Yellow long-afterglow ceramic low-temperature overglaze color pigment as well as preparation method and application thereof

Abstract

The invention provides a yellow long-afterglow ceramic low-temperature overglaze color pigment as well as a preparation method and application thereof, and belongs to the technical field of ceramic pigments. Noctilucent powder SrAl2O4: Eu < 2 + > and Dy < 3 + > and fluorescent powder Y3Al5O12: Ce < 3 + > or Y3Al5O12: Ce < 3 + > and Gd < 3 + > are combined according to different proportions to form a yellow long-afterglow luminescent pigment, then the yellow long-afterglow luminescent pigment is mixed with a glaze surface combination auxiliary agent, and the low-temperature overglaze color pigment with yellow long-afterglow emission is obtained by utilizing a new principle and technology of energy transfer and reflection-compensation, can be fired on a glaze surface at a relatively low temperature, and has the characteristics of long-afterglow emission and long-afterglow emission. Bright yellow body color is displayed under sunlight or an artificial light source; in the dark, afterglow emission which is adjustable from yellow green to yellow is shown. The yellow long-afterglow ceramic low-temperature overglaze color pigment provided by the invention can improve the unique decorative effect of porcelain, enrich the color of the porcelain and improve the added value of ceramic products, and is a novel luminous pigment with excellent performance.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic pigments, and in particular to a yellow long afterglow ceramic low-temperature overglaze pigment and a preparation method and application thereof. Background Art

[0002] Overglaze painting refers to a ceramic decoration technique that uses various pigments to paint on the fired ceramic glaze surface and fire it at low temperature. It makes the ceramic objects look bright and shiny, with strong visual impact and decorativeness. At the same time, the overglaze painting process is relatively simple, easy to operate, with a short production cycle, and easy to customize. However, overglaze painting may fade or change color under long-term use and light, affecting the integrity and beauty of the color. In addition, some pigments may contain harmful substances, posing potential risks to the environment and human health.

[0003] Long afterglow luminescent material is a functional material that can absorb and store light energy under sunlight or artificial light, and slowly emit light for a period of time after stopping charging. It is also called "luminous material". It is currently mainly used in night lighting, safety instructions, architectural decoration and other application fields. According to different decoration and functional requirements, different colors of long afterglow materials (such as red, yellow, green and blue) can be selected, but the afterglow effect of some colors (such as blue and green) is significantly better than other colors. The only long afterglow material used in a large number of practical applications is SrAl2O4:Eu 2+ ,Dy 3+ (green, >24h), which leads to limitations in color selection. In addition, due to the limited penetration of blue and green light, their application in complex natural environments (rain, snow, strong winds) is more restricted. In contrast, yellow light has better penetration and visibility, especially in low light conditions. Safety signs designed with yellow long afterglow luminescent materials have a stronger warning effect.

[0004] In the prior art, there are also some related patents that apply long afterglow luminous materials to ceramic pigments. For example, Chinese patent CN115536439A discloses a one-time high-temperature fired luminous ceramic tile and its preparation method. The raw materials are composed of encapsulated luminous powder and frit powder. The encapsulated luminous powder is made of 40-50 parts of luminous powder, 8.5-10 parts of zirconium oxychloride, 11-19 parts of water glass, 0.1-0.2 parts of dispersant, and 0.4-0.8 parts of mineralizer. It is fired at 700-900℃ for 30-60 minutes. The glazed body is placed in a wide roller kiln at 1180-1220℃ and fired in a reducing atmosphere for 65-80 minutes. The ceramic tile obtained by this method can be used in the field of fire protection. Chinese patent CN114133274A discloses a long afterglow fluorescent glaze ceramic product and its preparation method. The long afterglow fluorescent ceramic glaze layer contains a raw material group and an auxiliary reagent group, wherein the raw material group contains, by weight, 26-35 parts of long afterglow fluorescent powder, 10-15 parts of strontium aluminate, 20-33 parts of perovskite, and 20-33 parts of ilmenite. The ceramic glaze is applied to the surface of the body, fired in a reducing atmosphere, gradually heated to 1300°C, and then dried and cooled to obtain a ceramic product. However, the above patent also has the problems of relatively complex preparation process, too high firing temperature, single luminous color (mainly concentrated in green), dull color, etc., and the color after glazing is not mentioned.

[0005] Whether used for the decoration of ceramic products or as a colorant for ceramic glaze or color base, yellow long-lasting luminescent pigments are indispensable decorative materials for ceramic decorative art. However, there are no low-temperature ceramic overglaze pigments with yellow afterglow on the market. This is mainly due to: (1) the yellow light spectrum is very narrow, and the generation of afterglow emission requires the matrix, luminescence center and trap to jointly determine its performance, which is difficult to meet simultaneously when facing practical applications; (2) traditional yellow pigments mainly rely on absorbing and reflecting ambient light to obtain yellow body color, and they do not have afterglow luminescence properties themselves; (3) due to the unstable chemical properties of some materials, they may easily change their body color under light, humidity or chemical reactions; (4) the high-temperature firing process will destroy the crystal structure of the luminescent material, affect the luminescence properties of the material, and cause the luminescence brightness to decrease; (5) some traditional yellow pigments may contain harmful substances, such as lead yellow (lead chrome yellow), which is restricted or prohibited due to environmental pollution problems. This also leads to a small number of yellow pigments and a small number of them. Therefore, it is difficult to develop yellow long-lasting pigments on this basis. Summary of the invention

