A fluorescent glaze

Abstract

The present application relates to the technical field of glaze, and discloses a fluorescent glaze, which comprises base glaze frit, luminescent powder and auxiliary additive; the base glaze frit comprises the following components in parts by weight: 45-52 parts of SiO2, 12-15 parts of Al2O3, 4.5-6 parts of K2O, 10-13 parts of Na2O, 0.5-0.7 parts of Li2O, 5-8 parts of CaO, 2-3 parts of SrO, 0.1-0.3 parts of MgO, 6-8.5 parts of BaO, 1-2.5 parts of ZnO, and the rest is loss on ignition; the luminescent powder is a long afterglow luminescent material of Sr2MgSi2O7:Eu 2+ ,Dy 3+ ,Li + , which is wrapped with a wrapper composed of alumina particles and a polymer matrix. By wrapping the long afterglow luminescent material with alumina particles and a polymer matrix, the number of long afterglow luminescent materials damaged under the high-temperature sintering condition of the fluorescent glaze can be reduced, the luminescent performance of the long afterglow luminescent material is ensured, and the anti-skid performance of the glaze layer can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glazes, in particular to a fluorescent glaze. BACKGROUND

[0002] Ceramic tile glaze is a material coated on the surface of ceramic tile, which can be used to enhance the aesthetic appearance of ceramic tile, and can also be used as a glaze to protect ceramic tile, so that the glazed tile presents bright, matte or soft light, the performance characteristics of the glazed tile mainly depend on the performance of the glaze, such as antibacterial glaze, anti-skid glaze, pearlescent glaze, anti-fouling glaze and other functional glazes, the fluorescent glaze contains luminescent material, which can emit bright fluorescent color under dark light or ultraviolet irradiation, and can be used for the decoration of the surface of the tile, bringing a unique and bright visual effect to the ceramic tile, the Eu 2+ is easily oxidized to Eu 3+ at a conventional firing temperature, resulting in a decrease in luminescent performance, so there is an urgent need to develop a temperature-resistant fluorescent glaze. SUMMARY

[0003] In view of the deficiencies of the prior art described above, the purpose of the present application is to provide a fluorescent glaze, aiming to improve the temperature resistance of the luminescent material in the fluorescent glaze.

[0004] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0005] A fluorescent glaze, comprising a base glaze frit, a luminescent powder and an auxiliary additive; the base glaze frit comprises the following components by weight: SiO2 is 45-52 parts, Al2O3 is 12-15 parts, K2O is 4.5-6 parts, Na2O is 10-13 parts, Li2O is 0.5-0.7 parts, CaO is 5-8 parts, SrO is 2-3 parts, MgO is 0.1-0.3 parts, BaO is 6-8.5 parts, ZnO is 1-2.5 parts, and the balance is loss on ignition; the luminescent powder is a long afterglow luminescent material of Sr2MgSi2O7:Eu 2+ ,Dy 3+ ,Li + , the long afterglow luminescent material is wrapped on the outside with a wrapping material composed of alumina particles and a polymer matrix.

[0006] The fluorescent glaze, wherein the preparation method of the wrapping material is that the alumina particles, the polymer matrix and the long afterglow luminescent material are fully stirred and mixed, and then solidified.

[0007] The fluorescent glaze, wherein the particle size of the alumina particles is 300-350 mesh; the polymer matrix is one of polyurethane, silicone glue, polyester and polyimide.

[0008] The fluorescent glaze, wherein the preparation method of the long afterglow luminescent material is as follows: raw materials of SrCO3, MgO, SiO2, Eu2O3, Dy2O3, H3BO3 and Li2CO3 are put into a mortar, and then anhydrous ethanol is added to grind them uniformly, and then the mixture is dried in a drying box, and then the dried mixture is loaded into a crucible, and then active carbon is used to provide a reducing atmosphere, and then the crucible is placed in a high-temperature muffle furnace to be calcined and sieved.

[0009] The fluorescent glaze, wherein the long afterglow luminescent material contains Eu 2+ The ion doping concentration is (1.0-1.5) mol%, the Dy 3+ The ion doping concentration is (1.5-2.0) mol%, the H3BO3 doping concentration is (15-20) mol%, and the Li + The ion doping concentration is (2-2.5) mol%.

