Building ceramic tile with fluorescent magical color effect and preparation method thereof

Abstract

The invention discloses a building ceramic tile with a fluorescent magical color effect and a preparation method of the building ceramic tile, and relates to the technical field of building ceramic tiles. The ceramic tile sequentially comprises a green body layer, a cover glaze layer, a pattern layer, a fluorescent material layer and a transparent color-emitting glaze layer from bottom to top, the pattern layer is formed by printing a multi-layer multicolor pattern file on the cover glaze layer by using a digital ink jet machine; according to the fluorescent material layer, after patterns are printed in an ink-jet mode, a printing machine is used for accurately aligning designed marking positions, the patterns printed by an ink jet printer and the fluorescent material layers with different colors are positioned and overlapped, it is ensured that the patterns of the fluorescent material layer and the colorful patterns printed by the digital ink jet printer are completely matched and overlapped, and the multi-layer colorful effect of the brick surface is achieved. According to the invention, a fluorescent material is introduced, a novel transparent color-developing protective glaze is researched and developed, and a proper firing process is combined, so that the brick surface can show a magical color effect in both bright and dark places.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building ceramic tiles, in particular to a building ceramic tile with fluorescent fantasy effect and a preparation method thereof. BACKGROUND

[0002] Fluorescent material refers to photoluminescent material, mainly various fluorescent powders, commonly known as night light powder, which is usually divided into two categories: photostoring night light powder and radioactive night light powder. Photostoring night light powder is a fluorescent powder that stores light energy after being irradiated by natural light, daylight lamp light, ultraviolet light, etc., and then slowly releases it in the form of fluorescence after stopping light irradiation, so it can still be seen to emit light in the night or darkness, with a duration of several hours to tens of hours, which is the long afterglow function of fluorescent powder. Long afterglow function materials can be used in luminous coatings, luminous inks, luminous plastics, luminous paper, luminous markers, night pearls, luminous ceramics, etc.

[0003] Currently, there are luminous ceramic products made of long afterglow materials on the market, and the specific manufacturing methods are as follows: 1. Directly mix long afterglow materials with other raw materials to make glaze water, which is coated on the ceramic body, such as patent CN109206013A, which discloses a long afterglow ceramic with no cracking on the glaze surface and its manufacturing process. The long afterglow material is mixed with other raw materials to make glaze water, which is coated on the ceramic body, and then fired to produce luminous ceramic. The effect of this scheme is relatively simple, and it cannot achieve more other effect types that customers want, nor can it achieve fluorescent fantasy effect.

[0004] 2. Spray a layer of long afterglow fluorescent material on the surface of the body, and then fire it, but the long afterglow fluorescent material coating of this method is not wear-resistant and can easily fall off during use.

[0005] 3. Apply a layer of transparent glaze on the body coated with long afterglow fluorescent material, and form a transparent protective layer after firing to alleviate the problem of fluorescent material coating falling off due to wear, but after applying the transparent protective layer, the light absorption and storage performance of different color fluorescent materials is reduced, affecting the light emission effect.

[0006] Therefore, how to obtain a ceramic tile with fluorescent fantasy effect and excellent light emission effect is a problem that needs to be solved in the current ceramic tile field. SUMMARY

[0007] To address the above shortcomings, this invention provides a building ceramic tile with a fluorescent iridescent effect and its preparation method. The method involves first printing a pattern layer on the ceramic body using a digital inkjet printer, then printing a fluorescent material layer using a printing machine. The printing machine precisely aligns the fluorescent material layer with the iridescent pattern printed by the digital inkjet printer through designed markings, ensuring complete overlap and a multi-layered iridescent effect on the tile surface. Finally, a novel transparent color-developing glaze is applied, combined with an appropriate firing process, enhancing the light absorption, storage, and emission effects of the different colored fluorescent materials after firing. The specific technical solution is as follows: A building ceramic tile with fluorescent iridescent effect, wherein the building ceramic tile with fluorescent iridescent effect comprises, from bottom to top, a body layer, a surface glaze layer, a pattern layer, a fluorescent material layer and a transparent color-emitting glaze layer; The formula for the transparent colored glaze layer is as follows: a parts of sodium feldspar (0≤a≤43), b parts of potassium feldspar (a+b=43), 8 parts of kaolin, 3 parts of calcined kaolin, c parts of strontium carbonate (6≤c≤12), d parts of quartz (6≤d≤14), e parts of dolomite (8≤e≤12), f parts of calcite (5≤f≤8), g parts of boric acid (4≤g≤12), h parts of zinc oxide (1≤h≤3), and 1 part of zirconium silicate, wherein c+d+e+f+g+h=45.

[0008] Further, the chemical composition of the green body powder on the green body layer includes, by mass percentage: loss on ignition: 3.8-4.8%, SiO2: 65-70%, Al2O3: 18-22%, Fe2O3: 0.3-1.3%, TiO2: 0.1-0.2%, CaO: 0.3-0.8%, MgO: 0.5-1.5%, K2O: 3.0-4.0%, and Na2O: 2.0-3.0%; the particle size distribution of the green body powder includes, by mass percentage: 20 mesh: ≤1%, 30 mesh and above: 10-20%, 30-60 mesh: 65-75%, 60-80 mesh: ≤12%, and below 80 mesh: ≤6%.

