Ceramic tile based on medium temperature sintering one-time sintering leopard pattern composite texture and preparation method

Abstract

This invention relates to ceramic tiles with a leopard print composite texture based on medium-temperature sintering and single firing, and a preparation method thereof. The preparation method includes: (1) green body preparation: obtaining a green body through powder preparation, material distribution, pressing, and drying; (2) applying slip: applying glaze by pouring, with a specific gravity of 1.80–1.85 and a glaze amount of 450–650 g / m³. 2 (3) Adhesive fixing agent printing: 3D ceramic inkjet printing is used, with a blank temperature of 40-65℃ and a printing volume of 50-120g / m³. 2 (4) Special dry granule application: Mix metal oxide-based and zirconium-based dry granules in a certain proportion and apply them to the adhesive area. The mesh size of the dry granules is 80-300 mesh, and the application rate is 150-650 g / m². 2 (5) Dust removal and recovery of excess dry particles; (6) Drying: Infrared drying, temperature 100-200℃, time 1-3 min; (7) Applying protective glaze: Spray glaze, specific gravity 1.20-1.35, glaze amount 120-300 g / m³ 2 (7) Firing: Medium-temperature sintering in a roller kiln at 1100-1220℃ for 30-60 minutes; (8) Post-treatment: Polishing or edge grinding without polishing to obtain the finished product.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics technology, specifically relating to an art ceramic tile with leopard print composite texture based on a medium-temperature sintering one-time firing process and its method. In particular, it relates to a ceramic tile preparation process that combines digital adhesive positioning, special dry granule application and medium-temperature sintering technology to achieve high efficiency, energy saving, three-dimensional texture and stable physical and chemical properties. Background Technology

[0002] In recent years, while architectural ceramics have made some progress in decorative technology, they still face many challenges. Traditional art ceramic tiles often employ multiple firings or high-temperature sintering (usually above 1180℃) to achieve complex textures, resulting in high energy consumption, weak glaze adhesion, blurred textures, and a low rate of high-quality products. Furthermore, limitations in glaze formulations and mismatched sintering processes easily lead to poor glaze surface smoothness and unstable mechanical properties, making it difficult to meet the demands of large-scale architectural ceramic production.

[0003] In existing technologies, such as CN110922057A, although the tiger and leopard pattern glaze effect is achieved, it relies on high-temperature kiln transformation, which is complex, costly, and limited to daily-use ceramics. CN117682766A achieves natural textures through glaze layering, but there are risks of glaze peeling, color mixing, and micro-cracks, requiring extremely high process control. CN118495813A uses alkali-aggregate reaction to form cracks, resulting in a single decorative effect with poor repeatability, and still requires high-temperature sintering.

[0004] Therefore, there is an urgent need to develop a medium-temperature sintering and one-time firing process suitable for architectural ceramics, which can achieve efficient and stable preparation of biomimetic textures such as leopard print while ensuring the glaze effect and physicochemical properties. This would break through the excessive reliance on inkjet printing in existing technologies and enhance the decorative diversity and market competitiveness of products. Summary of the Invention

[0005] This invention aims to address the problems of complex processes, high energy consumption, difficulty in texture control, and unstable glaze performance in existing technologies, and provides a method for preparing leopard-print composite textured ceramic tiles based on medium-temperature sintering and single-firing. This method combines digital adhesive positioning technology with a specially formulated ratio of dry granular materials to achieve a three-dimensional, natural, and varied leopard-print effect in a single firing, possessing both aesthetic value and excellent physicochemical properties. Another objective of this invention is to provide a preparation method using a heat-sensitive binder and multi-layered glaze composite, further optimizing the glaze structure and enhancing texture clarity and glaze adhesion.

[0006] The technical solution of this invention is the method for preparing ceramic tiles with a leopard print composite texture based on medium-temperature sintering and one-time firing, which is characterized by including the following steps: (1) Green body preparation: The green body is obtained through powdering, spreading, pressing and drying; (2) Applying slip: Apply glaze by pouring, with a specific gravity of 1.80–1.85 and a glaze weight of 450–650 g / m³. 2 ; (3) Adhesive fixing agent printing: 3D ceramic inkjet printing is used, with a blank temperature of 40-65℃ and a printing volume of 50-120g / m³. 2 ; (4) Special dry granule application: Mix metal oxide-based and zirconium-based dry granules in a certain proportion and apply them to the adhesive area. The mesh size of the dry granules is 80-300 mesh, and the application rate is 150-650 g / m². 2 Excess dry particles are collected and recycled. (5) Drying: Infrared drying is used at a temperature of 100-200℃ for 1-3 minutes; (6) Apply protective glaze: Use spray glazing method; the specific gravity of the protective glaze is 1.20–1.35, and the glaze amount is 120–300 g / m³. 2 ; (7) Firing: Medium-temperature sintering is carried out in a roller kiln at a temperature of 1100-1220℃ for a cycle of 30-60 minutes; (8) Post-processing: Polishing or edge grinding without polishing to obtain the finished product.

[0007] Preferably, the adhesive fixative in step (3) consists of the following components by weight percentage: cyclohexane 7-15 wt%, isopropyl lauryl 10-25 wt%, polyurethane 0.5-7 wt%, sodium carboxymethyl cellulose 0.1-1 wt%, inorganic powder 4-15 wt%, and water 45-70 wt%. The preparation method of the adhesive fixative includes: mixing and stirring, sand milling, sieving, and performance testing to ensure that its particle size D50 ≤ 0.4 μm, viscosity 3~12 mPa·s, and surface tension 25~50 mN / m.

[0008] Preferably, the special dry granules in step (4) are composed of 10-50% metal oxide dry granules and 50-90% zirconium dry granules, wherein the metal oxides are one or more of manganese oxide, iron oxide, cobalt oxide, nickel oxide, and chromium oxide; different metal oxide dry granules may exhibit different colors. The metal oxide dry granules and the zirconium dry granules are respectively obtained from the corresponding raw materials by ball milling, spray granulation, light calcination at 750-950℃, crushing and screening.

