High-temperature-resistant long-afterglow luminescent ceramic ink and application thereof

Abstract

The application relates to the technical field of ceramic functional materials, in particular to a high-temperature-resistant long-afterglow luminescent ceramic ink and application thereof. The raw material composition of the high-temperature-resistant long-afterglow luminescent ceramic ink comprises, in percentage by mass, 30-50% of a luminescent ceramic glaze and 0.1-1% of nano silicon carbide; the mineral composition of the luminescent ceramic glaze comprises, in percentage by mass, 50-65% of a frit, 0.1-1% of a rare earth metal oxide, 20-30% of calcined talc and 5-28% of quartz; the chemical composition of the frit comprises, in percentage by mass, 15-35% of SiO 2 , 3-8% of Al2O3, 3.5-6.5% of MgO, 3-7% of K2O, 5-7% of Na2O, 6-10% of BaO, 22-38% of SrO, 4-7% of ZnO, 3-7% of Bi2O3 and 1-9% of B2O3. The high-temperature-resistant long-afterglow luminescent ceramic ink is suitable for an inkjet printing process and can realize patterned luminescent application in the fields of building ceramics, daily-use ceramics, safety identification and information encryption anti-counterfeiting and the like.

Description

Technical Field

[0001] This invention relates to the field of ceramic functional materials technology, and in particular to a high-temperature resistant long-afterglow luminescent ceramic ink and its application, especially to a method for preparing long-afterglow luminescent decorative ceramic slabs using the high-temperature resistant long-afterglow luminescent ceramic ink. Background Technology

[0002] Long-afterglow luminescent materials, also known as photoluminescent materials, are photoluminescent materials that can continue to emit light for a long time after the excitation light source is stopped. Applying long-afterglow luminescent materials to ceramic products can produce luminescent ceramics, which have the characteristic of retaining visible light and emitting light for a long time in dark environments, and have important application value.

[0003] Currently, there are three main methods for synthesizing luminescent ceramics: directly firing luminescent material powder into ceramic blocks; mixing luminescent materials with traditional ceramic raw materials and then firing; and preparing luminescent ceramic glazes and then applying them to the surface of ceramic blanks for firing. However, developing material systems that combine high-temperature resistance and dynamic afterglow performance still faces the technical challenge of oxidation. In existing technologies, the dual-emission integration strategy based on thermally activated delayed fluorescence and room-temperature phosphorescence is considered a simple method for obtaining long-afterglow luminescent materials, but this method relies on a heat-sensitive reducing atmosphere, making it difficult to achieve truly widespread applications of luminescent ceramics. Especially in the field of ceramic inks, achieving stable long-afterglow performance after high-temperature firing places higher demands on ink formulation design and preparation processes. Therefore, there is an urgent need to develop a new type of high-temperature resistant, long-afterglow luminescent ceramic ink to leverage the technological advantages of digital printing to expand its applications in high-end architectural ceramics, information encryption, and other fields.

[0004] Chinese patent ZL201310324230.9 discloses an environmentally friendly fluorescent-enhanced printing anti-counterfeiting ink, containing water-soluble fluorescent dye, water-soluble resin, surfactant, pH adjuster, preservative, drier, auxiliary solvent, and water. Chinese patent ZL201710579477.3 discloses using rare-earth ion-doped lanthanum vanadate nanocrystals as ink, but the use of rare-earth compounds significantly increases the cost. Chinese patent CN110093064B discloses a method for preparing and applying a long-afterglow luminescent ink, solving the problems of complex composition, high cost, and poor anti-counterfeiting and confidentiality effects of existing anti-counterfeiting inks.

[0005] However, the above patents are all limited to use in low-temperature or room-temperature environments and do not involve high-temperature (1200℃ and above) materials, thus limiting the technical application of luminescent ceramic inks in conventional building ceramic production. Summary of the Invention

[0006] To address the aforementioned issues, this invention optimizes the formulation of a high-temperature resistant, long-afterglow luminescent ceramic ink. The resulting ink exhibits excellent high-temperature resistance (withstanding firing temperatures above 1200℃) and stable long-afterglow luminescence characteristics (afterglow time exceeding 10 hours). This high-temperature resistant, long-afterglow luminescent ceramic ink is suitable for inkjet printing processes and can be used for patterned luminescent applications in fields such as architectural ceramics, daily-use ceramics, security markings, and information encryption and anti-counterfeiting.

