Golden yellow metallic dry granular glaze and its preparation method and application

Abstract

The present invention relates to the field of architectural ceramic technology, and in particular to a golden metallic dry granular glaze and its preparation method and application, comprising the following steps: A. completely melting copper, aluminum, zinc, tin, chromium, and terbium in an inert atmosphere, and crushing the liquid to obtain copper alloy droplets; cooling the copper alloy droplets in a natural environment to obtain copper alloy dry particles; B. uniformly mixing kaolin, quartz, calcite, dolomite, barium carbonate, and zinc oxide, calcining, water quenching, grinding, and sieving to obtain a crystalline frit; and C. uniformly mixing the copper alloy dry particles, the crystalline frit, and a suspending agent to obtain a golden metallic dry granular glaze. The preparation method of the golden metallic dry granular glaze proposed by the present invention is highly operable and, while ensuring a uniform golden metallic texture, can simultaneously achieve excellent golden metallic texture, transparency, and anti-fouling properties, as well as high wear resistance and hardness.

Description

Technical Field

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

[0002] Metallic glaze is a special type of glaze. When applied to the surface of a ceramic tile and fired at high temperature, it imparts a metallic texture to the surface of the tile, making it widely used in the architectural decoration industry. Existing metallic glazes primarily consist of metal granules and frit. However, the frit typically requires the addition of fluxes such as lithium oxide (Li2O), boron oxide (B2O3), potassium oxide (K2O), and sodium oxide (Na2O) to lower its melting point. However, these fluxes are highly chemically active and gradually dissolve the metal oxides on the surface of the granules, creating pores and microcracks. The flux then penetrates through these pores and cracks into the granules, reacting with them and ultimately corroding and discoloring them, ultimately losing their original metallic texture.

[0003] To prevent corrosion and discoloration of the metal particles, existing frits typically utilize feldspathic frits with low flux content and high silicon and aluminum content. Kaolin and quartz serve as the primary aluminum and silicon sources in these frits. However, due to the high melting temperature of quartz and the relatively low flux content, the frit contains a high proportion of residual unmelted quartz. The refractive index of unmelted quartz (approximately 1.65) differs significantly from that of the glass phase (approximately 1.50). This refractive index mismatch can lead to strong light scattering, reducing the transparency of the glaze. As the unmelted quartz content increases, the light scattering phenomenon intensifies, further affecting the transparency of the glaze.

[0004] At the same time, due to insufficient flux in the system, the aluminum oxide produced by the decomposition of kaolin at high temperatures (>950°C) is difficult to completely melt. Instead, it exists as inert α-Al2O3 and mullite crystals. The refractive index of the inert α-Al2O3 (corundum phase, refractive index 1.76) and mullite crystals (refractive index 1.64) differs significantly from the refractive index of the glass phase (approximately 1.50), further exacerbating light scattering and reducing the transparency of the glaze. This reduced transparency can obscure the original pattern of the tile's decorative layer, affecting the overall decorative effect of the tile. In addition, due to the serious lack of flux content in the feldspar frit, the glass phase generated in the feldspar frit is seriously insufficient, and the generated glass phase is difficult to completely wrap the unmelted quartz, unmelted α-Al2O3 and mullite crystals, resulting in pores between the unmelted quartz, unmelted α-Al2O3 and mullite crystals. As a result, the porosity of the glaze surface of the metal glaze with added feldspar frit after calcination is high, pollutants are easily penetrated, and the anti-fouling performance is poor.

[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 golden metallic dry particle glaze. The preparation method is simple and easy to operate. On the premise of ensuring the uniformity of the golden metallic texture effect, the method not only has excellent golden 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.

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

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

[0012] A. Under an inert atmosphere, 95-97 parts by mass of copper, 3-5 parts by mass of aluminum, 0.1-0.2 parts by mass of zinc, 0.02-0.05 parts by mass of tin, 0.001-0.004 parts by mass of chromium, and 0.1-0.2 parts by mass of terbium are completely melted and crushed to obtain copper alloy droplets;

[0013] The copper alloy droplets are cooled under natural conditions to obtain copper alloy dry 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, grinding 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 copper alloy dry particles, crystalline frit and suspending agent to obtain golden yellow metallic dry particle glaze.

