CN113912292A - Ce/Dy/Mn doped colored fluorescent glass and preparation method thereof - Google Patents

Ce/Dy/Mn doped colored fluorescent glass and preparation method thereof Download PDF

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Publication number
CN113912292A
CN113912292A CN202111465582.7A CN202111465582A CN113912292A CN 113912292 A CN113912292 A CN 113912292A CN 202111465582 A CN202111465582 A CN 202111465582A CN 113912292 A CN113912292 A CN 113912292A
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glass
parts
temperature
fluorescent glass
rise rate
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徐青山
朱超峰
周耀
张玉宗
沈建兴
徐长腾
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Shandong Yuncheng Zhenghua Glass Technology Co ltd
Qilu University of Technology
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Shandong Yuncheng Zhenghua Glass Technology Co ltd
Qilu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium

Abstract

The invention belongs to the technical field of novel material preparation, and relates to Ce/Dy/Mn doped colored fluorescent glass and a preparation method thereof. The composite material comprises the following components in parts by mole: SiO 22: 40-65 parts, B2O3: 0 to 20 portions of Al2O3: 0 to 15 portions of CaF2: 10-25 parts of CaO: 0-15 parts; doping agent: 0.01-4 parts of Ce as a dopant2O3，Dy2O3Or one kind of MnO, a combination of two kinds or three kinds. The dopant adopted by the invention has the functions of the colorant and the luminescence center, thereby realizingThe existing glass has coloring and fluorescence functions; the prepared glass has good mechanical property, stable chemical property and uniform glass coloring. The color coordinate and the color temperature of the fluorescent glass can be adjusted by controlling the species and the concentration of the doping agent, the energy transfer among the doping ions, the glass matrix and the excitation wavelength.