[0009] Furthermore, the chemical composition of the surface glaze layer includes, by mass percentage: loss on ignition: 2.0-5.0%, SiO2: 55-65%, Al2O3: 18-21%, Fe2O3: 0.1-0.2%, TiO2: 0.03-0.05%, CaO: 0.5-1.0%, MgO: 1.0-2.0%, K2O: 0.8-1.2%, Na2O: 4.0-5.0%, BaO: 5.0-6.0%, ZrO2: 4.0-5.0%, with the sum of the mass percentages of the chemical composition being 100%; the fineness requirement of the surface glaze is that the residue on a 325-mesh sieve reaches 0.5-0.8 wt%.

[0010] Furthermore, the fluorescent material layer comprises one or more of rare earth elements, including europium oxide, dysprosium oxide, aluminum oxide, and aluminates.

[0011] Furthermore, the compositional parameters of the fluorescent material layer include: a density of 3.8 ± 0.2 g / cm³. 3 Particle size distribution (center diameter d50) is 20±5μm or passes through a sieve with an aperture of 75 (200 mesh); afterglow time is 1800-2000min (based on the complete disappearance of the bright light).

[0012] This invention also provides a method for preparing building ceramic bricks with fluorescent iridescent effects, comprising the following steps: (1) Make a blank. After grinding and drying, a green blank with a certain strength is obtained, and a blank layer is obtained. (2) Spray water to wet the surface of the blank layer and apply the surface glaze layer; (3) Print the pattern layer on the surface of the blank after the surface glaze layer is applied using a digital inkjet printer, that is, print a multi-layer holographic pattern file; (4) Print a fluorescent material layer on the surface of the brick blank containing the pattern layer using a printing machine; that is, after the digital inkjet printer prints the pattern layer, the printing machine is used to accurately align the design mark position so that the pattern of the fluorescent material layer completely matches and overlaps with the iridescent pattern printed by the digital inkjet printer, thereby achieving a multi-layer iridescent effect on the brick surface. (5) Spray a transparent color-developing glaze onto the surface of the brick blank containing fluorescent materials; (6) Dry and fire the brick blank containing transparent color glaze to obtain building ceramic brick with fluorescent iridescent effect.

[0013] Furthermore, in step (1), the drying is carried out in a drying kiln, which is a four-layer drying kiln with a length of 100M, and the drying time is 40-60min. After drying, the moisture content of the green body is controlled to be 0.2-0.4wt%.

[0014] Furthermore, in step (2), the water spraying is performed using two spray guns with nozzles of 0.52-0.62mm in size, and the water spraying volume is 60-100g / m³. 2 The process parameters for the surface glaze layer are: glaze application rate of 480-580 g / m³. 2 The specific gravity is 1.82-1.92 g / ml, and the flow rate is 26-32 seconds.

[0015] Furthermore, in step (5), the process parameters for spraying the transparent color-developing glaze are: glaze application rate: 350-450 g / m³ 2The specific gravity is 1.40-1.50 g / ml; two types of spray guns with different nozzle diameters are used for spraying transparent colored glaze: 0.52mm spray gun A and 0.62mm spray gun B; there are two sets of spray gun A and four sets of spray gun B; the installation sequence of the six sets of spray guns is: spray gun A → spray gun B → spray gun B → spray gun B → spray gun A; the distance between spray gun A and spray gun B is 30cm, and the distance between spray gun B and spray gun B is 20cm. With the center of the brick blank as the reference line, the six sets of spray guns are each 5cm away from the reference line and are arranged alternately on the left and right sides of the reference line; the height of the nozzle from the surface of the brick blank is 80-90cm, and the spray gun is at a 45-degree angle to the surface of the brick blank; when spraying transparent colored glaze, the pressure of the high-pressure glazing machine is set to 4-4.5 MPa.

[0016] Furthermore, in step (6), the firing cycle is 40-50 minutes, the highest temperature in the high-temperature zone is 1200-1215℃, and the firing atmosphere is a reducing atmosphere.

[0017] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention uses fluorescent materials with rare earth europium oxide, dysprosium oxide, aluminum oxide and aluminates as the main components to prepare a fluorescent material layer. Combined with the inkjet printing pattern and the positioning and overlapping design of different fluorescent color materials, a multi-layered fluorescent iridescent effect is achieved on the brick surface.

[0018] 2. This invention develops a novel transparent color-developing glaze formula. By continuously adjusting the boric acid content, as well as the ratio of strontium carbonate, dolomite, calcite, and zinc oxide, and firing under appropriate conditions, the glaze color development is stabilized, the tile surface has excellent transparency and stain resistance, with a stain resistance level of up to 5, thereby enhancing the fluorescent iridescent effect of the ceramic tile.

[0019] 3. This invention first prints a pattern layer, then prints a fluorescent material layer, and finally applies a novel transparent color-emitting glaze. By optimizing the transparent color-emitting glaze formula and firing under appropriate conditions, it can effectively prevent the structure of the fluorescent material from being damaged, thus reducing its light absorption and light storage capacity, thereby improving the light emission effect of different fluorescent materials. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below.

