CN110156332B - Transparent long-afterglow microcrystalline glass and preparation method thereof - Google Patents

Transparent long-afterglow microcrystalline glass and preparation method thereof Download PDF

Info

Publication number
CN110156332B
CN110156332B CN201910388917.6A CN201910388917A CN110156332B CN 110156332 B CN110156332 B CN 110156332B CN 201910388917 A CN201910388917 A CN 201910388917A CN 110156332 B CN110156332 B CN 110156332B
Authority
CN
China
Prior art keywords
glass
afterglow
long
powder
microcrystalline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910388917.6A
Other languages
Chinese (zh)
Other versions
CN110156332A (en
Inventor
余运龙
周思莹
李小燕
关翔锋
罗培辉
钟小铃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Jiangxia University
Original Assignee
Fujian Jiangxia University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Jiangxia University filed Critical Fujian Jiangxia University
Priority to CN201910388917.6A priority Critical patent/CN110156332B/en
Publication of CN110156332A publication Critical patent/CN110156332A/en
Application granted granted Critical
Publication of CN110156332B publication Critical patent/CN110156332B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides a transparent long afterglow microcrystalline glass and a preparation method thereof, and the microcrystalline glass is structurally characterized in that SrAl is embedded in an oxide glass matrix2O4Eu and Dy long afterglow microcrystal, wherein the glass component content in the microcrystal glass is P2O5+SiO2:40‑80mol％；BaO+SrO+CaO:3‑15mol％；ZnO+Al2O3+La2O3:5‑20mol％；Na2O+Li2O:5‑15mol％；B2O3+Bi2O3+Sb2O35-20 mol%; the sum of the contents of the components is 100 mol%; SrAl2O4The content of Eu and Dy microcrystals is 1-15 wt% of the oxide glass matrix. The long-afterglow microcrystalline glass has the characteristics of high transparency, stable physical and chemical properties, high afterglow brightness and long service life, and can be used as a long-afterglow material to be applied to the fields of solar batteries, building escape signs, road traffic instructions, artware and the like.

