Decorative ceramic tile with golden or white gold metallic luster and preparation method of decorative ceramic tile

Abstract

The invention discloses a decorative ceramic tile with golden or white gold metallic luster and a preparation method thereof, and belongs to the technical field of ceramic production processes. The decorative ceramic tile with the golden or white golden metallic luster comprises metal dry particles and metal dry particle protective glaze, according to the invention, metal particles are directly used as a metallic luster source instead of forming metal oxide crystals: firstly, the metal particles are used as main components to prepare metal dry particles, and a controllable precise arrangement technology of the metal particles is combined; secondly, metal dry particle protective glaze is developed, and metal particles are further prevented from being oxidized. The optimized protective glaze formula promotes formation of uniform and compact aluminosilicate wrapping layers on the surfaces of metal particles in the sintering process, and lays a foundation for simplified and controllable design of ceramic tile metallic luster decoration. And finally, optimizing the formula of the ground glaze in the preferable scheme, so that the ground glaze is matched with the metal dry particles.

Description

Technical Field

[0001] This invention belongs to the field of ceramic production technology, specifically relating to a decorative ceramic tile with a golden or white-gold metallic luster and its preparation method. Background Technology

[0002] Metallic glaze is a type of glaze that forms a metallic texture on the surface of ceramic tiles through a special process. Metallic glaze has the following three main characteristics: (1) Metallic glaze can present a decorative effect that is very close to that of metal, enhancing the expressiveness of ceramic tiles and providing them with a wider creative space in the field of decorative design. (2) Metallic glaze has strong flexibility in production process. Ceramic factories can formulate a variety of glaze colors with metallic luster according to different design needs of customers without changing the existing production conditions. (3) Metallic glaze has a long-lasting and stable metallic luster during use, and the glaze surface is hard and durable, giving the decorative wall a unique visual effect. At the same time, the glaze has excellent physical and chemical properties, such as high thermal stability, good weather resistance, strong stain resistance, and is not easy to absorb dust. It is also not easy to react with gases in the air, and can keep the surface clean for a long time. In practical applications, metallic glaze can also be used in combination with brightly colored light-colored glazed tiles to form an artistic effect of dynamic and static combination and light and dark interplay, achieving overall decoration harmony and unity.

[0003] The main methods for preparing metallic glazes include the following four: (1) Coating pyrolysis method. Metals or oxides are made into a colloidal liquid, applied to the ceramic surface, and treated at a temperature of 750~830℃, resulting in a metallic luster on the glaze. The most commonly used decorative materials include gold water, platinum water, and various electro-gloss waters.

[0004] (2) Thermal spraying method. A metal salt solution with a low decomposition temperature is sprayed onto a hot glaze surface, causing it to decompose instantly and react with the glaze surface to form a metal oxide film or metal colloidal film with a Si-OM structure.

[0005] (3) Vapor deposition method. A coating can be directly vapor-deposited onto the ceramic glaze surface; alternatively, an oxycarbonyl iron coating can be applied to the product first, then reacted with ammonia to form an iron nitride film. This method belongs to chemical vapor deposition (CVD) technology, but does not require vacuum equipment and is relatively simple. Another process involves reacting liquid titanium tetrachloride with gaseous ammonia to generate a solid Ti-N-Cl compound. This compound, along with the ceramic product, is placed in a heating zone and heated while ammonia is introduced. The Ti-N-Cl compound then sublimates to form TiN, which accumulates on the ceramic surface. Although TiN can be used for general ceramic decoration, obtaining a TiN film with pure color requires a high-precision preparation process, thus limiting its widespread application.

[0006] (4) Sintering method. Similar to the preparation methods of most ceramic glazes, metal oxides (such as Co, Mn, Fe, etc.) need to be added to the glaze to make it saturated at high temperature, thereby precipitating specific crystals. This is also the most commonly used method for preparing metallic glazes. Among the above methods, coating pyrolysis, thermal spraying and vapor deposition all have problems such as high preparation cost and complex process. In addition, the introduction of these technologies often requires major modifications to existing tile production lines, which brings many inconveniences to actual production. In contrast, the sintering method is more advantageous because of its good compatibility with existing production processes and lower cost. However, the gloss effect of metallic glazes comes from the formation of crystals of metal oxides such as Fe, Mn, Ni, Co, V, Cu in the glaze layer. These crystals grow regularly and parallel to the glaze surface, thereby causing specular reflection of light. Therefore, whether crystals can form and their growth behavior such as arrangement, size and morphology directly determine the presentation effect of metallic luster; and these growth behaviors are strictly constrained by a series of complex process parameters such as metal ion concentration, firing regime and cooling rate. The complexity of this multi-factor interplay makes the control of the final decorative effect full of uncertainty. Summary of the Invention