[0021] Figure 1 This is a flowchart illustrating the preparation process of the fluorescent iridescent building ceramic brick of the present invention. Detailed Implementation

[0022] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0023] Example 1 This embodiment of a fluorescent iridescent building ceramic tile comprises, from bottom to top, a body layer, a glaze layer, a pattern layer, a fluorescent material layer, and a transparent color-developing glaze layer. The specific preparation method is as follows: (1) The green body is obtained by pressing. The chemical composition of the green body powder includes, by mass percentage: loss on ignition: 3.8%, SiO2: 68%, Al2O3: 21%, Fe2O3: 0.3%, TiO2: 0.1%, CaO: 0.3%, MgO: 0.5%, K2O: 3.0%, Na2O: 3.0%. The particle size distribution of the powder includes, by mass percentage: 20 mesh: 0.5%, 30 mesh and above: 10%, 30-60 mesh: 75%, 60-80 mesh: 12%, below 80 mesh: 2.5%.

[0024] (2) After the shaped blank is ground by a grinding machine, it is dried in a drying kiln to obtain a green blank with a certain strength. The drying kiln is a four-layer drying kiln, 100M long, and the drying time can be 40min. The moisture content of the blank after drying is controlled at 0.4wt%.

[0025] (3) Spray water to wet the surface of the billet, water spraying amount: 60g / m 2 It uses two spray guns with a nozzle size of 0.52mm.

[0026] (4) Apply the surface glaze using a bell-shaped glazing method. The process parameters for applying the surface glaze are: glaze application rate of 480g / m². 2 The specific gravity is 1.82 g / ml, and the flow rate is 26 seconds. The chemical composition of the glaze, by mass percentage, is as follows: Loss on ignition: 2.0%, SiO2: 63%, Al2O3: 19.57%, Fe2O3: 0.1%, TiO2: 0.03%, CaO: 0.5%, MgO: 1.0%, K2O: 0.8%, Na2O: 4.0%, BaO: 5.0%, ZrO2: 4.0%, with the sum of the mass percentages of the chemical composition being 100%. The fineness requirement for the glaze is that the residue on a 325-mesh sieve reaches 0.5 wt%.

[0027] (5) Use a digital inkjet printer to print iridescent pattern files on the surface of the blank after the surface glaze is applied. The color and texture of the pattern can be adjusted appropriately according to the required fluorescent effect.

[0028] (6) Use a printing machine to print fluorescent material on the surface of the brick blank after the multi-layer iridescent pattern is printed by inkjet printing; that is, after the pattern layer is printed by digital inkjet printer, the printing machine is used to accurately align the design mark position so that the pattern of the fluorescent material layer is completely matched and overlapped with the iridescent pattern printed by digital inkjet printer, so as to achieve the multi-layer iridescent effect on the brick surface.

[0029] (7) Spray a transparent color-developing glaze on the surface of the brick blank after printing the fluorescent material: Transparent coloring glaze formula: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 10 parts quartz, 10 parts dolomite, 5 parts calcite, 9 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0030] The process parameters for spraying transparent color-developing glaze are: glaze amount: 350g / m³ 2 Its specific gravity is 1.40 g / ml.

[0031] The specific spraying method is as follows: Mix the required raw materials evenly according to the proportion, put them into a ball mill and add 38% water, 0.13% carboxymethyl cellulose and 0.3% sodium tripolyphosphate. Control the fineness of the balls to 0.4% (325 mesh sieve), age for 18 hours, control the specific gravity to 1.40, and use the glazing process to apply the glaze to the surface of the dry granules of the brick blank.

[0032] Two types of spray guns with different nozzle diameters are used for spraying transparent color glaze: 0.52mm spray gun A and 0.62mm spray gun B. There are two sets of spray gun A and four sets of spray gun B. The installation sequence of the six sets of spray guns is: Spray gun A → Spray gun B → Spray gun B → Spray gun B → Spray gun A. To avoid uneven glazing and large deviations in the amount of glaze sprayed between the sides and the center, the distance between spray guns A and B is 30cm, and the distance between spray guns B and B is 20cm. Using the center of the brick as a reference line, the six sets of spray guns are each 5cm away from the reference line, arranged alternately to the left and right of the reference line, effectively ensuring that the amount of glaze sprayed between the sides and the center of the brick is similar. The nozzle is 80cm above the brick surface, and the spray gun is at a 45-degree angle to the brick surface with the nozzle tilted backward. If the spray gun is perpendicular to the brick surface, the dry granules of the cloth will easily be blown away when spraying transparent color glaze. When spraying transparent colored glaze, the pressure of the high-pressure glazing machine is set to 4 MPa.

[0033] (8) After the brick blanks are sprayed with transparent colored glaze and dried in the kiln before being dried, they are fired in the kiln at a temperature of 1140℃ for 40 minutes. The firing atmosphere is a reducing atmosphere. After firing, ceramic tiles with fluorescent iridescent effects are obtained. The gloss and dirt absorption are measured, and the glaze surface is observed and the afterglow of the fluorescent iridescent effect is visually measured.