[0009] Preferably, the metal oxide raw material is composed of the following components by weight percentage: calcined zinc oxide 1-5 wt%, barium carbonate 2-7 wt%, potassium feldspar 15-25 wt%, sodium feldspar 8-20 wt%, calcite 3-10 wt%, Zhangzhou kaolin 3-8 wt%, calcined kaolin 3-8 wt%, manganese oxide 2-8 wt%, iron oxide 0-8 wt%, cobalt oxide 0-8 wt%, nickel oxide 0-8 wt%, chromium oxide 0-8 wt%, A-type frit 6-12 wt%, and low-temperature frit powder 10-30 wt%. The chemical composition of the metal oxide raw material is as follows by weight percentage: SiO2 45-55wt%, Al2O3 8-15wt%, Fe2O3 0-8wt%, K2O 2-5wt%, Na2O 2-5wt%, CaO 3-8wt%, MgO 0.1-1wt%, ZnO 5-10wt%, MnO 3-8wt%, CoO 0-8wt%, NiO 0-8wt%, CrO 0-8wt%, B2O3 2-6wt%, BaO 2-6wt%, and loss on ignition 1-6wt%. The zirconium-based raw material is composed of the following components by weight percentage: calcined zinc oxide 1-3 wt%, barium carbonate 2-6 wt%, zirconium silicate 7-15 wt%, potassium feldspar 12-22 wt%, sodium feldspar 7-15 wt%, calcite 3-8 wt%, dolomite 1-5 wt%, Zhangzhou kaolin 3-8 wt%, A-type frit 7-15 wt%, and low-temperature frit powder 20-40 wt%. The chemical composition of the zirconium-based raw material is as follows by weight percentage: SiO2 45-55wt%, Al2O3 6-12wt%, Fe2O3 ≤0.17wt%, K2O 2-6wt%, Na2O 2-5wt%, CaO 5-10wt%, MgO 1-3wt%, ZnO 3-8wt%, ZrO2 5-10wt%, B2O3 3-8wt%, BaO 2-6wt%, and loss on ignition 2-7wt%.

[0010] Preferably, the low-temperature frit powder is obtained by melting a low-temperature raw material formula at a temperature of 1400-1600℃ to form a melt, then adding water and rapidly cooling it to obtain a blocky glassy state, which is then crushed and sieved by a pulverizer to obtain low-temperature frit powder; the mesh size of the low-temperature frit powder is controlled to be 120-250 mesh. The low-temperature raw material formulation consists of the following components by weight percentage: zinc oxide 7-12 wt%, barium carbonate 1-5 wt%, aluminum oxide 3-8 wt%, quartz 30-50 wt%, wollastonite 15-25 wt%, magnesium oxide 1-3 wt%, boron oxide 10-20 wt%, sodium carbonate 2-6 wt%, and potassium carbonate 2-6 wt%. The chemical composition of the low-temperature raw material consists of the following components by weight percentage: SiO2 50-60wt%, Al2O3 3-10wt%, Fe2O3 ≤0.3wt%, K2O 2-5wt%, Na2O 2-5wt%, CaO 3-8wt%, MgO 0.1-2.0wt%, ZnO 5-10wt%, B2O3 10-20wt%, BaO 0.5-2wt%, and loss on ignition 0.01-5wt%. The chemical composition of the A-type frit consists of the following components by weight percentage: SiO2 55-65wt%, Al2O3 3-10wt%, Fe2O3 ≤0.15wt%, K2O 2-6wt%, Na2O 0.1-1wt%, CaO 7-15wt%, MgO 1-3wt%, ZnO 10-20wt%, B2O3 0.1-1wt%, BaO 0.1-1wt%, and loss on ignition 0.01-1%.

[0011] Another technical solution of the present invention is a method for preparing leopard print composite textured ceramic tiles based on medium-temperature sintering and one-time firing, characterized by the following structural layers: Ceramic tile body; slip layer applied to the surface of the ceramic tile body; adhesive fixative pattern layer applied to the slip layer by digital printing; A special dry granule layer applied to the adhesive fixative pattern layer, the special dry granules being a mixture of metal oxide dry granules and zirconium dry granules in a set ratio; a protective glaze layer covering the special dry granule layer; and a glaze layer with a leopard print composite texture formed after medium-temperature sintering.

[0012] Another technical solution of the present invention is the preparation method of the single-fired leopard print art ceramic tile based on a thermosensitive binder and a multi-layer glaze, which is characterized by including the following steps: (1) Preparation of the blank: The brick blank is obtained after powdering, spreading, pressing and drying; (2) Application of the base glaze: Apply the base glaze by pouring or spraying, with a glaze thickness of 0.3 to 0.8 mm; (3) Printing of thermal adhesive: The thermal adhesive pattern is printed on the underlying glaze using digital inkjet printing. (4) Dry granule application: Apply leopard print effect dry granules to the areas printed with thermal adhesive; (5) Application of intermediate glaze: Apply an intermediate transparent glaze to cover the dry granule layer; (6) Application of protective glaze: Apply a protective glaze to the surface; (7) Single firing: Firing once in a roller kiln at 1080-1180℃ for 35-70 minutes.

[0013] Preferably, the heat-sensitive adhesive comprises the following components by weight percentage: Thermoplastic resin 10–20 wt%; inorganic binder 5–15 wt%; solvent 65–85 wt%; surfactant 0.1–1 wt%; The thermoplastic resin is polyvinyl butyral (PVB) or polyacrylate. The leopard print effect dry particles consist of 40-60% metal oxide crystalline dry particles and 40-60% zirconium-based opaque dry particles. The metal oxide content of the metal oxide-based crystalline dry particles is 5-10 wt%, and the ZrO2 content of the zirconium-based opaque dry particles is 8-12 wt%. The brick blank is a flat or mold-faced blank with a water absorption rate of ≤0.5%.

[0014] Preferably, the bottom glaze is an opaque glaze with a specific gravity of 1.75 to 1.90. The refractive index of the intermediate transparent glaze is higher than that of the bottom glaze, and the glaze thickness is 0.1–0.3 mm. The protective glaze is a high-hardness transparent glaze with a Mohs hardness of ≥6.

[0015] Preferably, the primary firing parameters in step (7) include: Heating rate: 10–20 °C / min; Peak temperature: 1120~1160℃; Keep warm for 5 to 15 minutes; Cooling rate: 15~25℃ / min.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention provides a method for preparing one-time leopard print composite textured art ceramic tiles based on medium-temperature sintering technology. Dry granules with different performance effects are prepared by calcination using medium-temperature sintering technology. Digital adhesive positioning decoration technology is used instead of traditional art glaze as the main process. Dry granules of different proportions are mixed and matched according to design requirements to form varied three-dimensional biomimetic leopard print textures on the surface of the tile blank. This effectively solves the problems of previous glazes causing fluctuations in glaze application, resulting in unnatural textures when different glazes are superimposed, and issues such as glaze peeling or color mixing. It breaks through the monotonous flatness of traditional ceramic tiles, enhances the decorative expression and simulation effect of the product, restores the natural wild beauty, and allows for flexible and diverse application scenarios, meeting the market demand for personalized, high-quality biomimetic ceramic tiles.