[0007] In a first aspect, the present invention provides a high-temperature resistant, long-afterglow luminescent ceramic ink. The raw material composition of the high-temperature resistant, long-afterglow luminescent ceramic ink includes, by mass percentage: 30%~50% luminescent ceramic enamel and 0.1%~1% nano-silicon carbide; the mineral composition of the luminescent ceramic enamel includes, by mass percentage: 50%~65% frit, 0.1%~1% rare earth metal oxides, 20%~30% calcined talc, and 5%~28% quartz; the chemical composition of the frit includes, by mass percentage: 15%~35% SiO2, 3%~8% Al2O3, 3.5%~6.5% MgO, 3%~7% K2O, 5%~7% Na2O, 6%~10% BaO, 22%~38% SrO, 4%~7% ZnO, 3%~7% Bi2O3, and 1%~9% B2O3.

[0008] In an optional embodiment, the mineral composition of the frit includes, by mass percentage: 5%~15% washed kaolin, 5%~10% calcined borax, 6%~15% calcined talc, 3%~9% potassium carbonate, 3%~8% sodium carbonate, 30%~45% strontium carbonate, 6%~10% barium carbonate, 4%~8% zinc oxide, and 3%~6% bismuth oxide.

[0009] In an optional embodiment, the rare earth metal oxide is one or a mixture of lanthanum oxide, europium oxide, and cerium oxide.

[0010] In an optional embodiment, raw materials are weighed according to the mineral composition of the luminescent ceramic glaze, placed in a sealed environment for calcination in air, and then crushed to obtain the luminescent ceramic glaze; the calcination temperature is 960~1150℃, and the calcination time is 2~4 hours.

[0011] In an optional embodiment, the raw material composition of the high-temperature resistant long afterglow luminescent ceramic ink includes: by mass percentage, luminescent ceramic glaze 30%~50%, nano silicon carbide 0.5%~1%, solvent white oil 15%~50%, ester solvent 5%~22%, dispersant 3%~10%, and defoamer 0.2%~1%.

[0012] Secondly, the present invention provides a method for preparing a long-afterglow luminescent decorative ceramic slab. The preparation method includes:

[0013] Apply a glaze to the surface of the brick blank;

[0014] Ordinary ink patterns are printed on the surface of the brick blank after the glaze has been applied.

[0015] The high-temperature resistant long-afterglow luminescent ceramic ink is inkjet printed onto the surface of the brick blank after the inkjet ordinary ink pattern is formed.

[0016] Apply a protective glaze to the surface of the brick blank after inkjet printing a high-temperature resistant, long-afterglow luminescent ceramic ink pattern;

[0017] After applying a protective glaze, the brick blanks are fired to obtain long-afterglow luminescent ceramic slabs.

[0018] In an optional implementation, at least two channels are used to print high-temperature resistant, long-afterglow luminescent ceramic ink, and the grayscale of each channel is at least 20%.

[0019] In an optional embodiment, the chemical composition of the surface glaze includes, by mass percentage: 1%~6% loss on ignition, 54%~56% SiO2, 23%~26% Al2O3, 0.1%~0.6% Fe2O3, 0.01%~0.1% TiO2, 0.5%~1.5% CaO, 0.1%~1% MgO, 3%~6% K2O, 2%~4% Na2O, and 4.5%~6.5% ZrO2.

[0020] In an optional embodiment, the glaze is applied by pouring; the specific gravity of the glaze is 1.8~1.9 g / cm³. 3 The application rate is 400~600 g / m³ 2 .

[0021] In an optional embodiment, the chemical composition of the protective glaze includes, by mass percentage: 0.5%~12% loss on ignition, 42%~50% SiO2, 11%~20% Al2O3, 0.1%~0.3% Fe2O3, 0.01%~0.1% TiO2, 1%~10% CaO, 1%~5% MgO, 0.5%~3% K2O, 3%~6% Na2O, 2%~4% ZnO, 1%~5% BaO, and 1%~3% SrO.

[0022] In an optional embodiment, the protective glaze is applied by spraying; the specific gravity of the protective glaze is 1.4~1.6 g / cm³. 3 The application rate is 450~750 g / m 2 .

[0023] In an optional embodiment, the firing temperature is 1160~1210℃ and the firing time is 40~60 minutes.