[0007] To address the shortcomings of existing metallic-luster ceramic tiles, this invention develops a decorative ceramic tile exhibiting a golden or white-gold metallic luster, along with its preparation method. This method directly utilizes metallic particles as the source of the metallic luster, rather than forming metal oxide crystals. First, dry metallic particles are prepared as the main component, combined with a controllable and precise particle arrangement technology. Second, a protective glaze for the dry metallic particles is developed to further prevent oxidation. An optimized protective glaze formula promotes the formation of a uniform and dense aluminosilicate coating on the surface of the metallic particles during firing, laying the foundation for simplified and controllable design of metallic-luster ceramic tile decoration. Finally, the preferred embodiment also optimizes the base glaze formula to ensure compatibility with the dry metallic particles.

[0008] To solve the above problems, the present invention is achieved through the following technical solution: The first objective of this invention is: A decorative ceramic tile with a gold or white gold metallic luster is provided, comprising: metallic dry particles and a metallic dry particle protective glaze; The aforementioned dry metal granules comprise the following raw material components by mass percentage: The metallic luster functional component comprises 40-60%, boric acid 7-15%, aluminum silicate 30-50%, titanium dioxide 5-10%, and silicate 5-10%, with the sum of all components being 100%. The silicate mentioned is one or a combination of sodium silicate, potassium silicate, calcium silicate, magnesium silicate and zinc silicate; The metallic luster functional components are: intermetallic compound AlCu3 particles (golden color) or Fe-Cr-Mn alloy particles (white gold color); the particle size range is controlled between 120 and 200 mesh. The aforementioned metal dry granule protective glaze comprises the following raw material components by weight percentage: Inorganic components: 40-50%; Organic binders: 50-60%; The inorganic components include the following raw material components by mass percentage: potassium feldspar 26-30%, sodium feldspar 28-33%, calcined talc 2-5%, calcite 8-10%, kaolin 9-10%, zinc oxide 7-9%, zirconium silicate 4-6%, quartz powder 2-3%, barium carbonate 1-2%, and alumina 4-6%, with the sum of all components being 100%; and external auxiliary materials, including 0.13% sodium tripolyphosphate, 0.18% methylcellulose, and an appropriate amount of water.

[0009] A further optimization of the decorative ceramic tile of the present invention, which exhibits a golden or white-gold metallic luster, is as follows: The chemical composition of the aforementioned metal dry granule protective glaze by weight percentage is as follows: SiO2 48.03–58.60%, Al2O3 15.81–19.62%, ZnO 6.98–8.98%, CaO 4.6–5.7%, MgO 0.7–1.6%, K2O 2.6–3.1%, Na2O 3.2–3.8%, ZrO2 2.6–4.0%, BaO 0.99–1.98%, and others 0.11–0.3%, with a loss on ignition of 4.89–5.98%, and the sum of all components is 100%.

[0010] A further optimization of the decorative ceramic tile of the present invention, which exhibits a golden or white-gold metallic luster, is as follows: The organic adhesive comprises the following raw material components in parts by weight: 100 parts water, 6 parts hydroxypropyl methylcellulose, 4 parts ethylene glycol, 0.3 parts sodium tripolyphosphate, and 0.14 parts preservative.

[0011] The second objective of this invention is: A method for preparing the decorative ceramic tile with a golden or white-gold metallic luster as described above is provided: It includes the following preparation steps: S1. Apply a base glaze to the body; S2. Inkjet print the design pattern and then spray adhesive onto the design pattern; S3. Apply metal dry granules to the adhesive area described in step S2 using a high-precision dry granulator; S4. Apply a protective glaze of dry metallic particles using a glazing machine; S5. The finished product is obtained after drying, high-temperature firing, polishing, and sorting and inspection.

[0012] A further optimization of the preparation method of the decorative ceramic tile exhibiting a golden or white-gold metallic luster according to the present invention is as follows: The aforementioned dry metal granules include the following preparation steps: Weigh the raw material components according to the corresponding formula ratio, mix the raw material components evenly, melt at 1255℃~1340℃, keep at the temperature for 4~6 hours, and then slowly cool to room temperature at a cooling rate of 8~15℃ / h to precipitate crystals. After crushing and screening into 120~200 mesh dry particles, the metal dry particles are prepared.