[0017] (2) This invention provides a calcined dry granule, which is fired at a temperature of 750-950°C using medium-temperature sintering technology. Since the calcined dry granule only undergoes dehydration, decomposition, and solid-phase reaction stages and does not have time to melt, it contains very little glass phase. Compared with the almost 100% glass phase of the completely melted frit, it still has a higher initial melting point and can replace the frit for ceramic tile surface decoration, effectively reducing production costs and improving the product's market competitiveness.

[0018] (3) The calcined dry granules provided by this invention have a low firing temperature and do not undergo a melting reaction stage. The dry granules have a relatively loose structure and low strength. The dry granules can be processed from calcined materials into dry granules with only simple crushing, sieving and grading. The processing technology is simple, reduces environmental pollution and lowers production costs.

[0019] (4) The entire process of this invention is highly efficient and convenient. Different biomimetic ceramic tile products can be produced simply by switching different texture and pattern designs according to production needs, which greatly improves production efficiency and adaptability. At the same time, the dry granules of the calcined material after the first light firing have high surface activity, and the secondary roller kiln firing temperature is relatively low. This solves the problems of high firing temperature and long firing cycle of traditional art glazes, and incompatibility with the firing system of building ceramic tiles. The physical and chemical properties of the product are stable, which is conducive to large-scale production.

[0020] (5) The medium-temperature single-firing process significantly reduces energy consumption and improves production efficiency; the dry granules are precisely positioned using digital adhesive, resulting in clear textures and good consistency, avoiding glaze peeling and color mixing; the self-made metal oxide / zirconium-based calcined dry granules have high activity, high initial melting point, and low cost, making them suitable for medium-temperature sintering; the protection of the glaze layer and the optimization of the sintering regime ensure the smoothness of the glaze surface and the stability of its physicochemical properties; the process is highly digitalized, the dry granules are recyclable, highly adaptable, and facilitate large-scale production and diverse texture designs.

[0021] Attached Figure Description

[0022] Figure 1 This is a surface effect image of the leopard-print ceramic tile obtained in Embodiment 1 of the present invention; Figure 2 This is a surface effect image of the leopard-print ceramic tile obtained in Embodiment 2 of the present invention; Figure 3 This is a surface effect image of the leopard-print ceramic tile obtained in Embodiment 3 of the present invention. Detailed Implementation

[0023] The present invention will now be described in further detail with reference to the accompanying drawings: Figure 1 The first embodiment of the present invention is shown.

[0024] Please see Figure 1As shown, the method for preparing ceramic tiles with a leopard print composite texture based on medium-temperature sintering and single firing includes the following steps: (1) Preparation of the green body: a planar green body is obtained after powdering, feeding, pressing and drying. (2) Apply slip: Use a bell-shaped applicator to apply slip to the dried brick blank. The specific gravity is 1.82, and the glaze application rate is 550g / m². 2 ; (3) Adhesive fixative printing: Adhesive fixative is printed on the surface of the clay-coated blank using a 3D ceramic inkjet printer. The blank temperature is 50℃, and the adhesive fixative dosage is 60g / m². 2 ; The adhesive fixative described in step (3) consists of the following components by weight percentage: cyclohexane 10%, isopropyl lauryl 15%, polyurethane 3.7%, sodium carboxymethyl cellulose 0.3%, inorganic powder 10%, and water 61%. The preparation method of the adhesive fixative includes: (1) Weigh and mix each component of the adhesive fixative according to its weight percentage, and then put it into a mixer for 60 minutes at a speed of 250 r / min to obtain a mixture; (2) Introduce the mixture into a sand mill and mill it for 180 minutes at a speed of 1500 r / min. Then sieve it for later use. (3) The mixture after sieving is tested using a laser particle size analyzer. The performance requirements of the mixture are: ① Particle size D50≤0.4±0.05μm, D100≤1μm±0.05, ② Viscosity controlled at 40℃ is 3~12mPa.s, ③ Surface tension coefficient is 25~50mN·m -1 To obtain adhesive fixatives with performance that meet the requirements for use; (4) Special dry granule application: Special dry granules are evenly applied to the surface of the ceramic blank coated with adhesive fixative using a ceramic dry granule application device. The dry granule mesh size is 80–300 mesh, and the dry granule weight is 420 g / m². 2 Use a dry particle suction dust removal device to remove dust from the green body and recycle excess dry particles for reuse. The special dry granules described in step (4) are composed of 10-50% metal oxide dry granules and 50-90% zirconium dry granules. The metal oxides are one or more of manganese oxide, iron oxide, cobalt oxide, nickel oxide, and chromium oxide. Different metal oxide dry granules can exhibit different colors.

[0025] As a further preferred embodiment, the special dry granules in step (4) are prepared by mixing 30% of self-made metal oxide dry granules and 70% of self-made zirconium dry granules evenly.

[0026] The metal oxide-based dry granules and the zirconium-based dry granules are respectively calcined from metal oxide-based raw materials and zirconium-based raw materials. The preparation method of the metal oxide-based dry particles and the zirconium-based dry particles includes the following steps: ① After the raw materials are proportioned according to the weight percentage of the corresponding raw material components in the metal oxide system and zirconium system raw material formula, they are fed into a continuous ball mill for wet ball milling for 6 hours. The glaze slurry obtained after ball milling is passed through a 325-mesh vibrating screen, and then iron is removed and aged for later use. ② The glaze slurry after ball milling and aging is fed into a spray drying tower and spray granulated to obtain powder particles. The obtained powder particles are controlled to be 60-320 mesh. ③ The powder particles are naturally piled into a rotary kiln for light firing. The rotary kiln is 48m long. The firing temperature of the self-made metal oxide dry particles is controlled at 800℃, and the firing temperature of the self-made zirconium dry particles is controlled at 850℃. The firing cycle is 220min, and the high temperature holding time is 45min to obtain calcined material. ④ The above-mentioned calcined material was crushed, and a combination of 80 mesh, 200 mesh and 300 mesh was selected for screening to obtain self-made metal oxide dry particles and self-made zirconium dry particles with particle sizes of 0.5 wt% above 80 mesh, 48 wt% above 200 mesh and 51.5 wt% below 300 mesh, respectively.

