CN107686243B - Preparation method of low-melting-point fluorescent glass - Google Patents
Preparation method of low-melting-point fluorescent glass Download PDFInfo
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- CN107686243B CN107686243B CN201710648484.4A CN201710648484A CN107686243B CN 107686243 B CN107686243 B CN 107686243B CN 201710648484 A CN201710648484 A CN 201710648484A CN 107686243 B CN107686243 B CN 107686243B
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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
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
Abstract
The invention discloses a preparation method of low-melting-point fluorescent glass, belongs to the field of glass material preparation, and is characterized in that (NaPO) is provided through the optimized design of glass components3)6‑NaF‑CaO‑B2O3‑Sb2O3‑Li2An O-ZnO low-melting-point glass system, and provides the following specific preparation steps: (1) preparing low-melting-point raw glass; (2) then mixing commercial yellow fluorescent powder with an yttrium aluminum garnet structure and the low-melting-point glass powder, placing the mixture into an alumina crucible, and firing and forming. The fluorescent glass component provided by the invention has the advantages of low cost, simple and rapid operation process, good heat resistance, excellent machining performance, low production energy consumption and excellent chemical stability, provides a solution for solving the problems of light decay, color temperature drift and the like of a high-power LED device, and is expected to break through the limitation brought by the traditional fluorescent powder.
Description
Technical Field
The invention belongs to the technical field of glass material preparation, and particularly relates to a preparation method of low-melting-point fluorescent glass.
Background
With the continuous research and development of white light LEDs, the luminous efficiency and the optical performance of the white light LEDs are continuously improved, so that the white light LEDs become a novel all-solid-state illumination light source. At present, most of white light LEDs are mainly coated on LED chips by traditional fluorescent powder such as commercial yellow fluorescent powder with an yttrium aluminum garnet structure (Ce: YAG) and silica gel or epoxy resin, but after long-time use, the silica gel is aged, the luminous intensity of the fluorescent powder is attenuated, and the fluorescent powder shows light color deviation and poor color, so that the service life of LED devices is influenced. At present, fluorescent glass is formed by combining fluorescent powder and glass, and is the best choice for solving the problem of traditional LED packaging. Compared with the existing epoxy resin encapsulated LED, the fluorescent glass has the following unique advantages: (1) the aging of the package is inhibited, and the service life is prolonged; (2) the heat resistance and the water resistance are improved; (3) the high-power LED can be prepared, high current is supported, and high brightness is realized. Therefore, the fluorescent glass provides the direction of future lighting sources for human beings, and the research and development of the fluorescent glass material are used for solving the problem of high-power LED device lightThe problems of decay, color temperature drift and the like provide a novel solution, and the novel solution is expected to break through the limitation brought by the traditional fluorescent powder. However, the research of fluorescent glass also faces a series of problems, one of which is the problem of over-high temperature of the fired glass, and the other is the problem of reaction between the commercial yttrium aluminum garnet structure yellow phosphor (Ce: YAG) and the glass matrix. The current solution to these two problems is primarily to find a low melting glass component that is inert. Therefore, the reaction between the commercial yellow fluorescent powder with the yttrium aluminum garnet structure and the glass matrix can be effectively prevented, and the temperature for firing the fluorescent glass can be greatly reduced, so that the energy can be better saved. Up to now, low melting point glasses have been concentrated on TeO2Glass System research (Lin, Z., et al., A chromaticity-tunable gate-in-glass color converter application in w-LED. Journal of the European Ceramic Society, 2016.36 (7): p.1723-1729.; Lin, Z., et al., high thermal-stable wall w-LED-bonded on Ce: YAG pinned with arm phosphor layer. Journal of Alloys and Compounds, 2015.649: p.661.), but TeO2The cost of the fluorescent glass is too high to realize commercialization, however, the firing temperature of other glass systems is higher, which is not in accordance with the low-carbon life advocated by the modern times, so that the development of a fluorescent glass preparation method which can reduce the firing temperature of the fluorescent glass and the production cost is required.
Disclosure of Invention
The invention aims to provide a low-melting-point fluorescent glass component for a white light LED and a method for preparing the fluorescent glass through a reasonable heat treatment process.
The specific technical scheme of the invention comprises the following steps:
(1) firstly sintering a raw glass block body through a muffle furnace according to the component ratio of a low-melting-point glass raw material, and crushing the raw glass block body into raw glass powder, wherein the low-melting-point glass raw material is (NaPO)3)6-NaF-CaO-B2O3-Sb2O3-Li2O-ZnO; (2) then mixing the yellow fluorescent powder (Ce: YAG) with the commercial yttrium aluminum garnet structure with the low-melting-point raw glass powder and then placing the mixture into an alumina crucible; (3) then placing the glass into a muffle furnace for burning fluorescent glass, taking out the glass at 730 ℃, and pouring the glass into a copper mold for molding; (4) then keeping the temperature of the mould in an oven at 200-400 ℃ for 2-4 h; (5) and finally, turning off a power supply of the oven, cooling to room temperature, and taking out the mold to obtain the fluorescent glass with the low melting point.