[0013] A further optimization of the preparation method of the decorative ceramic tile exhibiting a golden or white-gold metallic luster according to the present invention is as follows: The aforementioned metal dry granule protective glaze comprises the following preparation steps: Weigh the corresponding inorganic components and organic binders according to the corresponding formula ratio, mix them evenly, and pass them through a 325-mesh sieve to prepare a metal dry granule protective glaze with a specific gravity of 1.23±0.02g / ml.

[0014] A further optimization of the preparation method of the decorative ceramic tile exhibiting a golden or white-gold metallic luster according to the present invention is as follows: The inorganic component comprises the following preparation steps: Weigh the raw materials according to the corresponding formula ratio, mix them evenly, melt them at 1550℃ and keep them at that temperature for 10 to 12 hours; then slowly cool them to room temperature at a rate of 6 to 20℃ / hour to allow crystals to precipitate. After the obtained crystals are crushed, particles of 250-400 mesh are screened out to obtain the inorganic component. The organic adhesive comprises the following preparation steps: Weigh the raw materials according to the corresponding formula ratio, stir all the raw materials evenly, grind them finely, and pass them through a 325-mesh sieve to prepare the organic adhesive.

[0015] A further optimization of the preparation method of the decorative ceramic tile exhibiting a golden or white-gold metallic luster according to the present invention is as follows: The base glaze comprises the following raw material components by weight percentage: Potassium feldspar 46-53%, calcite 5-6%, kaolin 15-18%, quartz powder 9-12%, barium carbonate 2-4%, alumina 2-4%, wollastonite 7-9%, calcined talc 4-7%, zinc oxide 1-3%, the sum of all components is 100%; Add 0.14% sodium carboxymethyl cellulose and 0.2% sodium tripolyphosphate. Mix all raw materials evenly, and then ball mill, discharge the slurry, pass through a 325-mesh sieve and remove iron to prepare the base glaze.

[0016] A further optimization of the preparation method of the decorative ceramic tile exhibiting a golden or white-gold metallic luster according to the present invention is as follows: The base glaze comprises the following chemical composition by mass percentage: SiO2 58.23–65.35%, Al2O3 15.77–17.53%, CaO 5.50–8.08%, MgO 1.32–2.28%, K2O 4.15–4.99%, Na2O 1.42–1.72%, ZnO 1.0–3.0%, BaO 1.98–3.95%, Fe2O3 0.23–0.27% with a loss on ignition of 3.10–5.68%, and the remainder being trace elements (TiO2, etc.). The sum of all components is 100%.

[0017] The primary function of the base glaze is to cover the base color of the ceramic body and provide an excellent color base for inkjet printing patterns. Therefore, it needs to possess high whiteness and strong hiding power. In this technical solution, because high-density metal particles are deposited on the surface of the base glaze, and the metal dry-particle protective glaze used has a low low-temperature viscosity and contains a large amount of organic components that easily generate gas at high temperatures, these factors may adversely affect the effect of the base glaze and must be overcome by specifically adjusting the base glaze formula. Compared with conventional base glazes, the base glaze used in the metallic decorative tiles of this technical solution has a higher initial melting temperature and high-temperature viscosity. In the preferred chemical composition of the base glaze in this technical solution, the content of silicon oxide, calcium oxide, and potassium oxide is increased, while the proportion of aluminum oxide is correspondingly reduced.

[0018] A further optimization of the preparation method of the decorative ceramic tile exhibiting a golden or white-gold metallic luster according to the present invention is as follows: The adhesive is a polyvinyl alcohol solution, with the addition of a silane coupling agent at a mass percentage of 0.1% of the polyvinyl alcohol solution and a polycationic electrolyte at a mass percentage of 0.5% of the polyvinyl alcohol solution. The three are mixed evenly and then sieved to obtain the final product.

[0019] The aforementioned adhesive enables precise positioning of dry metal particles. By introducing a cationic electrolyte, the adhesive acquires a positive charge, enhancing its adsorption and positioning ability for negatively charged dry metal particles and promoting their interlocking with the glaze layer.

[0020] Currently, the mainstream preparation methods for metallic glazes include coating pyrolysis, thermal spraying, vapor deposition, and sintering. The first three methods suffer from drawbacks such as complex processes, high costs, and the need to modify existing tile production lines, causing significant inconvenience in actual production. While sintering offers advantages due to its superior compatibility with existing production processes and lower cost, its coloring mechanism relies on specular reflection of light caused by the directional alignment of metal oxide crystals of specific morphologies and sizes. Since the morphology, size, and arrangement of these crystals are influenced by various process parameters, the control of the final decorative effect is inherently uncertain.