Description

Ce/Dy/Mn doped colored fluorescent glass and preparation method thereof
Technical Field
The invention belongs to the technical field of novel material preparation, and relates to Ce/Dy/Mn doped colored fluorescent glass and a preparation method thereof.
Background
Glass has wide application as an amorphous material. Fluorescent glasses can be obtained by introducing active ions (e.g., rare earth/transition metal ions) into the glass composition, which can produce luminescence under certain excitation. In recent years, attention has been paid to glasses that fluoresce in the visible spectral range by ultraviolet excitation, and such glasses have practical application values in lamps, lighting, displays, and some glass products. The color glass can absorb, reflect and transmit light rays with different wavelengths, thereby showing different colors, can be applied to the aspects of art decoration, illumination, laser, filtering and the like, and has important significance in the fields of daily life, industrial and agricultural production, science and technology of people.
The fluorescent glass mainly adopts rare earth ions as an activator, and Eu is generally adopted to obtain red light (orange light) emission3+Or Sm3+The emission spectrum and the excitation spectrum of the two rare earth ions are relatively sharp, the absorption band is relatively narrow, and the excitation light cannot be efficiently absorbed. The prior art mainly relates to the adjustment of the concentration of doped ions and the influence of the energy transfer among ions on the excitation spectrum of the prepared material. There are some fluorescent glasses and colored glasses, but there are few reports focusing on the color and fluorescent property control of glass.
Disclosure of Invention
The invention provides novel Ce/Dy/Mn doped colored fluorescent glass and a preparation method thereof, aiming at the problems in the regulation and control of the color and the fluorescence property of the traditional glass.
The invention relates to a colored inorganic material with a fluorescent function, in particular to rare earth/transition metal doped colored fluorescent glass with excellent transparency, a preparation method and a performance regulation and control method thereof.
The invention relates to Ce/Dy/Mn doped glass, wherein a doping agent can selectively absorb visible light to enable the glass to present a specific color; on the other hand, under the excitation of ultraviolet light, the dopant can generate electronic transition and emit visible light. The invention prepares the Ce/Dy/Mn doped colored fluorescent glass by a high-temperature melt cooling method, the glass is colorless, milky white, light brown, dark brown and the like according to different compositions, and emits purple light, blue light, yellow light, orange light and even white light under the excitation of ultraviolet light. The color of the glass and the light color quality of fluorescence can be realized by adjusting the composition of matrix glass, the species and concentration of doped ions, the wavelength of excitation light and the energy transfer among ions. The color fluorescent glass prepared by the method has high transparency, safety, environmental protection, uniform light emission, easy processing and high light emitting efficiency, has potential application prospect in the fields of art decoration, color display and illumination, can be applied to manufacturing light emitting devices (such as illumination devices), and is beneficial to popularization and application.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
the Ce/Dy/Mn activated color fluorescent glass comprises the following components in parts by mole: SiO 22: 40-65 parts, B2O3: 0 to 20 portions of Al2O3: 0 to 15 portions of CaF2: 10-25 parts of CaO: 0-15 parts; doping agent: 0.01-4 parts of Ce as a dopant2O3，Dy2O3Or MnO.
The preparation method of the Ce/Dy/Mn activated colored fluorescent glass comprises the following steps:
(1) CaO and MnO can be added in the form of calcium carbonate and manganese carbonate according to corresponding proportion, B2O3 is introduced through boric acid, and according to the proportion, silicon dioxide, boric acid, aluminum oxide, calcium fluoride, calcium carbonate, cerium nitrate, dysprosium oxide and manganese carbonate (one, two or three of cerium nitrate, dysprosium oxide and manganese carbonate can be respectively added according to actual requirements) are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: placing the glass batch mixture at the temperature of 1400 ℃ plus 1500 ℃ for heat preservation for 0.5-1.5 hours, and melting to obtain glass liquid;
(3) forming and annealing: pouring the glass liquid into a preheated copper mold, cooling and molding at room temperature, and then annealing at 400-550 ℃ for 1-3 hours to obtain the Ce/Dy/Mn doped colored fluorescent glass.
Preferably, the ratio of 2 to 6 in step (2)oThe temperature rise rate of C/min is up to 1400 ℃ and 1500 ℃.
Preferably, in the step (2), the melting method is as follows: from room temperature by 4oThe temperature rises to 350-450 ℃ at the temperature rising rate of C/min, and then 5 DEG CoThe temperature rise rate of C/min is increased to 1000-oC, then 3oThe temperature rise rate of C/min is up to 1400-oAnd C, melting for 0.5-1.5 hours at the temperature to obtain glass liquid. The temperature rising mode can fully decompose the raw materials, so that the obtained molten glass has better clarification and homogenization effects, and is beneficial to obtaining glass with uniform color, good luminescence performance and other characteristics, excellent structure and excellent performance.
The method for regulating and controlling the Ce/Dy/Mn doped colored fluorescent glass regulates and controls the color and the fluorescent property of the glass by changing the composition of a glass matrix or regulating the species and the concentration of a doping agent and the energy transfer among ions; or the emission spectrum, the color coordinate, the color temperature and the like of the glass are regulated and controlled by changing the excitation wavelength.
