Environment-friendly 3D micro-sculpture ceramic tile and preparation method thereof

Abstract

This invention discloses an environmentally friendly 3D micro-carved ceramic tile and its preparation method, belonging to the field of architectural ceramic materials technology. The method includes steps such as raw material preparation, application of base glaze and relief glaze, gradient functional relief ink printing, slow drying, and segmented firing. The core innovation lies in the three-layer gradient design of the relief ink: "adhesion layer - expansion layer - visual layer." By precisely controlling the particle size and composition ratio of raw materials in each layer, combined with gradient temperature (800-950℃) and oxygen concentration control, the directional formation and firm bonding of the three-dimensional texture are achieved. Simultaneously, the ratio and application interval of the base glaze and relief glaze are optimized, and environmentally friendly organic solvents and waste heat utilization processes are used, balancing decorative effect and green production. The resulting ceramic tile has sharp texture boundaries, rich color layers, and excellent three-dimensionality and stability, and can be widely used in high-end architectural decoration scenarios, effectively solving the pain point of traditional products' difficulty in simultaneously achieving three-dimensionality and color expression.

Description

Technical Field

[0001] This invention belongs to the field of building ceramic materials technology, and relates to an environmentally friendly 3D micro-carved ceramic brick and its preparation method. Background Technology

[0002] In recent years, with the continuous improvement of residents' living standards, the consumption demand for building decoration materials is upgrading from a single function to one that takes into account aesthetics, personalization, and artistry. Under this trend, glazed ceramic tile products such as soft-sculpted silk-glazed tiles and matte tiles have become the mainstream choice in the market due to their advantages such as soft texture, low light pollution, and strong environmental adaptability. However, while these products perform well in terms of comfort and practicality, their decorative expression still has obvious limitations: the surface color layers are thin, and the texture design is mostly limited to the superposition of two-dimensional planar patterns, lacking a real three-dimensional texture and dynamic light and shadow changes, making it difficult to meet the in-depth needs of high-end consumers for a spatial artistic atmosphere.

[0003] To overcome this bottleneck, some companies have initially achieved a technological upgrade in brick surface three-dimensional effects by integrating relief carving techniques. Although these products offer significant improvements in texture and tactile experience compared to traditional flat glazed tiles, they still face issues such as blurred relief boundaries and insufficient detail precision. Their artistic expression and level of refinement still have considerable room for improvement. Summary of the Invention

[0004] The purpose of this invention is to provide an environmentally friendly 3D micro-carved ceramic brick and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions: This invention provides a method for preparing environmentally friendly 3D micro-carved ceramic tiles, comprising the following steps: S1. Mix the basic raw materials in proportion, ball mill, spray dry, age and then press into shape; S2. Apply a base glaze and a relief glaze sequentially to the surface of the dried body; the chemical composition of the relief glaze, by mass percentage, is: 46.0-52.0% SiO2, 10-12% Al2O3, 0.1-0.3% Fe2O3, 0.05-0.1% TiO2, 5-5.6% MgO, 7.0-8.0% CaO, 4.0-4.5% K2O, 1.5-2% Na2O, 0.02-0.06% ZrHfO2, 4-5% ZnO, 0.3-0.4% B2O3, 7.5-8.5% BaO, and 5.5-7% loss on ignition; S3. Using digital inkjet technology, embossing ink and pattern ink are simultaneously printed onto the embossed glaze surface according to the grayscale file design; the chemical composition of the embossing ink, by mass percentage, is: 15-18% SiO2, 0.5-1.0% Al2O3, 0.02-0.05% Fe2O3, 0.02-0.05% TiO2, 0.01-0.03% MgO, 0.1-0.2% CaO, 0.03-0.05% K2O, 0.01-0.02% Na2O, 7-8% ZnO, 16-17% Bi2O3, 5.0-6.0% V2O5, and 50-53% loss on ignition; S4, slow drying, firing, edge grinding and packaging, to produce environmentally friendly 3D micro-carved ceramic tiles.

[0006] Preferably, the embossed ink comprises the following raw materials: alumina powder, quartz powder, zinc oxide, bismuth trioxide, vanadium pentoxide, titanium dioxide, iron oxide pigment, calcium carbonate, magnesium oxide, potassium carbonate, sodium carbonate, and organic solvent.

[0007] Preferably, the organic solvent includes terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant, Tween-80 surfactant, and organobentonite thixotropic agent.

[0008] Preferably, the preparation of the embossed ink includes the following steps: A1. Take 70-80% of the total alumina powder, 45-55% of the total quartz powder, and 35-45% of the total zinc oxide, mix and ball mill until the D50 particle size is 2.2-2.8μm to prepare the adhesion layer raw material. A2. Take all of the bismuth trioxide and vanadium pentoxide, mix and ball mill until the D50 particle size is 1.1-1.4μm, to prepare the expansion layer raw material; A3. Take all the titanium dioxide and iron oxide pigments, mix and ball mill until the D50 particle size is 0.3-0.4μm, to prepare the visual layer raw material; A4. Mix the remaining alumina powder, quartz powder, zinc oxide with all the calcium carbonate, magnesium oxide, potassium carbonate and sodium carbonate, and ball mill until the D50 particle size is 0.85-1.15μm to prepare the basic dispersed phase; A5. Mix terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant, Tween-80 surfactant and organic bentonite thixotropic agent evenly to prepare an organic carrier; A6. Add the organic carrier to the mixing equipment, and then add the basic dispersed phase, the adhesion layer material, the expansion layer material and the visual layer material in sequence. Disperse at high speed and adjust the pH to obtain the embossed ink.

[0009] Preferably, the chemical composition of the base blank, by mass percentage, is: 67-69% SiO2, 18-19% Al2O3, 1-1.5% Fe2O3, 0.15-0.2% TiO2, 1-1.5% MgO, 0.4-0.6% CaO, 3-4% K2O, 1.5-1.8% Na2O, and 3-5.5% loss on ignition.

[0010] Preferably, the amount of base glaze used per square meter of body surface is 450-500g, the amount of relief glaze used is 380-420g, and the application interval between the base glaze and the relief glaze is 45-60 seconds.

[0011] Preferably, the slow drying process uses waste heat from the kiln, with a drying temperature of 200±10℃, a drying cycle of 120±10 seconds, and a heating rate controlled at 8-10℃ / second.