[0006] The purpose of the present invention is to provide a yellow long afterglow ceramic low-temperature overglaze color pigment and its preparation method and application, so as to solve the problem of lack of yellow afterglow low-temperature overglaze color pigment in the prior art. The yellow long afterglow overglaze color prepared by the present invention presents a bright yellow color under sunlight, and can be excited and charged by sunlight, etc., and emits a yellow afterglow in the dark, and has a high application value in the fields of decoration, indication, lighting, etc.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The present invention provides a yellow long afterglow ceramic low-temperature overglaze color pigment, comprising the following raw materials in parts by weight: 10-40 parts of yellow long afterglow luminous pigment, 60-90 parts of glaze bonding additive; The yellow long afterglow luminescent pigment comprises 0.25 to 5 parts of luminous powder and 1 to 55 parts of fluorescent powder in parts by mass; The chemical composition of the luminous powder is SrAl2O4:Eu 2+ ,Dy 3+ The chemical composition of the phosphor is Y3Al5O 12 :Ce 3+ or Y3Al5O 12 :Ce 3+ ,Gd 3+ ; The glaze bonding aid includes a flux and / or a yellow mineral pigment.

[0008] Preferably, the melting point of the flux is 600-800°C.

[0009] Preferably, the preparation method of the yellow long afterglow luminous pigment comprises: mixing luminous powder, fluorescent powder and a dispersing solvent, and sequentially performing ultrasonic dispersion, drying and grinding to obtain the yellow long afterglow luminous pigment; the grinding particle size is ≤40 μm.

[0010] Preferably, the dispersion solvent includes water or anhydrous ethanol; the ultrasonic dispersion time is 15-60 min, and the ultrasonic power is 50-400 W; the drying temperature is 50-90° C., and the time is 0.1-0.5 h; the grinding speed is 50-150 rpm, and the grinding time is 15-30 min.

[0011] The present invention provides a method for preparing the yellow long afterglow ceramic low-temperature overglaze pigment described in the above technical solution, comprising the following steps: The yellow long afterglow luminous pigment and the glaze surface bonding auxiliary agent are ground and mixed, and then dried to obtain the yellow long afterglow ceramic low-temperature on-glaze color pigment.

[0012] Preferably, the grinding and mixing conditions include: the grinding medium is water or anhydrous ethanol, the grinding speed is 50-100 rpm, and the grinding time is 15-30 min; the drying temperature is 50-90° C., and the drying time is 0.1-0.5 h.

[0013] The present invention provides the yellow long afterglow ceramic low-temperature overglaze color pigment described in the above technical solution, or the present invention provides the use of the yellow long afterglow ceramic low-temperature overglaze color pigment prepared by the preparation method described in the above technical solution in ceramic decoration.

[0014] Preferably, the application method comprises the following steps: The yellow long afterglow ceramic low-temperature overglaze color pigment is blended with frankincense oil, the obtained pigment is painted on the surface of a ceramic substrate, and the ceramic substrate is dried by heat preservation and then fired to obtain the ceramic overglaze color.

[0015] Preferably, the temperature of the heat preservation and drying is 50-60° C., and the time is 0.1-0.5 h.

[0016] Preferably, the target temperature of the firing is 600-800°C, the firing atmosphere is air or a reducing atmosphere; and the heating rate from room temperature to the target temperature is 3-6°C / min.

[0017] The invention provides a yellow long afterglow ceramic low-temperature glaze pigment, which adopts luminous powder SrAl2O4:Eu 2+ ,Dy 3+ With phosphor Y3Al5O 12 :Ce 3+ or Y3Al5O 12 :Ce 3+ ,Gd 3+ Yellow long afterglow luminescent pigments are formed by combining them in different proportions and then mixed with glaze bonding additives. The new principles and technologies of energy transfer and reflection-compensation are used to obtain low-temperature overglaze pigments with yellow long afterglow emission. The pigments can be fired on the glaze at a lower temperature and show a bright yellow body color under sunlight or artificial light; in the dark, they exhibit an afterglow emission that is adjustable from yellow-green to yellow.

[0018] The technical principle involved in the present invention is: 1. Utilize the new energy transfer strategy of "phosphor + luminous powder" to absorb the afterglow emission of the blue and green parts of the long afterglow phosphor through the yellow phosphor, and use it to stimulate the yellow light emission of the yellow phosphor to enhance the afterglow emission of the yellow part, thus achieving high-brightness yellow long afterglow luminescence that can be stimulated by sunlight.