[0020] 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.

[0021] Furthermore, in step A, the melting temperature of the melting is 1000-1100°C.

[0022] Furthermore, in step A, the particle size distribution of the copper 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 45-55%, the sieve residue of 200 mesh sieve is 75-85%, the sieve residue of 250 mesh sieve is 95-98%, and the sieve residue of 325 mesh sieve is 99-100%.

[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 golden yellow metallic 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.

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

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

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

[0033] 1. This technical solution utilizes copper, aluminum, zinc, tin, chromium, and terbium as raw materials. After melting and liquid fragmentation under an inert atmosphere to form copper alloy droplets, the 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, forming a composite oxide protective film containing aluminum oxide, chromium oxide, and zinc oxide, ultimately forming copper alloy dry particles with a "core-shell" structure, with the core being a copper-based multi-element alloy matrix (containing aluminum, zinc, tin, chromium, and terbium) and the shell being a composite oxide protective film. It should be noted that liquid fragmentation in this technical solution refers to the process of accelerating the alloy melt obtained by melting copper, aluminum, zinc, tin, chromium, and terbium through a microporous nozzle. The high-speed jet rubs against the air or impacts a target plate, fragmenting the molten metal into copper alloy droplets.

[0034] 2. When a crystalline frit containing unmelted quartz, anorthite, and cordierite crystals is added to a golden metallic dry granule glaze, at a calcination temperature of 1100-1250°C, the anorthite and cordierite crystals in the crystalline frit remain essentially insoluble. While the unmelted quartz can further melt, it remains difficult to completely melt, leaving unmelted quartz in the golden metallic dry granule glaze. Consequently, the glaze surface of the fired golden metallic dry granule glaze contains anorthite, cordierite, and quartz crystals. These three crystals not only form a physical "armor" on the surface of the copper alloy dry granules, directly blocking the directional migration of alkali metal ions from the quaternary composite flux into the copper 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 lengthens the diffusion path, strengthening the diffusion barrier and effectively inhibiting corrosion of the copper alloy dry granules by the alkali metal ions in the quaternary composite flux. That is, the three crystals mentioned above inhibit the corrosion of the copper alloy dry particles by the alkali metal ions in the quaternary composite flux by physically blocking and extending the diffusion path, which is beneficial to maintaining the stability of the performance of the copper alloy dry particles.

[0035] 3. The glass phase within the crystalline frit completely enters a liquid molten state, and through dissolution, it causes the unmelted quartz particles to partially melt. The molten glass phase and the melted quartz components interpenetrate and diffuse evenly at high temperatures, ultimately forming a continuous and dense glaze glass phase. This glaze glass phase significantly reduces the glaze porosity by encapsulating the copper alloy dry particles and unmelted quartz, filling the grain boundary voids, and strengthening the bonding of the crystal particles, thereby blocking the channels for stain penetration and imparting excellent anti-fouling properties to the golden 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 copper alloy dry particle encapsulation, grain boundary filling, and particle bonding, maintaining its anti-fouling properties while ensuring a dense glaze structure. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0037] This technical solution provides a method for preparing golden yellow metallic dry granular glaze, comprising the following steps:

[0038] A. Under an inert atmosphere, 95-97 parts by mass of copper, 3-5 parts by mass of aluminum, 0.1-0.2 parts by mass of zinc, 0.02-0.05 parts by mass of tin, 0.001-0.004 parts by mass of chromium, and 0.1-0.2 parts by mass of terbium are completely melted and crushed to obtain copper alloy droplets;

[0039] The copper alloy droplets are cooled under natural conditions to obtain copper 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, grinding 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 copper alloy dry particles, crystalline frit and suspending agent to obtain golden yellow metallic dry particle glaze.