In the raw material components of the low-melting-point glass, the feeding mole fraction ratios of sodium hexametaphosphate, sodium fluoride, calcium oxide, boron trioxide, antimony trioxide, lithium oxide and zinc oxide are respectively as follows: 10% -20%; 30% -45%; 0 to 10 percent; 35% -50%; 0 to 10 percent; 0 to 10 percent; 0 to 10 percent.
The mass of the added commercial yttrium aluminum garnet structure yellow fluorescent powder (Ce: YAG) is 1wt% -5wt% of the total mass fraction of the glass components.
The firing process of the raw glass is to control the temperature rise time, the temperature rise time from room temperature to 200 ℃ is 20min-40min, the temperature is preserved for 20min-30min at 200 ℃, then 100min-160min is used for reaching 750 ℃ and the temperature is preserved for 30-60min, and finally the raw glass is taken out at the high temperature of 750 ℃ and poured into a copper mold for quick cooling to form a raw glass block.
The glass powder is mixed with commercial yttrium aluminum garnet structure yellow fluorescent powder (Ce: YAG) and fully ground for 30-40min to form mixed powder.
The firing process of the fluorescent glass comprises the steps of heating from room temperature to 200 ℃ for 20-40 min, keeping the temperature at 200 ℃ for 20-30 min, and keeping the temperature at 730 ℃ for 5-30 min after 60-150 min.
The invention has the technical effects and advantages that:
the preparation method of the fluorescent glass provided by the invention provides a new low-melting-point glass system, prepares transparent low-melting-point raw glass, mixes ground glass powder with yellow fluorescent powder and then burns the mixture into the fluorescent glass, controls the chemical reaction between commercial yttrium aluminum garnet structure yellow fluorescent powder (Ce: YAG) and a glass substrate, ensures the chemical stability of yellow fluorescent powder particles in the glass substrate, and provides a solution for solving the problems of light decay, color temperature drift and the like of a high-power LED device. The components of the fired raw glass are inert at high temperature, do not react with yellow fluorescent powder (Ce: YAG) particles with an yttrium aluminum garnet structure, and the fluorescent powder particles entering a glass matrix still keep integrity without influencing the luminous performance.
The method of the invention prepares the low-melting-point fluorescent glass with excellent performance, the firing temperature of the method is 730-750 ℃, and the production energy consumption of the whole process is low. With the raw material component TeO2Compared with a glass system, the raw material components for preparing the raw glass have low cost, and the raw material price of each component of the glass is relative to that of TeO in terms of the price of each raw material component2The price of the raw materials of the glass system is reduced by 54%, the preparation process is simple and easy to operate, the heat resistance and water resistance of the fluorescent glass are good, the production energy consumption in the whole process is low, and the fluorescent glass is suitable for popularization and application.
Drawings
FIG. 1 is a graph showing the transmittance of the base glass prepared according to the present invention.
FIG. 2 is a comparison graph of X-ray diffraction patterns of the yellow phosphor powder with the structure of the fluorescent glass prepared by the invention and the commercial yttrium aluminum garnet and the raw glass.
FIG. 3 is an excitation spectrum of the fluorescent glass prepared by the present invention.
FIG. 4 is an emission spectrum of the fluorescent glass prepared by the present invention.
FIG. 5 is a SEM image of the fluorescent glass of the present invention.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
(1) Preparing low-melting-point raw glass:
the low-melting glass component (14%) was weighed with a tray balance (NaPO)3)6-44%NaF-3%CaO-35%B2O3-2%Sb2O3-2%Li2O (all are mole fractions), then putting the weighed components into a mortar for grinding uniformly for 30min, after grinding, putting the ground glass into a cleaned alumina crucible, placing the alumina crucible into a muffle furnace for sintering, wherein the temperature rise time from room temperature to 200 ℃ is 30min in the sintering process, the temperature is kept for 20min at 200 ℃, then the temperature is kept for 30min after the temperature reaches 750 ℃ in 130min, finally the glass is taken out at the high temperature of 750 ℃ and poured into a mold for fast cooling to form an original glass block, and then the low-melting-point glass can be obtained.