[0027] The metal oxide raw material is composed of the following components by weight percentage: calcined zinc oxide 3wt%, barium carbonate 5wt%, potassium feldspar 20wt%, sodium feldspar 15wt%, calcite 6wt%, Zhangzhou kaolin 6wt%, calcined kaolin 6wt%, manganese oxide 5wt%, A-type frit 9wt%, and low-temperature frit powder 25wt%. The chemical composition of the metal oxide raw material is as follows by weight percentage: SiO2 50.27wt%, Al2O3 12.96wt%, Fe2O3 0.16wt%, K2O 3.05wt%, Na2O 2.50wt%, CaO 6.08wt%, MgO 0.51wt%, ZnO 6.37wt%, MnO 5.00wt%, B2O3 3.81wt%, BaO 4.38wt%, and loss on ignition 4.91wt%. The zirconium-based raw material is composed of the following components by weight percentage: calcined zinc oxide 2wt%, barium carbonate 4wt%, zirconium silicate 10wt%, potassium feldspar 18wt%, sodium feldspar 12wt%, calcite 5wt%, dolomite 3wt%, Zhangzhou kaolin 6wt%, A-type frit 10wt%, and low-temperature frit powder 30wt%. The chemical composition of the zirconium-based raw material is as follows by weight percentage: SiO2 50.58wt%, Al2O3 9.69wt%, Fe2O3 0.15wt%, K2O 2.95wt%, Na2O 2.29wt%, CaO 6.85wt%, MgO 1.20wt%, ZnO 5.94wt%, ZrO2 6.43wt%, B2O3 4.57wt%, BaO 3.71wt%, and loss on ignition 5.64wt%.

[0028] The low-temperature frit powder is obtained by melting a low-temperature raw material formula at 1450℃ to form a melt, then adding it to water and rapidly cooling it to obtain a blocky glassy state. The melt is then crushed and sieved by a pulverizer to obtain the low-temperature frit powder. The mesh size of the low-temperature frit powder is controlled to be 120-250 mesh. The low-temperature raw material formulation consists of the following components by weight percentage: zinc oxide 8wt%, barium carbonate 2wt%, aluminum oxide 6wt%, quartz 41wt%, wollastonite 20wt%, magnesium oxide 1wt%, boron oxide 15wt%, sodium carbonate 4wt%, and potassium carbonate 3wt%. The chemical composition of the low-temperature raw material consists of the following components by weight percentage: SiO2 55.20wt%, Al2O3 6.72wt%, Fe2O3 0.09wt%, K2O 2.25wt%, Na2O 2.54wt%, CaO 6.50wt%, MgO 1.11wt%, ZnO 8.34wt%, B2O3 15.58wt%, BaO 1.62wt%, and loss on ignition 0.05wt%.

[0029] The A-type fused block is composed of the following chemical components by weight: SiO2 60.03wt%, Al2O3 6.69wt%, Fe2O3 0.07wt%, K2O 4.04wt%, Na2O 0.51wt%, CaO 12.17wt%, MgO 1.79wt%, ZnO 13.44wt%, B2O3 0.52wt%, BaO 0.37wt%, and loss on ignition 0.37%.

[0030] (5) Drying: The brick blanks with applied dry particles are dried with infrared light to control the humidity of the dry particle layer. The drying temperature is 160℃ and the drying time is 2 minutes. (6) Protective glaze spraying: Apply protective glaze to the brick blanks with dry particles adhering to the surface using a spray glaze method. The specific gravity of the protective glaze is 1.28, and the glaze amount is 180g / m². 2 ; (7) Kiln firing: The brick blanks that have completed all the decoration steps are sent into the roller kiln for firing at a temperature of 1165℃ for 50 minutes. The semi-finished ceramic bricks are then ground without polishing to obtain the finished ceramic bricks.

[0031] The leopard print composite textured art ceramic tile prepared by the aforementioned method includes the following structural layers: Ceramic tile blank; A layer of slip applied to the surface of the blank; A pattern layer of adhesive fixative applied to a layer of cosmetic clay using digital printing; A special dry granule layer applied on the adhesive fixative pattern layer, wherein the special dry granules are a mixture of metal oxide dry granules and zirconium dry granules in a certain proportion; A protective glaze layer covering the dry granule layer; A glaze layer with a leopard print composite texture is formed after medium-temperature sintering.

[0032] Figure 2 A second embodiment of the present invention is shown.

[0033] Please see Figure 2 As shown, the method for preparing ceramic tiles with a leopard print composite texture based on medium-temperature sintering and single firing includes the following steps: (1) Preparation of blank: After powdering, spreading, pressing and drying, a mold-faced blank is obtained; (2) Apply slip: Use a bell-shaped applicator to apply slip to the dried brick blank. The specific gravity is 1.80, and the glaze application rate is 630g / m². 2 ; (3) Adhesive fixative printing: Adhesive fixative is printed on the surface of the coated clay using a 3D ceramic inkjet printer. The blank temperature is 50℃, and the adhesive fixative dosage is 100g / m². 2 ; The adhesive fixative described in step (3) consists of the following components by weight percentage: cyclohexane 10wt%, isopropyl lauryl 15wt%, polyurethane 3.7wt%, sodium carboxymethyl cellulose 0.3wt%, inorganic powder 10wt%, and water 61wt%. The preparation method of the adhesive fixative includes: (1) Weigh and mix each component of the adhesive fixative according to its weight percentage, and then put it into a mixer for 60 minutes at a speed of 250 r / min to obtain a mixture; (2) Introduce the mixture into a sand mill and mill it for 180 minutes at a speed of 1500 r / min. Then sieve it for later use. (3) The mixture after sieving is tested using a laser particle size analyzer. The performance requirements of the mixture are: ① Particle size D50≤0.4±0.05μm, D100≤1μm±0.05, ② Viscosity controlled at 40℃ is 3~12mPa.s, ③ Surface tension coefficient is 25~50mN·m -1 To obtain adhesive fixatives with performance that meet the requirements for use.

[0034] (4) Special dry granule application: Special dry granules are evenly applied to the surface of the ceramic blank coated with adhesive fixative using a ceramic dry granule application device. The dry granule mesh size is 100–250 mesh, and the dry granule weight is 520 g / m³. 2 Use a dry particle suction dust removal device to remove dust from the green body and recycle excess dry particles for reuse. The special dry granules mentioned in step (4) are made by mixing 50 wt% of self-made metal oxide dry granules and 50 wt% of self-made zirconium dry granules evenly.