The invention adopts rare earth ion Ce3+、Dy3+Transition metal ion Mn2+Doping, wherein the dopant has the functions of a coloring agent and a luminescence center, so that the coloring and fluorescence functions of the glass are realized; the prepared glass has good mechanical property, stable chemical property and excellent optical property: the glass is uniformly colored and has high transmittance, and the glass can be realized by a simple methodThe color and the fluorescence property of the glass can be adjusted and controlled. The fluorescent glass of the present invention can be used as a glass material for lighting devices and displays.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention uses SiO2-B2O3-Al2O3-CaF2Glass of-CaO system as matrix, rare earth metal ion Ce3+And Dy3+Transition metal ion Mn2+The prepared glass is a colorant and a luminous center, has a color, and can efficiently absorb exciting light under the excitation of ultraviolet light so as to emit visible light. The Ce/Dy/Mn is introduced into the glass composition, and the glass can present a specific color by the selective absorption of Ce/Dy/Mn ions on visible light wave bands; the Ce/Dy/Mn ions can generate electronic transition under the excitation of ultraviolet wavelength to emit visible light, and the material has a wider excitation band through the energy transfer among the ions, so that the high-efficiency absorption of the excitation light can be realized. The invention can adjust and control the color and the fluorescence property of the material by changing the components of the glass matrix, changing the glass structure, and adjusting the type and the concentration of the doped ions and the energy transfer among the doped ions. In addition, the fluorescence performance of the glass can be regulated and controlled by changing the excitation wavelength. The glass provided by the invention has the characteristics that various components supplement each other, the synergistic effect is realized, so that the glass provided by the invention has different colors and different fluorescence properties, the color and the luminescence properties (emission spectrum, excitation spectrum, color coordinate, color temperature and the like) are adjustable and controllable, and the glass has the characteristics of good mechanical property, stable chemical property and good light transmittance.
2. The preparation method is simple, and the prepared glass has good mechanical property and stable chemical property, has the functions of color and fluorescence, and can be applied to the fields of LED light-emitting devices, artistic decoration, color display and the like.
Drawings
FIG. 1 is an emission spectrum of a glass prepared in example 1 under excitation of different wavelengths;
FIG. 2 is an emission spectrum of glasses prepared in examples 2 and 3 under excitation at a wavelength of 312 nm;
FIG. 3 is an infrared spectrum of glasses prepared in examples 2 and 3;
FIG. 4 is an excitation spectrum of glasses prepared in examples 4 and 5, monitored at a wavelength of 573 nm;
FIG. 5 is an emission spectrum of glasses prepared in examples 2 and 5 under excitation at a wavelength of 312 nm;
FIG. 6 is an emission spectrum of glasses prepared in examples 6 to 9 under excitation at a wavelength of 364 nm;
FIG. 7 is an emission spectrum of glasses prepared in examples 6 to 9 under excitation at a wavelength of 349 nm;
FIG. 8 is an emission spectrum of a glass prepared in example 7 under excitation of different wavelengths;
FIG. 9 is a color coordinate graph (original is color) of the glass prepared in example 7 under different wavelength excitations.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, the present invention will be further described with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1
The Ce-doped fluorescent glass provided by the embodiment comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.075 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate and 0.2412 g of cerium nitrate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in the embodiment is colorless and transparent in appearance, the glass prepared in the embodiment is subjected to a fluorescence test, an emission spectrum under the excitation of wavelengths of 312nm, 316 nm, 324 nm and 349nm is shown in fig. 1, the light emission is broadband emission, and an emission peak generates a red shift along with the increase of the excitation wavelength, which shows that the light emission color of the glass can be regulated and controlled through the change of the excitation wavelength.
Example 2
The Ce-doped fluorescent glass provided by the embodiment comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.0375 portion.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate and 0.1206g of cerium nitrate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was colorless and transparent in appearance, and the emission spectrum and infrared spectrum under excitation at a wavelength of 312nm were as shown in FIGS. 2 and 3, and the emission spectrum was broad band spectrum.
Example 3
The embodiment provides Ce-doped fluorescent glass, which comprises the following components in parts by mole: SiO 22: 55 parts of, B2O3: 15 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.0375 portion.
The preparation method of the glass comprises the following steps:
(1) accurately weighing 12.2385 g of silicon dioxide, 6.8700g of boric acid, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate and 0.1206g of cerium nitrate according to the components of the glass, and fully grinding and uniformly mixing the raw materials to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was milky white in appearance and showed emission and infrared spectra under excitation at a wavelength of 312nm as shown in FIGS. 2 and 3.
As can be seen from FIG. 2, the emission peak of the glass of this example was 365 nm. A reduction in Al in the glass composition is demonstrated in comparison with example 2 (emission peak at 357 nm)2O3Increasing SiO2In an amount to achieve a shift of the emission peak toward long wavelengths.
In the infrared spectrum of fig. 3, each absorption band corresponds to the vibration of the relevant group in the glass: absorption band 1 corresponds to [ BO3]Stretching vibration of the middle B-O; absorption band 2 corresponds to [ BO4]In which B-O and [ SiO ]4]Stretching vibration of the medium Si-O; absorption band 3 corresponds to [ AlO ]4]Bending vibration of medium Al-O; the absorption band 4 corresponds to the bending vibration of Si-O-Si. As can be seen from FIG. 3, the difference in the intensity of the absorption bands of the infrared spectra of examples 2 and 3 indicates that the change in the glass composition causes a change in the glass structure.
Comprehensive analysis shows that the change of the glass matrix composition obviously affects the luminescence spectrum and the infrared spectrum of the Ce-doped glass, thereby affecting the Ce3+The electron transition behavior of the ions further regulates and controls the luminescent property of the glass.