[0010] The fluorescent glaze, wherein the long afterglow luminescent material is calcined at a temperature of 1200-1250℃.

[0011] The fluorescent glaze, wherein the particle size of the long afterglow luminescent material obtained after sieving is 150-180 mesh, and the particle size of the base glaze block is 200-250 mesh.

[0012] The fluorescent glaze, wherein the weight addition content of the long afterglow luminescent material is 10-15% of the weight of the base glaze block.

[0013] The fluorescent glaze, wherein the fluorescent glaze further comprises alumina powder, the particle size of the alumina powder is composed of 250-300 mesh, 100-150 mesh and 60-80 mesh, and the weight ratio of the alumina powder with the particle size of 250-300 mesh, 100-150 mesh and 60-80 mesh is 3-4:3-4:4-5.

[0014] The fluorescent glaze, wherein the sintering and forming conditions of the fluorescent glaze are 1200-1250℃, and the sintering and forming time is 50 min.

[0015] Beneficial effects:

[0016] The present application provides a fluorescent glaze, by adopting alumina particles and a polymer matrix to wrap the long afterglow luminescent material, so that the long afterglow luminescent material can reduce the number of destruction under the high-temperature sintering condition of the fluorescent glaze, ensure the luminescent performance of the long afterglow luminescent material, and form fine alumina particles on the glaze layer to improve the anti-skid performance of the glaze layer. A very strong fluxing system exists in the fluorescent glaze, so that the structure of the glaze layer is more dense, the anti-fouling performance and chemical corrosion resistance of the glaze layer can be improved, and the tile surface of the prepared fluorescent ceramic tile is soft, the tile surface is not dazzling and soft, the touch is delicate, and after the long afterglow luminescent material absorbs energy in the dark condition, the tile surface can emit a faint fluorescent light, like the stars in the night sky, which is very ornamental. DETAILED DESCRIPTION

[0017] The present application provides a fluorescent glaze, in order to make the purpose, technical scheme and effect of the present application more clear and definite, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the protection scope of the present application.

[0018] The present application provides a fluorescent glaze, including base glaze frit, luminescent powder and auxiliary additive; the base glaze frit includes the following components: SiO2 is 45-52 parts, Al2O3 is 12-15 parts, K2O is 4.5-6 parts, Na2O is 10-13 parts, Li2O is 0.5-0.7 parts, CaO is 5-8 parts, SrO is 2-3 parts, MgO is 0.1-0.3 parts, BaO is 6-8.5 parts, ZnO is 1-2.5 parts, and the balance is loss on ignition; the luminescent powder is a long afterglow luminescent material of Sr2MgSi2O7∶Eu 2+ ,Dy 3+ ,Li + The long afterglow luminescent material is wrapped outside by a wrapping material composed of alumina particles and a polymer matrix.

[0019] Specifically, the auxiliary additive is sodium tripolyphosphate, carboxymethyl cellulose and the like, which plays a role in stabilizing the glaze system, improving the viscosity of the glaze, and improving the uniformity and fluidity of the glaze during coating. The auxiliary additive is a conventional addition, which is not described in detail here.

[0020] The preparation process of the base glaze frit is as follows: after the raw materials are ball milled and mixed, they are calcined, the molten material is poured into cold water for quenching, and a glassy frit is obtained, which is dried, crushed, ball milled and sieved. The raw materials are made into frits, which can remove the gas in the mineral raw materials, reduce the pores of the glaze, and improve the flatness and anti-fouling ability of the glaze.

[0021] The silicon oxide in the base glaze frit serves as a forming skeleton and can be used to form a glass phase. The aluminum oxide serves as a refractory substance and can be used to adjust the firing conditions of the fluorescent glaze. The base glaze frit contains a very strong fluxing system, including potassium oxide, a large amount of sodium oxide, lithium oxide, calcium oxide, and zinc oxide, which can promote the silicon oxide to form a glass phase and promote the leveling of the glaze, so as to form a dense glaze layer and improve the stain resistance of the glaze. The barium oxide within the above range increases the melting point of the fluorescent glaze, precipitates barium ice feldspar, and produces crystal particles on the glaze surface, thereby increasing the friction coefficient and hardness and reducing the gloss of the glaze. The high content of aluminum oxide can still form micro protrusions on the glaze surface under the above fluxing system, thereby improving the slip resistance of the glaze.