[0024] The present invention has the following beneficial effects:

[0025] Existing fluorescent materials typically employ europium-doped strontium aluminate or europium-dysprosium co-doped strontium aluminate. However, strontium aluminate undergoes oxidative decomposition at temperatures exceeding 1100°C, causing europium or dysprosium to easily detach from the original doping lattice, resulting in fluorescence failure or significant weakening. This invention develops an in-situ synthesized fluorescent material capable of withstanding high temperatures and prepares it into a ceramic ink, which has significant application value in areas such as long-afterglow high-temperature fluorescent decorative effects. Attached Figure Description

[0026] Figure 1 These are renderings of the brick surface in Example 1. The left image shows the decorative pattern effect under natural light, and the right image shows the luminous decorative pattern effect after 6 hours of natural light exposure.

[0027] Figure 2 These are renderings of the brick surface in Example 2. The left image shows the decorative pattern effect under natural light, and the right image shows the luminous decorative pattern effect after 6 hours of natural light.

[0028] Figure 3 This is a comparison of the brick surface effect (under natural light).

[0029] Figure 4 This is a comparison of the brick surface effect (under natural light). Detailed Implementation

[0030] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0031] Preparation of luminescent ceramic glaze (also known as luminescent glaze). The mineral composition of the luminescent ceramic glaze includes, by mass percentage: 50%~65% frit, 0.1%~1% rare earth metal oxides, 20%~30% calcined talc, and 5%~28% quartz.

[0032] The chemical composition of the fused block includes, by mass percentage: SiO2 15%~35%, Al2O3 3%~8%, MgO 3.5%~6.5%, K2O 3%~7%, Na2O 5%~7%, BaO 6%~10%, SrO 22%~38%, ZnO 4%~7%, Bi2O3 3%~7%, and B2O3 1%~9%.

[0033] It should be understood that any mineral composition of the frit that causes its chemical composition to fall within the above-mentioned range is applicable to the present invention. As an example, the mineral composition of the frit includes, by mass percentage: 5%–15% washed kaolin, 5%–10% calcined borax, 6%–15% calcined talc, 3%–9% potassium carbonate, 3%–8% sodium carbonate, 30%–45% strontium carbonate, 6%–10% barium carbonate, 4%–8% zinc oxide, and 3%–6% bismuth oxide. The raw materials are weighed according to the mineral composition of the frit, mixed evenly, and melted at 1480–1580°C for 2–3 hours to obtain a glass melt; the glass melt is then quenched with water and crushed to obtain the frit. The particle size of the frit can be 250–300 mesh.

[0034] In an optional embodiment, the rare earth metal oxide is selected from one or more of lanthanum oxide, europium oxide, and cerium oxide, or a mixture thereof.

[0035] Raw materials are weighed according to the mineral composition of the luminescent ceramic glaze, placed in a sealed environment for calcination in air, and then crushed to obtain the luminescent ceramic glaze. For example, the mineral composition raw materials of the luminescent ceramic glaze are mixed, placed in a sagger for calcination, and then crushed to obtain the luminescent ceramic glaze. In an optional embodiment, the calcination temperature is 960~1150℃, and the calcination time is 2~4 hours. Calcination allows the silicate system frit to react fully with the rare earth metal oxide to obtain a composite silicate system luminescent glaze. As an example, but not limited to, the temperature is increased to the calcination temperature at a heating rate of 2~10℃ / min. Preferably, the heating rate is 5℃ / min.

[0036] In an optional embodiment, the high-temperature resistant long-afterglow luminescent ceramic ink comprises 30% to 50% luminescent ceramic glaze by weight percentage.

[0037] In an optional embodiment, the high-temperature resistant long-afterglow luminescent ceramic ink comprises: 30%~50% luminescent ceramic enamel and 0.1%~1% nano-silicon carbide by mass percentage. The particle size of the nano-silicon carbide can be 100~400 nanometers.

[0038] Among the electronic transition types in rare earth materials, fd transitions mainly occur in divalent rare earth ion systems. Compared to trivalent rare earth ions, divalent rare earth ions have one more electron. The presence of this electron significantly reduces the energy difference between the 4f and 5d orbitals and alters the energy state distribution of these two orbitals. (Eu) 2+ Yb 2+ 、Sm 2+ and Ce 3+Rare earth ions are typical examples of those capable of undergoing fd transitions. This invention develops a long-afterglow ceramic ink suitable for sintering conventional architectural ceramic bodies, and fully utilizes the in-situ reaction of carbon monoxide formed by the high-temperature decomposition of nano-silicon carbide to protect rare earth ions from redox reactions, thereby achieving in-situ synthesis of long-afterglow luminescent materials.