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

[0047] Specifically, this technical solution uses copper, aluminum, zinc, tin, chromium, and terbium as raw materials. After melting and liquid fragmentation under an inert atmosphere to form copper alloy droplets, the 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, forming a composite oxide protective film containing components such as aluminum oxide, chromium oxide, and zinc oxide. Ultimately, copper alloy dry particles with a "core-shell" structure are formed, with the core being a copper-based multi-element alloy matrix (containing aluminum, zinc, tin, chromium, and terbium) and the shell being a composite oxide protective film. It should be noted that liquid fragmentation in this technical solution refers to the alloy melt obtained by melting copper, aluminum, zinc, tin, chromium, and terbium, which is accelerated by a high-pressure pump and passed through a microporous nozzle. The high-speed jet friction with air or impact with a target plate breaks the metal melt into copper alloy droplets.

[0048] This composite oxide protective film consists of an inner film, a transition film, and an outer film. The inner film, composed of aluminum oxide and chromium oxide, forms a dense, continuous barrier layer. If the inner film is damaged, the exposed aluminum oxide and chromium oxide will reoxidize and repair the damage, effectively blocking the intrusion of corrosive media such as flux. The transition film, composed of zinc oxide, tin oxide, and terbium oxide, fills microcracks in the inner film and enhances the overall adhesion of the composite oxide protective film. The outer film, composed of copper oxide, exhibits a porous structure and sacrificial protective properties, preferentially reacting with corrosive media such as flux to slow the erosion 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.

[0049] 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 inner layer of aluminum oxide and chromium oxide, and the melting point of the inner layer 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 performance stability can still be maintained after the glaze is calcined at high temperature.

[0050] Next, kaolin, quartz, calcite, dolomite, barium carbonate, and zinc oxide are uniformly mixed, calcined, water-quenched, ground, and sieved to produce a crystalline frit. During the calcination of the crystalline frit, both calcite (primarily calcium carbonate) and dolomite (primarily calcium-magnesium carbonate complex salt) decompose upon heating to form calcium oxide. Dolomite also decomposes upon heating to form magnesium oxide. Barium carbonate decomposes at high temperatures to form barium oxide. The calcium oxide, magnesium oxide, and barium oxide interact with the zinc oxide in the crystalline frit to form a quaternary composite flux: calcium oxide-magnesium oxide-barium oxide-zinc oxide. Because calcium, magnesium, barium, and zinc ions all have low polarizability, large radii, and weak polarizability, they result in high lattice energy and strong bonding strength. This requires higher energy to disrupt the flux network, resulting in a relatively high initial melting point for this quaternary composite flux. Furthermore, a size-matching effect exists between calcium, magnesium, barium, and zinc ions (e.g., the radius ratio of barium to zinc ions conforms to the Hume-Rothery rule), allowing the formation of a high-temperature finite solid solution. This solid solution 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 temperatures to produce aluminum oxide and silicon dioxide. Quartz can also provide silicon dioxide. Calcium oxide produced by the 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 the thermal decomposition of 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 complete melting point of quartz (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 affect the degree of quartz melting and glaze properties. 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, this technical solution uses the above-mentioned multiple effects to cooperate with each other to increase the initial melting temperature of the crystalline frit, thereby overall increasing the melting threshold of the golden metal dry particle glaze, and significantly shortening the contact time between the quaternary composite flux (i.e., flux) and the copper alloy dry particles during the high-temperature firing stage, thereby effectively inhibiting the corrosion of the flux on the copper alloy dry particles, which is beneficial to maintaining the stability of the performance of the copper alloy dry particles.

