the premise of ensuring the uniformity of the golden metallic texture effect, the obtained golden metallic texture ceramic tiles can not only simultaneously have excellent golden metallic texture effect, transparency and stain resistance, but also have high wear resistance and hardness, so that the golden metallic texture ceramic tiles combine decoration and practicality.

[0010] To achieve this purpose, the present invention adopts the following technical solutions: A method for preparing a golden metallic dry particle glaze, comprising the following steps: A. Under an inert atmosphere, 95-97 parts of copper, 3-5 parts of aluminum, 0.1-0.2 parts of zinc, 0.02-0.05 parts of tin, 0.001-0.004 parts of chromium and 0.1-0.2 parts of terbium are completely melted by weight, and the liquid is crushed to obtain copper alloy droplets; The copper alloy droplets are cooled under natural conditions to obtain copper alloy dry particles; B. 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 are mixed uniformly by mass, and calcined, water-quenched, ground and sieved to obtain a crystalline frit; Wherein, the calcination temperature curve of the crystalline frit is: It takes 1.5 to 3 hours to rise from room temperature to 300°C; From 300℃ to 1530℃, it takes 1.5 to 2.5h; 1530℃, keep warm for 0.5~1h; C. Evenly mix the copper alloy dry particles, crystalline frit and suspending agent to obtain golden yellow metal dry particle glaze.

[0011] Furthermore, in step A, calculated by weight, the raw materials of the copper alloy dry particles include 95.32 parts of copper, 4.37 parts of aluminum, 0.159 parts of zinc, 0.025 parts of tin, 0.0032 parts of chromium and 0.12 parts of terbium.

[0012] Furthermore, in step A, the melting temperature of the melting is 1000-1100°C.

[0013] Furthermore, in step A, the particle gradation of the copper alloy dry particles is calculated by mass percentage as follows: the residue on the 100-mesh sieve is 0.1-0.5%, the residue on the 160-mesh sieve is 45-55%, the residue on the 200-mesh sieve is 75-85%, the residue on the 250-mesh sieve is 95-98%, and the residue on the 325-mesh sieve is 99-100%.

[0014] Furthermore, in step B, the calcination temperature curve of the crystalline frit is: It takes 2h to rise from room temperature to 300℃; From 300℃ to 1530℃, it takes 2.5h; 1530℃, keep warm for 1h.

[0015] 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.

[0016] Further, in step B, 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%.

[0017] Further, in step C, calculated by mass parts, the golden metallic dry granule glaze is composed of 6-10 parts of copper alloy dry granules, 90-94 parts of crystalline frit, and 180-200 parts of suspending agent.

[0018] A golden metallic dry granule glaze is prepared by the preparation method of the above-mentioned golden metallic dry granule glaze.

[0019] An application of the golden metallic dry granule glaze in the preparation of golden metallic texture tiles, using the above-mentioned golden metallic dry granule glaze, and the application method is as follows: the golden metallic dry granule glaze is applied on the surface of the green body layer to form a golden metallic dry granule glaze layer, dried and then calcined at a temperature of 1100-1250°C, and then polished to obtain golden metallic texture tiles.

[0020] The technical solution provided by the present invention may include the following beneficial effects: 1. This technical solution uses copper, aluminum, zinc, tin, chromium, and terbium as raw materials. After melting and liquid fragmentation in an inert atmosphere to form copper alloy droplets, copper alloy dry granules are prepared by natural cooling. During the natural cooling process, the surface of the copper alloy droplets exposed to air reacts with oxygen, and a composite oxide protective film containing components such as aluminum oxide, chromium oxide, and zinc oxide is formed. Eventually, copper alloy dry granules with a "core-shell" structure are formed, with the inner core being a multi-element alloy matrix mainly composed of copper (containing aluminum, zinc, tin, chromium, and terbium), and the outer shell being a composite oxide protective film. It should be noted that the liquid fragmentation in this technical solution refers to that the alloy melt obtained by melting copper, aluminum, zinc, tin, chromium, and terbium is accelerated by a high-pressure pump and then passes through a microporous nozzle, and the high-speed jet rubs against the air or impacts the target plate to break the metal melt into copper alloy droplets.

[0021] 2. When the crystalline frit containing the three crystals of unmelted quartz, anorthite crystals and cordierite crystals is added to the golden metal dry particle glaze, at the calcination temperature of 1100-1250°C of the golden metal dry particle glaze, the anorthite crystals and cordierite crystals in the crystalline frit are basically insoluble, and although the unmelted quartz can be further partially melted, it is still difficult to melt completely, so that the golden metal dry particle glaze can still contain unmelted quartz. Therefore, the glaze surface of the golden metal dry particle glaze after calcination contains the three crystals of anorthite crystals, cordierite crystals and quartz. The above three crystals can not only form a physical "armor" on the surface of the copper alloy dry particles, thereby directly blocking the directional migration of the alkali metal ions of the quaternary composite flux to the copper alloy dry particles, but also the random distribution of the above three crystals transforms the diffusion path of the alkali metal ions in the quaternary composite flux from linear to three-dimensional serrated, and the diffusion barrier is strengthened by extending the geometric path, which effectively inhibits the corrosion of the alkali metal ions in the quaternary composite flux to the copper alloy dry particles. That is, the above three crystals inhibit the corrosion of the copper alloy dry particles by the alkali metal ions in the quaternary composite flux by means of physical barrier and extended diffusion path, which is beneficial to maintain the stability of the performance of the copper alloy dry particles.