Example 4
This example provides a Dy-doped fluorescent glass comprising the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of Dy2O3: 0.05 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate and 0.0691g of dysprosium oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was colorless and transparent in appearance, and the excitation spectrum under monitoring at a wavelength of 573nm is shown in FIG. 4, each excitation band corresponding to Dy3+Electron transition from the ion ground state to the excited state.
Example 5
This example provides Ce/Dy ionsThe doped fluorescent glass comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.0375 part of Dy2O3: 0.05 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate, 0.1206g of cerium nitrate and 0.0691g of dysprosium oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in the embodiment is colorless and transparent in appearance, the excitation spectrum under the monitoring of the wavelength of 573nm is shown in FIG. 4, compared with the excitation spectrum of the embodiment 5 and 4, a strong wide excitation band appears near 306nm, and the fact that the excitation light of 306nm can sufficiently excite the glass of the embodiment 5 to emit fluorescence of 573nm is demonstrated; the glass of the embodiment 4 has no obvious excitation band near 306nm, which shows that the excitation light of 306nm can not effectively excite the glass of the embodiment 4 to emit fluorescence; in summary, it is described that Ce can be generated by introducing Ce3+To Dy3+Energy transfer of (2). The emission spectrum of this example under excitation at a wavelength of 312nm is shown in FIG. 5, and the emission spectrum shows Ce3+And Dy3+The transmission band of (1).
Example 6
The Ce/Dy/Mn doped fluorescent glass comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.0375 part of Dy2O30.1 part, MnO: 1 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate, 0.1206g of cerium nitrate, 0.1381g of dysprosium oxide and 0.4257g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was brown in appearance, and the emission spectra under excitation at wavelengths of 364nm and 349nm are shown in FIGS. 6 and 7, and the color coordinates and color temperature are shown in Table 1.
Example 7
The embodiment provides Ce/Dy/Mn ion doped fluorescent glass which comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.0375 part of Dy2O3: 0.05 part, MnO: and 2 parts.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate, 0.1206g of cerium nitrate, 0.0691g of dysprosium oxide and 0.8515 g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was dark brown in appearance, and the emission spectra under excitation at wavelengths of 364nm and 349nm are shown in FIGS. 6 and 7, and the color coordinates and color temperature are shown in Table 1. The emission spectra of this implementation under excitation at different wavelengths (312, 349, 364, 387, 414 nm) and the corresponding color coordinates are shown in fig. 8 and 9. The relative intensity ratios of the emission bands and the corresponding color coordinates depend on the variation of the excitation wavelength.
Example 8
The embodiment provides Ce/Dy/Mn ion doped fluorescent glass which comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.02 part of Dy2O3: 0.05 part, MnO: and 2 parts.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate, 0.0643g of cerium nitrate, 0.0691g of dysprosium oxide and 0.8515 g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was dark brown in appearance, and the emission spectra under excitation at wavelengths of 364nm and 349nm are shown in FIGS. 6 and 7, and the color coordinates and color temperature are shown in Table 1.
Example 9
The embodiment provides Ce/Dy/Mn ion doped fluorescent glass which comprises the following components in parts by mole: SiO 22: 45 parts of, B2O315 parts of Al2O3: 10 parts of CaF2: 20 parts, CaO: 10 parts of, Ce2O3: 0.02 part of Dy2O3: 0.025 parts, MnO: and 2 parts.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.0133 g of silicon dioxide, 6.8700g of boric acid, 3.7763 g of aluminum oxide, 5.7830g of calcium fluoride, 3.7070 g of calcium carbonate, 0.0643g of cerium nitrate, 0.0345g of dysprosium oxide and 0.8515 g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible from room temperature at 4oThe temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 5 DEG CoThe temperature rises to 1000 at a temperature rise rate of C/minoC, then 3oThe temperature rise rate of C/min is increased to 1460oC, melting for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment is carried out for 2 hours at 450 ℃, and glass is obtained.
The glass prepared in this example was dark brown in appearance, and the emission spectra under excitation at wavelengths of 364nm and 349nm are shown in FIGS. 6 and 7, and the color coordinates and color temperature are shown in Table 1.
TABLE 1 glass color coordinates and color temperature
Figure 344143DEST_PATH_IMAGE001
As can be seen from FIGS. 6 and 7, the emission spectra of the glasses prepared in examples 6 to 9 exhibited Ce3+，Dy3+And Mn2+The relative intensity ratio of each emission band of the emission bands of the ions can pass through Ce3+，Dy3+And Mn2+Regulating and controlling the concentration of ions; table 1 shows that the color coordinates and color temperature of each example can be adjusted by the concentration of dopant ions and the excitation wavelength, and the color coordinates of some examples are located in the white light region (example 6 is excited at a wavelength of 349 nm).
The dopant adopted by the invention has the functions of a coloring agent and a luminescence center, thereby realizing the coloring and fluorescence functions of the glass; the prepared glass has good mechanical property, stable chemical property and uniform glass coloring, and the color and the fluorescence property of the glass can be adjusted and controlled by a simple method. The fluorescent glass of the present invention can be suitably used for producing a large plate material having a size of several tens of centimeters or more at low cost by a simple operation, and exhibits sufficient color (white) fluorescence by ultraviolet irradiation. The color coordinate and the color temperature of the fluorescent glass can be adjusted by controlling the species and the concentration of the dopant, the energy transfer among the doped ions, the glass matrix and the excitation wavelength.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.