[0035] The metal oxide-based dry granules and the zirconium-based dry granules are respectively calcined from self-made metal oxide-based raw materials and self-made zirconium-based raw materials. The preparation methods for the self-made metal oxide-based dry granules and the self-made zirconium-based dry granules are as follows: ① After the raw materials are proportioned according to the weight percentage of the corresponding raw material components in the self-made metal oxide system and the self-made zirconium system raw material formula, they are fed into a continuous ball mill for wet ball milling for 6 hours. The glaze slurry obtained after ball milling is passed through a 325-mesh vibrating screen, and then iron is removed and aged for later use. ② The glaze slurry after ball milling and aging is fed into a spray drying tower and spray granulated to obtain powder particles. The obtained powder particles are controlled to be 60-320 mesh. ③ The powder particles are naturally piled into a rotary kiln for light firing. The rotary kiln is 48m long. The firing temperature of the self-made metal oxide dry particles is controlled at 750℃, and the firing temperature of the self-made zirconium dry particles is controlled at 850℃. The firing cycle is 260min, and the high temperature holding time is 45min to obtain calcined material. ④ The above calcined materials were crushed and sieved separately. A combination of 100 mesh, 160 mesh and 250 mesh was selected for sieving to obtain self-made metal oxide dry particles with a particle size distribution of 0.5 wt% above 80 mesh, 48 wt% above 160 mesh and 51.5 wt% below 250 mesh, and self-made zirconium dry particles with a particle size distribution of 0.8 wt% above 80 mesh, 40 wt% above 160 mesh and 59.2 wt% below 250 mesh.

[0036] The metal oxide raw material is composed of the following components by weight percentage: calcined zinc oxide 2wt%, barium carbonate 6wt%, potassium feldspar 22wt%, sodium feldspar 15wt%, calcite 6wt%, Zhangzhou kaolin 5wt%, calcined kaolin 5wt%, manganese oxide 5wt%, A-type frit 9wt%, and low-temperature frit powder 25wt%. The chemical composition of the metal oxide raw material consists of the following components by weight percentage: SiO2 50.14wt%, Al2O3 12.86wt%, Fe2O3 0.16wt%, K2O 3.81wt%, Na2O 2.49wt%, CaO 5.41wt%, MgO 0.51wt%, ZnO 7.15wt%, MnO 5.02wt%, B2O3 3.75wt%, BaO 4.38wt%, and loss on ignition 4.32wt%.

[0037] The zirconium-based raw material is composed of the following components by weight percentage: calcined zinc oxide 2wt%, barium carbonate 4wt%, zirconium silicate 11wt%, potassium feldspar 17wt%, sodium feldspar 12wt%, calcite 6wt%, dolomite 3wt%, Zhangzhou kaolin 6wt%, A-type frit 10wt%, and low-temperature frit powder 29wt%. The chemical composition of the zirconium-based raw material is as follows by weight percentage: SiO2 50.43wt%, Al2O3 9.58wt%, Fe2O3 0.15wt%, K2O 2.63wt%, Na2O 2.29wt%, CaO 6.85wt%, MgO 1.14wt%, ZnO 5.94wt%, ZrO2 7.31wt%, B2O3 4.53wt%, BaO 3.63wt%, and loss on ignition 5.52wt%.

[0038] The low-temperature frit powder is obtained by melting a low-temperature raw material formula at 1450°C to form a melt, then adding it to water and rapidly cooling it to obtain a blocky glassy state, which is then crushed and sieved by a pulverizer to obtain the low-temperature frit powder. The mesh size of the low-temperature frit powder crushing and screening is controlled to be 120-250 mesh; The low-temperature raw material formulation consists of the following components by weight percentage: zinc oxide 9wt%, barium carbonate 2wt%, aluminum oxide 4wt%, quartz 40wt%, wollastonite 20wt%, magnesium oxide 1wt%, boron oxide 15wt%, sodium carbonate 5wt%, and potassium carbonate 4wt%. The chemical composition of the low-temperature raw material consists of the following components by weight percentage: SiO2 55.23wt%, Al2O3 6.15wt%, Fe2O3 0.08wt%, K2O 2.39wt%, Na2O 2.61wt%, CaO 6.50wt%, MgO 1.11wt%, ZnO 8.65wt%, B2O3 15.58wt%, BaO 1.64wt%, and loss on ignition 0.06wt%.

[0039] The A-type frit is composed of the following chemical components by weight: SiO2 60.14wt%, Al2O3 6.58wt%, Fe2O3 0.08wt%, K2O 4.03wt%, Na2O 0.51wt%, CaO 12.21wt%, MgO 1.75wt%, ZnO 13.43wt%, B2O3 0.52wt%, BaO 0.38wt%, and loss on ignition 0.37%. (5) Drying: The brick blanks with applied dry particles are dried with infrared light to control the humidity of the dry particle layer. The drying temperature is 200℃ and the drying time is 1 minute. (6) Protective glaze spraying: Apply protective glaze to the brick blanks with dry particles adhering to the surface using a spray glaze method. The specific gravity of the protective glaze is 1.20, and the glaze amount is 300g / m². 2 ; (7) Kiln firing: The brick blanks that have completed all the decoration steps are sent into the roller kiln for firing at a temperature of 1165℃ for a firing cycle of 52 minutes. The semi-finished ceramic bricks after firing are then ground without polishing to finally obtain the finished ceramic bricks.

[0040] The leopard print composite textured art ceramic tile prepared by the aforementioned method includes the following structural layers: Ceramic tile blank; A layer of slip applied to the surface of the blank; A pattern layer of adhesive fixative applied to a layer of cosmetic clay using digital printing; A special dry granule layer applied on the adhesive fixative pattern layer, wherein the special dry granules are a mixture of metal oxide dry granules and zirconium dry granules in a certain proportion; A protective glaze layer covering the dry granule layer; A glaze layer with a leopard print composite texture is formed after medium-temperature sintering.

[0041] Figure 3 A third embodiment of the present invention is shown.