[0019] 2. Using the advanced reflection-compensation principle, yellow mineral pigments that strongly absorb blue light and strongly reflect yellow light and / or fluxes that strongly reflect white light are mixed with yellow long afterglow luminescent pigments that absorb blue and green light and emit yellow light at the micron, submicron or even nanometer level (the smaller the particle size, the better the reflection compensation effect). Since the refractive index of the flux is about 1.5, the refractive index of the mineral pigment is about 1.5, and the refractive index of the luminescent pigment is about 1.55. The mixing of the glaze bonding additive and the luminescent pigment can reduce the interface scattering and total reflection between the pigments inside the overglaze color, so that the light is better reflected. Therefore, the mixed powder of the yellow long afterglow luminescent pigment and the glaze bonding additive obtains the superposition effect of reflection enhancement and fluorescence compensation in the visible light region, further improving the color rendering performance of the pigment and the glossiness of the final overglaze color (the mineral pigment itself is more yellow in color and has the characteristics of strong reflection of yellow light, which can improve the color rendering of the overglaze color; the flux itself is colorless and can reflect white light, which can improve the glossiness of the overglaze color.) The energy transfer and reflection-compensation of "phosphor + luminous powder" in the present invention have a synergistic effect. In the yellow long afterglow pigment, there is an energy transfer mechanism between the phosphor and the luminous powder. After the luminous powder absorbs light energy, it can transfer energy to the phosphor, so that the phosphor can emit light under lower light conditions, thereby improving its luminous efficiency. In addition, the phosphor usually stops emitting light quickly after the light stops. When the two are used in combination, the luminous powder can make up for this shortcoming of the phosphor. In addition, the luminous powder can absorb part of the sunlight and convert it into visible light, and the phosphor can absorb and reflect the light released by the luminous powder, and be excited to emit at the same time, thereby improving the luminous efficiency and the overall brightness and color rendering of the pigment.

[0020] The present invention uses a glaze bonding aid to produce a coating effect during the firing process, so that the yellow long afterglow pigment is fired on the surface of the ceramic substrate and achieves a firm bond: on the one hand, the coated long afterglow material can be isolated from the air to prevent the long afterglow material from being oxidized and avoid a decrease in afterglow performance.

[0021] The yellow long afterglow luminescent pigment used in the present invention shows a bright yellow body color under sunlight or artificial light source; in the dark, it shows an afterglow luminescence adjustable from yellow-green to yellow, with a wavelength band of 500nm to 700nm, an emission peak adjustable in the range of 542~562nm, and an afterglow brightness controlled at 2000mcd / m 2 Above, the afterglow time is controlled to be more than 10h.

[0022] The yellow long afterglow low-temperature overglaze color pigment provided by the present invention can be fired on the surface of a white porcelain substrate at 600-800°C. Under the action of rapid heating and glaze bonding additives, the residence time of the overglaze color in a high temperature environment can be reduced, thereby reducing the damage of the flux to the crystal structure of the long afterglow luminescent material at high temperature, avoiding the degradation of afterglow performance and reducing the degree of oxidation of the luminescent center. The fired overglaze color shows a bright yellow body color under sunlight or artificial light; in the dark, it exhibits an adjustable afterglow luminescence from yellow-green to yellow, with a wavelength band of 500nm to 700nm, an emission peak adjustable in the range of 542-562nm, and an afterglow brightness controlled at 400mcd / m 2 Above, the afterglow time is controlled to be more than 1h.

[0023] The preparation method of the ceramic low-temperature overglaze pigment with yellow long afterglow provided by the present invention has no pollution, and the synthesis method is simple and efficient, and no auxiliary solvent needs to be added, no waste water and waste gas are discharged, and the environment is friendly, and it is particularly suitable for industrial and continuous production.

[0024] The yellow long afterglow ceramic low-temperature overglaze color pigment provided by the invention can enhance the unique decorative effect of porcelain, enrich the color of porcelain, and increase the added value of ceramic products. It is a new type of luminous pigment with excellent performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a scanning electron microscope image of the yellow long afterglow luminescent pigment prepared in Example 1; Figure 2 This is a scanning electron microscope image of the yellow long afterglow low-temperature overglaze color pigment prepared in Example 1; Figure 3 The afterglow attenuation curve of the yellow long afterglow luminescent pigment prepared in Example 1; Figure 4 The afterglow spectra of the yellow long afterglow luminescent pigments prepared in Examples 1 to 3; Figure 5 The afterglow spectra of the yellow long afterglow luminescent pigments prepared in Examples 5 to 7; Figure 6 This is a graph showing the afterglow attenuation curve of the yellow long afterglow ceramic overglaze color prepared in Example 1; Figure 7 This is a graph showing the afterglow attenuation curve of the yellow long afterglow ceramic overglaze color prepared in Example 2; Figure 8 This is a graph showing the afterglow attenuation curve of the yellow long afterglow ceramic overglaze color prepared in Example 3; Fig. 9 This is a graph showing the afterglow attenuation curve of the yellow long afterglow ceramic overglaze color prepared in Example 5; Fig.10 This is a graph showing the afterglow attenuation curve of the yellow long afterglow ceramic overglaze color prepared in Example 6; Fig.11 This is a graph showing the afterglow attenuation curve of the yellow long afterglow ceramic overglaze color prepared in Example 7; Fig.12 The color coordinate diagram of the afterglow spectrum of the yellow long afterglow ceramic overglaze color prepared in Examples 1 to 3; Fig.13 The color coordinate diagram of the afterglow spectrum of the yellow long afterglow ceramic overglaze color prepared in Examples 5 to 7; Fig.14 This is a real picture of the yellow long afterglow low-temperature overglaze color pigment prepared in Examples 1 to 8 after being coated on the surface of white porcelain; Fig.15 The actual picture of the yellow long afterglow ceramic overglaze color prepared in Examples 1 to 8; Fig.16 This is a physical picture of the afterglow luminescence of the yellow long afterglow ceramic overglaze color prepared in Examples 1 to 3 and 5 to 7 in a dark environment; Fig.17 The chromaticity values ​​of the yellow long afterglow ceramic overglaze color prepared in Example 1 and the overglaze color prepared using commercially available thin yellow mineral pigment are compared. DETAILED DESCRIPTION