[0022] The alkali metal Li is added to the luminescent powder. The radius of Li is small, and Li can be easily doped. Li can promote Eu 2+ to enter the crystal lattice, increase the quenching concentration of Eu 2+ , increase the oxygen vacancies in the matrix, and thus improve the luminescent performance of the luminescent material. The particle size of the luminescent material without Li + doping is uneven, and there is a certain agglomeration phenomenon. However, the particle size of the luminescent material doped with an appropriate amount of Li + increases and tends to be uniform, and the agglomeration phenomenon is improved. Therefore, Li + can be used as a fluxing agent.

[0023] By using the high-temperature refractory substance aluminum oxide to coat the surface of the long-afterglow luminescent material, and by using the polymer matrix to form a dense crosslinked network structure, the temperature resistance of the long-afterglow luminescent material can be improved, so as to reduce the number of long-afterglow luminescent materials that are dissolved at high temperatures, reduce the destruction of the structure of the long-afterglow luminescent material, that is, reduce the amount of Eu 2+ oxidized to Eu 3+ , and thus ensure the luminescent performance of the long-afterglow luminescent material.

[0024] In some embodiments, the preparation method of the coating is that the aluminum oxide particles, the polymer matrix, and the long-afterglow luminescent material are fully stirred and mixed, and then solidified. Specifically, the system further includes a crosslinking agent and a high-temperature stabilizer. The crosslinking agent can initiate the crosslinking polymerization reaction of the polymer matrix to form a hard network structure. Specifically, the solidification can be performed at room temperature, under heating, under ultraviolet light, or the like. The high-temperature stabilizer is an organosilicon compound, which can protect the polymer matrix at high temperatures, reduce the reaction between the polymer matrix and the aluminum oxide, and improve the thermal stability and temperature resistance of the coating.

[0025] In some embodiments, the particle size of the alumina particles is 300-350 mesh; the polymer matrix is one of polyurethane, silicone glue, polyester, and polyimide. In this embodiment, the particle size of the long afterglow luminescent material is 150-180 mesh, and the alumina particles with a particle size of 300-350 mesh are coated thereon, so that the network structure is more compact, the loss of the long afterglow luminescent material can be reduced at a high sintering temperature, and the alumina particles in the particle size range can gradually melt during the sintering process and form finer protrusions in the glaze layer, further improving the slip resistance coefficient of the glaze layer.

[0026] In some embodiments, the long afterglow luminescent material is prepared by placing SrCO3, MgO, SiO2, Eu2O3, Dy2O3, H3BO3, and Li2CO3 raw materials into a mortar, grinding them uniformly with anhydrous ethanol, drying them in a drying box, loading the dried mixture into a crucible, providing a reducing atmosphere with activated carbon, placing the crucible in a high-temperature muffle furnace for calcination and sieving. The long afterglow luminescent material is prepared by the high-temperature solid-phase method, and the prepared long afterglow luminescent material has higher crystallinity and larger particle size.

[0027] In some embodiments, the content of Eu 2+ The doping concentration of Dy 3+ The doping concentration of H3BO3 is (15-20) mol%, and the doping concentration of Li + The doping concentration of Li

[0028] As a fluxing agent, boric acid can reduce the sintering temperature of the Sr2MgSi2O7 crystal phase and promote the doping agents Eu 2+ and Dy 3 + and Li + to enter the crystal lattice. When the content of boric acid is too low, the Sr2MgSi2O7 crystal phase needs to be grown at a higher temperature, and under a lower sintering temperature, the Sr2MgSi2O7 crystal phase cannot be completely generated or has poor crystallinity, affecting the electron migration rate and reducing the luminescent performance of the luminescent material. When the content of boric acid is too high, excessive liquid phase is generated, leading to excessive sintering and also causing a serious decline in the luminescent performance of the luminescent material.

[0029] When the content of Li +When the doping concentration of ions is within the above range, lithium carbonate has fluxing effect, can change the contact surface between reactants, promote interface diffusion, and is beneficial to the formation of crystal phase, and can promote the entry of activator into the matrix. When the doping concentration exceeds the above range, the crystal grains further grow, the melt phase increases, and the agglomeration intensifies. When the crushed sample is sieved, the crystal form of the luminescent material is damaged, the luminescent performance of the luminescent material is reduced, the luminescent intensity is reduced, and the afterglow decay is faster.