[0022] 3. The glass phase in the crystalline frit completely enters the liquid molten state, and the unmelted quartz particles are partially melted through the melting effect. The molten glass phase and the melted quartz components penetrate and diffuse uniformly at high temperature, and finally form a continuous and dense glaze glass phase; the glaze glass phase significantly reduces the porosity of the glaze surface and blocks the stain penetration channel by wrapping the copper alloy dry particles and unmelted quartz, filling the grain boundary voids and strengthening the bonding of crystal particles, thereby giving the golden 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 copper 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

[0023] Figure 1 This is a glaze effect diagram of a golden yellow metallic texture tile made by using the golden yellow metallic dry granular glaze in Example 1 of the present invention. DETAILED DESCRIPTION

[0024] The present technical solution provides a method for preparing a golden yellow metallic dry granular glaze, comprising the following steps: A. Under an inert atmosphere, 95-97 parts of copper, 3-5 parts of aluminum, 0.1-0.2 parts of zinc, 0.02-0.05 parts of tin, 0.001-0.004 parts of chromium and 0.1-0.2 parts of terbium are completely melted by weight, and the liquid is crushed to obtain copper alloy droplets; Cool the copper alloy droplets in a natural environment to obtain copper alloy dry particles; B. Mix 30 - 40 parts by mass 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 evenly, and obtain crystalline frit after calcination, water quenching, grinding, and sieving; Among them, 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 1.5 - 2.5 h; At 1530 °C, hold for 0.5 - 1 h; C. Mix the copper alloy dry particles, crystalline frit, and suspending agent evenly to obtain golden - yellow metallic dry particle glaze.

[0025] In order to overcome the technical defects existing in the prior art, this technical solution proposes a preparation method of golden - yellow metallic dry particle glaze. By optimizing the preparation method and raw materials, on the premise of ensuring the uniformity of the golden - yellow metallic texture effect, it not only has excellent golden - yellow metallic texture effect, transparency, and stain - resistance performance at the same time, but also has high wear resistance and hardness to meet the actual use requirements.

[0026] Specifically, this technical solution uses copper, aluminum, zinc, tin, chromium, and terbium as raw materials. After melting and liquid - fragmentation in an inert atmosphere to form copper alloy droplets, copper alloy dry particles are prepared by natural cooling. During the natural cooling process, the surface of the copper alloy droplets exposed to air reacts with oxygen, and a composite oxide protective film containing components such as aluminum oxide, chromium oxide, and zinc oxide is formed. Eventually, copper alloy dry particles with a "core - shell" structure are formed, where the core is a multi - element alloy matrix mainly composed of copper (containing aluminum, zinc, tin, chromium, and terbium), and the shell is a composite oxide protective film. It should be noted that the liquid - fragmentation in this technical solution refers to the alloy melt obtained by melting copper, aluminum, zinc, tin, chromium, and terbium being accelerated by a high - pressure pump and passing through a microporous nozzle, and the high - speed jet friction with air or impact on a target plate to break the metal melt into copper alloy droplets.

[0027] The composite oxide protective film consists of two layers: an inner film, a transition film and an outer film. The inner film is composed of aluminum oxide and chromium oxide to form a dense and continuous barrier layer. If the inner film is damaged, the exposed aluminum oxide and chromium oxide will re-oxidize and repair the damaged part, thereby effectively blocking the intrusion of corrosive media such as flux. The transition film is composed of zinc oxide, tin oxide and terbium oxide, which can fill the microcracks of the inner film and improve the overall adhesion of the composite oxide protective film; the outer film is composed of copper oxide, which has a porous structure and sacrificial protection characteristics. It can preferentially react with corrosive media such as flux to delay the erosion process of the inner film. That is, the composite oxide protective film of the present technical solution not only ensures the reliability of the inner film through the synergistic protection mechanism of "dense inner layer barrier + loose transition layer repair + porous outer layer buffer", but also has excellent corrosion resistance in the glaze environment through the repair effect of the inner film and the sacrificial protection of the outer film, making it not easily corroded by corrosive media such as flux, which is beneficial to maintaining the stability of the performance of copper alloy dry particles.