[0012] Preferably, the firing conditions are as follows: firing temperature is 1200-1210℃, firing time is 25-27 minutes, continuous firing is carried out in a roller kiln, and the heating rate is 8-10℃ / minute before 600℃, 5-6℃ / minute from 600-900℃, and 3-4℃ / minute from 900℃ to the maximum temperature.

[0013] Preferably, a gradient structure forming section is set in the temperature range of 800-950℃, including: holding at 800-850℃ for 50-70 seconds with oxygen concentration controlled at 4-5%; holding at 850-900℃ for 60-80 seconds with oxygen concentration controlled at 3-4%; and holding at 900-950℃ for 40-60 seconds with oxygen concentration controlled at 3-4%.

[0014] Secondly, the present invention provides an environmentally friendly 3D micro-carved ceramic tile, which is prepared by the above-described method for preparing environmentally friendly 3D micro-carved ceramic tiles.

[0015] The beneficial effects of this invention are: (1) Gradient functional embossed ink achieves a dual breakthrough in three-dimensional texture and structural stability. This invention innovatively designs a three-layer gradient structure of "adhesion layer - expansion layer - visual layer". By precisely controlling the particle size and composition ratio of raw materials in each layer, different functional components can form a synergistic effect during the firing process: The bottom adhesion layer uses large-particle alumina powder, quartz powder and zinc oxide with a D50 particle size of 2.2-2.8μm, which react with SiO2 and Al2O3 in the relief glaze to form a strong bonding interface, completely solving the hidden danger of peeling between the three-dimensional layer and the glaze surface in traditional products; The middle expansion layer uses bismuth trioxide and vanadium pentoxide with a core of 1.1-1.4μm, which achieves directional and controllable expansion under a gradient temperature of 800-950℃ and precise oxygen concentration control, so that the texture height difference is uniform and stable, and the boundary is sharp and clear, effectively avoiding the problems of blurry texture and uneven undulation in traditional relief technology; The surface visual layer uses ultrafine titanium dioxide and iron oxide pigments to optimize the light and shadow reflection effect, so that the color saturation and three-dimensional layering are naturally integrated, achieving a high-end decorative experience of "harmonious unity from a distance and exquisite details up close".

[0016] (2) By precisely controlling the ratio of base glaze to relief glaze (450-500g / m 2 With 380-420g / m 2 The application interval (45-60 seconds), combined with the kiln waste heat slow drying process (200±10℃, 120±10 seconds), reduces the risk of stress concentration and cracking in the glaze layer. The firing process adopts segmented heating and gradient oxygen concentration control, which not only ensures the orderly formation of the gradient structure, but also reduces energy consumption and pollutant emissions. The relief ink uses environmentally friendly organic solvents such as terpineol and diethylene glycol butyl ether acetate, which do not contain harmful substances such as lead and cadmium. The raw material utilization rate is improved in the production process, and waste glaze and waste residue can be recycled and reused, which is in line with the concept of green manufacturing and achieves the organic unity of decorative effect and environmental protection requirements.

[0017] (3) By combining the multi-dimensional grayscale gradation control of digital inkjet with gradient function ink depth, the ink deposition amount is precisely adjusted according to the grayscale distribution of the pattern, so that the grayscale changes and the three-dimensional texture undulations correspond one-to-one, and the two-dimensional design pattern is accurately restored to the three-dimensional effect. This collaborative mechanism not only makes the surface of ceramic tiles present natural and smooth color gradients and distinct three-dimensional textures, but also vividly restores the texture of natural materials such as wood grain, flowers, and stone. It solves the industry pain point of "difficulty in balancing three-dimensionality and color expression" in traditional products, greatly expands the application adaptability of products in high-end residences, commercial spaces, art venues and other scenarios, and enhances the artistic expression and personalized expression space of architectural decoration. Detailed Implementation

[0018] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0019] The following descriptions of some of the raw materials used in the examples and comparative examples are as follows: The pattern ink is commercially available ceramic digital inkjet pattern ink (red, yellow, blue, and black, compatible with 600dpi inkjet printers).

[0020] Except for the raw materials explicitly mentioned above, all other raw materials not specifically mentioned are conventional industrial-grade products that can be easily obtained through commercial channels.

[0021] Example 1

[0022] A method for preparing an environmentally friendly 3D micro-carved ceramic tile includes the following steps: S1. Preparation of basic billet; Raw materials: By mass percentage, the chemical composition of the basic billet is: 68.74% SiO2, 18.25% Al2O3, 1.22% Fe2O3, 0.16% TiO2, 1.2% MgO, 0.48% CaO, 3.66% K2O, 1.69% Na2O, and 4.6% loss on ignition (L). The raw materials for the basic billet are: quartz sand, kaolin, iron oxide, titanium dioxide, magnesium oxide, calcium carbonate, potassium feldspar, and sodium feldspar. These raw materials are weighed and mixed according to the above chemical composition proportions.

[0023] Preparation steps: The basic raw material is added to a ball mill and wet ball milling is used to control the slurry moisture content to 35%, specific gravity to 1.68 g / ml, and flowability to 75 s. After ball milling, the material is granulated in a spray drying tower to obtain powder with a moisture content of 6.8%. After aging the powder for 24 hours, it is pressed using a Keda KD8500 four-cavity press with a specification of 400×800 mm, a forming pressure of 56000 kN, and a pressing frequency of 8.3 times / minute to obtain green bodies. The green bodies are then dried in a tunnel drying tower to control the moisture content of the dried body to ≤0.5%.

[0024] S2, Glazing; Raw materials: The base glaze is a conventional ceramic base glaze that conforms to the GB / T4100-2015 standard. The raw materials are industrial-grade raw materials such as quartz powder, potassium feldspar, sodium feldspar, kaolin, and calcium carbonate, which are made into glaze slurry by wet ball milling.

[0025] The chemical composition of the relief glaze, by mass percentage, is: 49.98% SiO2, 11.30% Al2O3, 0.17% Fe2O3, 0.06% TiO2, 5.33% MgO, 7.58% CaO, 4.11% K2O, 1.75% Na2O, 0.04% ZrHfO2, 4.86% ZnO, 0.36% B2O3, 8.13% BaO, and 6.33% loss on ignition (L). The raw materials for the relief glaze are: quartz powder, alumina powder, iron oxide pigment (industrial grade), zirconium oxide (industrial grade), zinc oxide, boric acid, barium carbonate, magnesium carbonate, calcium carbonate, potassium feldspar, and sodium feldspar, weighed according to the above proportions and prepared for use.