Description

Transparent long-afterglow microcrystalline glass and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of solid luminescent materials, in particular to transparent long-afterglow microcrystalline glass and a preparation method thereof.
[ background of the invention ]
The long-afterglow luminescent material is a photoluminescence material which can emit visible light under the excitation of a light source, can store part of the obtained light energy and slowly release the energy in the form of the visible light after the excitation is stopped, has important application in various fields such as night traffic emergency indication, instrument display, national defense and military (such as night maps) and the like, and is more expected to be applied to the advanced scientific and technological fields such as solar cells, life science, universe and the like.
The traditional long afterglow material is mainly powder, is used in outdoor environments of wind, sun and rain, is quick in aging and has a limited service life. The Chinese patent with application publication No. CN102765894A proposes a long-afterglow luminescent glass particle and a preparation method thereof, and the method wraps the long-afterglow powder on the surface of the transparent colorless glass particle by resin. However, organic materials are easily aged, and the long-term weather resistance thereof is still a problem. Therefore, the development of a long-afterglow luminescent material with stable physical and chemical properties, high afterglow brightness and long service life is a problem to be urgently solved in the current practical application.
The microcrystal glass is a composite material with micro/nanocrystalline embedded in an inorganic glass matrix, integrates the advantages of the crystal and the glass material, can have optical performance similar to or even better than that of the crystal, and has the advantages of simple preparation method similar to the glass material, high thermal stability and chemical stability, good weather resistance and long service life. There are two common methods for preparing microcrystalline glass: one is to prepare precursor glass and then carry out heat treatment to separate out microcrystals from the glass matrix. Chinese patent with application publication No. CN105481250A discloses colorless transparent glass ceramics with long afterglow down-conversion luminescence characteristics and a preparation method thereof, wherein germanium dioxide, gallium oxide, zinc oxide, lanthanum oxide and lithium oxide are selected as glass matrixes, manganese and ytterbium ions are co-doped, and a crystal phase is precipitated through heat treatment to obtain long afterglow performance. However, the microcrystalline glass raw material needs to use expensive reagents such as gallium oxide and germanium dioxide, a reducing atmosphere is needed in the preparation process, the production cost is high, the process is complex, and the problem of how to regulate doping active ions to enter and separate out a crystal phase in the method is difficult, so that the microcrystalline glass has great limitation in practical application.
The other method is to directly mix and fuse the micron crystal powder and the low-melting-point glass to form the glass ceramics. Chinese patent with application publication No. CN104986953A discloses a preparation method of blue-green long-afterglow luminescent glass, which adopts SrAl2O4Eu, Dy long afterglow powder and silicate glass powder are mixed and then melted to prepare the blue-green long afterglow luminescent glass. However, this method requires casting on molten tin metal to form long persistence luminescent glassThe appearance is green. However, the mixed eutectic glass ceramics adopting the silicate glass substrate have poor transparency and poor luminescence property. In 2015, Massera et al [ J Eur. Ceram. Soc.35(2015)1255]Report Sr4Al14O25:Eu2+,Dy3+The long-afterglow powder is doped into a phosphate glass matrix to obtain the long-afterglow glass, but the known phosphate glass has poor physical and chemical stability and is easy to absorb moisture, so that the practical application environment is limited.
In short, the existing long afterglow microcrystalline glass has some defects in the aspects of preparation process or performance and the like.
The invention provides transparent long-afterglow microcrystalline glass based on a new component formula and a preparation method thereof, and the obtained material has good transparency, stable physical and chemical properties, high afterglow brightness and long service life, is an excellent long-afterglow material, and can be applied to the fields of solar cells, building escape signs, road traffic instructions, artware and the like.
[ summary of the invention ]
The invention aims to solve one of the technical problems and provides transparent long-afterglow microcrystalline glass which has good transparency, stable physical and chemical properties, high afterglow brightness and long service life and is an excellent long-afterglow material.
The present invention achieves one of the above technical problems:
the structure of transparent long-afterglow microcrystal glass features that SrAl is embedded in oxide glass matrix2O4Eu and Dy microcrystal; the glass component content of the glass matrix of the microcrystalline glass is P2O5+SiO2:40-80mol％；BaO+SrO+CaO:3-15mol％；ZnO+Al2O3+La2O3:5-20mol％；Na2O+Li2O:5-15mol％；B2O3+Bi2O3+Sb2O35-20 mol%; the sum of the contents of the components is 100mol percent.
Further, SrAl in the glass ceramics2O4The content of Eu, Dy long afterglow powder is 1-15 wt% of glass matrix.
Further, SrAl in the glass ceramics2O4Eu and Dy long afterglow powder in 2-10 wt% of the glass base.
Further, SrAl in the glass ceramics2O4The content of Eu and Dy long afterglow powder is 3-8 wt% of glass matrix.
The second technical problem to be solved by the invention is to provide a preparation method of the transparent long afterglow microcrystalline glass, which has low melting temperature, simple preparation method and low cost.
The invention realizes the second technical problem in the following way:
a method for preparing transparent long-afterglow microcrystalline glass comprises a two-step melt quenching method, and comprises the following steps:
step (1) adding P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3Weighing the powder raw materials according to the component proportion, heating and preserving heat to melt the powder raw materials to obtain blocky precursor glass;