[0028] Furthermore, the copper alloy dry particles of the present technical solution achieve excellent high-temperature stability through the following effects: (1) the intermetallic compounds generated by the reaction of terbium with aluminum and copper can not only promote the oxidation of metal elements such as aluminum, chromium, zinc and tin, but also inhibit grain boundary sliding and diffusion creep, so that the copper alloy dry particles have good structural stability at high temperatures; (2) terbium can act as a heterogeneous nucleus to refine the structure and increase the number of grain boundaries, which is also conducive to the copper alloy dry particles having good structural stability at high temperatures; (3) the addition of elemental aluminum promotes the formation of a dense aluminum oxide-chromium oxide inner film, and the melting point of the inner film can be as high as 2000°C, which is conducive to improving the high-temperature stability of the copper alloy dry particles. Based on the high-temperature stability of the copper alloy dry particles, the copper alloy dry particles can be introduced into the glaze system, and the stability of its performance can be maintained after the glaze is calcined at high temperature.

[0029] Secondly, kaolin, quartz, calcite, dolomite, barium carbonate and zinc oxide are uniformly mixed and then calcined, water quenched, ground and sieved to obtain a crystalline frit. First, during the calcination of the crystalline frit, calcite (mainly composed of calcium carbonate) and dolomite (mainly composed of calcium magnesium carbonate double salt) can be decomposed by heat to generate calcium oxide, and dolomite can also be decomposed by heat to generate magnesium oxide. Barium carbonate decomposes at high temperature to generate barium oxide. 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. Since calcium ions, magnesium ions, barium ions and zinc ions are all low polarizability ions with relatively large radii and weak polarization ability, the lattice energy is high and the bonding strength is large, and higher energy is required to break the flux network structure, so that the initial melting point of the above quaternary composite flux is relatively high. In addition, there is a size matching effect among calcium ions, magnesium ions, barium ions and zinc ions (for example, the radius ratio of barium ions to zinc ions conforms to the Hume-Rothery rule), and a high-temperature limited solid solution can be formed. This solid solution destroys the eutectic point formation condition through atomic-level mutual dissolution, so that the initial melting point of the formed quaternary composite flux is higher than that of a single flux. That is, the quaternary composite flux in the present technical solution makes the crystalline frit have a relatively high initial melting point through the above-mentioned various effects.

[0030] Furthermore, kaolin decomposes at high temperature to produce aluminum oxide and silicon dioxide, and quartz can also provide silicon dioxide. Calcium oxide generated by the decomposition of calcite and dolomite by heat reacts with aluminum oxide and silicon dioxide in the formulation system to form anorthite crystals (CaAl2Si2O8); at the same time, magnesium oxide generated by the decomposition of dolomite by heat reacts with aluminum oxide and silicon dioxide in the formulation system to form cordierite crystals (Mg2Al2Si2O 18 )

[0031] At the same time, the degree of melting of quartz is related to factors such as the calcination curve of the crystalline frit and the total content of the quaternary composite flux (i.e., calcium oxide, magnesium oxide, barium oxide and zinc oxide). When the calcination temperature is lower than the temperature at which quartz is completely melted (about 1700 °C) and the calcination time is insufficient, especially when the total content of the quaternary composite flux is insufficient, it will cause quartz to not be completely melted. Among them, the insufficient total content of the quaternary composite flux will significantly increase the eutectic point of the crystalline frit formulation system, while insufficient calcination temperature and time cannot provide sufficient thermodynamic driving force and kinetic conditions to complete the transformation of quartz into the glass phase. The above factors act together to ultimately affect the degree of melting of quartz and the glaze properties. Therefore, in the present technical solution, by optimizing the calcination temperature curve of the crystalline frit (where the highest calcination temperature of the calcination temperature curve is 1530 °C, which is lower than the melting point of quartz of 1700 °C), combined with the formulation design of "quartz supersaturation - quaternary composite flux under-ratio" in the crystalline frit, the quartz in the crystalline frit cannot be completely melted, so that the crystalline frit contains unmolten quartz.

[0032] In summary, the crystalline frit of this technical solution includes three kinds of crystals: anorthite crystals, cordierite crystals, and unmolten 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 kinds of crystals make the crystalline frit have a relatively high melting point.

[0033] Therefore, through the mutual cooperation of the above-mentioned various effects, this technical solution improves the initial melting temperature of the crystalline frit, thereby overall increasing the melting threshold of the golden metallic dry granule glaze, significantly shortening the contact time between the quaternary composite flux (i.e., the flux) and the copper alloy dry granules during the high-temperature firing stage, effectively inhibiting the corrosion of the flux on the copper alloy dry granules, and being beneficial to maintaining the stability of the performance of the copper alloy dry granules.