[0026] The preparation of relief glaze includes the following steps: Quartz powder, alumina powder, iron oxide pigment, zirconium oxide, zinc oxide, boric acid, barium carbonate, magnesium carbonate, calcium carbonate, potassium feldspar, sodium feldspar, and other solid raw materials weighed according to the above proportions are added to a mixer and stirred at 500 r / min for 15 minutes to achieve preliminary uniform mixing; then, the premixed raw materials are transferred to a ball mill, deionized water is added, and high-alumina balls are used as the grinding medium, with a ball-to-material-to-water mass ratio of 3:1:0.8, and ball milling is performed at 21 r / min for 4 hours. During this period, samples are taken to test the fineness until the glaze slurry has a residue of ≤1.6% on a 10,000-mesh sieve, a flowability of 30s, and a specific gravity of 1.87 g / ml, at which point ball milling is stopped; finally, the ball-milled relief glaze slurry is transferred to an aging tank, sealed, and aged for 24 hours to eliminate internal stress in the glaze slurry, thus obtaining the relief glaze.

[0027] Preparation steps: The base glaze is applied using a glazing process, with the glaze slurry specific gravity controlled at 1.90 g / ml and the fluidity at 30 s. The amount of base glaze used per square meter of body surface is 480 g. After the base glaze is applied, wait 50 seconds, and then apply the relief glaze using a glazing process, with the relief glaze slurry specific gravity controlled at 1.87 g / ml and the fluidity at 31 s. The amount of relief glaze used per square meter of body surface is 400 g.

[0028] S3, digital inkjet printing; Raw materials: By mass percentage, the chemical composition of the embossing ink is: 16.87% SiO2, 0.79% Al2O3, 0.03% Fe2O3, 0.03% TiO2, 0.02% MgO, 0.14% CaO, 0.04% K2O, 0.01% Na2O, 7.44% ZnO, 16.86% Bi2O3, 5.55% V2O5, and 52.22% loss on ignition (IL).

[0029] Organic solvents: terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant (molecular weight 5000), Tween-80 surfactant, and organobentonite thixotropic agent, mixed in a mass ratio of 30:25:2:1:0.8 to prepare the organic carrier. The raw materials for the embossed ink are inorganic materials: alumina powder, quartz powder, zinc oxide, bismuth trioxide, vanadium pentoxide, titanium dioxide, iron oxide pigment (industrial grade), calcium carbonate, magnesium oxide, potassium carbonate, and sodium carbonate.

[0030] The preparation of embossed ink includes the following steps: A1. Preparation of the coating material: Take 75% of the total amount of alumina powder, 50% of the total amount of quartz powder, and 40% of the total amount of zinc oxide, mix them, add them to a ball mill, and ball mill until the D50 particle size is 2.5μm to obtain the coating material.

[0031] A2. Preparation of expansion layer raw materials: Take all of the bismuth trioxide and vanadium pentoxide, mix them, and ball mill them to a D50 particle size of 1.2 μm to obtain the expansion layer raw materials.

[0032] A3. Preparation of visual layer raw materials: Take all titanium dioxide and iron oxide pigments, mix them, and ball mill them until the D50 particle size is 0.35μm to obtain the visual layer raw materials.

[0033] A4. Preparation of basic dispersed phase: The remaining 25% alumina powder, 50% quartz powder, and 60% zinc oxide are mixed with all calcium carbonate, magnesium oxide, potassium carbonate, and sodium carbonate, and ball-milled until the D50 particle size is 1.0 μm to obtain the basic dispersed phase.

[0034] A5. Preparation of organic carrier: Terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant, Tween-80 surfactant, and organic bentonite thixotropic agent are mixed evenly in the above proportions, and stirred at a speed of 800 r / min for 30 minutes to obtain the organic carrier.

[0035] A6. Relief Ink Synthesis: Add the organic carrier to a high-speed disperser, then add the basic dispersed phase, the adhesion layer material, the expansion layer material, and the visual layer material in sequence. Control the stirring speed at 1500 r / min, the dispersion time at 60 minutes, adjust the pH to 7.2, and filter to obtain the relief ink.

[0036] Preparation steps: Use a Jingtao 1170-10 inkjet printer (600dpi resolution), with the printhead 3-5mm from the embossed glaze surface and a printing speed of 30m / min. Before printing, convert the decorative pattern into a 0-255 level multi-dimensional grayscale file. Grayscale values ​​0-85 correspond to low spray volume areas (8-12g / m² of embossed ink), grayscale values ​​86-170 correspond to medium spray volume areas (13-18g / m² of embossed ink), and grayscale values ​​171-255 correspond to high spray volume areas (19-25g / m² of embossed ink). During printing, according to the grayscale file design, embossed ink and pattern ink are sprayed synchronously. Emboss ink is sprayed first as a base layer (spraying sequence advanced by 0.3 seconds), followed by pattern ink to fill the color. By precisely controlling the ink spray volume of different areas through the grayscale file, the texture height difference can be accurately controlled to ensure a high degree of consistency between the three-dimensional texture and the color pattern.

[0037] S4. Slow drying, firing, edge grinding and packaging; Slow drying: The residual heat of the kiln is used for slow drying at a temperature of 200℃, a drying cycle of 120 seconds, and a heating rate of 9℃ / second, so that the moisture in the glaze layer is released evenly. Firing: Continuous firing was carried out using a Keda 400m roller kiln at a firing temperature of 1205℃ for a total firing time of 26 minutes. The heating rate was: 9℃ / min before 600℃, 5.5℃ / min from 600-900℃, and 3.5℃ / min from 900℃ to the maximum temperature. A gradient structure forming section was set between 800-950℃: holding at 800-850℃ for 60 seconds with an oxygen concentration of 4.5%; holding at 850-900℃ for 70 seconds with an oxygen concentration of 3.5%; and holding at 900-950℃ for 50 seconds with an oxygen concentration of 3.5%. Edge grinding and packaging: After firing, the ceramic tiles are edged and trimmed by edge grinding equipment. After passing the appearance inspection and physical and chemical performance test, they are packaged and stored to produce environmentally friendly 3D micro-carved ceramic tiles.