[0021] This innovative technical solution proposes using metal particles of a specific size as the metallic luster source directly based on the sintering method. This strategy requires no modification to existing tile production lines and has good compatibility with current production processes. Furthermore, since the metallic luster effect primarily depends on the intrinsic properties of the metal particles, its sensitivity to tile production process parameters is low. Therefore, this strategy effectively reduces the uncertainty of the decorative effect and significantly improves the controllability of the tile's decorative effect. However, a key technical challenge that this strategy cannot avoid is how to prevent high-temperature oxidation of the metal particles during the tile sintering process.

[0022] Therefore, this technical solution mainly improves the high-temperature oxidation resistance of metal particles through the synergistic effect of the following three levels: (1) At the intrinsic level of materials, the composition and structure of metal particles are optimized to lay the foundation for their anti-oxidation: alloy particles with high anti-oxidation properties and intermetallic compounds are selected as functional components for metallic luster source.

[0023] (2) At the surface engineering level, metal particles are made into metal dry particles with aluminum silicate and other silicate raw materials, thereby pre-constructing an oxide coating on their surface as an effective barrier: a nano-silica layer is wrapped on the surface of metal particles using the "dry granulation" technology.

[0024] (3) In terms of glaze protection, a special "protective glaze" was developed to form a dense coating in the early stage of sintering, thereby constructing a triple synergistic protection mechanism: the optimized polishing glaze formula promotes the formation of a uniform and dense aluminosilicate coating layer on the surface of metal particles during the firing process. This strategy lays the foundation for the simplified and controllable design of metallic luster decoration on ceramic tiles.

[0025] This technical solution, based on the selection of alloys and intermetallic compounds with high oxidation resistance as the source of metallic luster, employs a "dry granulation" technique to coat the surface of metal particles with an amorphous layer of aluminosilicate to further enhance their oxidation resistance. According to traditional ceramic tile manufacturing processes, a layer of transparent polished glaze is typically applied to the surface to protect the inkjet-printed pattern, fix the dry granules, and enhance gloss. Based on this process characteristic, this technical solution cleverly utilizes existing conditions and, through optimization of the basic polished glaze formula, successfully develops a dedicated polished glaze suitable for metallic decorative ceramic tiles—a metallic dry-granule protective glaze.

[0026] Compared to conventional polished glazes, the metal dry-granule protective glaze in this technical solution not only needs to possess excellent optical properties and surface smoothness, but more importantly, it must meet the following special requirements: (1) It has a low melting point so that it can form an effective coating on the surface of metal particles at low temperature. (2) It has low surface tension, which promotes good bonding between the glaze melt and metal particles; (3) It has the characteristics of low viscosity at low temperature and high viscosity at high temperature, which ensures that the glaze and metal particles are fully wetted at low temperature, while at high temperature it can effectively prevent high-density metal particles from settling into the base glaze.

[0027] The metal dry granule protective glaze formulation of this technical solution increases the content of silicon oxide, aluminum oxide, potassium oxide and sodium oxide, and correspondingly reduces the proportion of calcium oxide, magnesium oxide, barium oxide and zinc oxide to achieve the above performance objectives.

[0028] The method for preparing decorative ceramic tiles with a golden or white-gold metallic luster, as described in this invention, also includes the following special optimization designs: (1) Charge-driven controllable and precise positioning technology for metal particles: Traditional metallic glazes typically involve uniformly incorporating metal ions into the glaze, relying on the formation and directional alignment of metal oxide crystals of specific sizes during firing to achieve the metallic luster effect. However, this mechanism presents significant uncertainties in controlling the final decorative effect. To overcome this technical bottleneck, this technology attempts to directly utilize metal particles as the source of metallic luster. However, simply mixing metal particles with polished glaze using a simple mechanical method also fails to achieve precise control over the decorative effect.

[0029] In this technical solution, before spraying the metal granules, the granules are subjected to agitation and friction treatment using a micro-agitator, causing their surface to acquire a negative charge. Based on the principle of attraction between opposite charges, the metal granules can adhere firmly and precisely to the adhesive area. Furthermore, if an Italian-imported high-precision granulator or more advanced related equipment is used, the positioning error can be kept to within 0.3mm, achieving millimeter-level precision in metal granule spraying.