[0034] Furthermore, since the current building ceramic production line generally adopts a high-temperature rapid firing process of 1100 - 1250 °C, and the green body and the glaze are fired synchronously, the firing temperature of the golden metallic dry granule glaze is also 1100 - 1250 °C. When the crystalline frit containing three kinds of crystals, namely unmolten quartz, anorthite crystals, and cordierite crystals, is added to the golden metallic dry granule glaze, at the firing temperature of 1100 - 1250 °C of the golden metallic dry granule glaze, the anorthite crystals and cordierite crystals in the crystalline frit are basically not melted, and although the unmolten quartz can be further melted partially, it is still difficult to be completely melted, so that the golden metallic dry granule glaze can still contain unmolten quartz. Therefore, the fired glaze surface of the golden metallic dry granule glaze contains three kinds of crystals: anorthite crystals, cordierite crystals, and quartz. The above three kinds of crystals can not only form a physical "armor" on the surface of the copper alloy dry granules, thereby directly blocking the directional migration of the alkali metal ions in the quaternary composite flux to the copper alloy dry granules, but also the random distribution of the above three kinds of crystals converts the diffusion path of the alkali metal ions in the quaternary composite flux from linear to three-dimensional zigzag, and strengthens the diffusion barrier by extending the geometric path, effectively inhibiting the corrosion of the alkali metal ions in the quaternary composite flux on the copper alloy dry granules. That is, the above three kinds of crystals inhibit the corrosion of the alkali metal ions in the quaternary composite flux on the copper alloy dry granules by means of physical barrier and extending the diffusion path, which is beneficial to maintaining the stability of the performance of the copper alloy dry granules.

[0035] In summary, through the mutual cooperation of the above-mentioned various effects, this technical solution prevents the copper alloy dry granules from being corroded and maintains the stability of their performance. When the golden metallic dry granule glaze is applied to the surface of the green body, only by polishing to remove the composite oxide protective film on the surface of the copper alloy dry granules, the multi-element alloy matrix mainly composed of copper (the color of the multi-element alloy matrix is golden yellow) inside the copper alloy dry granules can be exposed, thus presenting a golden metallic texture effect.

[0036] It should be noted that since the glazed surface after calcination of the golden metallic dry granule glaze contains three kinds of crystals, namely anorthite crystals, cordierite crystals and unmolten quartz, and the above three kinds of crystals have high hardness and wear resistance, the golden metallic dry granule glaze is given high hardness and wear resistance.

[0037] Again, in addition to participating in the formation of anorthite crystals and cordierite crystals and some quartz remaining in an unmolten state, the quartz in the crystalline frit can also form a silicate glass network with the decomposition products of the quaternary composite flux and kaolin to form the glass phase of the crystalline frit. When the crystalline frit is introduced into the golden metallic dry granule 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 exist stably as a rigid skeleton structure. At this time, the glass phase in the crystalline frit completely enters the liquid molten state, and through the melting effect, it promotes the partial melting of the unmolten quartz particles. The molten glass phase and the melted quartz components penetrate and diffuse uniformly at high temperature, and finally form a continuous and dense glazed surface glass phase; the above glazed surface glass phase significantly reduces the porosity of the glaze by wrapping the copper alloy dry granules and unmolten quartz, filling the grain boundary voids and strengthening the bonding of crystal particles, blocking the stain penetration channels, thereby endowing the golden metallic dry granule glaze with excellent stain resistance. 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 generated amount of the glazed surface glass phase is sufficient to achieve multiple functions such as copper alloy dry granule wrapping, grain boundary filling and particle bonding, and maintain its stain resistance on the premise of ensuring the dense structure of the glaze surface.

[0038] Furthermore, the anorthite crystals generated by this technical solution are triclinic system with a dense structure, and its refractive index is close to that of the glass phase, making it have no significant light scattering center, so that the anorthite crystals have extremely high transparency. Therefore, by regulating the addition amounts of kaolin, calcite and dolomite in the crystalline frit, this technical solution induces the generation of a high content of anorthite crystals, endows the crystalline frit with high transparency, and adding the crystalline frit to the golden metallic dry granule glaze is beneficial to improving the transparency of the golden metallic dry granule glaze.

[0039] In addition, in addition to its fluxing effect, the raw material zinc oxide in the crystalline frit can act as a crystal nucleation agent, reducing the crystallization activation energy and crystallization peak temperature, which is beneficial to the crystallization of anorthite crystals, thereby further improving the transparency of the golden metallic dry granule glaze.

[0040] Therefore, the technical solution makes the glaze surface obtained by calcining the golden yellow metal dry granular glaze have a higher transparency through the above two effects. It should be noted that although the glaze surface obtained by calcining the golden yellow metal dry granular glaze in the technical solution contains unfused quartz with lower transparency, the amount of unfused quartz is limited and is not enough to affect the transparency of the glaze surface, so that the glaze surface still has a higher transparency.