[0039] In a preferred embodiment, the nano-silicon carbide accounts for 0.15% to 1% of the mass percentage of the high-temperature resistant long-afterglow luminescent ceramic ink. In a more preferred embodiment, the high-temperature resistant long-afterglow luminescent ceramic ink comprises: 30% to 50% luminescent ceramic enamel and 0.5% to 1% nano-silicon carbide by mass percentage.

[0040] As an example, but not limited to, high-temperature resistant long-afterglow luminescent ceramic ink includes long-afterglow luminescent ceramic glaze, nano-silicon carbide, solvent, dispersant, leveling agent, fast-drying agent, defoamer, etc. For example, the raw material composition of high-temperature resistant long-afterglow luminescent ink includes, by mass percentage: 30%~50% luminescent ceramic glaze, 0.5%~1% nano-silicon carbide, 15%~50% solvent white oil, 5%~22% ester solvent, 3%~10% dispersant, and 0.2%~1% defoamer. The solvent white oil can be No. 3 white mineral oil and / or No. 10 white oil. No. 3 white mineral oil was selected in the examples and comparative examples. The ester solvent is selected from one or more of isooctyl palmitate, methyl laurate, isopropyl laurate, and isooctyl laurate. The isooctyl palmitate dispersant, leveling agent, fast-drying agent, and defoamer selected in the examples and comparative examples are all commonly used additives in the art and can be purchased commercially. In the examples and comparative examples, HP3100 was selected as the dispersant, and BYK066 was selected as the defoamer. In optional embodiments, the raw material composition of the high-temperature resistant long afterglow luminescent ink further includes: 0.3%~2% leveling agent and 0.3%~1% quick-drying agent by mass percentage.

[0041] After mixing luminescent ceramic enamel, nano-silicon carbide, solvent white oil, ester solvent, dispersant, and defoamer, the mixture is processed in a sand mill and filtered. Following the conventional ceramic ink preparation process, a high-temperature resistant, long-afterglow luminescent ceramic ink can be obtained.

[0042] The following describes a method for preparing long-afterglow luminescent decorative ceramic slabs using the aforementioned high-temperature resistant long-afterglow luminescent ceramic ink.

[0043] The raw material powder is pressed into brick blanks. The chemical composition of the raw material powder is not limited; any raw material powder commonly used in the art can be used. As an example, the chemical composition of the raw material powder may include, by mass percentage: 3.5%~4.5% loss on ignition, 58%~63% SiO2, 25%~30% Al2O3, 0.5%~0.8% Fe2O3, 0.3%~0.6% TiO2, 0.3%~0.5% CaO, 1.1%~1.5% MgO, 2.0%~2.5% K2O, and 2.3%~2.7% Na2O.

[0044] Dry the brick blanks. A drying kiln can be used. For example, the drying time can be 1 to 1.2 hours, and the moisture content of the dried brick blanks should be controlled below 0.5 wt%.

[0045] A surface glaze is applied to the surface of the brick blank. Conventional surface glazes in the art can be used. For example, the chemical composition of the surface glaze includes, by mass percentage: 1%~6% loss on ignition, 54%~56% SiO2, 23%~26% Al2O3, 0.1%~0.6% Fe2O3, 0.01%~0.1% TiO2, 0.5%~1.5% CaO, 0.1%~1% MgO, 3%~6% K2O, 2%~4% Na2O, and 4.5%~6.5% ZrO2. It should be understood that any surface glaze mineral composition that causes the chemical composition of the surface glaze to fall within the above range is applicable to this invention.

[0046] The surface glaze can be applied by pouring glaze. Preferably, the specific gravity of the surface glaze is 1.8~1.9 g / cm³. 3 The application rate is 400~600 g / m³ 2 .

[0047] Ordinary ink patterns are printed on the surface of the brick after the glaze has been applied. The texture and color of the ordinary ink patterns can be adaptively adjusted according to the design requirements.

[0048] A high-temperature resistant, long-afterglow luminescent ceramic ink pattern is then printed onto the surface of the brick blank after a regular ink pattern has been printed using inkjet printing. At least two channels are used for inkjet printing of the high-temperature resistant, long-afterglow luminescent ceramic ink pattern. The grayscale of each channel is at least 20%, preferably 40% to 60%.