(2) Preparing fluorescent glass:
the fired low-melting-point raw glass is crushed into required glass powder, and the glass powder is uniformly ground with 0.4g of yellow fluorescent powder (Ce: YAG) with a commercial yttrium aluminum garnet structure by a mortar, and the ground glass is dried for standby after 30 min. And (2) putting the well-mixed powder into a cleaned alumina crucible, placing the alumina crucible into a muffle furnace for sintering, wherein the preparation process comprises the steps of heating the powder from room temperature to 200 ℃ for 40min, preserving heat at 200 ℃ for 30min, preserving heat at 730 ℃ for 20min after 120min, pouring the fluorescent glass into a copper mold at 730 ℃ for molding, then preserving heat of the copper mold containing the fluorescent glass in an oven for 3h at 300 ℃, finally closing the power supply of the oven, cooling to room temperature, and taking out the mold to obtain the fluorescent glass.
Example 2
(1) Preparing low-melting-point raw glass:
weighing 11% of the Low melting glass component (NaPO) with a tray balance3)6-35%NaF-6%CaO-37%B2O3-3%Sb2O3-2%Li2And (2) adding the weighed components into a mortar to grind uniformly for 40min, putting the ground components into a cleaned alumina crucible, placing the alumina crucible into a muffle furnace to sinter, wherein the temperature rise time from room temperature to 200 ℃ is 30min, keeping the temperature at 200 ℃ for 10min, then keeping the temperature at 750 ℃ for 120min and keeping the temperature for 30min, and finally taking out the components at 750 ℃ and pouring the components into a mold to quickly cool the components to form an original glass block, thus obtaining the low-melting-point glass.
(2) Preparing fluorescent glass:
the fired low-melting-point raw glass is crushed into required glass powder, and the glass powder is uniformly ground with 0.3g of yellow fluorescent powder (Ce: YAG) with a commercial yttrium aluminum garnet structure by a mortar, and the ground glass is dried for standby after 40 min. And (2) putting the well-mixed powder into a cleaned alumina crucible, placing the alumina crucible into a muffle furnace for sintering, wherein the preparation process comprises the steps of heating the powder from room temperature to 200 ℃ for 30min, preserving heat at 200 ℃ for 20min, preserving heat at 730 ℃ for 10min after 80min, pouring the fluorescent glass into a copper mold at 730 ℃ for molding, then preserving heat of the copper mold containing the fluorescent glass in an oven at 250 ℃ for 3h, finally closing the power supply of the oven, cooling to room temperature, and taking out the mold to obtain the fluorescent glass.
Example 3
(1) Preparing low-melting-point raw glass:
weighing 15% of the low melting glass component (NaPO) with a tray balance3)6-38%NaF-4%CaO-35%B2O3-3%Sb2O3-2%Li2And (2) adding the weighed components into a mortar to grind uniformly for 35min, putting the ground components into a cleaned alumina crucible, placing the alumina crucible into a muffle furnace to sinter, wherein the temperature rise time from room temperature to 200 ℃ is 35min, keeping the temperature at 200 ℃ for 15min, then keeping the temperature at 750 ℃ for 140min to 20min, and finally taking out the components at 750 ℃ and pouring the components into a mold to be rapidly cooled to form an original glass block, thus obtaining the low-melting-point glass.
(2) Preparing fluorescent glass:
the fired low-melting-point raw glass is crushed into required glass powder, and the glass powder is uniformly ground with 0.2g of yellow fluorescent powder (Ce: YAG) with a commercial yttrium aluminum garnet structure by a mortar, and the ground glass is dried for standby after 35 min. And (2) putting the well-mixed powder into a cleaned alumina crucible, placing the alumina crucible into a muffle furnace for sintering, wherein the preparation process comprises the steps of heating the powder from room temperature to 200 ℃ for 35min, preserving heat at 200 ℃ for 15min, preserving heat at 730 ℃ for 15min after 120min, pouring the fluorescent glass into a copper mold at 730 ℃ for molding, then preserving heat of the copper mold containing the fluorescent glass in an oven for 3h at 300 ℃, finally closing the power supply of the oven, cooling to room temperature, and taking out the mold to obtain the fluorescent glass.
The optical base glass obtained in example 1 was excellent in transparency, and as can be seen from the transmittance curve in FIG. 1, its transmittance was as high as 84%. The obtained fluorescent glass can excite the Ce: the YAG grains produce yellow light and interact with blue light to form white light, and thus can be made into LED devices. In the X-ray diffraction pattern of fig. 2, the diffraction peaks appear as characteristic peaks of the YAG phase and are well matched to the YAG standard, PDF card, indicating Ce: YAG phosphor has been incorporated into the glass matrix. Ce is expressed from 345nm3+4f-5d of1Excited transition of energy level, Ce is shown at 467nm3+4f-5d of2Excited transition of energy levels (as shown in figure 3). Showing Ce at 551nm3+As shown in fig. 4. From the SEM image (fig. 5) of the scanning electron microscope, Ce: YAG phosphor is distributed in the glass matrix and Ce: the YAG particles are complete in the glass matrix and do not react with the glass component matrix, so that the Ce: YAG particles are chemically stable, and the luminous intensity is basically unchanged.