[0041] In addition, since the content of calcium feldspar crystals in the crystalline frit after calcination is significant, when such crystalline frit with high calcium feldspar crystal content is introduced into the golden metal dry granular glaze system, the calcium feldspar crystals are evenly distributed in the glaze layer structure in the form of a rigid skeleton. This skeleton structure inhibits the high-temperature softening rate of the glass phase through physical constraints, effectively slowing down the fluidity of the glaze during the high-temperature firing stage, thereby widening the calcination temperature range of the golden metal dry granular glaze.

[0042] Finally, the technical solution uses a suspending agent to achieve waterless dispersion of copper alloy dry particles, which solves the technical problem that copper alloy dry particles are easy to settle in glazes containing water, so that the copper alloy dry particles can be evenly dispersed in the glaze, so that the golden metal dry particle glaze has a glaze surface with a higher uniformity of metallic texture effect.

[0043] 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.

[0044] Further explanation, in step A, calculated by weight, the raw materials of the copper alloy dry particles include 95.32 parts of copper, 4.37 parts of aluminum, 0.159 parts of zinc, 0.025 parts of tin, 0.0032 parts of chromium and 0.12 parts of terbium.

[0045] By optimizing the ratio of the raw materials of the copper alloy dry particles, the thickness ratio of the copper matrix and the composite oxide protective film is precisely controlled. Under the premise that the composite oxide protective film is sufficient to prevent the copper alloy dry particles from being corroded, after polishing and removing the composite oxide protective film on the surface of the copper alloy dry particles, the multi-alloy matrix retains a larger volume, forming a continuous, highly exposed metal phase, thereby improving the metal texture effect of the glaze.

[0046] Further, in step A, the melting temperature of the melting is 1000-1100°C.

[0047] By limiting the melting temperature, copper, aluminum, zinc, tin, chromium, and terbium are completely melted and doped with each other, which helps to ensure the performance of the finally obtained copper alloy dry granules. It should be noted that although the melting point of copper is 1083.4 °C, the melting point of aluminum is 660 °C, the melting point of zinc is 419.5 °C, the melting point of tin is 232 °C, the melting point of chromium is 1907 °C, and the melting point of terbium is 1356 °C, during the melting process, the above metal elements can form eutectic structures with low melting points, so that the above metal elements can be completely melted at a temperature of 1000 - 1100 °C. In addition, due to the refinement of terbium in the alloy and the formation of a film layer on the surface of the obtained copper alloy dry granules, even if the firing temperature of the glaze added with the copper alloy dry granules is higher than the melting temperature, the copper alloy dry granules can still maintain the solid lattice structure and surface integrity, thus avoiding the deterioration of performance caused by the high-temperature melting of the copper alloy dry granules.

[0048] Furthermore, in step A, calculated by mass percentage, the particle size distribution of the copper alloy dry granules is as follows: the residue on a 100-mesh sieve is 0.1 - 0.5%, the residue on a 160-mesh sieve is 45 - 55%, the residue on a 200-mesh sieve is 75 - 85%, the residue on a 250-mesh sieve is 95 - 98%, and the residue on a 325-mesh sieve is 99 - 100%.

[0049] By optimizing the particle size distribution of the copper alloy dry granules, it not only helps to improve its suspension stability, thereby enhancing the uniformity of the metallic texture effect, but also helps to improve the fluidity of the golden metallic dry granule glaze after high-temperature firing, ensuring the flatness of the glaze layer obtained after firing the golden metallic dry granule glaze, and thus improving the stain resistance.

[0050] Calculated by mass percentage, the particle size distribution of the copper alloy dry granules is as follows: the residue on a 100-mesh sieve is 0.3%, the residue on a 160-mesh sieve is 53%, the residue on a 200-mesh sieve is 83.38%, the residue on a 250-mesh sieve is 96.67%, and the residue on a 325-mesh sieve is 99.9%.

[0051] Furthermore, in step B, the firing 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 2.5 hours; At 1530 °C, hold for 1 hour.

[0052] This technical solution further optimizes the firing temperature curve of the crystalline frit, making the firing temperature curve optimal, which helps to ensure that the performance of the crystalline frit reaches the best.

[0053] Further explanation, in step B, calculated by mass parts, 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.

[0054] By further optimizing the ratio of the raw materials of the crystalline frit, it is more conducive to ensuring the performance of the golden metallic dry granule glaze.

[0055] Further explanation, in step B, 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 an 180-mesh sieve is 40 - 50%, and the residue on a 200-mesh sieve is 70 - 80%.

[0056] By optimizing the particle size distribution of the crystalline frit, not only does the golden metallic dry granule glaze obtained by mixing the crystalline frit with the suspending agent and the copper alloy dry granules have high fluidity, ensuring the flatness of the glaze layer obtained after firing the golden metallic dry granule glaze, but also during the firing process of the golden metallic dry granule glaze, the crystalline frit can be fully melted, so that the glaze layer obtained after firing the golden metallic dry granule glaze has high density, which is further conducive to improving the anti-fouling performance.