[0049] A protective glaze is applied to the surface of a brick blank after inkjet printing a pattern of high-temperature resistant, long-afterglow luminescent ceramic ink. Conventional protective glazes in the art can be used. In an optional embodiment, the chemical composition of the protective glaze includes, by mass percentage: 0.5%–12% loss on ignition, 42%–50% SiO2, 11%–20% Al2O3, 0.1%–0.3% Fe2O3, 0.01%–0.1% TiO2, 1%–10% CaO, 1%–5% MgO, 0.5%–3% K2O, 3%–6% Na2O, 2%–4% ZnO, 1%–5% BaO, and 1%–3% SrO. It should be understood that any protective glaze mineral composition that causes the chemical composition of the protective glaze to fall within the above range is applicable to this invention.

[0050] The protective glaze can be applied by spraying. Preferably, the specific gravity of the protective glaze is 1.4~1.6 g / cm³. 3 The application rate is 450~750 g / m 2 .

[0051] After applying a protective glaze, the brick blank is fired to obtain a long-afterglow luminescent ceramic slab. For example, the firing temperature is 1160~1210℃ and the firing time is 40~60 minutes.

[0052] This invention develops a novel high-temperature resistant (1200℃ or higher) long-afterglow luminescent ceramic ink. The resulting ink has excellent high-temperature resistance (can withstand firing temperatures above 1200℃) and stable long-afterglow luminescence characteristics (afterglow time can reach more than 5 hours), meeting the requirements of conventional fluorescent decorative effects and is of great significance to the research and mass production of luminescent ceramics.

[0053] The high-temperature luminescent ceramic ink developed in this invention, with its unique weather resistance, digital decorative expression, and self-luminescent properties, extends beyond the field of architectural ceramics to a broader range of energy-saving and aesthetic applications. This special ink, capable of maintaining stable color at 1200℃, demonstrates unique development potential in fields such as intelligent manufacturing and functional materials. This invention, combined with digital processes, achieves various fluorescent pattern decorative effects through industrialized digital design without affecting the conventional decoration of ceramic products. The ceramic tiles prepared by this invention not only overcome the technical shortcomings of traditional fluorescent materials in withstanding high-temperature oxidation but also effectively showcase the three-dimensional simulation effect of natural stone. This invention can realize patterned luminescent applications in architectural ceramics, daily-use ceramics, security markings, and information encryption and anti-counterfeiting, significantly expanding the application areas and scope of architectural ceramics.

[0054] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0055] Example 1

[0056] The method for creating long-afterglow luminescent decorative ceramic slabs includes the following steps:

[0057] Step 1. Press the raw material into brick blanks.

[0058] Step 2. Apply a surface glaze to the brick blank. The chemical composition of the surface glaze includes, by mass percentage: 5.31% loss on ignition, 55.1% SiO2, 25.5% Al2O3, 0.32% Fe2O3, 0.01% TiO2, 0.73% CaO, 0.1% MgO, 4.34% K2O, 2.57% Na2O, and 6.02% ZrO2. The surface glaze is applied by pouring. The specific gravity of the surface glaze is 1.83 g / cm³. 3 The application rate is 485 g / m 2 .

[0059] Step 3. Print a regular ink pattern on the surface of the tile after the glaze has been applied.

[0060] Step 4. Print a high-temperature resistant, long-afterglow luminescent ceramic ink pattern onto the surface of the brick blank after inkjet printing a pattern with ordinary ink. The raw material composition of the high-temperature resistant, long-afterglow luminescent ceramic ink includes, by mass percentage: 41.4% luminescent ceramic glaze, 0.6% nano-silicon carbide, 40% solvent white oil, 7% ester solvent, 10% dispersant, and 1% defoamer. The mineral composition of the luminescent ceramic glaze includes, by mass percentage: 50% frit, 0.5% europium oxide, 0.3% cerium oxide, 23% calcined talc, and 26.2% quartz. After mixing the mineral components of the luminescent ceramic glaze, place it in a sagger for calcination, and then crush it to obtain the luminescent ceramic glaze. The calcination temperature is 980℃, and the calcination time is 2 hours. The chemical composition of the frit includes, by mass percentage: SiO2 16.21%, Al2O3 3.43%, MgO 5.52%, K2O 5.17%, Na2O 5.82%, BaO 6.96%, SrO3 7.11%, ZnO 5.43%, B2O3 8.33%, Bi2O3 6.02%. The mineral composition of the frit includes, by mass percentage: washed kaolin 7%, calcined borax 10%, calcined talc 15%, potassium carbonate 7%, sodium carbonate 4%, strontium carbonate 40%, barium carbonate 7.5%, zinc oxide 4.5%, bismuth oxide 5%. Raw materials are weighed according to the mineral composition of the frit, mixed evenly, and melted at 1510℃ for 2 hours to obtain a glass melt; the glass melt is then quenched with water and crushed to obtain the frit. The particle size of the frit is 250 mesh.