[0026] In the present invention, unless otherwise specified, the required raw materials or reagents are commercially available products well known to those skilled in the art.

[0027] The present invention provides a yellow long afterglow ceramic low-temperature overglaze color pigment, comprising the following raw materials in parts by weight: 10-40 parts of yellow long afterglow luminous pigment, 60-90 parts of glaze bonding additive; The yellow long afterglow luminescent pigment comprises 0.25 to 5 parts of luminous powder and 1 to 55 parts of fluorescent powder in parts by mass; The chemical composition of the luminous powder is SrAl2O4:Eu 2+ ,Dy 3+ The chemical composition of the phosphor is Y3Al5O 12 :Ce 3+ or Y3Al5O 12 :Ce 3+ ,Gd 3+ ; The glaze bonding aid includes a flux and / or a yellow mineral pigment.

[0028] In the present invention, the yellow long afterglow luminescent pigment is preferably 15 to 38 parts, more preferably 24 to 36 parts, and more preferably 27 to 34 parts.

[0029] In the present invention, the yellow long afterglow luminous pigment includes 0.25 to 5 parts of luminous powder, preferably 0.5 to 4 parts, more preferably 0.75 to 3 parts, and more preferably 1 to 2 parts; the yellow long afterglow luminous pigment includes 1 to 55 parts of fluorescent powder, preferably 5 to 50 parts, more preferably 10 to 45 parts, and more preferably 15 to 40 parts.

[0030] In the present invention, the preparation method of the yellow long afterglow luminescent pigment preferably comprises: mixing luminescent powder, fluorescent powder and a dispersing solvent, and sequentially performing ultrasonic dispersion, drying and grinding to obtain the yellow long afterglow luminescent pigment; the grinding particle size is ≤40 μm.

[0031] In the present invention, the dispersion solvent preferably includes water or anhydrous ethanol; the present invention has no special limitation on the amount of the dispersion solvent, as long as the material is fully dispersed.

[0032] The ultrasonic dispersion time is preferably 15-60 min, more preferably 20-50 min, more preferably 32-36 min; the ultrasonic power is preferably 50-400 W, more preferably 100-350 W, more preferably 150-300 W; the drying temperature is preferably 50-90 ° C, more preferably 55-80 ° C, more preferably 62-66 ° C; the time is preferably 0.1-0.5 h, more preferably 0.15-0.4 h, more preferably 0.25-0.35 h; the grinding is preferably carried out in a ball mill, the grinding speed is preferably 50-150 rpm, more preferably 60-130 rpm, more preferably 90-100 rpm; the grinding time is preferably 15-30 min, more preferably 16-23 min, more preferably 18-20 min. In the present invention, the grinding particle size is preferably ≤40 μm, more preferably ≤38 μm, more preferably ≤36 μm; the present invention preferably selects submicron or nanometer size to determine the grinding particle size according to needs.

[0033] The present invention controls the particle size of the yellow long afterglow luminescent pigment to be below 40 microns (or actually controls it to submicron or nanometer size as needed), and can simultaneously obtain better overglaze color quality and afterglow luminescent properties (if the particle size is too large, it will affect the binding force, glossiness and flatness of the overglaze color).

[0034] In the present invention, the glaze bonding aid is preferably 63 to 85 parts, more preferably 66 to 80 parts, and more preferably 70 to 75 parts.

[0035] In the present invention, the glaze bonding aid comprises a flux and / or a yellow mineral pigment; the glaze bonding aid is used to bond the yellow long afterglow luminescent pigment to the glaze.

[0036] In the present invention, the melting point of the flux is preferably 600-800°C. The flux is a low-melting-point flux, which is conducive to the preparation of overglaze colors at a lower temperature. It can not only reduce energy consumption, but also reduce the deformation and shrinkage of the ceramic body during high-temperature firing. More importantly, it can avoid the destruction of the crystal structure of the yellow long afterglow luminescent pigment at high temperature, thereby ensuring good afterglow luminescence characteristics.

[0037] The yellow mineral pigment of the present invention preferably includes a light yellow mineral pigment or a dark yellow mineral pigment; the yellow mineral pigment contains 70-80% of a flux component, which can have the same effect as a flux.

[0038] The present invention has no particular limitation on the source of the flux and / or yellow mineral pigment, and any commercially available product known in the art may be used.