[0030] In some embodiments, the long afterglow luminescent material is calcined at a temperature of 1200-1250℃. When the calcination temperature is too low, the Sr2MgSi2O7 crystal phase cannot be completely generated or has poor crystallinity, affecting the migration rate of electrons, thereby causing poor luminescent performance of the long afterglow luminescent material. When the calcination temperature is too high, the crystal grains excessively grow, the agglomeration increases, or the melt phase is formed, the sintering is dense, and when the long afterglow luminescent material is crushed, the crystal form of the luminescent material is damaged, causing the luminescent performance of the luminescent material to be severely reduced.

[0031] In some embodiments, the particle size of the long afterglow luminescent material obtained after sieving is 150-180 mesh, and the particle size of the base glaze melt block is 200-250 mesh. The particle size of the base glaze melt block is generally 200-250 mesh, the mesh number of the long afterglow luminescent material is less than that of the base glaze melt block, and the particle size of the long afterglow luminescent material is greater than that of the base glaze melt block. The luminescent performance of the long afterglow luminescent material in the above particle size range can be suitable for the glaze layer formed by the fluorescent glaze, and forms point fluorescent in the glaze layer, and the visual effect is better. When the particle size of the long afterglow luminescent material is too large, under the same addition content, the fluorescent of the glaze surface presents a sheet shape, and the fluorescent with an excessively large area loses the feeling of starlight points in the night sky.

[0032] In some embodiments, the weight addition content of the long afterglow luminescent material is 10-15% of the weight of the base glaze melt block. Generally, the addition content of the long afterglow luminescent material is 30%, but since the long afterglow luminescent material is protected by the wrapping effect of the high-temperature-resistant aluminum oxide and the polymer matrix, the long afterglow luminescent material is prevented from being damaged during the sintering process of the fluorescent glaze, and therefore the addition amount of the long afterglow luminescent material can be reduced. In addition, when the addition amount of the long afterglow luminescent material is too large, Sr 2+ The ions and rare earth element Eu are melted in the glaze, which reduces the melting temperature of the glaze, increases the viscosity, hinders the escape of gas, and thus makes the glaze surface rough and uneven, produces bubbles, and affects the apparent quality of the glaze surface.

[0033] In some embodiments, the fluorescent glaze further comprises alumina powder, the particle size of the alumina powder is composed of 250-300 mesh, 100-150 mesh and 60-80 mesh, and the weight ratio of the alumina powder with particle size of 250-300 mesh, 100-150 mesh and 60-80 mesh is 3-4:3-4:4-5. The alumina powder is added to the fluorescent glaze, that is, the alumina powder is not ball milled with the base glaze frit, so as to prevent the particle size of the three kinds of powders from changing after ball milling. By adding the three kinds of high-temperature-resistant materials (alumina) with different particle sizes, the edges and corners of the alumina are melted during the sintering of the fluorescent glaze, and the surface becomes smooth. The gaps between the particles with large particle size can be filled by the adaptation of different particle sizes, so as to improve the density of the glaze layer. At the same time, the alumina with large particle size forms a concave-convex structure with different heights in the glaze layer, which cooperates with the alumina in the base glaze frit and the alumina particles wrapped in the long-afterglow luminescent material, so as to form finer particles in the concave-convex structure, further improve the anti-skid effect, and the long-afterglow luminescent material is also fixed in the concave-convex structure, so as to emit fluorescent light with different refraction angles, further improving the visual effect of the stars in the night sky.

[0034] In some embodiments, the sintering condition of the fluorescent glaze is 1200-1250°C, and the sintering time is 50 min. The sintering condition is suitable for the components of the fluorescent glaze, so as to make the glaze dense, form a fine concave-convex structure, and cause less damage to the long-afterglow luminescent material, so as to not excessively affect the luminescent performance of the long-afterglow luminescent material.

[0035] In order to further illustrate the fluorescent glaze provided by the present application, the following examples are provided.