[0034] Example 2 This embodiment of a fluorescent iridescent building ceramic tile comprises, from bottom to top, a body layer, a glaze layer, a pattern layer, a fluorescent material layer, and a transparent color-developing glaze layer. The specific preparation method is as follows: (1) The green body is obtained by pressing. The chemical composition of the green body powder includes, by mass percentage: loss on ignition: 4.2%, SiO2: 68%, Al2O3: 18%, Fe2O3: 0.8%, TiO2: 0.2%, CaO: 0.8%, MgO: 1.0%, K2O: 4.0%, Na2O: 3.0%. The particle size distribution of the powder includes, by mass percentage: 20 mesh: 1%, 30 mesh and above: 20%, 30-60 mesh: 68%, 60-80 mesh: 8%, below 80 mesh: 3%.

[0035] (2) After the shaped billet is ground by a grinding machine, it is dried in a drying kiln to obtain a green billet with a certain strength. The drying kiln is a four-layer drying kiln with a length of 100M. The drying time can be 60min, and the moisture content of the billet after drying is controlled at 0.2wt%.

[0036] (3) Spray water to wet the surface of the billet, water spraying amount: 100g / m 2 It uses two spray guns with a nozzle size of 0.62mm.

[0037] (4) Apply the surface glaze using a bell-shaped glazing method. The process parameters for applying the surface glaze are: glaze application rate of 580g / m². 2 The specific gravity is 1.92 g / ml, and the flow rate is 32 seconds. The chemical composition of the glaze, by mass percentage, is as follows: Loss on ignition: 5.0%, SiO2: 59%, Al2O3: 18%, Fe2O3: 0.1%, TiO2: 0.05%, CaO: 1.0%, MgO: 2.0%, K2O: 1.2%, Na2O: 4.65%, BaO: 5.0%, ZrO2: 4.0%, with the sum of the mass percentages of the chemical composition being 100%. The fineness requirement for the glaze is that the residue on a 325-mesh sieve reaches 0.8 wt%.

[0038] (5) Use a digital inkjet printer to print iridescent pattern files on the surface of the body after the surface glaze is applied. The color and texture of the pattern can be adjusted appropriately according to the required fluorescent effect. (6) Use a printing machine to print fluorescent material on the surface of the brick blank after the multi-layer iridescent pattern is printed by inkjet printing; that is, after the pattern layer is printed by digital inkjet printer, the printing machine is used to accurately align the design mark position so that the pattern of the fluorescent material layer is completely matched and overlapped with the iridescent pattern printed by digital inkjet printer, so as to achieve the multi-layer iridescent effect on the brick surface.

[0039] (7) Spray a transparent color-developing glaze on the surface of the brick blank after printing the fluorescent material: Transparent coloring glaze formula: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 6 parts quartz, 11 parts dolomite, 6 parts calcite, 12 parts boric acid, 1 part zinc oxide, and 1 part zirconium silicate.

[0040] The process parameters for spraying transparent color-developing glaze are: glaze amount: 450g / m³ 2 Its specific gravity is 1.50 g / ml.

[0041] The specific spraying method is as follows: Mix the required raw materials evenly according to the proportion, put them into a ball mill and add 38% water, 0.13% carboxymethyl cellulose and 0.3% sodium tripolyphosphate. Control the fineness of the balls to 0.6% (325 mesh sieve), age for 24 hours, control the specific gravity to 1.50, and use the glazing process to apply the glaze to the surface of the dry granules of the brick blank.

[0042] Two types of spray guns with different nozzle diameters are used for spraying transparent color glaze: 0.52mm spray gun A and 0.62mm spray gun B. There are two sets of spray gun A and four sets of spray gun B. The installation sequence of the six sets of spray guns is: Spray gun A → Spray gun B → Spray gun B → Spray gun B → Spray gun A. To avoid uneven glazing and large deviations in the amount of glaze sprayed between the sides and the center, the distance between spray guns A and B is 30cm, and the distance between spray guns B and B is 20cm. Using the center of the brick as a reference line, the six sets of spray guns are each 5cm away from the reference line, arranged alternately to the left and right of the reference line, effectively ensuring that the amount of glaze sprayed on the sides and center of the brick is similar. The nozzle is 80cm above the brick surface, and the spray gun is at a 45-degree angle to the brick surface with the nozzle tilted backward. If the spray gun is perpendicular to the brick surface, the dry granules of the cloth will easily be blown away when spraying the transparent color glaze. When spraying transparent colored glaze, the pressure of the high-pressure glazing machine is set to 4.5 MPa.

[0043] (8) After the brick blanks are sprayed with transparent colored glaze and dried in the kiln before being dried, they are fired in the kiln at a temperature of 1140℃ for 40 minutes. The firing atmosphere is a reducing atmosphere. After firing, ceramic tiles with fluorescent iridescent effects are obtained. The gloss and dirt absorption are measured, and the glaze surface is observed and the afterglow of the fluorescent iridescent effect is visually measured.

[0044] Example 3 This embodiment of a fluorescent iridescent building ceramic tile comprises, from bottom to top, a body layer, a glaze layer, a pattern layer, a fluorescent material layer, and a transparent color-developing glaze layer. The specific preparation method is as follows: (1) The green body is obtained by pressing. The chemical composition of the green body powder includes, by mass percentage: loss on ignition: 4.6%, SiO2: 70%, Al2O3: 19.2%, Fe2O3: 0.3%, TiO2: 0.1%, CaO: 0.3%, MgO: 0.5%, K2O: 3.0%, Na2O: 2.0%. The particle size distribution of the powder includes, by mass percentage: 20 mesh: 0.6%, 30 mesh and above: 18%, 30-60 mesh: 72%, 60-80 mesh: 7%, below 80 mesh: 2.4%.