[0039] The present invention provides a method for preparing the yellow long afterglow ceramic low-temperature overglaze pigment described in the above technical solution, comprising the following steps: The yellow long afterglow luminous pigment and the glaze surface bonding auxiliary agent are ground and mixed, and then dried to obtain the yellow long afterglow ceramic low-temperature on-glaze color pigment.

[0040] In the present invention, the grinding and mixing conditions preferably include: the grinding medium is water or anhydrous ethanol, the grinding speed is 50-100 rpm, and the grinding time is 15-30 min; the present invention has no special limitation on the amount of the grinding medium, and it can be adjusted according to demand to ensure that the grinding is completed.

[0041] The grinding and mixing is carried out in a ball mill, and the grinding rotation speed is further preferably 55-85 rpm, more preferably 64-70 rpm; the grinding time is further preferably 16-27 min, more preferably 17-24 min; the drying temperature is preferably 50-90° C., more preferably 55-80° C., more preferably 60-70° C.; the drying time is preferably 0.1-0.5 h, more preferably 0.15-0.4 h, more preferably 0.24-0.3 h.

[0042] The present invention provides the yellow long afterglow ceramic low-temperature overglaze color pigment described in the above technical solution, or the present invention provides the use of the yellow long afterglow ceramic low-temperature overglaze color pigment prepared by the preparation method described in the above technical solution in ceramic decoration.

[0043] In the present invention, the application method comprises the following steps: The yellow long afterglow ceramic low-temperature overglaze color pigment is blended with frankincense oil, the obtained pigment is painted on the surface of a ceramic substrate, and the ceramic substrate is dried by heat preservation and then fired to obtain the ceramic overglaze color.

[0044] The present invention has no special limitation on the usage ratio of the frankincense oil and the yellow long afterglow ceramic low-temperature overglaze color pigment, which can be adjusted according to needs according to methods well known in the art; the present invention has no special limitation on the blending, which can be mixed evenly according to processes well known in the art.

[0045] The present invention preferably uses a brush or a writing brush to dip the blended pigment to draw a pattern on the surface of the white porcelain base, and after heat preservation and drying, puts the pattern into a box furnace or a tube furnace for firing to obtain ceramic glaze color.

[0046] In the present invention, the temperature of the heat preservation and drying is preferably 50-60°C, more preferably 52-59°C, and more preferably 53-55°C; the time is preferably 0.1-0.5h, more preferably 0.15-0.45h, and more preferably 0.2-0.4h; the target temperature of the firing is preferably 600-800°C, more preferably 650-780°C, and more preferably 740-760°C; the heating rate from room temperature to the target temperature is preferably 3-6°C / min, more preferably 3.2-5°C / min, and more preferably 3.4-4°C / min; after heating to the target temperature, no heat preservation is performed, that is, the heating or heat preservation is stopped immediately after reaching the target temperature, and the temperature is directly lowered.

[0047] In the present invention, the firing atmosphere is preferably air or a reducing atmosphere; the reducing atmosphere is preferably a mixture of nitrogen and hydrogen, and the volume fraction of nitrogen in the mixture is preferably 85-95%, more preferably 87-93%, and more preferably 89-91%.

[0048] After the firing is completed, the present invention preferably cools to room temperature with the furnace, or opens the furnace to cool to room temperature after 50-200°C, closes the furnace door, and cools to room temperature with the furnace; the temperature of the furnace cooling is further preferably 70-150°C, and more preferably 90-100°C.

[0049] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0050] In the embodiment, the selected SrAl2O4:Eu 2+ ,Dy 3+ From Guangzhou Chuangrong Chemical Technology Co., Ltd.; Y3Al5O 12 :Ce 3+ or Y3Al5O 12 :Ce 3+ , Gd 3+ The fluorescent powder comes from Jiangmen Keheng Industrial Co., Ltd.; the flux comes from Taiyuan Hengtai Mineral Materials Co., Ltd., with a melting point of 600~800℃; the yellow mineral pigment is the thin yellow mineral pigment produced by Jingdezhen Zhongqi Ceramic Culture Co., Ltd.

[0051] Example 1 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 2g Y3Al5O 12 :Ce 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 150 W for 32 min, and then the slurry was dried at 62 ° C for 0.25 h, and finally the powder was ground in a ball mill at a speed of 90 rpm for 18 min, and the grinding particle size was ≤40 μm to obtain a yellow long afterglow luminescent pigment; Weigh 0.27 g of the yellow long afterglow luminescent pigment and 0.63 g of flux, add 10 mL of anhydrous ethanol and grind in a ball mill at 64 rpm for 17 min, then dry the slurry at 64° C. for 0.24 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.16 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.2 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base. After the ceramic with the drawn pattern is baked at 55°C for 0.2 h, the sample is placed in an air box furnace, and the temperature is increased from room temperature to 740°C at a heating rate of 3.4°C / min. The furnace is then stopped and cooled to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0052] Example 2 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 3g Y3Al5O 12 :Ce 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 150 W for 34 min, and then the slurry was dried at 64 ° C for 0.3 h. Finally, the above powder was ground in a ball mill at a speed of 100 rpm for 19 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.24 g of the yellow long afterglow luminescent pigment and 0.56 g of flux, add 10 mL of anhydrous ethanol and grind in a ball mill at 66 rpm for 18 min, then dry the slurry at 66° C. for 0.26 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.24 g of the above-mentioned yellow long afterglow low-temperature overglaze color pigment, add 0.3 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base, bake the ceramic with the drawn pattern at 55°C for 0.2h, put the sample into an air box furnace, and heat it from room temperature to 750°C at a heating rate of 3.5°C / min, then stop the furnace and cool it to room temperature with the furnace to obtain the ceramic overglaze color with yellow long afterglow.