[0036] Example 1

[0037] A fluorescent glaze comprises a base glaze frit, a luminescent powder, alumina powder (composed of 250 mesh, 130 mesh and 70 mesh, and the weight ratio of the alumina powder with particle size of 250 mesh, 130 mesh and 70 mesh is 3:4:5), and an auxiliary additive. The particle size of the base glaze frit is 200 mesh. The base glaze frit comprises the following components by weight: SiO2 is 52 parts, Al2O3 is 15 parts, K2O is 4.5 parts, Na2O is 13 parts, Li2O is 0.5 parts, CaO is 8 parts, SrO is 3 parts, MgO is 0.3 parts, BaO is 8.5 parts, ZnO is 2.5 parts, and the balance is loss on ignition. The sintering condition of the fluorescent glaze is 1240°C, and the sintering time is 50 min.

[0038] The luminescent powder is Sr2MgSi2O7:Eu2+ Dy 3+ Li + A long afterglow luminescent material of Sr2MgSi2O7∶Eu

[0039] The preparation method of the long afterglow luminescent material is as follows: raw materials of SrCO3, MgO, SiO2, Eu2O3, Dy2O3, H3BO3 and Li2CO3 are put into a mortar, and then are grinded uniformly with anhydrous ethanol, and then are dried in a drying box, and then the dried mixture is loaded into a crucible, and then the crucible is placed in a high-temperature muffle furnace for calcination (the temperature is 1230℃), and then the long afterglow luminescent material is sieved (the particle size of the long afterglow luminescent material obtained after the sieving is 150 mesh). 2+ The concentration of Dy 3+ The concentration of H3BO3 is 20mol%, and the concentration of Li + The concentration of Li The weight addition content of the long afterglow luminescent material is 15% of the weight of the base glaze frit.

[0040] Example 2

[0041] A fluorescent glaze includes a base glaze frit, a luminescent powder, alumina powder (composed of 300 mesh, 100 mesh and 80 mesh; the weight ratio of the alumina powder with particle sizes of 300 mesh, 100 mesh and 80 mesh is 1:1:1), and an auxiliary additive. The particle size of the base glaze frit is 230 mesh. The base glaze frit includes the following components in weight parts: SiO2 is 45 parts, Al2O3 is 12 parts, K2O is 5 parts, Na2O is 10 parts, Li2O is 0.7 parts, CaO is 5 parts, SrO is 2 parts, MgO is 0.1 parts, BaO is 6 parts, ZnO is 1 part, and the balance is a loss on ignition. The sintering forming condition of the fluorescent glaze is 1250℃, and the sintering forming time is 50 minutes.

[0042] The luminescent powder is Sr2MgSi2O7∶Eu 2+ Dy 3+ Li + A long afterglow luminescent material of Sr2MgSi2O7∶Eu

[0043] The preparation method of the long afterglow luminescent material is as follows: raw materials of SrCO3, MgO, SiO2, Eu2O3, Dy2O3, H3BO3 and Li2CO3 are put into a mortar, and then anhydrous ethanol is added to grind them uniformly, and then the mixture is dried in a drying box, and then the dried mixture is loaded into a crucible, and then activated carbon is used to provide a reducing atmosphere, and then the crucible is calcined in a high-temperature muffle furnace (the temperature is 1200°C), and then the long afterglow luminescent material is sieved (the particle size of the long afterglow luminescent material obtained after the sieving is 160 mesh). The Eu 2+ The ion doping concentration is 1.2 mol%, the Dy 3+ The ion doping concentration is 2.0 mol%, the H3BO3 doping concentration is 18 mol%, the Li + The ion doping concentration is 2.5 mol%. The weight addition content of the long afterglow luminescent material is 13% of the weight of the base glaze clinker.

[0044] Example 3

[0045] A fluorescent glaze includes a base glaze clinker, a luminescent powder, alumina powder (composed of 280 mesh, 150 mesh and 60 mesh; the weight ratio of the alumina powder with particle sizes of 280 mesh, 150 mesh and 60 mesh is 4:3:5), and an auxiliary additive. The particle size of the base glaze clinker is 250 mesh. The base glaze clinker includes the following components in weight parts: SiO2 is 48 parts, Al2O3 is 14 parts, K2O is 5 parts, Na2O is 11 parts, Li2O is 0.6 parts, CaO is 6 parts, SrO is 2.5 parts, MgO is 0.2 parts, BaO is 7 parts, ZnO is 2 parts, and the balance is loss on ignition. The sintering forming condition of the fluorescent glaze is 1200°C, and the sintering forming time is 50 min.