[0038] Example 2

[0039] A method for preparing an environmentally friendly 3D micro-carved ceramic tile includes the following steps: S1. Preparation of basic billet; Raw materials: By mass percentage, the chemical composition of the basic billet is: 67.5% SiO2, 18.5% Al2O3, 1.3% Fe2O3, 0.15% TiO2, 1.3% MgO, 0.5% CaO, 3.8% K2O, 1.7% Na2O, and 5.25% loss on ignition (L). The raw materials for the basic billet are: quartz sand, kaolin, iron oxide, titanium dioxide, magnesium oxide, calcium carbonate, potassium feldspar, and sodium feldspar. These raw materials are weighed and mixed according to the above chemical composition proportions.

[0040] Preparation steps: The basic raw material is added to a ball mill and wet ball milling is used to control the slurry moisture content to 34.8%, specific gravity to 1.69 g / ml, and flowability to 80 s. After ball milling, the material is granulated in a spray drying tower to obtain powder with a moisture content of 6.6%. After aging the powder for 26 hours, it is pressed using a Keda KD8500 four-cavity press with a specification of 400×800 mm, a forming pressure of 56000 kN, and a pressing frequency of 8.3 times / minute to obtain green bodies. The green bodies are then dried in a tunnel drying tower to control the moisture content of the dried body to ≤0.5%.

[0041] S2, Glazing; Raw materials: The base glaze is a conventional ceramic base glaze that conforms to the GB / T4100-2015 standard. The raw materials are industrial-grade raw materials such as quartz powder, potassium feldspar, sodium feldspar, kaolin, and calcium carbonate, which are made into glaze slurry by wet ball milling. The chemical composition of the relief glaze, by mass percentage, is: 49.0% SiO2, 12.0% Al2O3, 0.2% Fe2O3, 0.08% TiO2, 5.6% MgO, 7.5% CaO, 4.3% K2O, 1.8% Na2O, 0.05% ZrHfO2, 4.5% ZnO, 0.35% B2O3, 8.0% BaO, and 6.62% loss on ignition (L). The raw materials for the relief glaze are: quartz powder, alumina powder, iron oxide pigment, zirconium oxide, zinc oxide, boric acid, barium carbonate, magnesium carbonate, calcium carbonate, potassium feldspar, and sodium feldspar, weighed according to the above proportions for later use.

[0042] The preparation of relief glaze includes the following steps: The solid raw materials weighed according to the above proportions are added to a mixer and stirred at 550 r / min for 12 minutes to achieve preliminary uniform mixing; then the premixed raw materials are transferred to a ball mill, deionized water is added (controlling the final water content of the glaze slurry to 31%), high-alumina balls are used as the grinding medium, the ball-to-material-to-water mass ratio is 3:1:0.75, and the milling is carried out at 20 r / min for 4.5 hours. During this period, samples are taken to test the fineness until the glaze slurry has a residue of ≤1.5% on a 10,000-mesh sieve, a flowability of 29s, and a specific gravity of 1.86 g / ml, at which point the ball milling is stopped; finally, the ball-milled relief glaze slurry is transferred to an aging tank, sealed, and aged for 22 hours to eliminate internal stress in the glaze slurry, thus obtaining the relief glaze.

[0043] Preparation steps: Apply the base glaze using a glazing process, controlling the glaze slurry specific gravity to 1.89 g / ml and the fluidity to 29 s. The amount of base glaze used per square meter of body surface is 460 g. After the base glaze is applied, wait 45 seconds, and then apply the relief glaze using a glazing process, controlling the relief glaze slurry specific gravity to 1.86 g / ml and the fluidity to 30 s. The amount of relief glaze used per square meter of body surface is 390 g.

[0044] S3, digital inkjet printing; Raw materials: By mass percentage, the chemical composition of the embossing ink is: 17.0% SiO2, 0.8% Al2O3, 0.04% Fe2O3, 0.04% TiO2, 0.02% MgO, 0.15% CaO, 0.04% K2O, 0.01% Na2O, 7.6% ZnO, 16.5% Bi2O3, 5.8% V2O5, and 52.0% loss on ignition (IL); Organic solvents: terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant (molecular weight 5000), Tween-80 surfactant, and organic bentonite thixotropic agent were mixed in a mass ratio of 29:26:2.1:1.1:0.7 to prepare an organic carrier; The raw materials for embossed ink are inorganic: alumina powder, quartz powder, zinc oxide, bismuth trioxide, vanadium pentoxide, titanium dioxide, iron oxide pigment (industrial grade), calcium carbonate, magnesium oxide, potassium carbonate, and sodium carbonate.

[0045] The preparation of embossed ink includes the following steps: A1. Preparation of the coating material: Take 72% of the total amount of alumina powder, 48% of the total amount of quartz powder, and 38% of the total amount of zinc oxide, mix them, add them to a ball mill, and ball mill them until the D50 particle size is 2.3μm to obtain the coating material.

[0046] A2. Preparation of expansion layer raw materials: Take all of the bismuth trioxide and vanadium pentoxide, mix them, and ball mill them to a D50 particle size of 1.3 μm to obtain the expansion layer raw materials.

[0047] A3. Preparation of visual layer raw materials: Take all titanium dioxide and iron oxide pigments, mix them, and ball mill them until the D50 particle size is 0.32μm to obtain the visual layer raw materials.

[0048] A4. Preparation of basic dispersed phase: The remaining 28% alumina powder, 52% quartz powder, and 62% zinc oxide were mixed with all calcium carbonate, magnesium oxide, potassium carbonate, and sodium carbonate, and ball-milled until the D50 particle size was 0.95 μm to obtain the basic dispersed phase.

[0049] A5. Organic carrier preparation: Mix the organic solvent evenly according to the above proportions, stir at 850 r / min for 28 minutes to obtain the organic carrier. A6. Embossed ink synthesis: Add the organic carrier to a high-speed disperser, then add the base dispersed phase, adhesion layer material, expansion layer material, and visual layer material sequentially. Control the stirring speed at 1400 r / min and the dispersion time at 65 minutes. Adjust the pH to 7.1, filter, and obtain the embossed ink.