[0045] (2) After the shaped billet is ground by a grinding machine, it is dried in a drying kiln to obtain a green billet with a certain strength. The drying kiln is a four-layer drying kiln with a length of 100M. The drying time can be 50min, and the moisture content of the billet after drying is controlled at 0.3wt%.

[0046] (3) Spray water to wet the surface of the billet, water spraying amount: 90g / m 2 It uses two spray guns with a nozzle size of 0.60mm.

[0047] (4) Apply the surface glaze using a bell-shaped glazing method. The process parameters for applying the surface glaze are: glaze application rate of 550g / m². 2 The specific gravity is 1.89 g / ml, and the flow rate is 29 seconds. The chemical composition of the glaze, by mass percentage, is as follows: Loss on ignition: 3.0%, SiO2: 60%, Al2O3: 20%, Fe2O3: 0.12%, TiO2: 0.04%, CaO: 0.5%, MgO: 1.2%, K2O: 0.9%, Na2O: 4.24%, BaO: 5.5%, ZrO2: 4.5%, with the sum of the mass percentages of the chemical composition being 100%. The fineness requirement for the glaze is that the residue on a 325-mesh sieve reaches 0.7 wt%.

[0048] (5) Use a digital inkjet printer to print iridescent pattern files on the surface of the body after the surface glaze is applied. The color and texture of the pattern can be adjusted appropriately according to the required fluorescent effect. (6) Use a printing machine to print fluorescent material on the surface of the brick blank after the multi-layer iridescent pattern is printed by inkjet printing; that is, after the pattern layer is printed by digital inkjet printer, the printing machine is used to accurately align the design mark position so that the pattern of the fluorescent material layer is completely matched and overlapped with the iridescent pattern printed by digital inkjet printer, so as to achieve the multi-layer iridescent effect on the brick surface.

[0049] (7) Spray a transparent color-developing glaze on the surface of the brick blank after printing the fluorescent material: Transparent coloring glaze formula: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 12 parts quartz, 10 parts dolomite, 7 parts calcite, 4 parts boric acid, 3 parts zinc oxide, and 1 part zirconium silicate.

[0050] The process parameters for spraying transparent color-developing glaze are: glaze amount: 400g / m³ 2 Its specific gravity is 1.45 g / ml.

[0051] The specific spraying method is as follows: Mix the required raw materials evenly according to the proportion, put them into a ball mill and add 38% water, 0.13% carboxymethyl cellulose and 0.3% sodium tripolyphosphate. Control the fineness of the balls to 0.5% (325 mesh sieve), age for 20 hours, control the specific gravity to 1.45, and use the glazing process to apply the glaze to the surface of the dry granules of the brick blank.

[0052] Two types of spray guns with different nozzle diameters are used for spraying transparent color glaze: 0.52mm spray gun A and 0.62mm spray gun B. There are two sets of spray gun A and four sets of spray gun B. The installation sequence of the six sets of spray guns is: Spray gun A → Spray gun B → Spray gun B → Spray gun B → Spray gun A. To avoid uneven glazing and large deviations in the amount of glaze sprayed between the sides and the center, the distance between spray guns A and B is 30cm, and the distance between spray guns B and B is 20cm. Using the center of the brick as a reference line, the six sets of spray guns are each 5cm away from the reference line, arranged alternately to the left and right of the reference line, effectively ensuring that the amount of glaze sprayed between the sides and the center of the brick is similar. The nozzle is 80cm above the brick surface, and the spray gun is at a 45-degree angle to the brick surface with the nozzle tilted backward. If the spray gun is perpendicular to the brick surface, the dry granules of the cloth will easily be blown away when spraying transparent color glaze. When spraying transparent colored glaze, the pressure of the high-pressure glazing machine is set to 4 MPa.

[0053] (8) After the brick blanks are sprayed with transparent colored glaze and dried in the kiln before being dried, they are fired in the kiln at a temperature of 1140℃ for 40 minutes. The firing atmosphere is a reducing atmosphere. After firing, ceramic tiles with fluorescent iridescent effects are obtained. The gloss and dirt absorption are measured, and the glaze surface is observed and the afterglow of the fluorescent iridescent effect is visually measured.

[0054] Example 4 This embodiment of a fluorescent iridescent building ceramic tile comprises, from bottom to top, a body layer, a glaze layer, a pattern layer, a fluorescent material layer, and a transparent color-developing glaze layer. The specific preparation method is as follows: (1) The green body is obtained by pressing. The chemical composition of the green body powder includes, by mass percentage: loss on ignition: 4.7%, SiO2: 69.9%, Al2O3: 19.2%, Fe2O3: 0.3%, TiO2: 0.1%, CaO: 0.3%, MgO: 0.5%, K2O: 3.0%, Na2O: 2.0%. The particle size distribution of the powder includes, by mass percentage: 20 mesh: 0.6%, 30 mesh and above: 18%, 30-60 mesh: 72%, 60-80 mesh: 7%, below 80 mesh: 2.6%.