[0055] Furthermore, because current architectural ceramic production lines generally employ a high-temperature, rapid firing process of 1100-1250°C, with the green body and glaze fired simultaneously, the firing temperature of the golden metallic granular glaze is also 1100-1250°C. When a crystalline frit containing unmelted quartz, anorthite crystals, and cordierite crystals is added to the golden metallic granular glaze, at the 1100-1250°C firing temperature of the golden metallic granular glaze, the anorthite and cordierite crystals in the crystalline frit remain essentially insoluble. While the unmelted quartz can further dissolve partially, it remains difficult to completely melt, resulting in the golden metallic granular glaze still containing unmelted quartz. Therefore, after firing, the golden 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 copper alloy dry granules, thereby directly blocking the directional migration of alkali metal ions from the quaternary composite flux into the copper 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 copper alloy dry granules by the alkali metal ions in the quaternary composite flux. In other words, these three crystals inhibit the corrosion of the copper alloy dry granules by the alkali metal ions in the quaternary composite flux by physically blocking and extending the diffusion path, which helps maintain the stability of the copper alloy dry granule performance.

[0056] In summary, the technical solution prevents the copper alloy dry particles from being corroded and maintains the stability of their performance through the mutual cooperation of the above-mentioned multiple effects. When the golden metal 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 copper alloy dry particles. The copper-based multi-alloy matrix (the color of the multi-alloy matrix is golden yellow) inside the copper alloy dry particles can be exposed, thereby presenting a golden metallic texture effect.

[0057] It should be noted that since the glaze surface of the golden 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 golden metallic dry granular glaze is given 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 golden 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 the 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 copper 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 golden metallic dry particle glaze. It should be noted that while the total content of the quaternary composite flux is insufficient to completely melt the quartz, its total content ensures that the glaze glass phase is generated in sufficient quantities to achieve the multiple functions of encapsulating the copper alloy dry particles, filling grain boundaries, and bonding the particles, maintaining the 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 a lack of 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 high-content anorthite crystals, imparting high transparency to the crystalline frit. Adding this crystalline frit to a golden metallic dry granular glaze can help improve the glaze's transparency.

[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 to reduce 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 golden metallic dry granular glaze.

[0061] Therefore, through the above two effects, this technical solution makes the glaze surface obtained by calcining the golden yellow metallic dry granular glaze have a high transparency. It should be noted that although the glaze surface obtained by calcining the golden yellow 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 fired crystalline frit, when this high-anorthite content is introduced into the golden 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 glaze's fluidity during high-temperature firing, thereby broadening the firing temperature range of the golden metallic dry granular glaze.

[0063] Finally, this technical solution uses a suspending agent to achieve water-free dispersion of copper alloy dry particles, solving the technical problem that copper alloy dry particles are easy to settle in glaze 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 high metallic texture effect uniformity.

[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 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.

[0066] 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 can be 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-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 1000-1100°C.

[0068] By limiting the melting temperature, the copper, aluminum, zinc, tin, chromium, and terbium elements are completely melted and intermixed, thereby ensuring the properties of the final copper alloy dry particles. It should be noted that although the melting points of copper, aluminum, zinc, tin, chromium, and terbium are 1083.4°C, 660°C, 419.5°C, 232°C, 1907°C, and 1356°C, the above-mentioned metal elements can form a low-melting-point eutectic structure during the melting process, allowing the above-mentioned metal elements to be completely melted at temperatures of 1000-1100°C. In addition, due to the refinement of terbium element inside the alloy and the film layer formed by surface oxides, the obtained copper alloy dry particles can maintain the solid lattice structure and surface integrity even if the calcination temperature of the glaze to which the copper alloy dry particles are added is higher than the melting temperature, thereby avoiding the performance degradation caused by high-temperature melting of the copper alloy dry particles.

[0069] Further explanation, in step A, the particle size distribution of the copper alloy dry particles is calculated according to mass percentage: the sieve residue of 100 mesh sieve is 0.1-0.5%, the sieve residue of 160 mesh sieve is 45-55%, the sieve residue of 200 mesh sieve is 75-85%, the sieve residue of 250 mesh sieve is 95-98%, and the sieve residue of 325 mesh sieve is 99-100%.

[0070] By optimizing the particle grading of copper 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 golden metal dry particle glaze after high-temperature calcination, ensuring the flatness of the glaze layer obtained after calcination of the golden metal dry particle glaze, thereby improving the anti-fouling property.