[0053] Example 3 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 4g Y3Al5O 12 :Ce 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 150 W for 36 min, and then the slurry was dried at 66 ° C for 0.35 h, and finally the above powder was ground in a ball mill at a speed of 100 rpm for 20 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.21 g of the yellow long afterglow luminescent pigment and 0.49 g of flux, add 10 mL of anhydrous ethanol, grind in a ball mill at 68 rpm for 19 min, and then dry the slurry at 68° C. for 0.28 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.28 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.35 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base, bake the ceramic with the drawn pattern at 55°C for 0.2h, put the sample into an air box furnace, and heat it from room temperature to 760°C at a heating rate of 3.6°C / min, then stop the furnace and cool it to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0054] Example 4 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 2g Y3Al5O 12 :Ce 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 150 W for 38 min, then the slurry was dried at 68 ° C for 0.4 h, and finally the powder was ground in a ball mill at a speed of 100 rpm for 21 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.27 g of the yellow long afterglow luminescent pigment and 0.81 g of the thin yellow mineral pigment, add 10 mL of anhydrous ethanol and grind in a ball mill at 70 rpm for 20 min, then dry the slurry at 70° C. for 0.3 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.12 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.15 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base, bake the ceramic with the drawn pattern at 55°C for 0.2 h, put the sample into an air box furnace, and heat it from room temperature to 770°C at a heating rate of 3.7°C / min, then open the furnace to cool to 660°C, close the furnace door and cool to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0055] Example 5 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 2g Y3Al5O 12 :Ce 3+ ,Gd 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 200 W for 32 min, then the slurry was dried at 62 ° C for 0.25 h, and finally the powder was ground in a ball mill at a speed of 90 rpm for 19 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.27 g of the yellow long afterglow luminescent pigment and 0.63 g of flux, add 10 mL of anhydrous ethanol, grind in a ball mill at 64 rpm for 21 min, and then dry the slurry at 64° C. for 0.24 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.16 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.2 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base. After the ceramic with the drawn pattern is baked at 55°C for 0.2 h, the sample is placed in an air box furnace, and the temperature is increased from room temperature to 745°C at a heating rate of 3.8°C / min. The furnace is then stopped and cooled to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0056] Example 6 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 3g Y3Al5O 12 :Ce 3+ ,Gd 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 200 W for 34 min, and then the slurry was dried at 64 ° C for 0.3 h. Finally, the above powder was ground in a ball mill at a speed of 100 rpm for 18 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.24 g of the yellow long afterglow luminescent pigment and 0.56 g of flux, add 10 mL of anhydrous ethanol and grind in a ball mill at 66 rpm for 22 min, then dry the slurry at 66° C. for 0.26 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.24 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.3 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base. After the ceramic with the drawn pattern is baked at 55°C for 0.2h, the sample is placed in an air box furnace, and the temperature is increased from room temperature to 755°C at a heating rate of 3.9°C / min. The furnace is then stopped and cooled to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0057] Example 7 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 4g Y3Al5O 12 :Ce 3+ ,Gd 3+ The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 200 W for 36 min, and then the slurry was dried at 66 ° C for 0.35 h, and finally the above powder was ground in a ball mill at a speed of 100 rpm for 19 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.21 g of the yellow long afterglow luminescent pigment and 0.49 g of flux, add 10 mL of anhydrous ethanol and grind in a ball mill at 68 rpm for 23 min, then dry the slurry at 68° C. for 0.28 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.28 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.35 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base, bake the ceramic with the drawn pattern at 55°C for 0.2h, put the sample into an air box furnace, and heat it from room temperature to 765°C at a heating rate of 4°C / min, then stop the furnace and cool it to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0058] Example 8 Weigh 0.1g SrAl2O4:Eu 2+ ,Dy 3+ Luminous powder and 2g Y3Al5O 12 :Ce 3+ ,Gd 3+The phosphor was used as a raw material, 10 mL of anhydrous ethanol was added and ultrasonically dispersed at a power of 200 W for 38 min, then the slurry was dried at 68 ° C for 0.4 h, and finally the powder was ground in a ball mill at a speed of 100 rpm for 20 min to obtain a yellow long afterglow luminescent pigment; Weigh 0.27 g of the yellow long afterglow luminescent pigment and 0.81 g of the thin yellow mineral pigment, add 10 mL of anhydrous ethanol and grind in a ball mill at 70 rpm for 24 min, then dry the slurry at 70 ° C for 0.3 h to obtain a yellow long afterglow low-temperature overglaze pigment; Weigh 0.12 g of the above-mentioned yellow long afterglow low-temperature overglaze pigment, add 0.15 mL of frankincense oil, mix the two, then use a brush to dip the pigment and draw it on the surface of the white porcelain base, bake the ceramic with the drawn pattern at 55°C for 0.2 h, put the sample into an air box furnace, and heat it from room temperature to 775°C at a heating rate of 3.4°C / min, then open the furnace to cool to 660°C, close the furnace door and cool to room temperature with the furnace to obtain a ceramic overglaze color with a yellow long afterglow.