[0055] (2) After the shaped billet is ground by a grinding machine, it is dried in a drying kiln to obtain a green billet with a certain strength. The drying kiln is a four-layer drying kiln with a length of 100M. The drying time can be 50min, and the moisture content of the billet after drying is controlled at 0.3wt%.

[0056] (3) Spray water to wet the surface of the billet, water spraying amount: 90g / m 2 It uses two spray guns with a nozzle size of 0.60mm.

[0057] (4) Apply the surface glaze using a bell-shaped glazing method. The process parameters for applying the surface glaze are: glaze application rate of 550g / m². 2 The specific gravity is 1.89 g / ml, and the flow rate is 29 seconds. The chemical composition of the glaze, by mass percentage, includes: loss on ignition: 2.9%, SiO2: 60%, Al2O3: 20%, Fe2O3: 0.12%, TiO2: 0.04%, CaO: 0.5%, MgO: 1.2%, K2O: 1.0%, Na2O: 4.24%, BaO: 5.5%, ZrO2: 4.5%, with the sum of the mass percentages of the chemical composition being 100%. The fineness requirement for the glaze is that the residue on a 325-mesh sieve reaches 0.7 wt%.

[0058] (5) Use a digital inkjet printer to print iridescent pattern files on the surface of the body after the surface glaze is applied. The color and texture of the pattern can be adjusted appropriately according to the required fluorescent effect. (6) Use a printing machine to print fluorescent material on the surface of the brick blank after the multi-layer iridescent pattern is printed by inkjet printing; that is, after the pattern layer is printed by digital inkjet printer, the printing machine is used to accurately align the design mark position so that the pattern of the fluorescent material layer is completely matched and overlapped with the iridescent pattern printed by digital inkjet printer, so as to achieve the multi-layer iridescent effect on the brick surface.

[0059] (7) Spray a transparent color-developing glaze on the surface of the brick blank after printing the fluorescent material: Transparent coloring glaze formula: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 12 parts quartz, 10 parts dolomite, 7 parts calcite, 4 parts boric acid, 3 parts zinc oxide, and 1 part zirconium silicate.

[0060] The process parameters for spraying transparent color-developing glaze are: glaze amount: 400g / m³ 2 Its specific gravity is 1.45 g / ml.

[0061] The specific spraying method is as follows: Mix the required raw materials evenly according to the proportion, put them into a ball mill and add 38% water, 0.13% carboxymethyl cellulose and 0.3% sodium tripolyphosphate. Control the fineness of the balls to 0.5% (325 mesh sieve), age for 20 hours, control the specific gravity to 1.45, and use the glazing process to apply the glaze to the surface of the dry granules of the brick blank.

[0062] Two types of spray guns with different nozzle diameters are used for spraying transparent color glaze: 0.52mm spray gun A and 0.62mm spray gun B. There are two sets of spray gun A and four sets of spray gun B. The installation sequence of the six sets of spray guns is: Spray gun A → Spray gun B → Spray gun B → Spray gun B → Spray gun A. To avoid uneven glazing and large deviations in the amount of glaze sprayed between the sides and the center, the distance between spray guns A and B is 30cm, and the distance between spray guns B and B is 20cm. Using the center of the brick as a reference line, the six sets of spray guns are each 5cm away from the reference line, arranged alternately to the left and right of the reference line, effectively ensuring that the amount of glaze sprayed between the sides and the center of the brick is similar. The nozzle is 80cm above the brick surface, and the spray gun is at a 45-degree angle to the brick surface with the nozzle tilted backward. If the spray gun is perpendicular to the brick surface, the dry granules of the cloth will easily be blown away when spraying transparent color glaze. When spraying transparent colored glaze, the pressure of the high-pressure glazing machine is set to 4 MPa.

[0063] (8) After the brick blanks are sprayed with transparent colored glaze and dried in the kiln before being dried, they are fired in the kiln at a temperature of 1140℃ for 40 minutes. The firing atmosphere is a reducing atmosphere. After firing, ceramic tiles with fluorescent iridescent effects are obtained. The gloss and dirt absorption are measured, and the glaze surface is observed and the afterglow of the fluorescent iridescent effect is visually measured.

[0064] Example 5 The transparent coloring glaze formula is as follows: 10 parts sodium feldspar, 33 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 12 parts strontium carbonate, 6 parts quartz, 9 parts dolomite, 8 parts calcite, 8 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0065] The other raw materials and preparation methods are the same as in Example 1.

[0066] Example 6 The transparent coloring glaze formula is as follows: 16 parts sodium feldspar, 27 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 8 parts strontium carbonate, 9 parts quartz, 12 parts dolomite, 5 parts calcite, 9 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0067] The other raw materials and preparation methods are the same as in Example 1.

[0068] Example 7 The transparent coloring glaze formula is as follows: 23 parts sodium feldspar, 20 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 6 parts strontium carbonate, 10 parts quartz, 12 parts dolomite, 8 parts calcite, 7 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0069] The other raw materials and preparation methods are the same as in Example 1.

[0070] Example 8 The transparent coloring glaze formula is as follows: 40 parts sodium feldspar, 3 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 11 parts strontium carbonate, 14 parts quartz, 8 parts dolomite, 5 parts calcite, 5 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0071] The other raw materials and preparation methods are the same as in Example 1.