[0042] Please see Figure 3 As shown, a method for preparing ceramic tiles with a leopard-print composite texture based on medium-temperature sintering and single-firing is presented. (1) Preparation of the green body: a planar green body is obtained after powdering, feeding, pressing and drying. (2) Apply slip: Apply slip to the dried brick blank using a straight-line glazing method. The specific gravity is 1.84, and the glaze application rate is 480g / m². 2 ; (3) Adhesive fixative printing: Adhesive fixative is printed on the surface of the clay-coated blank using a 3D ceramic inkjet printer. The blank temperature is 60℃, and the adhesive fixative dosage is 85g / m². 2 ; The adhesive fixative described in step (3) is composed of the following components by weight percentage: cyclohexane 10wt%, isopropyl lauryl 15wt%, polyurethane 3.7wt%, sodium carboxymethyl cellulose 0.3wt%, inorganic powder 10wt%, and water 61wt%. The preparation method of the adhesive fixative includes: (1) Weigh and mix each component of the adhesive fixative according to its weight percentage, and then put it into a mixer for 60 minutes at a speed of 250 r / min to obtain a mixture; (2) Introduce the mixture into a sand mill and mill it for 180 minutes at a speed of 1500 r / min. Then sieve it for later use. (3) The mixture after sieving is tested using a laser particle size analyzer. The performance requirements of the mixture are: ① Particle size D50≤0.4±0.05μm, D100≤1μm±0.05, ② Viscosity controlled at 40℃ is 3~12mPa.s, ③ Surface tension coefficient is 25~50mN·m -1 To obtain adhesive fixatives with performance that meet the requirements for use; (4) Special dry granule application: Special dry granules are evenly applied to the surface of the ceramic blank coated with adhesive fixative using a ceramic dry granule application device. The dry granule mesh size is 80–300 mesh, and the dry granule weight is 480 g / m². 2 Use a dry particle suction dust removal device to remove dust from the green body and recycle excess dry particles for reuse. The special dry granules mentioned in step (4) are made by mixing 65 wt% of self-made metal oxide dry granules and 35 wt% of self-made zirconium dry granules evenly.

[0043] The metal oxide-based dry granules and the zirconium-based dry granules are respectively calcined from self-made metal oxide-based raw materials and self-made zirconium-based raw materials. The preparation methods of the metal oxide-based dry particles and the zirconium-based dry particles include: ① After the raw materials are proportioned according to the weight percentage of the corresponding raw material components in the self-made metal oxide system and the self-made zirconium system raw material formula, they are fed into a continuous ball mill for wet ball milling for 6 hours. The glaze slurry obtained after ball milling is passed through a 325-mesh vibrating screen, and then iron is removed and aged for later use. ② The glaze slurry after ball milling and aging is fed into a spray drying tower and spray granulated to obtain powder particles. The obtained powder particles are controlled to be 60-320 mesh. ③ The powder particles are naturally piled into a rotary kiln for light firing. The rotary kiln is 48m long. The firing temperature of the self-made metal oxide dry particles is controlled at 800℃, and the firing temperature of the self-made zirconium dry particles is controlled at 870℃. The firing cycle is 200min, and the high temperature holding time is 50min to obtain calcined material. ④ The above calcined materials were crushed and sieved separately. The combination of 80 mesh, 200 mesh and 300 mesh was selected to obtain self-made metal oxide dry particles with a particle size distribution of 0.1 wt% above 80 mesh, 29.9 wt% above 200 mesh and 70 wt% below 300 mesh, and self-made zirconium dry particles with a particle size distribution of 0.6 wt% above 80 mesh, 36 wt% above 200 mesh and 63.4 wt% below 300 mesh.

[0044] The metal oxide raw material is composed of the following components by weight percentage: calcined zinc oxide 3wt%, barium carbonate 6wt%, potassium feldspar 16wt%, sodium feldspar 17wt%, calcite 7wt%, Zhangzhou kaolin 6wt%, calcined kaolin 6wt%, manganese oxide 5wt%, A-type frit 6wt%, and low-temperature frit powder 28wt%. The chemical composition of the metal oxide raw material consists of the following components by weight percentage: SiO2 51.02wt%, Al2O3 9.86wt%, Fe2O3 0.18wt%, K2O 2.57wt%, Na2O 3.91wt%, CaO 6.08wt%, MgO 0.51wt%, ZnO 6.37wt%, MnO 5.11wt%, B2O3 3.87wt%, BaO 5.71wt%, and loss on ignition 4.81wt%.

[0045] The zirconium-based raw material is composed of the following components by weight percentage: calcined zinc oxide 2wt%, barium carbonate 4wt%, zirconium silicate 11wt%, potassium feldspar 18wt%, sodium feldspar 12wt%, calcite 5wt%, dolomite 2wt%, Zhangzhou kaolin 6wt%, A-type frit 10wt%, and low-temperature frit powder 30wt%. The chemical composition of the zirconium-based raw material is as follows by weight percentage: SiO2 50.33wt%, Al2O3 9.58wt%, Fe2O3 0.16wt%, K2O 2.97wt%, Na2O 2.38wt%, CaO 6.89wt%, MgO 1.25wt%, ZnO 5.94wt%, ZrO2 6.49wt%, B2O3 4.97wt%, BaO 3.73wt%, and loss on ignition 5.31wt%.

[0046] The low-temperature frit powder is obtained by melting a low-temperature raw material formula at 1450°C to form a melt, then adding it to water and rapidly cooling it to obtain a blocky glassy state, which is then crushed and sieved by a pulverizer to obtain the low-temperature frit powder. The mesh size of the low-temperature frit powder crushing and screening is controlled to be 120-250 mesh; The low-temperature raw material formulation consists of the following components by weight percentage: zinc oxide 8wt%, barium carbonate 2wt%, aluminum oxide 6wt%, quartz 41wt%, wollastonite 20wt%, magnesium oxide 1wt%, boron oxide 15wt%, sodium carbonate 4wt%, and potassium carbonate 3wt%. The chemical composition of the low-temperature raw material consists of the following components by weight percentage: SiO2 55.17wt%, Al2O3 6.75wt%, Fe2O3 0.07wt%, K2O 2.19wt%, Na2O 2.49wt%, CaO 6.57wt%, MgO 1.09wt%, ZnO 8.39wt%, B2O3 15.58wt%, BaO 1.63wt%, and loss on ignition 0.07wt%.

[0047] The A-type fused block is composed of the following chemical components by weight: SiO2 60.03wt%, Al2O3 6.69wt%, Fe2O3 0.07wt%, K2O 4.04wt%, Na2O 0.51wt%, CaO 12.17wt%, MgO 1.79wt%, ZnO 13.44wt%, B2O3 0.52wt%, BaO 0.37wt%, and loss on ignition 0.37%.

[0048] (5) Drying: The brick blanks with applied dry particles are dried with infrared light to control the humidity of the dry particle layer. The drying temperature is 120℃ and the drying time is 3 minutes. (6) Protective glaze spraying: Apply protective glaze to the brick blanks with dry particles adhering to the surface using a spray glaze method. The specific gravity of the protective glaze is 1.34, and the glaze amount is 130g / m². 2 ; (7) Kiln firing: The brick blanks that have completed all the decoration steps are sent into the roller kiln for firing at a temperature of 1210℃ for a firing cycle of 38 minutes. The semi-finished ceramic bricks after firing are then polished and edged to finally obtain the finished ceramic bricks.