[0030] In summary, the charge-driven controllable positioning technology for metal particles in this technical solution effectively solves the problems of difficult positioning and unstable bonding of metal particles on the glaze surface by imparting opposite charges to the adhesive and the dry metal particles, and then achieving precise positioning with the help of a high-precision dry granulator. This technological breakthrough lays an important foundation for improving the decorative effect and design freedom of metallic-luster decorative tiles.

[0031] (2) Color control technology for metallic luster: The decorative effect of metallic ceramic tiles lies in the luster characteristics of the metallic particles. To overcome aesthetic fatigue caused by a single luster color, enriching the variety of metallic lusters has become key to enhancing product value. Essentially, metallic luster is an intrinsic physical property determined by the metallic bonds and band structure within a material, meaning its color and brightness directly depend on the chemical composition and microstructure of the metal.

[0032] This invention successfully developed two types of metallic luster decorative tiles with different visual effects by selecting intermetallic compound AlCu3 (which presents a golden color) and Fe-Cr-Mn alloy particles (which present a white gold color) as functional luster components.

[0033] In summary, the metallic decorative ceramic tiles developed in this project are characterized by simple and controllable processing, rich colors, and outstanding decorative effects.

[0034] The technical solution of this invention, without fundamentally altering the original ceramic tile production process, breaks through the traditional technical approach of metallic luster decoration and, through optimized supporting processes, develops a simple and controllable metallic luster decoration technology suitable for ceramic tiles. Compared with conventional ceramic tiles, the main technical features and innovations of this solution are reflected in: (1) Breaking through the bottleneck of high-temperature oxidation resistance, creating a direct metal particle decoration technology: Traditional metallic finish decorative techniques suffer from poor controllability. While directly using metal particles as the source of metallic luster in ceramic tiles improves controllability, it faces the challenge of easy oxidation of these particles at high temperatures. To address this, this technical solution successfully establishes a triple synergistic protection mechanism by selecting intrinsically high oxidation-resistant metal particles, employing a "dry granulation" technique to coat a nano-silica layer, and forming a dense aluminosilicate coating layer in the early stages of sintering. This overcomes the problem of oxidation resistance of metal particles under high-temperature conditions.

[0035] (2) A simple and controllable production technology for metallic decorative ceramic tiles has been developed: This invention utilizes intermetallic compounds AlCu3 and Fe-Cr-Mn alloy particles as the source of functional luster. Through systematic optimization of the glaze and base glaze formulations, and the development of charge-driven controllable and precise positioning technology for metallic particles and color regulation technology for metallic luster, a simple and controllable production technology for metallic decorative tiles has been developed without significantly altering the original tile manufacturing process. The resulting tiles exhibit a shimmering, metallic, laser-like texture, combining a fashionable aesthetic with artistic expression. By integrating natural materials with artistically created colors and textures, the high-level aesthetic experience of the tile products is further enhanced. Attached Figure Description

[0036] Figure 1 This is a flowchart illustrating the manufacturing process of the decorative ceramic tile with a metallic luster according to the present invention.

[0037] Figure 2 and Figure 3 The images show SEM images and corresponding energy dispersive spectroscopy (EDS) results of metallic ceramic tiles decorated with AlCu3 intermetallic compound particles (golden color) and Fe-Cr-Mn alloy particles (white gold color).

[0038] Figure 4 SEM images and energy dispersive spectroscopy (EDS) images of the surface of decorative ceramic tiles made with Fe-Cr-Mn alloy particles (white gold) after hydrofluoric acid etching. Detailed Implementation

[0039] To make the application, technical solution, and advantages of this invention clearer, the invention is described in detail with reference to specific embodiments. It should be understood that the embodiments are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Any simple improvements to the preparation method of this invention based on the inventive concept fall within the scope of protection of this invention.

[0040] The chemical composition of some of the glaze raw materials selected in this embodiment is detailed in Table 1: Table 1 Chemical composition of raw materials for metallic decorative ceramic tile glazes (mass percentage %)

[0041] In addition to mineral raw materials, there are also chemically pure raw materials as follows: alumina (Al2O3, purity > 99%, particle size 1-5μm), zirconium silicate (ZrSiO4, purity > 99%), quartz powder (SiO2, purity > 99.5%), lithium carbonate (Li2CO3, purity > 99.5%), zinc oxide (ZnO, purity > 99%), calcium carbonate (CaCO3, purity > 99%), calcium fluoride (CaF2, purity > 99%), barium carbonate (BaCO3, purity > 99%), titanium dioxide (TiO2, purity > 99%), aluminum silicate (Al2SiO5, purity > 99%), boric acid (H3BO3, purity > 99%), and sodium silicate (Na2SiO3, purity > 99%). Example 1