step (2) grinding the precursor glass obtained in the step (1) into powder, and adding SrAl2O4Eu and Dy long afterglow powder is further ground, heated and heat preserved to melt to obtain block microcrystal glass.
Further, the method comprises the following specific steps:
(1) will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3Weighing the powder raw materials according to the component proportion, grinding and uniformly mixing the raw materials, placing the mixture into a crucible, placing the crucible into a heating furnace, heating the mixture to the temperature of 900-1100 ℃, preserving heat for 1 hour to melt the mixture, and then taking out the glass melt and rapidly cooling the glass melt to obtain precursor glass;
(2) grinding the precursor glass obtained in the step (1) into powder, and adding SrAl2O4Eu and Dy long afterglow powder is further ground and set inside crucible, and the crucible is heated in electric furnace to 850 deg.c and maintained for 1 hr to melt, and the molten glass is taken out and fast poured into mold to form block microcrystal glass.
Further, SrAl in the glass ceramics2O4Eu and Dy long afterglow powder in 2-10 wt% of the glass base.
Further, SrAl in the glass ceramics2O4The content of Eu and Dy long afterglow powder is 3-8 wt% of glass matrix.
The invention has the following advantages:
the invention provides transparent long-afterglow microcrystalline glass based on a new component formula and a preparation method thereof, and the preparation method has the advantages of low melting temperature, simple preparation method and low cost; the obtained material has good transparency, stable physical and chemical properties, high afterglow brightness and long service life, is an excellent long afterglow material, and can be applied to the fields of solar batteries, building escape signs, road traffic instructions, artware and the like.
[ description of the drawings ]
The invention will be further described with reference to the following examples with reference to the accompanying drawings.
Fig. 1 is a graph showing a light transmittance of a crystallized glass of example 1 of the present invention.
Fig. 2 is an X-ray diffraction pattern of the crystallized glass of example 1 of the present invention.
FIG. 3 is an emission spectrum of a glass ceramics according to example 1 of the present invention.
FIG. 4 is a graph showing the decay curve of afterglow of a glass ceramic according to example 1 of the present invention.
[ detailed description ] embodiments
Referring to fig. 1-4, the invention relates to a transparent long afterglow microcrystalline glass, which is structurally characterized in that an oxide glass matrix is embedded with SrAl2O4Eu and Dy microcrystal; the glass component content of the glass matrix of the microcrystalline glass is P2O5+SiO2:40-80mol％；BaO+SrO+CaO:3-15mol％；ZnO+Al2O3+La2O3:5-20mol％；Na2O+Li2O:5-15mol％；B2O3+Bi2O3+Sb2O35-20 mol%; the sum of the contents of the components is 100mol percent.
SrAl in the microcrystalline glass2O4The content of Eu, Dy long afterglow powder is 1-15 wt% of glass matrix.
Preferably, the microcrystalline glass contains SrAl2O4Eu and Dy long afterglow powder in 2-10 wt% of the glass base.
More preferably, the microcrystalline glass contains SrAl2O4The content of Eu and Dy long afterglow powder is 3-8 wt% of glass matrix.
The invention also relates to a preparation method of the transparent long afterglow microcrystalline glass, which comprises a two-step melt quenching method, and comprises the following steps:
step (1) adding P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3Weighing the powder raw materials according to the component proportion, heating and preserving heat to melt the powder raw materials to obtain blocky precursor glass;
step (2) grinding the precursor glass obtained in the step (1) into powder, and adding SrAl2O4Eu and Dy long afterglow powder is further ground, heated and heat preserved to melt to obtain block microcrystal glass.
Preferably, the method comprises the following steps:
(1) will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3Weighing the powder raw materials according to the component proportion, grinding and uniformly mixing the raw materials, placing the mixture into a crucible, placing the crucible into a heating furnace, heating the mixture to the temperature of 900-1100 ℃, preserving heat for 1 hour to melt the mixture, and then taking out the glass melt and rapidly cooling the glass melt to obtain precursor glass;
(2) grinding the precursor glass obtained in the step (1) into powder, and adding SrAl2O4Eu and Dy long afterglow powder is further ground and set inside crucible, and the crucible is heated in electric furnace to 850 deg.c and maintained for 1 hr to melt, and the molten glass is taken out and fast poured into mold to form block microcrystal glass.
The present invention will be further described with reference to the following examples.
Example 1: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is according to 35P2O5-20SiO2-10BaO-2SrO-2CaO-8ZnO-2Al2O3-1La2O3-5Na2O-5Li2O-6B2O3-2Bi2O3-2Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 1050 ℃ in a resistance furnace and preserving the temperature for 1 hour to enable the mixture to be molten. And then, quickly pouring the glass solution into a copper mold for cooling and molding to obtain the transparent precursor glass. Then, the precursor glass was ground into a powder with 7 wt% SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 850 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass. After the illumination is stopped, the color of the liquid crystal display shows green long afterglow.
The transmittance curve in fig. 1 shows that the maximum transmittance of the microcrystalline glass reaches 61%. The X-ray diffraction data in FIG. 2 shows that SrAl is precipitated in the glass matrix2O4And (4) microcrystals. As shown in FIG. 3, the above samples were surface polished, and the emission wavelength peak of the produced glass-ceramic was measured at 525nm by FLS920 fluorescence spectrometer, the long afterglow decay curve thereof was as shown in FIG. 4, and the long afterglow time could reach 24 hours (the emission luminance decayed to the macroscopic lower limit of 0.32 mcd/m)2)。