[0072] Comparative Example 1 The transparent coloring glaze formula is as follows: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 10 parts quartz, 10 parts dolomite, 5 parts calcite, 0 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0073] The other raw materials and preparation methods are the same as in Example 1.

[0074] Comparative Example 2 The transparent coloring glaze formula is as follows: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 10 parts quartz, 10 parts dolomite, 5 parts calcite, 2 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0075] The other raw materials and preparation methods are the same as in Example 1.

[0076] Comparative Example 3 The transparent coloring glaze formula is as follows: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 10 parts quartz, 10 parts dolomite, 5 parts calcite, 13 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0077] The other raw materials and preparation methods are the same as in Example 1.

[0078] Comparative Example 4 The transparent coloring glaze formula is as follows: 3 parts sodium feldspar, 40 parts potassium feldspar, 8 parts kaolin, 3 parts calcined kaolin, 9 parts strontium carbonate, 10 parts quartz, 10 parts dolomite, 5 parts calcite, 15 parts boric acid, 2 parts zinc oxide, and 1 part zirconium silicate.

[0079] The other raw materials and preparation methods are the same as in Example 1.

[0080] Comparative Example 5 The raw materials are the same as those in Example 1, except that the firing atmosphere is an oxidizing atmosphere, and the other preparation methods are the same as those in Example 1.

[0081] Comparative Example 6 The raw materials are the same as those in Example 1, except that the firing time is 30 min and the other preparation methods are the same as those in Example 1.

[0082] Comparative Example 7 The raw materials were the same as in Example 1, except that the firing time was 70 min and the other preparation methods were the same as in Example 1.

[0083] The performance of the ceramic tiles prepared in Examples 1-8 and Comparative Examples 1-7 was tested, and the results are shown in Table 1.

[0084] Test methods and instruments used: Stain resistance performance: According to the stain resistance performance test method in GB / T3810.14-2015 Ceramic Tile Test Method, black, red and blue oil-based inks were applied to the tile surface for testing.

[0085] Water absorption rate: The water absorption rate was determined according to the test method in GB / T3810.3-2015 Ceramic Tile Test Method, using the TZY-3 digital display ceramic water absorption rate tester manufactured by Tianjin Yougong Test Equipment Co., Ltd.

[0086] Abrasion resistance: According to the test method for abrasion resistance of glazed tiles in GB / T3810.7-2015 Ceramic Tile Test Method, the abrasion resistance tester of ceramic tiles produced by Shenzhen Ouprui Testing Equipment Co., Ltd. was used for testing.

[0087] Gloss: The gloss was measured using an MN60 gloss meter manufactured by Shanghai Liangyan Intelligent Technology Co., Ltd., in accordance with the gloss determination method in GB / T13891-2015 Ceramic Tile Test Methods.

[0088] The product quality rate is tested according to the enterprise standard requirements. Generally, the enterprise standard requirements for ceramic products are higher than the industry standard requirements, and the industry standard requirements are higher than the national standard requirements.

[0089] Table 1 Performance of each tile The table shows that the ceramic tiles prepared by the present invention in Examples 1 to 8 achieve Grade A stain resistance, Grade 5 wear resistance, and qualified water absorption. They also exhibit a fluorescent iridescent effect with a long afterglow time. A comparison of Example 1 and the comparative examples shows that the transparent color-developing glaze formula of the present invention can achieve a fluorescent iridescent effect on the surface of the ceramic tiles and maintain an afterglow time of over 30 hours. The boric acid content in the formula is particularly crucial; too little or too much boric acid results in an unsatisfactory afterglow effect, with an afterglow time of 0. By adjusting the ratio of sodium feldspar, potassium feldspar, strontium carbonate, dolomite, calcite, quartz, and zinc oxide, the formula ensures stable glaze color development, improves stain resistance, and enhances the light absorption and storage performance of different colored fluorescent materials. Furthermore, firing conditions also affect the afterglow effect; only firing under the conditions of the present invention will produce the corresponding afterglow effect; otherwise, the afterglow time is 0.

[0090] In summary, this invention introduces fluorescent materials with long afterglow emission. A printing machine is used to precisely align the marked positions, and an inkjet printer is employed to overlap the printed pattern with different colored fluorescent material layers. This ensures a perfect match and overlap between the fluorescent material layer pattern and the iridescent pattern printed by the digital inkjet printer. Simultaneously, a novel transparent color-developing protective glaze is developed, enabling the tile surface to display an iridescent effect in both bright and dark environments. This invention requires a reducing atmosphere to achieve its effect. The novel transparent color-developing glaze formula developed in this invention can achieve a fluorescent iridescent effect on the tile surface, with an afterglow time exceeding 30 hours. The boric acid content in the formula is particularly critical; too little or too much will result in an unsatisfactory afterglow emission effect. The formula, by adjusting the proportions of sodium feldspar, potassium feldspar, strontium carbonate, dolomite, calcite, quartz, and zinc oxide, ensures stable glaze color and excellent stain resistance.