[0042] A decorative ceramic tile with a golden metallic luster and its preparation method A decorative ceramic tile with a golden metallic luster, comprising: metallic dry particles and a metallic dry particle protective glaze; The aforementioned dry metal granules comprise the following raw material components by mass percentage: The functional component with metallic luster is 45%, boric acid is 10%, aluminum silicate is 30%, titanium dioxide is 8%, and silicate is 7%. The silicate is a combination of sodium silicate, potassium silicate, calcium silicate, magnesium silicate and zinc silicate; The metallic luster functional component is: intermetallic compound AlCu3 particles; the particle size is controlled within the range of 120-200 mesh. The aforementioned metal dry granule protective glaze comprises the following raw material components by weight percentage: Inorganic components 50%, organic binder 50%; The inorganic components comprise the following raw material components by mass percentage: potassium feldspar 28%, sodium feldspar 30%, calcined talc 4%, calcite 9%, kaolin 9%, zinc oxide 8%, zirconium silicate 4%, quartz powder 2%, barium carbonate 2%, and alumina 4%. The additives include 0.13% sodium tripolyphosphate, 0.18% methylcellulose, and an appropriate amount of water.

[0043] The organic adhesive comprises the following raw material components in parts by weight: 100 parts water, 6 parts hydroxypropyl methylcellulose, 4 parts ethylene glycol, 0.3 parts sodium tripolyphosphate, and 0.14 parts preservative.

[0044] The method for preparing decorative ceramic tiles with a golden metallic luster includes the following preparation steps: S1. Apply a base glaze to the body; S2. Inkjet print the design pattern and then spray adhesive onto the design pattern; S3. Apply metal dry granules to the adhesive area described in step S2 using a high-precision dry granulator; S4. Apply a protective glaze of dry metallic particles using a glazing machine; S5. The finished product is obtained after drying, high-temperature firing, polishing, and sorting and inspection.

[0045] The aforementioned dry metal granules include the following preparation steps: Weigh the raw material components according to the corresponding formula ratio, mix the raw material components evenly, melt at 1255℃~1340℃, keep at the temperature for 4~6 hours, and then slowly cool to room temperature at a cooling rate of 8~15℃ / h to precipitate crystals. After crushing and screening into 120~200 mesh dry particles, the metal dry particles are prepared.

[0046] The aforementioned metal dry granule protective glaze comprises the following preparation steps: Weigh the corresponding inorganic components and organic binders according to the corresponding formula ratio, mix them evenly, and pass them through a 325-mesh sieve to prepare a metal dry granule protective glaze with a specific gravity of 1.23±0.02g / ml.

[0047] The inorganic component comprises the following preparation steps: Weigh the raw materials according to the corresponding formula ratio, mix them evenly, melt them at 1550℃ and keep them at that temperature for 10 to 12 hours; then slowly cool them to room temperature at a rate of 6 to 20℃ / hour to allow crystals to precipitate. After the obtained crystals are crushed, particles of 250-400 mesh are screened out to obtain the inorganic component. The organic adhesive comprises the following preparation steps: Weigh the raw materials according to the corresponding formula ratio, stir all the raw materials evenly, grind them finely, and pass them through a 325-mesh sieve to prepare the organic adhesive.

[0048] The base glaze comprises the following raw material components by weight percentage: Potassium feldspar 48%, calcite 5%, kaolin 17%, quartz powder 9%, barium carbonate 3%, alumina 3%, wollastonite 7%, calcined talc 6%, zinc oxide 2%; Add 0.14% sodium carboxymethyl cellulose and 0.2% sodium tripolyphosphate. Mix all raw materials evenly, and then ball mill, discharge the slurry, pass through a 325-mesh sieve and remove iron to prepare the base glaze.

[0049] The base glaze comprises the following chemical composition by mass percentage: SiO2 59.3%, Al2O3 16.59%, CaO 6.09%, MgO 1.92%, K2O 4.5%, Na2O 1.54%, ZnO 1.99%, BaO 2.97%, Fe2O3 0.25%, with a loss on ignition of 4.69%, and the remaining 0.16% being trace elements such as TiO2.

[0050] The adhesive is a polyvinyl alcohol solution, with the addition of a silane coupling agent at a mass percentage of 0.1% of the polyvinyl alcohol solution and a polycationic electrolyte at a mass percentage of 0.5% of the polyvinyl alcohol solution. The three are mixed evenly and then sieved to obtain the final product. Example 2

[0051] A decorative ceramic tile with a white-gold metallic luster and its preparation method The difference between Example 2 and Example 1 in terms of raw material composition and preparation method is as follows: In Example 2, Fe-Cr-Mn alloy particles were used instead of the intermetallic compound AlCu3 particles in Example 1.