[0050] Preparation steps: A Jingtao 1170-10 inkjet printer (600dpi resolution) was used, with the printhead 4mm from the embossed glaze surface and a printing speed of 28m / min. Before printing, the decorative pattern (floral pattern) was converted into a 0-255 level multi-dimensional grayscale file. Grayscale values ​​0-90 correspond to low spray volume areas (embossed ink spray volume 9-11g / m²), grayscale values ​​91-180 correspond to medium spray volume areas (embossed ink spray volume 14-17g / m²), and grayscale values ​​181-255 correspond to high spray volume areas (embossed ink spray volume 20-23g / m²). During printing, the embossed ink and pattern ink were sprayed synchronously according to the grayscale file design, with the embossed ink spraying sequence advanced by 0.25 seconds. The pattern ink was filled in the order of red, yellow, blue, and black. By precisely controlling the ink spray volume of different areas through the grayscale file, the texture height difference was accurately controlled, ensuring that the texture and three-dimensional undulations were highly consistent.

[0051] S4. Slow drying, firing, edge grinding and packaging; Slow drying: The residual heat of the kiln is used for slow drying. The drying temperature is 195℃, the drying cycle is 115 seconds, and the heating rate is 8.5℃ / second, so that the moisture in the glaze layer is released evenly.

[0052] Firing: Continuous firing is carried out using a Keda 400m roller kiln at a firing temperature of 1202℃ for a total firing time of 25 minutes. Heating rate: 8.5℃ / min before 600℃, 5℃ / min from 600-900℃, and 3℃ / min from 900℃ to the maximum temperature. A gradient structure forming section is set at 800-950℃: 800-850℃ for 55 seconds with an oxygen concentration of 4%; 850-900℃ for 65 seconds with an oxygen concentration of 3%; and 900-950℃ for 45 seconds with an oxygen concentration of 3%.

[0053] Edge grinding and packaging: After firing, the ceramic tiles are edged and trimmed by edge grinding equipment. After passing the appearance inspection and physical and chemical performance test, they are packaged and stored to produce environmentally friendly 3D micro-carved ceramic tiles.

[0054] Example 3

[0055] A method for preparing an environmentally friendly 3D micro-carved ceramic tile includes the following steps: S1. Preparation of basic billet; Raw materials: By mass percentage, the chemical composition of the basic billet is: 68.8% SiO2, 18.8% Al2O3, 1.4% Fe2O3, 0.18% TiO2, 1.5% MgO, 0.6% CaO, 3.2% K2O, 1.5% Na2O, and 4.02% loss on ignition (L). The raw materials for the basic billet are: quartz sand, kaolin, iron oxide, titanium dioxide, magnesium oxide, calcium carbonate, potassium feldspar, and sodium feldspar. These raw materials are weighed and mixed according to the above chemical composition proportions.

[0056] Preparation steps: The basic raw material is added to a ball mill and wet ball milling is used to control the slurry moisture content to 35.5%, specific gravity to 1.70 g / ml, and flowability to 85 s. After ball milling, the material is granulated in a spray drying tower to obtain powder with a moisture content of 7.1%. After aging the powder for 28 hours, it is pressed using a Keda KD8500 four-cavity press with a specification of 400×800 mm, a forming pressure of 56000 kN, and a pressing frequency of 8.3 times / minute to obtain green bodies. The green bodies are then dried in a tunnel drying tower to control the moisture content of the dried body to ≤0.5%.

[0057] S2, Glazing; Raw materials: The base glaze is a conventional ceramic base glaze that conforms to the GB / T4100-2015 standard. The raw materials are industrial-grade raw materials such as quartz powder, potassium feldspar, sodium feldspar, kaolin, and calcium carbonate, which are made into glaze slurry by wet ball milling. The chemical composition of the relief glaze, by mass percentage, is: 49.2% SiO2, 10.9% Al2O3, 0.28% Fe2O3, 0.09% TiO2, 5.2% MgO, 7.8% CaO, 4.4% K2O, 1.9% Na2O, 0.06% ZrHfO2, 4.9% ZnO, 0.39% B2O3, 8.4% BaO, and 6.48% loss on ignition (L). The raw materials for the relief glaze are: quartz powder, alumina powder, iron oxide pigment (industrial grade), zirconium oxide (industrial grade), zinc oxide, boric acid, barium carbonate, magnesium carbonate, calcium carbonate, potassium feldspar, and sodium feldspar, weighed according to the above proportions for later use.

[0058] The preparation of relief glaze includes the following steps: The solid raw materials weighed according to the above proportions are added to a mixer and stirred at 480 r / min for 18 minutes to achieve preliminary uniform mixing; then the premixed raw materials are transferred to a ball mill, deionized water is added (controlling the final water content of the glaze slurry to 33%), high-alumina balls are used as the grinding medium, the ball-to-material-to-water mass ratio is 3:1:0.85, and the milling is carried out at 22 r / min for 3.8 hours. During this period, samples are taken to test the fineness until the glaze slurry has a residue of ≤1.6% on a 10,000-mesh sieve, a flowability of 32s, and a specific gravity of 1.88 g / ml, at which point the ball milling is stopped; finally, the ball-milled relief glaze slurry is transferred to an aging tank and sealed for aging for 26 hours to eliminate internal stress in the glaze slurry, thus obtaining the relief glaze.

[0059] Preparation steps: Apply the base glaze using a glazing process, controlling the glaze slurry specific gravity to 1.91 g / ml and the fluidity to 32 s. The amount of base glaze used per square meter of body surface is 500 g. After the base glaze is applied, wait 60 seconds, and then apply the relief glaze using a glazing process, controlling the relief glaze slurry specific gravity to 1.88 g / ml and the fluidity to 32 s. The amount of relief glaze used per square meter of body surface is 420 g.

[0060] S3, digital inkjet printing; Raw materials: By mass percentage, the chemical composition of the embossing ink is: 15.5% SiO2, 0.95% Al2O3, 0.05% Fe2O3, 0.05% TiO2, 0.03% MgO, 0.18% CaO, 0.05% K2O, 0.02% Na2O, 7.9% ZnO, 16.9% Bi2O3, 5.9% V2O5, and 52.47% loss on ignition (IL); Organic solvents: terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant (molecular weight 5000), Tween-80 surfactant, and organobentonite thixotropic agent were mixed in a mass ratio of 31:24:1.9:0.9:0.9 to prepare an organic carrier; The raw materials for embossed ink are inorganic: alumina powder, quartz powder, zinc oxide, bismuth trioxide, vanadium pentoxide, titanium dioxide, iron oxide pigment (industrial grade), calcium carbonate, magnesium oxide, potassium carbonate, and sodium carbonate.