[0046] The luminescent powder is a long afterglow luminescent material of Sr2MgSi2O7:Eu 2+ ,Dy 3+ ,Li + The long afterglow luminescent material is externally wrapped with a wrapping material composed of alumina particles and a polymer matrix. The particle size of the alumina particles is 300 mesh; and the polymer matrix is polyimide.

[0047] The preparation method of the long afterglow luminescent material is as follows: raw materials of SrCO3, MgO, SiO2, Eu2O3, Dy2O3, H3BO3 and Li2CO3 are put into a mortar, and then anhydrous ethanol is added to grind them uniformly, and then the mixture is dried in a drying box, and then the dried mixture is loaded into a crucible, and then activated carbon is used to provide a reducing atmosphere, and then the crucible is calcined in a high-temperature muffle furnace (the temperature is 1250°C), and then the long afterglow luminescent material is sieved (the particle size of the long afterglow luminescent material obtained after the sieving is 180 mesh). The Eu 2+Ion doping concentration is 1.5 mol%, Dy 3+ Ion doping concentration is 2.0 mol%, H3BO3 doping concentration is 15 mol%, Li + Ion doping concentration is 2.3 mol%. The weight addition content of the long afterglow luminescent material is 10% of the weight of the base glaze frit.

[0048] Comparative Example 1

[0049] The fluorescent glaze of Comparative Example 1 is basically the same as the fluorescent glaze of Example 1, except that the luminescent powder in Comparative Example 1 is not wrapped with alumina particles and a polymer matrix.

[0050] Comparative Example 2

[0051] The fluorescent glaze of Comparative Example 2 is basically the same as the fluorescent glaze of Example 1, except that the luminescent powder in Comparative Example 2 has a Li + Ion doping concentration is 3.0 mol%.

[0052] Comparative Example 3

[0053] The fluorescent glaze of Comparative Example 3 is basically the same as the fluorescent glaze of Example 1, except that Comparative Example 3 does not additionally add alumina trihydrate powder.

[0054] Performance test

[0055] The fluorescent glazes prepared in Examples 1-3 and Comparative Examples 1-3 above are applied to the body by spraying, and the application amount is controlled at 500 g / m 2 .

[0056] Test items are as follows:

[0057] 1. Water absorption, tested according to GB / T 3810.3-2016 standard.

[0058] 2. Wear resistance, tested according to GB / T 3810.7-2016 standard.

[0059] 3. Friction coefficient, tested according to GB / T 4100-2015 Appendix M standard.

[0060] 4. Pollution resistance, tested according to GB / T 3810.14-2016 standard.

[0061] 5. Chemical corrosion resistance, tested according to GB / T 3810.13-2016 standard.

[0062]

[0063]

[0064] 6. Luminescence performance, according to GB / T 24981.2-2010 standard, using D65 standard light source with illumination of 1000 Lux to excite the samples for 10 min, and using luminance meter to record the luminescence brightness, the results are shown in the following table.

[0065]

[0066] From the above test results, it can be seen that the fluorescent glaze layer formed by the fluorescent glaze prepared in the embodiment has excellent wear resistance, hardness, anti-skid performance, anti-fouling performance and chemical corrosion resistance, and the comprehensive performance is better. The luminescent powder in Comparative Example 1 is not wrapped with a wrapping material, when it is mixed into the fluorescent glaze and sintered at high temperature, part of Eu 2+ in the long afterglow luminescent material is oxidized to Eu 3+ , which destroys part of the structure of the long afterglow luminescent material, seriously affecting the fluorescence effect of the fluorescent glaze layer. In Comparative Example 2, the fluxing agent Li element is not doped, which affects the brightness of the fluorescence emitted by the long afterglow luminescent material in the glaze layer. In Comparative Example 3, alumina powder with multiple particle size gradations is not added, which makes the surface of the glaze layer smooth and the glossiness increases. The smooth glaze layer reduces the anti-skid coefficient, and the fluorescence emitted by the long afterglow luminescent material fixed on the glaze layer cannot form multi-angle refraction, which affects the fluorescence brightness.