[0057] Further explanation, in step C, calculated by mass parts, the golden metallic dry granule glaze is composed of 6 - 10 parts of copper alloy dry granules, 90 - 94 parts of crystalline frit and 180 - 200 parts of suspending agent.

[0058] 6 - 10 parts of copper alloy dry granules can ensure that the glaze surface presents a full metallic texture effect, while avoiding the looseness of the glaze surface structure caused by excessive addition; 90 - 94 parts of crystalline frit, as the basic glass phase, can not only fully wrap the copper alloy dry granules to form a stable combination, but also maintain sufficient fluidity to achieve a flat glaze surface; 180 - 200 parts of suspending agent endow the glaze with ideal rheological properties, which can not only prevent the settlement of copper alloy dry granules with a large specific gravity, but also ensure uniform coating during glazing. Therefore, by limiting the addition amounts of copper alloy dry granules, crystalline frit and suspending agent in this technical solution, it is beneficial to make the performance of the product reach a better level, thereby improving the quality and stability of the product.

[0059] Preferably, in step C, calculated by mass parts, the golden metallic dry granule glaze is composed of 10 parts of copper alloy dry granules, 90 parts of crystalline frit and 200 parts of suspending agent.

[0060] By further limiting the addition amounts of copper alloy dry granules, crystalline frit and suspending agent, the performance of the golden metallic dry granule glaze reaches the best, thereby improving the quality and stability of the product.

[0061] A golden metallic dry granule glaze is prepared by the preparation method of the above-mentioned golden metallic dry granule glaze.

[0062] This proposal also proposes a golden metallic dry granular glaze, which, while ensuring a uniform golden metallic texture effect, not only has excellent golden metallic texture effects, transparency and anti-fouling properties, but also has high wear resistance and hardness, thereby making the golden metallic dry granular glaze both decorative and practical.

[0063] A golden yellow metallic dry granular glaze is used in the preparation of golden yellow metallic textured ceramic tiles. The golden yellow metallic dry granular glaze is used in the following application method: the golden yellow metallic dry granular glaze is applied on the surface of a body layer to form a golden yellow metallic dry granular glaze layer, which is then dried and calcined at a temperature of 1100 to 1250°C, and then polished to obtain the golden yellow metallic textured ceramic tiles.

[0064] This technical solution also proposes an application of a golden yellow metallic dry granular glaze, which is used to prepare golden yellow metallic texture tiles, ensuring that the obtained golden yellow metallic texture tiles can not only have excellent golden yellow metallic texture effects, transparency and anti-fouling performance, but also have high wear resistance and hardness, while achieving a uniform golden yellow metallic texture effect, so that the golden yellow metallic texture tiles are 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, which is not further described here.

[0065] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0066] The manufacturers of the suspending agents in the examples and comparative examples of the present invention are all Jiangxi Qiantao New Materials Co., Ltd., and the model number is 6122A.

[0067] Example 1 A. Under an argon atmosphere, 95.32 parts of copper, 4.37 parts of aluminum, 0.159 parts of zinc, 0.025 parts of tin, 0.0032 parts of chromium and 0.12 parts of terbium calculated by weight are completely melted at a temperature of 1050°C, and the liquid is crushed to obtain copper alloy droplets; the copper alloy droplets are cooled under a natural environment to obtain copper alloy dry particles; wherein, the particle gradation of the copper alloy dry particles is calculated by mass percentage: the sieve residue of 100 mesh screen is 0.1%, the sieve residue of 160 mesh screen is 53%, the sieve residue of 200 mesh screen is 83.4%, the sieve residue of 250 mesh screen is 96.6%, and the sieve residue of 325 mesh screen is 99.42%; B. Mix 35 parts by mass 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 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 2.5 h; at 1530 °C, holding for 1 h; the particle size distribution of the crystalline frit is: the residue on a 150-mesh sieve is 0.30%, the residue on an 180-mesh sieve is 44.5%, and the residue on a 200-mesh sieve is 72.8%; C. Mix 10 parts by mass of copper alloy dry granules, 90 parts of crystalline frit and 200 parts of suspending agent evenly to obtain a golden metallic dry granule glaze.

[0068] Apply the golden metallic dry granule glaze obtained in Example 1 on the surface of the green body layer to form a golden metallic dry granule glaze layer. After drying, calcine at a temperature of 1180 °C, and then obtain a golden metallic texture ceramic tile after full polishing. The glaze surface effect diagram is as Figure 1 shown. From Figure 1 it can be seen that its glaze surface can present a strong and uniform golden metallic texture effect under the condition of light.