[0061] Step 5. Apply a protective glaze to the surface of the brick blank after inkjet printing the high-temperature resistant, long-afterglow luminescent ceramic ink pattern. The chemical composition of the protective glaze includes, by mass percentage: loss on ignition 10.53%, SiO2 43.8%, Al2O3 19.2%, Fe2O3 0.2%, TiO2 0.01%, CaO 8.32%, MgO 3.55%, K2O 0.88%, Na2O 4.65%, ZnO 3.25%, BaO 3.88%, SrO 1.73%. The protective glaze is applied by spraying. The specific gravity of the protective glaze is 1.43 g / cm³. 3 The application rate is 480g / m 2 .

[0062] Step 6. Fire the brick blank after applying the protective glaze to obtain a long-afterglow luminescent ceramic slab. The firing temperature is 1200℃ and the firing time is 45 minutes.

[0063] Figure 1The images show the brick surface effect of Example 1. The left image shows the decorative pattern effect under natural light, and the right image shows the luminescent decorative pattern effect after 6 hours of natural light exposure. It can be seen that the obtained high-temperature resistant long-afterglow luminescent ceramic ink has excellent high-temperature resistance (can withstand firing temperatures above 1200℃) and stable long-afterglow luminescence characteristics (afterglow time can reach more than 5 hours).

[0064] Example 2

[0065] It is basically the same as Example 1, except that:

[0066] The raw material composition of the high-temperature resistant long-afterglow luminescent ceramic ink includes, by mass percentage: 41.7% luminescent ceramic glaze, 0.3% nano-silicon carbide, 40% solvent white oil, 7% ester solvent, 10% dispersant, and 1% defoamer. The mineral composition of the luminescent ceramic glaze includes, by mass percentage: 50% frit, 0.5% europium oxide, 0.3% lanthanum oxide, 23% calcined talc, and 26.2% quartz. After mixing the mineral components of the luminescent ceramic glaze, the mixture is placed in a sagger for calcination, and then crushed to obtain the luminescent ceramic glaze. The calcination temperature is 1100℃, and the calcination time is 2 hours. The chemical composition of the frit includes, by mass percentage: SiO2 19.72%, Al2O3 6.37%, MgO 5.19%, K2O 6.45%, Na2O 6.19%, BaO 9.36%, SrO2 7.9%, ZnO 6.05%, Bi2O3 4.83%, B2O3 7.94%. The mineral composition of the frit includes, by mass percentage: washed kaolin 14%, calcined borax 9.5%, calcined talc 14%, potassium carbonate 8.5%, sodium carbonate 5%, strontium carbonate 30%, barium carbonate 10%, zinc oxide 5%, bismuth oxide 4%. Raw materials are weighed according to the mineral composition of the frit, mixed evenly, and melted at 1560℃ for 2 hours to obtain a glass melt; the glass melt is then quenched with water and crushed to obtain the frit. The particle size of the frit is 250 mesh.

[0067] Figure 2 This is an illustration of the brick surface effect in Example 2. The left image shows the decorative pattern effect under natural light, and the right image shows the luminescent decorative pattern effect after 6 hours of natural light. It can be seen that the obtained high-temperature resistant long-afterglow luminescent ceramic ink has excellent high-temperature resistance (can withstand firing temperatures above 1200℃) and stable long-afterglow luminescence characteristics (afterglow time can reach more than 5 hours).

[0068] Comparative Example 1

[0069] It is basically the same as Example 1, except that the frit composition of the luminescent ceramic glaze is different.

[0070] The chemical composition of the frit comprises, by mass percentage: 27.8% SiO2, 9.05% Al2O3, 0.3% Fe2O3, 7.37% MgO, 7.7% K2O, 4.65% Na2O, 9.26% BaO, 18.5% SrO, 6.03% ZnO, 6.01% Bi2O3, and 3.33% B2O3. The mineral composition of the frit comprises, by mass percentage: 20% washed kaolin, 4% calcined borax, 20% calcined talc, 10% potassium carbonate, 6% sodium carbonate, 20% strontium carbonate, 10% barium carbonate, 5% zinc oxide, and 5% bismuth oxide.