Claims (5)
1. The preparation method of the low-melting-point fluorescent glass is characterized by comprising the following specific preparation steps: (1) firstly sintering a raw glass block body through a muffle furnace according to the component ratio of a low-melting-point glass raw material, and crushing the raw glass block body into raw glass powder, wherein the low-melting-point glass raw material is (NaPO)3)6-NaF-CaO-B2O3-Sb2O3-Li2O-ZnO, wherein the mole fraction ratios of sodium hexametaphosphate, sodium fluoride, calcium oxide, diboron trioxide, antimony trioxide, lithium oxide and zinc oxide are respectively as follows: 10% -20%; 30% -45%; 0 to 10 percent; 35% -50%; 0 to 10 percent; 0 to 10 percent; 0 to 10 percent; (2) then mixing the yellow fluorescent powder with a commercial yttrium aluminum garnet structure with the low-melting-point raw glass powder and placing the mixture into an alumina crucible; (3) then placing the glass into a muffle furnace for burning fluorescent glass, taking out the glass at 730 ℃, and pouring the glass into a copper mold for molding; (4) then keeping the temperature of the mould in an oven at 200-400 ℃ for 2-4 h; (5) finally, the drying oven is closedAnd the box power supply is cooled to room temperature, and then the mold is taken out to obtain the fluorescent glass with low melting point.
2. The method for preparing low-melting-point fluorescent glass according to claim 1, wherein the mass of the added commercial yttrium aluminum garnet structure yellow fluorescent powder is 1-5 wt% of the total mass of the glass components.
3. The method for preparing fluorescent glass with low melting point according to claim 1, wherein the firing process of the raw glass is to control the heating time, the heating time from room temperature to 200 ℃ is 20min-40min, the temperature is maintained at 200 ℃ for 20min-30min, then 100min-160min is used to reach 750 ℃ and the temperature is maintained for 30-60min, and finally the raw glass is taken out at 750 ℃ and poured into a copper mold for fast cooling to form a raw glass block.
4. The method for preparing a low melting point fluorescent glass according to claim 1 or 2, wherein the mixing of the glass powder and the commercial yttrium aluminum garnet structure yellow fluorescent powder is fully ground for 30-40min to form a mixed powder.
5. The method for preparing a low melting point fluorescent glass according to claim 1, wherein the heating time for the fluorescent glass to be fired is 20min to 40min from room temperature to 200 ℃, the temperature is maintained at 200 ℃ for 20min to 30min, and the temperature is maintained at 730 ℃ for 5min to 30min after 60min to 150 min.
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| JPS5043112A (en) * | 1973-08-22 | 1975-04-18 | ||
| CN102464450A (en) * | 2011-07-01 | 2012-05-23 | 华东理工大学 | Green and energy-saving fluorescent powder/glass compound luminous material and preparation method thereof |
| CN102745893A (en) * | 2012-06-20 | 2012-10-24 | 武汉理工大学 | Composite phosphor luminescent glass and preparation method for same |
| CN103043908A (en) * | 2013-01-11 | 2013-04-17 | 华南师范大学 | Novel fluorescent glass and preparation method thereof |
| CN103539359A (en) * | 2013-09-27 | 2014-01-29 | 南京邮电大学 | Rare earth doped fluoride micro-nano crystal-fluorophosphate glass composite material and preparation method thereof |
| CN106587641A (en) * | 2016-12-01 | 2017-04-26 | 天津理工大学 | Low-melting-point glass powder and laser-illumination glass ceramic made from low-melting-point glass powder |
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- 2017-08-01 CN CN201710648484.4A patent/CN107686243B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5043112A (en) * | 1973-08-22 | 1975-04-18 | ||
| CN102464450A (en) * | 2011-07-01 | 2012-05-23 | 华东理工大学 | Green and energy-saving fluorescent powder/glass compound luminous material and preparation method thereof |
| CN102745893A (en) * | 2012-06-20 | 2012-10-24 | 武汉理工大学 | Composite phosphor luminescent glass and preparation method for same |
| CN103043908A (en) * | 2013-01-11 | 2013-04-17 | 华南师范大学 | Novel fluorescent glass and preparation method thereof |
| CN103539359A (en) * | 2013-09-27 | 2014-01-29 | 南京邮电大学 | Rare earth doped fluoride micro-nano crystal-fluorophosphate glass composite material and preparation method thereof |
| CN106587641A (en) * | 2016-12-01 | 2017-04-26 | 天津理工大学 | Low-melting-point glass powder and laser-illumination glass ceramic made from low-melting-point glass powder |
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