[0061] The preparation of embossed ink includes the following steps: A1. Preparation of the coating material: Take 78% of the total amount of alumina powder, 52% of the total amount of quartz powder, and 43% of the total amount of zinc oxide, mix them, add them to a ball mill, and ball mill them until the D50 particle size is 2.8μm to obtain the coating material.

[0062] A2. Preparation of expansion layer raw materials: Take all of the bismuth trioxide and vanadium pentoxide, mix them, and ball mill them to a D50 particle size of 1.1 μm to obtain the expansion layer raw materials.

[0063] A3. Preparation of visual layer raw materials: Take all titanium dioxide and iron oxide pigments, mix them, and ball mill them until the D50 particle size is 0.4μm to obtain the visual layer raw materials.

[0064] A4. Preparation of the basic dispersed phase: The remaining 22% alumina powder, 48% quartz powder, and 57% zinc oxide were mixed with all of the calcium carbonate, magnesium oxide, potassium carbonate, and sodium carbonate, and ball-milled until the D50 particle size was 1.15 μm to obtain the basic dispersed phase. A5. Preparation of the organic carrier: The organic solvent was mixed uniformly according to the above proportions, stirred at 780 r / min for 32 minutes to obtain the organic carrier.

[0065] A6. Relief Ink Synthesis: Add the organic carrier to a high-speed disperser, then add the basic dispersed phase, the adhesion layer material, the expansion layer material, and the visual layer material in sequence. Control the stirring speed at 1600 r / min, the dispersion time at 55 minutes, adjust the pH to 7.3, and filter to obtain the relief ink. Preparation steps: A Jingtao 1170-10 inkjet printer (600dpi resolution) was used, with the printhead 5mm from the embossed glaze surface and a printing speed of 32m / min. Before printing, the decorative pattern (geometric texture) was converted into a 0-255 level multi-dimensional grayscale file. Grayscale values ​​0-80 corresponded to low spray volume areas (embossed ink spray volume 8-10g / m²), grayscale values ​​81-160 corresponded to medium spray volume areas (embossed ink spray volume 13-16g / m²), and grayscale values ​​161-255 corresponded to high spray volume areas (embossed ink spray volume 22-25g / m²). During printing, the embossed ink and pattern ink were sprayed synchronously according to the grayscale file design, with the embossed ink spraying sequence advanced by 0.35 seconds. The pattern ink was filled in the order of blue, black, red, and yellow. By precisely controlling the ink spray volume of different areas through the grayscale file, the texture height difference was accurately controlled, ensuring that the texture and three-dimensional undulations were highly consistent.

[0066] S4. Slow drying, firing, edge grinding and packaging; Slow drying: The residual heat of the kiln is used for slow drying. The drying temperature is 205℃, the drying cycle is 125 seconds, and the heating rate is 10℃ / second, so that the moisture in the glaze layer is released evenly.

[0067] Firing: Continuous firing is carried out using a Keda 400m roller kiln at a firing temperature of 1208℃ for a total firing time of 27 minutes. Heating rate: 10℃ / min before 600℃, 6℃ / min from 600-900℃, and 4℃ / min from 900℃ to the maximum temperature. A gradient structure forming section is set at 800-950℃: 800-850℃ for 70 seconds with an oxygen concentration of 5%; 850-900℃ for 80 seconds with an oxygen concentration of 4%; and 900-950℃ for 60 seconds with an oxygen concentration of 4%.

[0068] Edge grinding and packaging: After firing, the ceramic tiles are edged and trimmed by edge grinding equipment. After passing the appearance inspection and physical and chemical performance test, they are packaged and stored to produce environmentally friendly 3D micro-carved ceramic tiles.

[0069] Comparative Example 1 The difference from Example 1 is that the embossed ink does not adopt the three-layer gradient design of "adhesion layer-expansion layer-visual layer". All inorganic raw materials (alumina powder, quartz powder, zinc oxide, bismuth trioxide, vanadium pentoxide, titanium dioxide, iron oxide pigment, etc.) are mixed and ball-milled to a D50 particle size of 1.0μm in one go. The composition of other raw materials and preparation steps (glazing, slow drying, firing, etc.) are completely consistent with Example 1.

[0070] Comparative Example 2 The difference from Example 1 is that no gradient structure formation section was set in the 800-950℃ range during the firing process. Instead, a constant temperature of 900℃ and an oxygen concentration of 3.5% were used for continuous holding for 180 seconds. The other raw material composition and preparation steps (relief ink preparation, inkjet printing, slow baking, etc.) were completely consistent with Example 1.

[0071] Comparative Example 3 The difference from Example 1 is that grayscale file control was not used during digital inkjet printing, and both embossing ink and pattern ink were printed at a fixed volume (embossing ink volume 15g / m³). 2 The synchronous spraying and the composition of other raw materials and preparation steps (preparation of relief ink, glazing, firing, etc.) are completely consistent with Example 1.

[0072] Test 1: Texture Refinement and Boundary Sharpness Test Test Method: Three environmentally friendly 3D micro-carved ceramic tiles from Examples 1-3 and three ceramic tiles from Comparative Example 1 were selected. Three key texture areas (such as pattern lines and detail inflection points) were selected from each tile as observation objects. A metallurgical microscope with a magnification of 500x was used to perform high-definition imaging of each observation area. Ten measurement points were randomly selected, and the minimum texture width of each measurement point was read using the microscope's built-in size measurement software. The average value was taken as the minimum texture width test result of the sample. At the same time, an image sharpness analyzer was used to randomly select 15 texture boundaries in each observation area. The gray values ​​of the boundaries and adjacent background areas were detected, and the gray-scale contrast was calculated (contrast = (background gray value - boundary gray value) / background gray value × 100%). The average value of the 15 measurement points was taken as the boundary contrast value.

[0073] Test metrics: minimum texture width, boundary contrast value (the higher the value, the sharper the boundary).

[0074] The test 1 data is shown in Table 1.