[0071] Figure 3 This is a diagram of the brick surface effect in Comparative Example 1. In this example, the frit composition contains a higher proportion of washed kaolin and calcined talc, resulting in a higher melting temperature of the frit. Consequently, the ink produced will have white spots after firing at this higher temperature. Furthermore, the luminescent properties of the ceramic brick also deteriorate, exhibiting a significant weakening of luminescence characteristics after the loss of light exposure. This is because rare earth ions cannot effectively embed into the lattice of the ceramic solid solution, thus losing the photoelectric excitation and slow-release effect.

[0072] Comparative Example 2

[0073] It is basically the same as Example 1, except that the composition of the luminescent ceramic glaze is different.

[0074] The mineral composition of the luminescent ceramic glaze includes, by mass percentage: 30.2% frit, 0.5% europium oxide, 0.3% lanthanum oxide, 33% calcined talc, and 36% quartz. The raw materials of the luminescent ceramic glaze are mixed and calcined in a sagger, then crushed to obtain the luminescent ceramic glaze. The calcination temperature is 1100℃, and the calcination time is 2 hours. The chemical composition of the frit includes, by mass percentage: 19.72% SiO2, 6.37% Al2O3, 5.19% MgO, 6.45% K2O, 6.19% Na2O, 9.36% BaO, 27.9% SrO, 6.05% ZnO, 4.83% Bi2O3, and 7.94% B2O3. The mineral composition of the frit includes, by mass percentage: 14% washed kaolin, 9.5% calcined borax, 14% calcined talc, 8.5% potassium carbonate, 5% sodium carbonate, 30% strontium carbonate, 10% barium carbonate, 5% zinc oxide, and 4% bismuth oxide.

[0075] Figure 4 This is a rendering of the brick surface of Comparative Example 2. Comparative Example 2 reduced the proportion of frit and increased the content of calcined talc and quartz, resulting in a higher temperature for doping rare earth elements. This prevented the effective photoexcitation elements from being doped, and the glaze temperature was also too high. As a result, defects such as firing pits and pinholes appeared after the ink was prepared, and the photoelectric delay effect was also greatly reduced.

[0076] Comparative Example 3

[0077] It is basically the same as Example 1, except that the high-temperature resistant long afterglow luminescent ceramic ink does not use nano-silicon carbide.

[0078] The raw material composition of the high-temperature resistant long afterglow luminescent ceramic ink includes: by mass percentage, 42% luminescent ceramic glaze, 40% solvent white oil, 7% ester solvent, 10% dispersant, and 1% defoamer.

[0079] The ink prepared in Comparative Example 3 failed to effectively achieve a long-afterglow luminescence effect. The purpose of using nano-silicon carbide is to enhance the luminescence effect during high-temperature sintering, thereby improving the Eu... 2+ Yb 2+ 、Sm 2+ and Ce 3+ Rare earth ions are typical examples of those capable of undergoing fd transitions. This invention fully utilizes the in-situ chemical reaction characteristics of carbon monoxide formed by the high-temperature decomposition of nano-silicon carbide, effectively protecting rare earth ions from redox reactions and achieving the characteristic of in-situ synthesis of long-afterglow luminescent materials. Without the addition of nano-silicon carbide, the overall long-afterglow effect of the prepared ink is weakened, which is due to the change in the oxide lattice structure of rare earth ions at high temperatures.

[0080] Comparative Example 4

[0081] It is basically the same as Example 1, except that the order of printing ordinary ink patterns and printing high-temperature resistant long afterglow luminescent ceramic ink patterns is reversed.

[0082] If long-afterglow luminescent ceramic ink is printed first, and then ordinary color ink is printed to prepare luminescent ceramic slabs, the long-afterglow luminescent ceramic ink will be semi-transparent after firing, and a large amount of ink is needed to effectively ensure the luminescent properties. Therefore, ordinary color ink covering the long-afterglow luminescent ceramic ink is prone to color changes or shifts. In addition, the high-temperature melting reaction between inks will weaken the afterglow time and decorative effect of the long-afterglow luminescent ceramic ink.