[0091] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A type of building ceramic tile with fluorescent iridescent effect, characterized in that, The building ceramic tile with fluorescent iridescent effect comprises, from bottom to top, a body layer, a glaze layer, a pattern layer, a fluorescent material layer, and a transparent color-emitting glaze layer; The formula for the transparent colored glaze layer is as follows: a parts of sodium feldspar (0≤a≤43), b parts of potassium feldspar (a+b=43), 8 parts of kaolin, 3 parts of calcined kaolin, c parts of strontium carbonate (6≤c≤12), d parts of quartz (6≤d≤14), e parts of dolomite (8≤e≤12), f parts of calcite (5≤f≤8), g parts of boric acid (4≤g≤12), h parts of zinc oxide (1≤h≤3), and 1 part of zirconium silicate, wherein c+d+e+f+g+h=45.

2. The building ceramic tile with fluorescent iridescent effect according to claim 1, characterized in that, The chemical composition of the green body powder on the green body layer includes, by mass percentage: loss on ignition: 3.8-4.8%, SiO2: 65-70%, Al2O3: 18-22%, Fe2O3: 0.3-1.3%, TiO2: 0.1-0.2%, CaO: 0.3-0.8%, MgO: 0.5-1.5%, K2O: 3.0-4.0%, and Na2O: 2.0-3.0%; the particle size distribution of the green body powder includes, by mass percentage: 20 mesh: ≤1%, 30 mesh and above: 10-20%, 30-60 mesh: 65-75%, 60-80 mesh: ≤12%, and below 80 mesh: ≤6%.

3. The building ceramic tile with fluorescent iridescent effect according to claim 1, characterized in that, The chemical composition of the surface glaze layer includes, by mass percentage: loss on ignition: 2.0-5.0%, SiO2: 55-65%, Al2O3: 18-21%, Fe2O3: 0.1-0.2%, TiO2: 0.03-0.05%, CaO: 0.5-1.0%, MgO: 1.0-2.0%, K2O: 0.8-1.2%, Na2O: 4.0-5.0%, BaO: 5.0-6.0%, ZrO2: 4.0-5.0%, with the sum of the mass percentages of the chemical composition being 100%; the fineness requirement of the surface glaze is that the residue on a 325-mesh sieve reaches 0.5-0.8 wt%.

4. A building ceramic tile with fluorescent iridescent effect according to claim 1, characterized in that, The fluorescent material layer comprises one or more of rare earth elements, including europium oxide, dysprosium oxide, aluminum oxide, and aluminates.

5. A building ceramic tile with fluorescent iridescent effect according to claim 1, characterized in that, The composition parameters of the fluorescent material layer include: a density of 3.8 ± 0.2 g / cm³. 3 The particle size distribution is 20±5μm or can pass through a 75mm mesh screen; the afterglow time is 1800-2000min.

6. A method for preparing a building ceramic tile with fluorescent iridescent effect as described in any one of claims 1 to 5, characterized in that, Includes the following steps: (1) Make a blank. After grinding and drying, a green blank with a certain strength is obtained, and a blank layer is obtained. (2) Spray water to wet the surface of the blank layer and apply the surface glaze layer; (3) Print the pattern layer on the surface of the blank after the surface glaze layer has been applied using a digital inkjet printer; (4) Print a fluorescent material layer on the surface of the brick blank containing the pattern layer using a printing machine; (5) Spray a transparent color-developing glaze onto the surface of the brick blank containing fluorescent materials; (6) Dry and fire the brick blank containing transparent color glaze to obtain building ceramic brick with fluorescent iridescent effect.

7. The method for preparing a building ceramic tile with fluorescent iridescent effect according to claim 6, characterized in that, In step (1), the drying is carried out in a drying kiln, which is a four-layer drying kiln with a length of 100M. The drying time is 40-60min, and the moisture content of the green body after drying is controlled to be 0.2-0.4wt%.

8. The method for preparing a building ceramic tile with fluorescent iridescent effect according to claim 6, characterized in that, In step (2), the water spraying is performed using two spray guns with nozzles of 0.52-0.62mm in size, and the water volume is 60-100g / m³. 2 The process parameters for the surface glaze layer are: glaze application rate of 480-580 g / m³. 2 The specific gravity is 1.82-1.92 g / ml, and the flow rate is 26-32 seconds.

9. The method for preparing a building ceramic tile with fluorescent iridescent effect according to claim 6, characterized in that, In step (5), the process parameters for spraying the transparent color-developing glaze are: glaze application rate: 350-450 g / m³ 2 The specific gravity is 1.40-1.50 g / ml; two types of spray guns with different nozzle diameters are used for spraying transparent colored glaze: 0.52mm spray gun A and 0.62mm spray gun B; there are two sets of spray gun A and four sets of spray gun B; the installation sequence of the six sets of spray guns is: spray gun A → spray gun B → spray gun B → spray gun B → spray gun A; the distance between spray gun A and spray gun B is 30cm, and the distance between spray gun B and spray gun B is 20cm. With the center of the brick blank as the reference line, the six sets of spray guns are each 5cm away from the reference line and are arranged alternately on the left and right sides of the reference line; the height of the nozzle from the surface of the brick blank is 80-90cm, and the spray gun is at a 45-degree angle to the surface of the brick blank; when spraying transparent colored glaze, the pressure of the high-pressure glazing machine is set to 4-4.5 MPa.

10. The method for preparing a building ceramic tile with fluorescent iridescent effect according to claim 6, characterized in that, In step (6), the firing cycle is 40-50 minutes, the highest temperature in the high-temperature zone is 1200-1215℃, and the firing atmosphere is a reducing atmosphere.

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