[0075] Table 1

[0076] As shown in Table 1, the minimum texture width of Examples 1-3 is between 0.20-0.22 mm, and the boundary contrast value reaches 87%-89%. In contrast, Comparative Example 1, which does not adopt the three-layer gradient design of "adhesion layer-expansion layer-visual layer", has a minimum texture width of 0.37 mm and a boundary contrast of only 62%. This indicates that the gradient design can significantly improve the fineness of the ceramic tile texture and the sharpness of the boundary.

[0077] Test 2: Texture Height Difference and Uniformity Test Test Method: Three environmentally friendly 3D micro-carved ceramic tiles from Examples 1-3 and three ceramic tiles from Comparative Example 2 were selected and tested using a surface profilometer (measurement accuracy 0.01 μm). Three parallel scanning tracks were evenly arranged along the length of each tile surface. Each track was 5 cm long, with a track spacing of 2 cm, and the scanning rate was set to 0.5 mm / s. The texture height data of all measuring points on each track were recorded. The maximum height difference (maximum height value - minimum height value) and average height difference of each track were calculated. Then, the fluctuation error of each track was calculated according to the formula "height difference fluctuation error = (maximum height difference - minimum height difference) / average height difference × 100%". The average of the maximum height difference and the average of the fluctuation error of the three tracks were taken as the test result of the sample.

[0078] Test metrics: maximum texture height difference, height difference fluctuation error (the smaller the value, the better the uniformity).

[0079] The test data is shown in Table 2.

[0080] Table 2

[0081] As shown in Table 2, the maximum texture height difference in Examples 1-3 is 95-100 μm, with a height difference fluctuation error of only 8.5%-9.2%. In contrast, in Comparative Example 2 without a gradient structure forming segment, the maximum texture height difference is 88 μm, with a fluctuation error as high as 28.3%. This indicates that gradient temperature and oxygen concentration control in the 800-950℃ range can optimize the height difference of the three-dimensional texture and improve its uniformity.

[0082] Test 3: Interlayer Bond Strength Test Test Method: Three environmentally friendly 3D micro-carved ceramic tiles from Examples 1-3 and three ceramic tiles from Comparative Example 1 were selected. Three test points were selected on the three-dimensional texture area of ​​each tile. The surface of each test point was wiped clean with anhydrous ethanol and dried. A 10mm diameter metal pull-out head was attached to the test point with epoxy adhesive. The tile was cured for 24 hours at 23℃ and 50% relative humidity to ensure a firm bond between the pull-out head and the three-dimensional layer. The sample was fixed on the fixture of a tensile testing machine, and a tensile force was applied at a uniform rate of 5mm / min until the three-dimensional layer was completely peeled off from the glaze. The maximum tensile force value at the moment of peeling was recorded. The interlayer peel strength was calculated using the formula "interlayer peel strength = maximum tensile force value / pull-out head bonding area". The average value of the three test points was taken as the test result of the sample.

[0083] Test metric: interlayer peel strength (the higher the value, the stronger the bond).

[0084] The test data is shown in Table 3.

[0085] Table 3

[0086] As shown in Table 3, the interlayer peel strength of Examples 1-3 is 1.9-2.2 MPa, which is much higher than that of Comparative Example 1 (0.9 MPa) which did not adopt the three-layer gradient design. This confirms that the adhesion layer of the relief ink can effectively enhance the bonding strength between the three-dimensional layer and the glaze by reacting with the relief glaze in a solid phase, thus avoiding the risk of peeling.

[0087] Test 4: 3D Color Matching Test Test Method: Three environmentally friendly 3D micro-carved ceramic tiles from Examples 1-3 and three ceramic tiles from Comparative Example 3 were selected. Three typical pattern areas were chosen from each tile (the stamen and petal edges for floral patterns; the intersections of lines and the inflection points for geometric textures) as test areas. A high-precision image recognition system (pixel accuracy 0.01mm) was used to capture planar color images and three-dimensional contour images of each test area. The system software precisely aligned the two images, analyzed the coordinate deviation between the key points of the color pattern and the corresponding points of the three-dimensional texture, and recorded the maximum alignment deviation value. Meanwhile, the fit levels are classified according to the following standards: Level 5 (maximum alignment deviation ≤ 0.05 mm, perfect fit), Level 4 (0.05 mm < maximum alignment deviation ≤ 0.1 mm, basic fit), Level 3 (0.1 mm < maximum alignment deviation ≤ 0.2 mm, partial fit), Level 2 (0.2 mm < maximum alignment deviation ≤ 0.3 mm, slight misalignment), and Level 1 (maximum alignment deviation > 0.3 mm, severe misalignment). The average of the fit level and the maximum alignment deviation value of the three test sites is taken as the test result of the sample.

[0088] Test indicators: 3D color matching level, maximum alignment deviation value.

[0089] The data for Test 4 are shown in Table 4.

[0090] Table 4

[0091] As shown in Table 4, the stereo-color matching degree of Examples 1-3 all reached level 5, with a maximum alignment deviation of only 0.03-0.05mm. In contrast, Comparative Example 3, which did not use grayscale file control to control the inkjet volume, had a matching degree of only level 3, with a maximum alignment deviation of 0.17mm. This indicates that the combination of digital inkjet and grayscale grading control can achieve precise matching of stereo textures and color patterns.

[0092] Test 5: Stability Test During Thermal Cycling Test Method: Five environmentally friendly 3D micro-carved ceramic tiles from Examples 1-3 and five ceramic tiles from Comparative Examples 1 and 2 were selected. The samples were placed in a high-low temperature cycling chamber for stability testing. The test cycle was as follows: first, the samples were kept at -20°C for 2 hours, then quickly switched to 20°C for 2 hours, and then switched to 80°C for 2 hours, completing one cycle. A total of eight cycles were performed. During the test, the temperature switching rate was controlled to not exceed 5°C / min, and the relative humidity inside the chamber was maintained at 50%±5%. After the cycle, the samples were removed and placed in a room temperature environment for 24 hours. A 10x magnifying glass was used to observe whether the 3D layer of each sample exhibited peeling or whether cracks appeared on the glaze. The percentage of samples with 3D layer peeling (3D layer peeling rate) and the percentage of samples with glaze cracks (glaze cracking rate) were statistically analyzed.