[0052] The metallic decorative ceramic tile products prepared in Examples 1 and 2 met all the standard requirements. Performance test data are shown in Table 2.

[0053] Table 2. Performance characteristics of the metallic-luster decorative ceramic tile products from Examples 1 and 2.

[0054] Figure 2 and Figure 3 SEM images and corresponding energy dispersive spectroscopy (EDS) results of metallic ceramic tiles decorated with intermetallic compound AlCu3 particles (golden color) and Fe-Cr-Mn alloy particles (white gold color) are shown. Microstructural analysis indicates that the metal particles are uniformly dispersed within the glaze layer and well-bonded, without exhibiting thermal mismatch issues due to excessive surface tension differences. Further comparison of the morphology of the dry metal particles reveals that they retain their original form well, indicating that no significant oxidation or erosion by the glaze melt occurred during firing. EDS analysis further confirms that the chemical composition of the metal particles remains largely unchanged, without significant chemical reaction with the glaze melt.

[0055] To explore the mechanism of action of metal dry particle protective glaze, taking Fe-Cr-Mn alloy particle (white gold) decorative ceramic tile as an example, hydrofluoric acid was used to corrode the glaze surface to remove the glass phase, exposing the internal metal particles. Figure 4This paper presents SEM images and energy dispersive spectroscopy (EDS) analysis results of the ceramic tile surface after hydrofluoric acid etching. Microstructural observation reveals a dense shell approximately 3 μm thick uniformly coated on the surface of the Fe-Cr-Mn alloy particles. EDS analysis indicates that this shell is an aluminosilicate material, in which metal ions such as K, Mg, Na, Cr, and Mn are used to maintain equilibrium valence states. The presence of this dense shell effectively enhances the oxidation resistance of the metal particles and prevents them from being eroded by the glaze melt at high temperatures. The formation of this aluminosilicate shell can be attributed to the synergistic reaction between the aluminosilicate component in the dry metal particles and the specially designed positioning protective glaze during the firing process. Because the surface of the metal particles is pre-coated with an extremely thin layer of nano-silica, its high chemical reactivity allows it to preferentially react with the flux in the positioning protective glaze, thereby forming a uniform and dense aluminosilicate shell on the surface of the metal particles. Furthermore, EDS analysis also observed the diffusion of Cr and Mn elements from the Fe-Cr-Mn alloy particles into the outer shell.

[0056] In summary, the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any changes, modifications, and evolutions made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content shall be considered equivalent embodiments of the present invention. Furthermore, any changes, modifications, and evolutions made to the above embodiments based on the essential technology of the present invention shall still fall within the protection scope of the present invention.

[0057] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0058] Experimental methods not specified in this invention are generally performed under conventional conditions or as recommended by the manufacturer.

[0059] Unless otherwise stated, the various optimized technical solutions in this invention can be combined with each other.

[0060] Unless otherwise stated, percentages and parts are percentages and parts by mass.

[0061] Experimental methods not specified in the instructions and examples are generally performed under standard conditions or as recommended by the manufacturer.

[0062] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be used in the methods of this invention.

Claims

1. A decorative tile with golden or platinum metallic luster, characterized in that it comprises: metallic dry particles and a metallic dry particle protective glaze; the metallic dry particles comprise the following mass percentage raw material components: metallic luster functional components 40-60%, boric acid 7-15%, aluminum silicate 30-50%, titanium dioxide 5-10%, silicate 5-10%, and the sum of all components is 100%; the silicate is one or a combination of sodium silicate, potassium silicate, calcium silicate, magnesium silicate and zinc silicate; the metallic luster functional components are intermetallic compound AlCu3 particles or Fe-Cr-Mn alloy particles, and the particle size range is controlled at 120-200 mesh; the metallic dry particle protective glaze comprises the following mass percentage raw material components: inorganic components 40-50% and organic binder 50-60%; the inorganic components comprise the following mass percentage raw material components: potassium feldspar 26-30%, sodium feldspar 28-33%, calcined talc 2-5%, calcite 8-10%, kaolin 9-10%, zinc oxide 7-9%, zirconium silicate 4-6%, quartz powder 2-3%, barium carbonate 1-2%, aluminum oxide 4-6%, and the sum of all components is 100%; and additional auxiliary raw materials, which comprise 0.13% sodium tripolyphosphate, 0.18% methyl cellulose and an appropriate amount of water.