Claims

1. A high-temperature resistant, long-afterglow luminescent ceramic ink, characterized in that, The raw material composition of the high-temperature resistant long-afterglow luminescent ceramic ink includes: by mass percentage, 30%~50% luminescent ceramic enamel and 0.1%~1% nano-silicon carbide; the mineral composition of the luminescent ceramic enamel includes: by mass percentage, 50%~65% frit, 0.1%~1% rare earth metal oxides, 20%~30% calcined talc, and 5%~28% quartz; the rare earth metal oxides are one or a mixture of lanthanum oxide, europium oxide, and cerium oxide; the chemical composition of the frit includes: by mass percentage, 15%~35% SiO2, 3%~8% Al2O3, 3.5%~6.5% MgO, 3%~7% K2O, 5%~7% Na2O, 6%~10% BaO, 22%~38% SrO, 4%~7% ZnO, 3%~7% Bi2O3, and B2O3. 1%~9%; Weigh the raw materials according to the mineral composition of the luminescent ceramic glaze, place them in a sealed environment and calcine them in the air, and after crushing, obtain the luminescent ceramic glaze; The calcination temperature is 960~1150℃, and the calcination time is 2~4 hours.

2. The high-temperature resistant, long-afterglow luminescent ceramic ink according to claim 1, characterized in that, The mineral composition of the frit includes, by mass percentage: 5%~15% washed kaolin, 5%~10% calcined borax, 6%~15% calcined talc, 3%~9% potassium carbonate, 3%~8% sodium carbonate, 30%~45% strontium carbonate, 6%~10% barium carbonate, 4%~8% zinc oxide, and 3%~6% bismuth oxide.

3. The high-temperature resistant, long-afterglow luminescent ceramic ink according to claim 1, characterized in that, The raw material composition of the high-temperature resistant long afterglow luminescent ceramic ink includes, by mass percentage: 30%~50% luminescent ceramic glaze, 0.5%~1% nano silicon carbide, 15%~50% solvent white oil, 5%~22% ester solvent, 3%~10% dispersant, and 0.2%~1% defoamer.

4. The application of the high-temperature resistant long afterglow luminescent ceramic ink according to any one of claims 1 to 3 in ceramic products.

5. A method for preparing a long-afterglow luminescent decorative ceramic slab, characterized in that, The preparation method includes: Apply a glaze to the surface of the brick blank; Ordinary ink patterns are printed on the surface of the brick blank after the glaze has been applied. A high-temperature long-afterglow luminescent ceramic ink pattern is formed by inkjet printing on the surface of a brick blank after an inkjet ordinary ink pattern is formed by inkjet printing the high-temperature long-afterglow luminescent ceramic ink according to any one of claims 1 to 3. Apply a protective glaze to the surface of the brick blank after inkjet printing a high-temperature resistant, long-afterglow luminescent ceramic ink pattern; After applying a protective glaze, the brick blank is fired to obtain a decorative ceramic slab with long afterglow.

6. The preparation method according to claim 5, characterized in that, High-temperature resistant, long-afterglow luminescent ceramic ink is printed using inkjet printing with at least two channels, and the grayscale of each channel is at least 20%.

7. The preparation method according to claim 5, characterized in that, The chemical composition of the glaze includes, by mass percentage: 1%~6% loss on ignition, 54%~56% SiO2, 23%~26% Al2O3, 0.1%~0.6% Fe2O3, 0.01%~0.1% TiO2, 0.5%~1.5% CaO, 0.1%~1% MgO, 3%~6% K2O, 2%~4% Na2O, and 4.5%~6.5% ZrO2.

8. The preparation method according to claim 5, characterized in that, The face glaze is applied by spraying, and has a specific gravity of 1.8-1.9 g / cm 3 , and an application amount of 400-600 g / m 2 .

9. The preparation method according to claim 5, characterized in that, The chemical composition of the protective glaze includes, by mass percentage: 0.5%~12% loss on ignition, 42%~50% SiO2, 11%~20% Al2O3, 0.1%~0.3% Fe2O3, 0.01%~0.1% TiO2, 1%~10% CaO, 1%~5% MgO, 0.5%~3% K2O, 3%~6% Na2O, 2%~4% ZnO, 1%~5% BaO, and 1%~3% SrO.

10. The preparation method according to claim 5, characterized in that, The protective glaze is applied by spraying; the specific gravity of the protective glaze is 1.4~1.6 g / cm³. 3 The application rate is 450~750 g / m 2 .

11. The preparation method according to claim 5, characterized in that, The firing temperature is 1160~1210℃, and the firing time is 40~60 minutes.

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