[0069] Example 2 A. Under a nitrogen atmosphere, completely melt 95 parts by mass of copper, 3 parts of aluminum, 0.1 part of zinc, 0.02 part of tin, 0.003 part of chromium and 0.1 part of terbium at a temperature of 1100 °C, and obtain copper alloy droplets after liquid fragmentation; in the natural environment, cool the copper alloy droplets to obtain copper alloy dry granules; among them, calculated by mass percentage, the particle size distribution of the copper alloy dry granules is: the residue on a 100-mesh sieve is 0.2%, the residue on a 160-mesh sieve is 48.2%, the residue on a 200-mesh sieve is 78.7%, the residue on a 250-mesh sieve is 95.4%, and the residue on a 325-mesh sieve is 99.8%; B. Mix 38 parts by mass of kaolin, 32 parts of quartz, 23 parts of calcite, 5 parts of dolomite, 6 parts of barium carbonate and 7 parts of zinc oxide 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 3 h; rising from 300 °C to 1530 °C, taking 2 h; at 1530 °C, holding for 0.5 h; the particle size distribution of the crystalline frit is: the residue on a 150-mesh sieve is 0.1%, the residue on an 180-mesh sieve is 46.9%, and the residue on a 200-mesh sieve is 77.2%; C. Mix 8 parts by mass of copper alloy dry granules, 92 parts of crystalline frit and 190 parts of suspending agent evenly to obtain a golden metallic dry granule glaze.

[0070] Example 3 A. In an argon atmosphere, 97 parts of copper, 5 parts of aluminum, 0.1 parts of zinc, 0.04 parts of tin, 0.002 parts of chromium and 0.15 parts of terbium calculated by weight are completely melted at a temperature of 1000°C, and the liquid is crushed to obtain copper alloy droplets; the copper alloy droplets are cooled in a natural environment to obtain copper alloy dry particles; wherein, the particle gradation of the copper alloy dry particles is calculated by mass percentage: the sieve residue of 100 mesh screen is 0.2%, the sieve residue of 160 mesh screen is 48.3%, the sieve residue of 200 mesh screen is 75.8%, the sieve residue of 250 mesh screen is 96.3%, and the sieve residue of 325 mesh screen is 99.2%; B. 32 parts of kaolin, 30 parts of quartz, 20 parts of calcite, 4 parts of dolomite, 8 parts of barium carbonate and 4 parts of zinc oxide are mixed uniformly by weight, and calcined, water quenched, ground and sieved to obtain a crystalline frit; wherein, the calcination temperature curve of the crystalline frit is: from room temperature to 300°C, it takes 2 hours; from 300°C to 1530°C, it takes 2 hours; 1530°C, keep warm for 0.8 hours; the particle gradation of the crystalline frit is: the sieve residue of 150 mesh screen is 0.3%, the sieve residue of 180 mesh screen is 45.7%, and the sieve residue of 200 mesh screen is 78.2%; C. Mix 7 parts of copper alloy dry particles, 92 parts of crystalline frits and 180 parts of suspending agent by mass to obtain a golden metal dry particle glaze.

[0071] Comparative Example 1 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 copper alloy dry particles of Comparative Example 1 only include copper alone, without adding aluminum alone, zinc alone, tin alone, chromium alone and terbium alone.

[0072] Comparative Example 2 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.

[0073] 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 crystalline frit of Comparative Example 3.

[0074] Comparative Example 4 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.

[0075] The golden yellow metal dry granular glaze prepared in the embodiment and the comparative example is applied on the surface of the green body layer to form a golden yellow metal dry granular glaze layer, which is then dried and calcined at a temperature of 1180°C, and then fully polished to obtain a golden yellow metal texture tile. The surface effect of the golden yellow metal texture tile prepared by using the golden yellow metal dry granular glaze in the embodiment and the comparative example is observed, and the obtained golden yellow metal texture tile is subjected to conventional glossiness test, hardness and antifouling grade test in the field of architectural ceramic technology, and the results are shown in Table 1 below: Table 1 Performance test results of tiles of embodiments and comparative examples

[0076] It can be seen from the performance test results in Table 1 that the golden metallic texture tiles made by the golden metallic dry granular glaze of the present technical solution not only have excellent golden metallic texture effects, transparency and anti-fouling performance, but also have high wear resistance and hardness, while ensuring the uniformity of the golden metallic texture effect, and are both decorative and practical, which is more conducive to meeting the use needs of consumers.

[0077] In Comparative Example 1, since the raw materials in the copper alloy dry particles only include copper element, and no aluminum element, zinc element, tin element, chromium element and terbium element are added, the system can only rely on the oxide formed by the oxidation of copper element in air as the composite oxide protective layer. The structural density of the composite oxide protective layer is insufficient and the anti-corrosion ability is limited. Not only does it result in limited metallic texture effect of the ceramic tile obtained using Comparative Example 1, but the copper alloy dry particles also experience a certain degree of corrosion, introducing impurity color into the surface of the ceramic tile.