[0059] Characterization and performance testing 1) Figure 1 This is a scanning electron microscope image of the yellow long afterglow luminescent pigment prepared in Example 1. It can be seen that the particle size of the yellow long afterglow luminescent pigment is ≤36 microns.

[0060] 2) Figure 2 This is a scanning electron microscope image of the yellow long afterglow low-temperature overglaze color pigment prepared in Example 1, from which it can be seen that the particle size of the yellow long afterglow low-temperature overglaze color pigment is ≤36 microns.

[0061] 3) The yellow long afterglow luminescent pigment prepared in Example 1 was irradiated with sunlight and simulated sunlight (excitation by white light LED, illumination of 1000 lx) for 15 minutes, and then the excitation was stopped. The afterglow decay curves were as follows: Figure 3 As shown, the initial brightness of the afterglow of Example 1 after being excited and charged under sunlight reaches 2262mcd / m 2 The afterglow time reaches 20.8h; the initial brightness of the afterglow after excitation and charging under simulated sunlight reaches 2403mcd / m 2 , the afterglow time reaches 10.8h.

[0062] 4) The yellow long afterglow luminescent pigments prepared in Examples 1 to 3 and 5 to 7 were irradiated with simulated sunlight (illuminance of 1000 lx) for 15 min and then the excitation was stopped. After waiting for 10 s, the afterglow spectra were tested. The results were as follows: Figure 4 and 5 As shown. Figure 4It can be seen that the emission wavelength range of the material is 450nm~700nm, the emission peak of Example 1 is about 542nm; the emission peak of Example 2 is about 545nm; and the emission peak of Example 3 is about 548nm. Figure 5 It can be seen that the emission wavelength range of the material is 450nm~700nm, the emission peak of Example 5 is around 554nm; the emission peak of Example 6 is around 556nm; the emission peak of Example 7 is around 563nm. This shows that the afterglow spectrum of the prepared material is better than that of SrAl2O4:Eu at 520nm. 2+ ,Dy 3+ The emission is significantly red-shifted.

[0063] 5) The yellow long afterglow ceramic on-glaze colors prepared in Examples 1 to 3 and 5 to 7 were irradiated with simulated sunlight (illuminance of 1000 lx) for 15 minutes and then the excitation was stopped. The afterglow decay curves were as follows: Figures 6-8 As shown in 9 to 11, the initial brightness of the afterglow of Example 1 reaches 1510mcd / m 2 The afterglow time reaches 11040s; the afterglow initial brightness of Example 2 reaches 628.9mcd / m 2 The afterglow time reaches 6780s; the afterglow initial brightness of Example 3 reaches 264.3mcd / m 2 The afterglow time reaches 6000s; the afterglow initial brightness of Example 5 reaches 760.2mcd / m 2 The afterglow time reaches 8160s; the afterglow initial brightness of Example 6 reaches 485.1mcd / m 2 The afterglow time reaches 5100s; the afterglow initial brightness of Example 7 reaches 289.6mcd / m 2 , the afterglow time reaches 4380s. (The afterglow time is defined as the time when the afterglow brightness decays to 0.32mcd / m 2 The time required. 6) The color coordinate diagram of the afterglow spectrum of the yellow long afterglow ceramic glaze color prepared in Examples 1 to 3 is as follows: Fig.12 As shown, from Fig.12 It can be seen that the color of the afterglow luminescence of the sample is yellow-green as a whole. The color coordinates of Example 1 are (0.3801, 0.5797), the color coordinates of Example 2 are (0.3975, 0.5714), and the color coordinates of Example 3 are (0.4284, 0.5503). 12 :Ce 3+ With the increase of content, it gradually moves to the yellow area and is similar to SrAl2O4:Eu 2+ ,Dy 3+There are obvious differences in the color coordinates of the afterglow emission (0.2883, 0.5778).

[0064] 7) The color coordinate diagram of the afterglow spectrum of the yellow long afterglow ceramic glaze color prepared in Examples 5 to 7 is as follows: Fig.13 As shown, from Fig.13 It can be seen that the color of the afterglow of the sample is yellow as a whole. The color coordinates of Example 5 are (0.4231, 0.5671), the color coordinates of Example 6 are (0.4335, 0.5574), and the color coordinates of Example 7 are (0.4434, 0.5481). 12 :Ce 3+ ,Gd 3+ With the increase of content, it gradually moves to the yellow area and is similar to SrAl2O4:Eu 2+ ,Dy 3+ There are obvious differences in the color coordinates of the afterglow emission (0.2883, 0.5778).