2. The decorative tile with golden or platinum metallic luster according to claim 1, characterized in that the mass percentage chemical composition of the metallic dry particle protective glaze is: SiO2 48.03-58.60%, Al2O3 15.81-19.62%, ZnO 6.98-8.98%, CaO 4.6-5.7%, MgO 0.7-1.6%, K2O 2.6-3.1%, Na2O 3.2-3.8%, ZrO2 2.6-4.0%, BaO 0.99-1.98%, other 0.11-0.3%, loss on ignition 4.89-5.98%, and the sum of all components is 100%.

3. The decorative tile with golden or platinum metallic luster according to claim 1, characterized in that the organic binder comprises the following mass parts of raw material components: water 100 parts, hydroxypropyl methyl cellulose 6 parts, ethylene glycol 4 parts, sodium tripolyphosphate 0.3 parts, and preservative 0.14 parts.

4. A preparation method of the decorative tile with golden or platinum metallic luster according to claim 1, characterized in that it comprises the following preparation steps: S1. applying a base glaze on a body; S2. inkjet printing a design pattern and spraying an adhesive according to the design pattern; S3. spraying metallic dry particles on the adhesive area according to step S2 using a high-precision dry particle machine; S4. spraying a metallic dry particle protective glaze through a glaze spraying machine; S5. obtaining a finished product through drying, high-temperature firing, polishing and sorting inspection.

5. The preparation method of the decorative tile with golden or platinum metallic luster according to claim 4, characterized in that the metallic dry particles comprise the following preparation steps: ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ The raw material components are weighed according to the corresponding formula, mixed uniformly, melted at 1255-1340°C, and kept for 4-6 hours, then slowly cooled to room temperature at a rate of 8-15°C / h, so that crystals are precipitated, broken, and sieved to obtain dry particles of 120-200 mesh.

6. The method for preparing the decorative ceramic tile with golden or platinum metallic luster according to claim 4, characterized in that: The preparation steps of the metal dry particle protective glaze include: The corresponding inorganic components and organic binder are weighed according to the corresponding formula, mixed uniformly, and sieved through a 325 mesh screen to obtain a metal dry particle protective glaze with a specific gravity of 1.23±0.02 g / ml.

7. The method for preparing the decorative ceramic tile with golden or platinum metallic luster according to claim 6, characterized in that: The preparation steps of the inorganic components include: The raw materials are weighed according to the corresponding formula, mixed uniformly, melted at 1550°C, and kept for 10-12 hours, then slowly cooled to room temperature at a rate of 6-20°C / h, so that crystals are precipitated; The obtained crystals are broken and sieved to obtain particles of 250-400 mesh, thereby obtaining the inorganic components; The preparation steps of the organic binder include: The raw materials are weighed according to the corresponding formula, stirred uniformly, finely ground, and sieved through a 325 mesh screen to obtain the organic binder.

8. The method for preparing the decorative ceramic tile with golden or platinum metallic luster according to claim 4, characterized in that: The base glaze includes the following raw material components with the following mass percentages: Potassium feldspar 46-53%, calcite 5-6%, kaolin 15-18%, quartz powder 9-12%, barium carbonate 2-4%, alumina 2-4%, wollastonite 7-9%, burned talc 4-7%, zinc oxide 1-3%, and the sum of all components is 100%; In addition, 0.14% of sodium carboxymethyl cellulose and 0.2% of sodium tripolyphosphate are added, all raw materials are stirred uniformly, ball milled, slurry is discharged, sieved through a 325 mesh screen, and iron is removed to obtain the base glaze.

9. The method for preparing the decorative ceramic tile with golden or platinum metallic luster according to claim 4, characterized in that: The base glaze includes the following chemical components with the following mass percentages: SiO2 58.23-65.35%, Al2O3 15.77-17.53%, CaO 5.50-8.08%, MgO 1.32-2.28%, K2O 4.15-4.99%, Na2O 1.42-1.72%, ZnO 1.0-3.0%, BaO 1.98-3.95%, Fe2O3 0.23-0.27, loss on ignition 3.10-5.68%, and the rest are trace elements, and the sum of all components is 100%.

10. The method for preparing the decorative ceramic tile with golden or platinum metallic luster according to claim 4, characterized in that: The adhesion agent is a polyvinyl alcohol solution, and 0.1% of a silane coupling agent and 0.5% of a polycation electrolyte are additionally added to the polyvinyl alcohol solution, and the three are uniformly mixed to obtain the adhesion agent.

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