[0078] Quartz was not added to the crystalline frit of Comparative Example 2, resulting in the inability to utilize the unmelted quartz in Comparative Example 2 to inhibit the corrosion of the alkali metal ions in the quaternary composite flux on the copper alloy dry particles, thereby reducing the metallic texture effect of the tile and causing the obtained tile to have impurity color. At the same time, the fact that quartz was not added to the raw materials in the crystalline frit of Comparative Example 2 also resulted in the glaze surface of the golden yellow metal dry particle glaze after calcination not containing unmelted quartz, resulting in the inability to utilize the unmelted quartz to increase the hardness and wear resistance, thereby reducing the hardness and wear resistance of the tile obtained in Comparative Example 2.

[0079] Since calcite is not added to the crystalline frit in Comparative Example 3, 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 quaternary composite flux in the silvery-white metallic dry granular glaze is reduced, and the amount of glass phase generated after calcination is reduced. It is difficult for the glass phase to completely wrap the unmelted quartz, calcium feldspar crystals and cordierite crystals, resulting in pores between the unmelted quartz, calcium feldspar crystals and cordierite crystals, resulting in a decrease in the anti-fouling performance of the glaze; (3) The amount of calcium feldspar crystals precipitated after calcination of the silvery-white metallic dry granular glaze is reduced, resulting in a decrease in the transparency of the glaze. It should be noted that, although the amount of anorthite crystals generated in Comparative Example 3 is reduced and the anorthite crystals cannot play the role of inhibiting the corrosion of the alloy dry particles by the alkali metal ions in the quaternary composite flux, the total content of the quaternary 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] Since dolomite is not added to the crystalline frit in Comparative Example 4, the following effects will occur: (1) The amount of calcium feldspar crystals and cordierite crystals precipitated during calcination of the silvery-white metallic dry granular glaze is reduced, and the characteristics of calcium feldspar 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 calcium feldspar crystals, resulting in pores between the unmelted quartz and calcium feldspar crystals, resulting in a decrease in the anti-fouling performance of the glaze; (3) The amount of calcium feldspar crystals precipitated after calcination of the silvery-white metallic dry granular glaze is reduced, resulting in a decrease in the transparency of the glaze. It should be noted that, although the amount of anorthite crystals 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 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.

[0081] 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 preparation method of a golden metallic dry granular glaze, characterized in that, The following steps are involved: A. Under an inert atmosphere, 95-97 parts of copper, 3-5 parts of aluminum, 0.1-0.2 parts of zinc, 0.02-0.05 parts of tin, 0.001-0.004 parts of chromium and 0.1-0.2 parts of terbium are completely melted by weight, and the liquid is crushed to obtain copper alloy droplets; The copper alloy droplets are cooled under natural conditions to obtain copper alloy dry particles; B. 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 are mixed uniformly by mass, and calcined, water-quenched, ground and sieved to obtain a crystalline frit; Wherein, the calcination temperature curve of the crystalline frit is: It takes 1.5 to 3 hours to rise from room temperature to 300°C; From 300℃ to 1530℃, it takes 1.5 to 2.5h; 1530℃, keep warm for 0.5~1h; C. Evenly mix the copper alloy dry particles, crystalline frit and suspending agent to obtain golden yellow metal dry particle glaze.

2. The preparation method of a golden metallic dry granule glaze according to claim 1, characterized in that, In step A, calculated by weight, the raw materials of the copper alloy dry particles include 95.32 parts of copper, 4.37 parts of aluminum, 0.159 parts of zinc, 0.025 parts of tin, 0.0032 parts of chromium and 0.12 parts of terbium.

3. The preparation method of a golden metallic dry granular glaze according to claim 1, characterized in that, In step A, the melting temperature of the melting is 1000-1100°C.

4. The preparation method of a golden metallic dry granule glaze according to claim 1, characterized in that, In step A, the particle gradation of the copper alloy dry particles is calculated by mass percentage as follows: the residue on the 100-mesh sieve is 0.1-0.5%, the residue on the 160-mesh sieve is 45-55%, the residue on the 200-mesh sieve is 75-85%, the residue on the 250-mesh sieve is 95-98%, and the residue on the 325-mesh sieve is 99-100%.

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

6. The preparation method of a golden metallic dry granular glaze according to claim 1, characterized in that, 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.

7. A method for preparing a golden metallic dry granular glaze according to claim 1, characterized in that, In step B, the particle size distribution of the crystalline melt is as follows: the residue on the 150-mesh sieve is 0.1-0.5%, the residue on the 180-mesh sieve is 40-50%, and the residue on the 200-mesh sieve is 70-80%.

8. The preparation method of a golden metallic dry granule glaze according to claim 1, characterized in that, In step C, the golden yellow metal dry particle glaze is composed of 6 to 10 parts of copper alloy dry particles, 90 to 94 parts of crystalline frits and 180 to 200 parts of suspending agent, calculated by weight.

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

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

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