[0071] Calculated by mass percentage, the particle size distribution of the copper alloy dry particles is as follows: the sieve residue on the 100-mesh sieve is 0.3%, the sieve residue on the 160-mesh sieve is 53%, the sieve residue on the 200-mesh sieve is 83.38%, the sieve residue on the 250-mesh sieve is 96.67%, and the sieve residue on the 325-mesh sieve is 99.9%.

[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 raw materials of the crystalline frit, it is more conducive to ensuring the performance of the golden 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 the golden metal dry particle glaze obtained by mixing the crystalline frit with the suspending agent and the copper alloy dry particles has higher fluidity, ensuring the flatness of the glaze layer obtained after the golden metal dry particle glaze is calcined, but also the crystalline frit can be fully melted during the calcination of the golden metal dry particle glaze, so that the glaze layer obtained after the calcination of the golden metal dry particle glaze has a higher density, which is beneficial to improve the anti-fouling performance.

[0081] Further description, in step C, calculated by weight, the golden yellow metallic 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.

[0082] 6-10 parts of copper alloy dry particles ensure a rich metallic texture on the glaze while avoiding the loose glaze structure caused by excessive addition; 90-94 parts of crystalline frit, as the base glass phase, not only fully encapsulates the copper alloy dry 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 copper alloy dry particles from settling and ensuring uniform coating during glazing. Therefore, this technical solution, by limiting the addition amounts of copper alloy dry 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 golden yellow metallic dry particle glaze is composed of 10 parts of copper alloy dry particles, 90 parts of crystalline frits and 200 parts of suspending agent, calculated by weight.

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

[0085] A golden yellow metallic dry granular glaze is prepared by the above-mentioned preparation method of the golden yellow metallic dry granular glaze.

[0086] This proposal also proposes a golden metallic dry granular glaze, which, while ensuring a uniform golden metallic texture, 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.

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

[0088] This technical solution also proposes the application of a golden metallic dry granular glaze, which is used to prepare golden metallic texture tiles, ensuring that the obtained golden metallic texture tiles can not only have excellent golden metallic texture effects, transparency and anti-fouling properties, but also have high wear resistance and hardness, while achieving a uniform golden metallic texture effect. This makes the golden metallic texture tiles both decorative and practical. It should be noted that the green body layer in this solution is made by pressing and drying conventional ceramic green bodies in the ceramic field. The ceramic green bodies are not further described here. In addition, the polishing process is also a commonly used polishing process in the field, which 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, 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 size distribution of the copper 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 53%, the sieve residue on a 200-mesh sieve is 83.4%, the sieve residue on a 250-mesh sieve is 96.6%, and the sieve residue on a 325-mesh sieve is 99.42%;

[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, ground, 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 0.30%, the sieve residue on a 180-mesh sieve was 44.5%, and the sieve residue on a 200-mesh sieve was 72.8%;

[0094] C. Mix 10 parts of copper alloy dry particles, 90 parts of crystalline frits and 200 parts of suspending agent calculated by mass to obtain a golden metal dry particle glaze.

[0095] The golden yellow metallic dry granular glaze obtained in Example 1 is applied on the surface of the green body layer to form a golden yellow metallic dry granular glaze layer, which is then dried and calcined at 1180°C, and then fully polished to obtain a golden yellow 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 golden metallic texture effect under lighting conditions.

[0096] Example 2

[0097] A. Under a nitrogen atmosphere, 95 parts of copper, 3 parts of aluminum, 0.1 parts of zinc, 0.02 parts of tin, 0.003 parts of chromium, and 0.1 parts of terbium, calculated by weight, are completely melted at a temperature of 1100° 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 size distribution of the copper alloy dry particles, calculated by weight percentage, is as follows: the sieve residue on a 100-mesh sieve is 0.2%, the sieve residue on a 160-mesh sieve is 48.2%, the sieve residue on a 200-mesh sieve is 78.7%, the sieve residue on a 250-mesh sieve is 95.4%, and the sieve residue on a 325-mesh sieve is 99.8%;