[0065] 8) The yellow long afterglow low temperature overglaze color pigment prepared in Examples 1 to 8 was applied to the surface of 5cm*5cm white porcelain, with a coating area of ​​2.5cm*2.5cm. After firing, the thickness of the overglaze color was 0.3mm. Fig.14 ;from Fig.14 It can be seen that the yellow long afterglow low-temperature overglaze pigments prepared in Examples 1 to 8 can be coated on the surface of white porcelain and present a bright yellow color.

[0066] 9) Fig.15 The yellow long afterglow ceramic glaze color prepared in Examples 1 to 8 is a real picture; Fig.15 It can be seen that the yellow long afterglow low-temperature overglaze colors prepared in Examples 1 to 8 are coated evenly on the base glaze, with clear boundaries, good bonding, and no obvious particles and cracks; after being mixed and coated with the yellow mineral pigment, no discoloration occurs, and a bright yellow color is presented.

[0067] 10) After 10 minutes of sunlight irradiation, the yellow long afterglow ceramic glaze colors prepared in Examples 1 to 3 and 5 to 7 were stopped from being excited and moved into a dark room for observation. The actual photos are as follows: Fig.16 As shown, from Fig.16 It can be seen that the yellow long afterglow ceramic overglaze colors prepared in Examples 1 to 3 appear yellow-green as a whole in a dark environment, and the yellow long afterglow ceramic overglaze colors prepared in Examples 5 to 7 appear yellow as a whole in a dark environment.

[0068] 11) Fig.17The chromaticity results of the yellow long afterglow ceramic overglaze color prepared in Example 1 and the overglaze color prepared using the commercially available thin yellow mineral pigment are shown, wherein the commercially available thin yellow mineral pigment is directly mixed with frankincense oil according to the conditions of Example 1 to prepare the overglaze color; the comparison results show that the overglaze color obtained in Example 1 can significantly improve the brightness (L*), red-green color (a*) and yellow-blue color (b*), and optimize the color rendering performance of the overglaze color. It is proved that the present invention can effectively improve the chromaticity index of the pigment.

[0069] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A yellow long afterglow ceramic low-temperature glaze pigment, characterized in that: The preparation comprises the following raw materials in parts by weight: 10-40 parts of yellow long afterglow luminous pigment, 60-90 parts of glaze bonding additive; The yellow long afterglow luminescent pigment comprises 0.25 to 5 parts of luminous powder and 1 to 55 parts of fluorescent powder in parts by mass; The chemical composition of the luminous powder is SrAl2O4:Eu 2+ ,Dy 3+ The chemical composition of the phosphor is Y3Al5O 12 :Ce 3+ or Y3Al5O 12 :Ce 3+ ,Gd 3+ ; The glaze bonding aid includes a flux and / or a yellow mineral pigment.

2. The yellow long afterglow ceramic low-temperature overglaze pigment according to claim 1, characterized in that: The melting point of the flux is 600-800°C.

3. The yellow long afterglow ceramic low-temperature overglaze pigment according to claim 1, characterized in that: The preparation method of the yellow long afterglow luminous pigment comprises: mixing luminous powder, fluorescent powder and a dispersing solvent, and sequentially performing ultrasonic dispersion, drying and grinding to obtain the yellow long afterglow luminous pigment; the grinding particle size is ≤40 μm.

4. The yellow long afterglow ceramic low-temperature overglaze pigment according to claim 3, characterized in that: The dispersion solvent includes water or anhydrous ethanol; the ultrasonic dispersion time is 15-60 minutes, and the ultrasonic power is 50-400W; the drying temperature is 50-90°C, and the time is 0.1-0.5h; the grinding speed is 50-150rpm, and the grinding time is 15-30min.

5. The method for preparing the yellow long afterglow ceramic low-temperature overglaze pigment according to any one of claims 1 to 4, characterized in that: The following steps are involved: The yellow long afterglow luminous pigment and the glaze surface bonding auxiliary agent are ground and mixed, and then dried to obtain the yellow long afterglow ceramic low-temperature on-glaze color pigment.

6. The preparation method according to claim 5, characterized in that: The grinding and mixing conditions include: the grinding medium is water or anhydrous ethanol, the grinding speed is 50-100 rpm, and the grinding time is 15-30 min; the drying temperature is 50-90° C., and the drying time is 0.1-0.5 h.

7. Use of the yellow long afterglow ceramic low-temperature overglaze pigment according to any one of claims 1 to 4 in ceramic decoration.

8. The use according to claim 7, characterized in that: The method of application comprises the following steps: The yellow long afterglow ceramic low-temperature overglaze color pigment is blended with frankincense oil, the obtained pigment is painted on the surface of a ceramic substrate, and the ceramic substrate is dried by heat preservation and fired to obtain the ceramic overglaze color.

9. The use according to claim 8, characterized in that: The temperature of the heat preservation and drying is 50-60° C., and the time is 0.1-0.5 h.

10. The use according to claim 8, characterized in that: The target temperature of the firing is 600-800°C, and the firing atmosphere is air or a reducing atmosphere; the heating rate from room temperature to the target temperature is 3-6°C / min.

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