[0093] Test indicators: three-dimensional layer peeling rate, glaze cracking rate.

[0094] The data for Test 5 are shown in Table 5.

[0095] Table 5

[0096] As shown in Table 5, after 8 cycles of hot and cold, the three-dimensional layer peeling rate and glaze cracking rate of Examples 1-3 were both 0, while Comparative Example 1 (without three-layer design) and Comparative Example 2 (without gradient firing section) showed three-dimensional layer peeling rates of 36% and 28% and glaze cracking rates of 16% and 22%, respectively. This indicates that the overall process design of the present invention can significantly improve the stability of ceramic tiles during hot and cold cycles.

[0097] In summary, this invention, through the three-layer gradient design of relief ink, precise control of glazing and firing processes, and the synergistic effect of digital inkjet printing and grayscale control, enables environmentally friendly 3D micro-carved ceramic tiles to exhibit excellent performance in terms of texture refinement, boundary clarity, interlayer bonding strength, three-dimensional color matching, and environmental stability. It effectively solves the core pain points of traditional products and takes into account both high-end decorative effects and green production requirements.

[0098] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing an environmentally friendly 3D micro-carved ceramic tile, characterized in that, Includes the following steps: S1. Mix the basic raw materials in proportion, ball mill, spray dry, age and then press into shape; S2. Apply a base glaze and a relief glaze sequentially to the surface of the dried body; the chemical composition of the relief glaze, by mass percentage, is: 49.0-52.0% SiO2, 10-12% Al2O3, 0.1-0.3% Fe2O3, 0.05-0.1% TiO2, 5-5.6% MgO, 7.0-8.0% CaO, 4.0-4.5% K2O, 1.5-2% Na2O, 0.02-0.06% ZrHfO2, 4-5% ZnO, 0.3-0.4% B2O3, 7.5-8.5% BaO, and 5.5-7% loss on ignition; S3. Using digital inkjet technology, embossing ink and pattern ink are simultaneously printed onto the embossed glaze surface according to the grayscale file design; the chemical composition of the embossing ink, by mass percentage, is: 15-18% SiO2, 0.5-1.0% Al2O3, 0.02-0.05% Fe2O3, 0.02-0.05% TiO2, 0.01-0.03% MgO, 0.1-0.2% CaO, 0.03-0.05% K2O, 0.01-0.02% Na2O, 7-8% ZnO, 16-17% Bi2O3, 5.0-6.0% V2O5, and 50-53% loss on ignition; S4. Slow drying, firing, edge grinding and packaging are used to produce environmentally friendly 3D micro-carved ceramic tiles; The embossed ink comprises the following raw materials: alumina powder, quartz powder, zinc oxide, bismuth trioxide, vanadium pentoxide, titanium dioxide, iron oxide pigment, calcium carbonate, magnesium oxide, potassium carbonate, sodium carbonate, and an organic carrier. The organic carrier includes terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant, Tween-80 surfactant, and organic bentonite thixotropic agent; The preparation of the embossed ink includes the following steps: A1. Take 70-80% of the total alumina powder, 45-55% of the total quartz powder, and 35-45% of the total zinc oxide, mix and ball mill until the D50 particle size is 2.2-2.8μm to prepare the adhesion layer raw material. A2. Take all of the bismuth trioxide and vanadium pentoxide, mix and ball mill until the D50 particle size is 1.1-1.4μm, to prepare the expansion layer raw material; A3. Take all the titanium dioxide and iron oxide pigments, mix and ball mill until the D50 particle size is 0.3-0.4μm, to prepare the visual layer raw material; A4. Mix the remaining alumina powder, quartz powder, zinc oxide with all the calcium carbonate, magnesium oxide, potassium carbonate and sodium carbonate, and ball mill until the D50 particle size is 0.85-1.15μm to prepare the basic dispersed phase; A5. Mix terpineol, diethylene glycol butyl ether acetate, sodium polyacrylate dispersant, Tween-80 surfactant and organic bentonite thixotropic agent evenly to prepare an organic carrier; A6. Add the organic carrier to the mixing equipment, and then add the basic dispersed phase, the adhesion layer material, the expansion layer material and the visual layer material in sequence. Disperse at high speed and adjust the pH to obtain the embossed ink.

2. The method for preparing an environmentally friendly 3D micro-carved ceramic tile according to claim 1, characterized in that, The chemical composition of the base blank, by mass percentage, is: 67-69% SiO2, 18-19% Al2O3, 1-1.5% Fe2O3, 0.15-0.2% TiO2, 1-1.5% MgO, 0.4-0.6% CaO, 3-4% K2O, 1.5-1.8% Na2O, and 3-5.5% loss on ignition.

3. The method for preparing an environmentally friendly 3D micro-carved ceramic tile according to claim 1, characterized in that, The amount of base glaze used per square meter of body surface is 450-500g, and the amount of relief glaze used is 380-420g, with an interval of 45-60 seconds between the application of base glaze and relief glaze.

4. The method for preparing an environmentally friendly 3D micro-carved ceramic tile according to claim 1, characterized in that, The slow drying process uses waste heat from the kiln, with a drying temperature of 200±10℃, a drying cycle of 120±10 seconds, and a heating rate controlled at 8-10℃ / second.

5. The method for preparing an environmentally friendly 3D micro-carved ceramic tile according to claim 1, characterized in that, The firing conditions are as follows: firing temperature is 1200-1210℃, firing time is 25-27 minutes, continuous firing is carried out in a roller kiln, the heating rate is 8-10℃ / minute before 600℃, 5-6℃ / minute from 600-900℃, and 3-4℃ / minute from 900℃ to the maximum temperature.

6. The method for preparing an environmentally friendly 3D micro-carved ceramic tile according to claim 5, characterized in that, A gradient structure forming section is set in the temperature range of 800-950℃, including: holding at 800-850℃ for 50-70 seconds with oxygen concentration controlled at 4-5%; holding at 850-900℃ for 60-80 seconds with oxygen concentration controlled at 3-4%; and holding at 900-950℃ for 40-60 seconds with oxygen concentration controlled at 3-4%.

7. An environmentally friendly 3D micro-carved ceramic tile, characterized in that, It is prepared by the method for preparing environmentally friendly 3D micro-carved ceramic tiles as described in any one of claims 1-6.

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