Claims (5)

1. The Ce/Dy/Mn activated colored fluorescent glass is characterized by comprising the following components in parts by mole:
SiO2: 40-65 parts, B2O3: 0 to 20 portions of Al2O3: 0 to 15 portions of CaF2: 10-25 parts of CaO: 0-15 parts; doping agent: 0.01-4 parts of Ce as a dopant2O3、Dy2O3Or MnO.
2. The method for preparing the Ce/Dy/Mn activated color fluorescent glass according to claim 1, characterized by comprising the steps of:
(1) preparing a batch: weighing the materials according to the proportion in the claim 1, fully grinding and mixing to obtain a glass batch;
(2) melting: placing the glass batch in 1400-1500 oCPreserving heat for 0.5-1.5 hours, and melting to obtain glass liquid;
(3) forming and annealing: pouring the glass liquid into a preheated copper mold, cooling and molding at room temperature, and then annealing at 400-550 ℃ for 1-3 hours to obtain Ce/Dy/Mn doped colored fluorescent glass;
the color and the fluorescence property of the glass are regulated and controlled by adjusting the components and the dosage of the dopant.
3. The method for preparing Ce/Dy/Mn activated colored fluorescent glass according to claim 2, wherein in the step (1), CaO and MnO are added in the form of calcium carbonate and manganese carbonate in corresponding proportions, and B2O3By introduction of boric acid, Ce2O3Introduced by cerium nitrate.
4. The method for preparing the Ce/Dy/Mn activated colored fluorescent glass according to claim 2, wherein the amount of Ce/Dy/Mn activated colored fluorescent glass used in the step (2) is 2-6oThe temperature rise rate of C/min is up to 1400- oC。
5. The method for preparing the Ce/Dy/Mn activated colored fluorescent glass according to claim 2, wherein the temperature rising procedure in the step (2) is as follows:
4 at room temperatureoThe temperature rise rate of C/min is up to 350- oC，
5oThe temperature rise rate of C/min is increased to 1000-oC，
3oThe temperature rise rate of C/min is increased to 1400-oC, and melting for 0.5-1.5 hours under the condition of heat preservation.
CN202111465582.7A 2021-12-03 2021-12-03 Ce/Dy/Mn doped colored fluorescent glass and preparation method thereof Pending CN113912292A (en)

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Publication number Priority date Publication date Assignee Title
CN103387338A (en) * 2013-07-23 2013-11-13 南京邮电大学 Rare-earth-doped multicolor fluorescence emission glass suitable for white light emitting diode (LED) and preparation method of glass
CN103803797A (en) * 2013-12-25 2014-05-21 齐鲁工业大学 Luminescent glass for LED (Light-Emitting Diode) and preparation method of luminescent glass
CN105236750A (en) * 2015-07-20 2016-01-13 桂林电子科技大学 Rare earth-doped white-light fluorescent phosphate glass ceramics material and preparation method thereof
CN108517210A (en) * 2018-06-07 2018-09-11 齐鲁工业大学 A kind of Ce3+,Dy3+Fluorescent powder of color controllable of doping and preparation method thereof
CN113831015A (en) * 2021-11-16 2021-12-24 山东郓城正华玻璃科技有限公司 Cu/Mn doped colored glass with luminous function, and preparation method and regulation and control method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103387338A (en) * 2013-07-23 2013-11-13 南京邮电大学 Rare-earth-doped multicolor fluorescence emission glass suitable for white light emitting diode (LED) and preparation method of glass
CN103803797A (en) * 2013-12-25 2014-05-21 齐鲁工业大学 Luminescent glass for LED (Light-Emitting Diode) and preparation method of luminescent glass
CN105236750A (en) * 2015-07-20 2016-01-13 桂林电子科技大学 Rare earth-doped white-light fluorescent phosphate glass ceramics material and preparation method thereof
CN108517210A (en) * 2018-06-07 2018-09-11 齐鲁工业大学 A kind of Ce3+,Dy3+Fluorescent powder of color controllable of doping and preparation method thereof
CN113831015A (en) * 2021-11-16 2021-12-24 山东郓城正华玻璃科技有限公司 Cu/Mn doped colored glass with luminous function, and preparation method and regulation and control method thereof

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