[0049] The leopard print composite textured art ceramic tile prepared by the aforementioned method includes the following structural layers: Ceramic tile blank; A layer of slip applied to the surface of the blank; A pattern layer of adhesive fixative applied to a layer of cosmetic clay using digital printing; A special dry granule layer applied on the adhesive fixative pattern layer, wherein the special dry granules are a mixture of metal oxide dry granules and zirconium dry granules in a certain proportion; A protective glaze layer covering the dry granule layer; A glaze layer with a leopard print composite texture is formed after medium-temperature sintering. Example 4

[0050] The preparation method of one-fired leopard print art ceramic tiles based on heat-sensitive binder and multi-layer glaze composite includes the following steps: (1) Preparation of the brick body: After powdering, spreading, pressing and drying, the brick body is obtained with a water absorption rate of 0.3%; (2) Application of the base coat glaze: Apply the base coat glaze by pouring or spraying. The glaze thickness is 0.3–0.8 mm. It is an opaque glaze with a specific gravity of 1.80 and an application rate of 600 g / m³. 2 ; (3) Printing of thermal adhesive: The thermal adhesive pattern is printed on the underlying glaze using digital inkjet printing. Case 1847.47, PVB-based thermal adhesive: printing yield 80g / m² 2 ; (4) Dry granule application: Apply leopard print effect dry granules to the area printed with heat-sensitive adhesive, metal oxide:zirconium = 50:50, mesh size 100-200 mesh; (5) Application of intermediate glaze: Apply an intermediate transparent glaze to cover the dry granule layer, with a specific gravity of 1.25 and a glaze application rate of 150g / m³. 2 ; (6) Application of protective glaze: Apply a protective glaze, a high-hardness transparent glaze with a specific gravity of 1.30, at a rate of 200g / m². 2 ; (7) First firing: Hold at 1160℃ for 10 minutes in a roller kiln, with a firing cycle of 50 minutes; The parameters for the first firing in step (7) include: heating rate: 15℃ / min; peak temperature: 1150℃; holding time: 11 minutes; cooling rate: 20℃ / min. The heat-sensitive adhesive is composed of the following components by weight percentage: Thermoplastic resin 15wt%; inorganic binder 10wt%; solvent 74wt%; surfactant 1wt%; The thermoplastic resin is polyvinyl butyral (PVB) or polyacrylate. The leopard print effect dry particles consist of 40% metal oxide crystalline dry particles and 60% zirconium-based opaque dry particles. The metal oxide-based crystalline dry particles have a MnO content of 10 wt%, and the zirconium-based opaque dry particles have a ZrO2 content of 12 wt%. The brick blank is a flat or mold-faced blank with a water absorption rate of ≤0.5%.

[0051] The bottom glaze is a transparent glaze or an opaque glaze, with a glaze specific gravity of 1.8; The refractive index of the intermediate transparent glaze is higher than that of the bottom glaze, and the glaze layer thickness is 0.2 mm; The protective glaze is a high-hardness transparent glaze with a Mohs hardness ≥6. The products obtained in the above embodiments all possess clear, three-dimensional, and natural leopard print textures, with a smooth glaze surface and physical and chemical properties that meet the standards for architectural ceramics. They are suitable for interior and exterior wall and floor decoration. All equivalent variations and modifications made within the scope of the claims of this invention shall fall within the protection scope of this invention.

Claims

1. A method for preparing ceramic tiles based on a single-fired leopard-print composite texture using medium-temperature sintering, characterized in that, Includes the following steps: (1) Green body preparation: The green body is obtained through powdering, spreading, pressing and drying; (2) Applying slip: Apply glaze by pouring, with a specific gravity of 1.80–1.85 and a glaze weight of 450–650 g / m³. 2 ; (3) Adhesive fixing agent printing: 3D ceramic inkjet printing is used, with a blank temperature of 40-65℃ and a printing volume of 50-120g / m³. 2 ; (4) Special dry granule application: Mix metal oxide-based and zirconium-based dry granules in a certain proportion and apply them to the adhesive area. The mesh size of the dry granules is 80-300 mesh, and the application rate is 150-650 g / m². 2 Excess dry particles are collected and recycled. (5) Drying: Infrared drying is used at a temperature of 100-200℃ for 1-3 minutes; (6) Apply protective glaze: Use spray glazing method; the specific gravity of the protective glaze is 1.20–1.35, and the glaze amount is 120–300 g / m³. 2 ; (7) Firing: Medium-temperature sintering is carried out in a roller kiln at a temperature of 1100-1220℃ for a cycle of 30-60 minutes; (8) Post-processing: Polishing or edge grinding without polishing to obtain the finished product.

2. The method for preparing ceramic tiles with a leopard print composite texture based on medium-temperature sintering and single-firing as described in claim 1, characterized in that, The adhesive fixative described in step (3) consists of the following components by weight percentage: cyclohexane 7-15 wt%, isopropyl laurate 10-25 wt%, polyurethane 0.5-7 wt%, sodium carboxymethyl cellulose 0.1-1 wt%, inorganic powder 4-15 wt%, and water 45-70 wt%. The preparation method of the adhesive fixative includes: mixing and stirring, sand milling, sieving, and performance testing to ensure that its particle size D50 ≤ 0.4 μm, viscosity 3~12 mPa·s, and surface tension 25~50 mN / m.

3. The method for preparing ceramic tiles with a leopard print composite texture based on medium-temperature sintering and single-firing as described in claim 1, characterized in that, The special dry granules mentioned in step (4) are composed of 10-50% metal oxide dry granules and 50-90% zirconium dry granules; the metal oxides are one or more of manganese oxide, iron oxide, cobalt oxide, nickel oxide, and chromium oxide. The metal oxide dry granules and the zirconium dry granules are respectively obtained from the corresponding raw materials by ball milling, spray granulation, light calcination at 750-950℃, crushing and screening.