[0098] B. 38 parts 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, calculated by weight, were uniformly mixed, calcined, water-quenched, ground, 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 2 hours; and holding at 1530°C for 0.5 hours; the particle size distribution of the crystalline frit was as follows: the sieve residue on a 150-mesh sieve was 0.1%, the sieve residue on a 180-mesh sieve was 46.9%, and the sieve residue on a 200-mesh sieve was 77.2%;

[0099] C. 8 parts of copper alloy dry particles, 92 parts of crystalline frits and 190 parts of suspending agent calculated by mass are mixed evenly to obtain a golden metallic dry particle glaze.

[0100] Example 3

[0101] A. Under 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 under a natural environment to obtain copper alloy dry particles; wherein, the particle size distribution of the copper alloy dry particles, calculated by weight percentage, is as follows: the sieve residue on a 100-mesh sieve is 0.2%, the sieve residue on a 160-mesh sieve is 48.3%, the sieve residue on a 200-mesh sieve is 75.8%, the sieve residue on a 250-mesh sieve is 96.3%, and the sieve residue on a 325-mesh sieve is 99.2%;

[0102] 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, calculated by weight, were uniformly mixed, calcined, water-quenched, ground, 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 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 45.7%, and the sieve residue on a 200-mesh sieve was 78.2%;

[0103] C. Mix 7 parts of copper alloy dry particles, 92 parts of crystalline frits and 180 parts of suspending agent in proportions by mass to obtain a golden 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 copper alloy dry particles of Comparative Example 1 only include copper alone, without adding aluminum, zinc, tin, chromium and terbium.

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

[0113] Table 1 Performance test results of tiles of Examples and Comparative Examples

[0114]

[0115] It can be seen from the performance test results in Table 1 that the golden metallic texture tiles made from 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 uniform golden 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 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 corrosion resistance is limited. Not only does it lead to a 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.

[0117] The lack of quartz in the crystalline frit of Comparative Example 2 prevents the use of unfused quartz to inhibit the corrosion of the copper alloy dry particles by the alkali metal ions in the quaternary composite flux. This results in a reduced metallic texture of the tile and an impure coloration of the resulting tile. Furthermore, the lack of quartz in the raw materials used in the crystalline frit of Comparative Example 2 also means that the golden metallic dry particle glaze surface after calcination contains no unfused quartz, preventing the use of unfused quartz to increase hardness and wear resistance. Consequently, the hardness and wear resistance of the tile produced in Comparative Example 2 are reduced.

[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. 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 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 golden yellow metallic dry granular glaze, characterized in that: The following steps are involved: A. Under an inert atmosphere, 95-97 parts by mass of copper, 3-5 parts by mass of aluminum, 0.1-0.2 parts by mass of zinc, 0.02-0.05 parts by mass of tin, 0.001-0.004 parts by mass of chromium, and 0.1-0.2 parts by mass of terbium are completely melted and crushed to obtain copper alloy droplets; The copper alloy droplets are cooled under natural conditions to obtain copper alloy dry particles; The liquid fragmentation method specifically comprises the following steps: melting copper, aluminum, zinc, tin, chromium and terbium to obtain an alloy melt, accelerating the melt through a high-pressure pump and passing it through a micro-hole nozzle; the high-speed jet rubs with air or hits a target plate to fragment the metal melt into copper alloy droplets; 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, grinding 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 copper alloy dry particles, crystalline frit and suspending agent to obtain golden yellow metallic dry particle glaze.

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

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

5. The method for preparing a golden 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 golden 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 golden 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 golden metallic dry granular glaze according to claim 1, characterized in that: In step C, the golden yellow metallic 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 metallic dry granular glaze is prepared by the preparation method of any one of claims 1 to 8.

10. Application of a golden yellow metallic dry granular glaze in the preparation of golden yellow 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 it at a temperature of 1100-1250° C. after drying, and then polishing it to obtain golden yellow metallic textured tiles.

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