[0067] In summary, the alumina particles and the polymer matrix are used to wrap the long afterglow luminescent material, which can reduce the number of long afterglow luminescent materials destroyed under the high temperature sintering conditions of the fluorescent glaze, ensure the luminescence performance of the long afterglow luminescent material, and form fine alumina particles on the glaze layer to improve the anti-skid performance of the glaze layer. By adding alumina powder with different particle size gradations to the fluorescent glaze, a concave-convex structure with height difference is formed in the glaze layer to improve the anti-skid coefficient of the glaze layer. Moreover, there is a very strong fluxing system in the fluorescent glaze, which makes the structure of the glaze layer more dense, and improves the anti-fouling performance and chemical corrosion resistance of the glaze layer. The fluorescent ceramic tile prepared has a soft light brick surface, the brick surface is not dazzling and soft, the hand feeling is delicate, and the long afterglow luminescent material can emit a faint fluorescence on the brick surface after absorbing energy in the dark condition, like the stars in the night sky, which is very ornamental.

[0068] It can be understood that, for those skilled in the art, equivalent replacements or changes can be made according to the technical solutions and inventive concepts of the present application, and all such changes or replacements shall fall within the scope of protection of the present application.

Claims

1. A fluorescent glaze, characterized in that, The product comprises a base glaze frit, a luminescent powder, and auxiliary additives. By weight, the base glaze frit comprises the following components: 45-52 parts SiO2, 12-15 parts Al2O3, 4.5-6 parts K2O, 10-13 parts Na2O, 0.5-0.7 parts Li2O, 5-8 parts CaO, 2-3 parts SrO, 0.1-0.3 parts MgO, 6-8.5 parts BaO, and 1-2.5 parts ZnO, with the balance being loss on ignition. The luminescent powder is Sr2MgSi2O7∶Eu. 2+ ,Dy 3+ Li + The long-afterglow luminescent material is externally encapsulated by an encapsulation composed of alumina particles and a polymer matrix.

2. The fluorescent glaze according to claim 1, characterized in that, The preparation method of the encapsulation is as follows: alumina particles, polymer matrix and long afterglow luminescent material are thoroughly stirred and mixed, and then cured.

3. The fluorescent glaze according to claim 2, characterized in that, The alumina particles have a particle size of 300-350 mesh; the polymer matrix is ​​one of polyurethane, silicone, polyester, and polyimide.

4. The fluorescent glaze according to claim 1, characterized in that, The preparation method of the long afterglow luminescent material is as follows: SrCO3, MgO, SiO2, Eu2O3, Dy2O3, H3BO3 and Li2CO3 raw materials are placed in a mortar, anhydrous ethanol is added and ground evenly, and then placed in a drying oven to dry. The dried mixture is then placed in a crucible, and activated carbon is used to provide a reducing atmosphere. The crucible is then placed in a high-temperature muffle furnace for calcination and sieve.

5. The fluorescent glaze according to claim 4, characterized in that, Eu in the long afterglow luminescent material 2+ The ion doping concentration is (1.0–1.5) mol%, Dy 3+ The ion doping concentration was (1.5–2.0) mol%, the H3BO3 doping concentration was (15–20) mol%, and the Li + The ion doping concentration is (2–2.5) mol%.

6. The fluorescent glaze according to claim 4, characterized in that, The long afterglow luminescent material is calcined at a temperature of 1200–1250°C.

7. The fluorescent glaze according to claim 4, characterized in that, The particle size of the long afterglow luminescent material obtained after sieving is 150-180 mesh, and the particle size of the base glaze frit is 200-250 mesh.

8. The fluorescent glaze according to claim 1, characterized in that, The weight percentage of the long-afterglow luminescent material added is 10-15% of the weight of the base glaze frit.

9. The fluorescent glaze according to claim 1, characterized in that, It also includes aluminum oxide powder, wherein the particle size of the aluminum oxide powder is composed of 250-300 mesh, 100-150 mesh and 60-80 mesh; the weight ratio of the aluminum oxide powder with particle sizes of 250-300 mesh, 100-150 mesh and 60-80 mesh is 3-4:3-4:4-5.

10. The fluorescent glaze according to claim 1, characterized in that, The firing conditions for the fluorescent glaze are 1200–1250°C and the firing time is 50 min.

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