4. The method for preparing ceramic tiles with a leopard print composite texture based on medium-temperature sintering and single-firing as described in claim 3, characterized in that, The metal oxide raw material is composed of the following components by weight percentage: calcined zinc oxide 1-5 wt%, barium carbonate 2-7 wt%, potassium feldspar 15-25 wt%, sodium feldspar 8-20 wt%, calcite 3-10 wt%, Zhangzhou kaolin 3-8 wt%, calcined kaolin 3-8 wt%, manganese oxide 2-8 wt%, iron oxide 0-8 wt%, cobalt oxide 0-8 wt%, nickel oxide 0-8 wt%, chromium oxide 0-8 wt%, A-type frit 6-12 wt%, and low-temperature frit powder 10-30 wt%. The chemical composition of the metal oxide raw material is as follows by weight percentage: SiO2 45-55wt%, Al2O3 8-15wt%, Fe2O3 0-8wt%, K2O 2-5wt%, Na2O 2-5wt%, CaO 3-8wt%, MgO 0.1-1wt%, ZnO 5-10wt%, MnO 3-8wt%, CoO 0-8wt%, NiO 0-8wt%, CrO 0-8wt%, B2O3 2-6wt%, BaO 2-6wt%, and loss on ignition 1-6wt%. The zirconium-based raw material is composed of the following components by weight percentage: calcined zinc oxide 1-3 wt%, barium carbonate 2-6 wt%, zirconium silicate 7-15 wt%, potassium feldspar 12-22 wt%, sodium feldspar 7-15 wt%, calcite 3-8 wt%, dolomite 1-5 wt%, Zhangzhou kaolin 3-8 wt%, A-type frit 7-15 wt%, and low-temperature frit powder 20-40 wt%. The chemical composition of the zirconium-based raw material is as follows by weight percentage: SiO2 45-55wt%, Al2O3 6-12wt%, Fe2O3 ≤0.17wt%, K2O 2-6wt%, Na2O 2-5wt%, CaO 5-10wt%, MgO 1-3wt%, ZnO 3-8wt%, ZrO2 5-10wt%, B2O3 3-8wt%, BaO 2-6wt%, and loss on ignition 2-7wt%.

5. The method for preparing ceramic tiles with a leopard-print composite texture based on medium-temperature sintering and single-firing as described in claim 4, characterized in that, The low-temperature frit powder is obtained by melting a low-temperature raw material formula at a temperature of 1400-1600℃ to form a melt, then adding water and rapidly cooling it to obtain a blocky glassy state, which is then crushed and sieved by a pulverizer to obtain low-temperature frit powder; the mesh size of the low-temperature frit powder is controlled to be 120-250 mesh. The low-temperature raw material formulation consists of the following components by weight percentage: zinc oxide 7-12 wt%, barium carbonate 1-5 wt%, aluminum oxide 3-8 wt%, quartz 30-50 wt%, wollastonite 15-25 wt%, magnesium oxide 1-3 wt%, boron oxide 10-20 wt%, sodium carbonate 2-6 wt%, and potassium carbonate 2-6 wt%. The chemical composition of the low-temperature raw material consists of the following components by weight percentage: SiO2 50-60wt%, Al2O3 3-10wt%, Fe2O3 ≤0.3wt%, K2O 2-5wt%, Na2O 2-5wt%, CaO 3-8wt%, MgO 0.1-2.0wt%, ZnO 5-10wt%, B2O3 10-20wt%, BaO 0.5-2wt%, and loss on ignition 0.01-5wt%. The chemical composition of the A-type frit consists of the following components by weight percentage: SiO2 55-65wt%, Al2O3 3-10wt%, Fe2O3 ≤0.15wt%, K2O 2-6wt%, Na2O 0.1-1wt%, CaO 7-15wt%, MgO 1-3wt%, ZnO 10-20wt%, B2O3 0.1-1wt%, BaO 0.1-1wt%, and loss on ignition 0.01-1%.

6. A method for preparing leopard-print composite textured ceramic tiles based on medium-temperature sintering and single-firing, using the method described in any one of claims 1 to 5, characterized in that, Includes the following structural layers: Ceramic tile blank; A layer of slip applied to the surface of a ceramic tile body; A pattern layer of adhesive fixative applied to a layer of cosmetic clay using digital printing; A special dry granule layer applied on the adhesive fixative pattern layer, wherein the special dry granules are a mixture of metal oxide dry granules and zirconium dry granules in a set ratio; A protective glaze layer covering a special dry granule layer; A glaze layer with a leopard print composite texture is formed after medium-temperature sintering.

7. A method for preparing a one-fired leopard-print art ceramic tile based on a thermosensitive binder and a multi-layer glaze composite, characterized in that, Includes the following steps: (1) Preparation of the blank: The brick blank is obtained after powdering, spreading, pressing and drying; (2) Application of the base glaze: Apply the base glaze by pouring or spraying, with a glaze thickness of 0.3 to 0.8 mm; (3) Printing of thermal adhesive: The thermal adhesive pattern is printed on the underlying glaze using digital inkjet printing. (4) Dry granule application: Apply leopard print effect dry granules to the areas printed with thermal adhesive; (5) Application of intermediate glaze: Apply an intermediate transparent glaze to cover the dry granule layer; (6) Application of protective glaze: Apply a protective glaze to the surface; (7) Single firing: Firing once in a roller kiln at 1080-1180℃ for 35-70 minutes.

8. The method for preparing one-fired leopard-print art ceramic tiles based on a thermosensitive binder and multi-layer glaze composite according to claim 7, characterized in that, The heat-sensitive adhesive is composed of the following components by weight percentage: Thermoplastic resin 10–20 wt%; inorganic binder 5–15 wt%; solvent 65–85 wt%; surfactant 0.1–1 wt%; The thermoplastic resin is polyvinyl butyral (PVB) or polyacrylate. The leopard print effect dry particles consist of 40-60% metal oxide crystalline dry particles and 40-60% zirconium-based opaque dry particles. The metal oxide content of the metal oxide-based crystalline dry particles is 5-10 wt%, and the ZrO2 content of the zirconium-based opaque dry particles is 8-12 wt%. The brick blank is a flat or mold-faced blank with a water absorption rate of ≤0.5%.

9. The preparation method of the one-fired leopard print art ceramic tile based on a thermosensitive binder and a multi-layer glaze composite according to claim 7, characterized in that, The bottom glaze is an opaque glaze with a specific gravity of 1.75 to 1.

90. The refractive index of the intermediate transparent glaze is higher than that of the bottom glaze, and the glaze thickness is 0.1–0.3 mm. The protective glaze is a high-hardness transparent glaze with a Mohs hardness of ≥6.

10. The method for preparing one-fired leopard-print art ceramic tiles based on a thermosensitive binder and multi-layer glaze composite according to claim 7, characterized in that, The firing parameters mentioned in step (7) include: Heating rate: 10–20 °C / min; Peak temperature: 1120~1160℃; Keep warm for 5 to 15 minutes; Cooling rate: 15~25℃ / min.

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