Example 2: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is 25P2O5-25SiO2-10BaO-2SrO-3CaO-8ZnO-2Al2O3-2La2O3-6Na2O-6Li2O-7B2O3-2Bi2O3-2Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 1020 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder, and mixed with 10 wt% of SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 830 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmittance of 66% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 26 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 3: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is 30P2O5-10SiO2-5BaO-5SrO-5CaO-6ZnO-6Al2O3-8La2O3-8Na2O-5Li2O-9B2O3-1Bi2O3-2Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 900 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder, and mixed with 15 wt% of SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is set inside a resistance furnace at 700 deg.c for 1 hr, and the molten glass is taken outPouring into copper mould quickly to obtain transparent long-afterglow microcrystal glass with maximum light transmission rate of 43% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 20 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 4: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is according to 20P2O5-60SiO2-1BaO-1SrO-1CaO-3ZnO-2Al2O3-2La2O3-3Na2O-2Li2O-3B2O3-1Bi2O3-1Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 1100 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder, and mixed with 8 wt% of SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 850 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate of 51% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 18 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 5: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is 50P2O5-10SiO2-10BaO-2SrO-1CaO-8ZnO-4Al2O3-2La2O3-3Na2O-3Li2O-3B2O3-2Bi2O3-2Sb2O3(mol%) preparationAfter the ratio weighing, the raw materials are mixed evenly, poured into a crucible, heated to 1100 ℃ in a resistance furnace and kept warm for 1 hour to be melted. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder with 5 wt% SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 750 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate of 56% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 21 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 6: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is according to 35P2O5-18SiO2-8BaO-2SrO-1CaO-10ZnO-6Al2O3-4La2O3-5Na2O-3Li2O-3B2O3-2Bi2O3-2Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 1000 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass was ground into a powder with 3 wt% SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 800 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate of 48% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 16 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 7: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is 40P2O5-23SiO2-2BaO-2SrO-1CaO-3ZnO-2Al2O3-1La2O3-3Na2O-3Li2O-15B2O3-3Bi2O3-2Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 950 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass was ground into a powder with 1 wt% SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 720 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate of 31% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 16 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 8: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is 40P2O5-24SiO2-2BaO-2SrO-2CaO-3ZnO-2Al2O3-2La2O3-7Na2O-8Li2O-3B2O3-3Bi2O3-2Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 980 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder, and mixed with 10 wt% of SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 800 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate52%, it presents green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 23 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 9: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is 30P2O5-30SiO2-3BaO-3SrO-3CaO-5ZnO-5Al2O3-3La2O3-4Na2O-5Li2O-5B2O3-2Bi2O3-1Sb2O3After weighing the components according to the proportion (mol%), evenly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 950 ℃ in a resistance furnace and preserving the heat for 1 hour to melt the mixture. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder, and mixed with 11 wt% of SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 820 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate of 40% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 17 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
Example 10: will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3The powder raw material is according to 20P2O5-25SiO2-5BaO-7SrO-3CaO-6ZnO-6Al2O3-3La2O3-6Na2O-5Li2O-7B2O3-5Bi2O3-2Sb2O3Weighing the components according to the proportion (mol%), uniformly mixing the raw materials, pouring the mixture into a crucible, and heating the mixture to 970 ℃ in a resistance furnaceMelting the mixture by keeping the temperature at 1 ℃ for 1 hour. And then, quickly pouring the glass solution into a copper mold for molding to obtain the transparent precursor glass. Then, the precursor glass is ground into powder, and mixed with 11 wt% of SrAl2O4Eu and Dy long afterglow powder are mixed homogeneously, and the mixture is maintained in a resistance furnace at 820 deg.c for 1 hr, and the molten glass is taken out and poured into copper mold fast to form to obtain transparent long afterglow microcrystal glass with maximum light transmission rate of 46% and green long afterglow. The emission wavelength of the prepared microcrystalline glass is 525nm, and the long afterglow time can reach 20 hours (the luminous brightness is attenuated to the lower limit of 0.32mcd/m observed by naked eyes2)。
In conclusion, the invention can obtain the SrAl inlaid oxide glass substrate by adopting the material components and the preparation process2O4Eu and Dy microcrystalline transparent long-afterglow microcrystalline glass. Under the excitation of ultraviolet light, the microcrystalline glass can emit green light with the wavelength of about 525nm, and the long afterglow time can reach more than 24 hours. The transparent long-afterglow microcrystalline glass obtained by the invention has good transparency, stable physical and chemical properties, high afterglow brightness and long service life, is an excellent long-afterglow material, and can be applied to the fields of solar cells, building escape signs, road traffic instructions, artware and the like.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.

Claims (8)

1. A transparent long afterglow microcrystalline glass is characterized in that: the structural characteristic of the microcrystalline glass is that SrAl is embedded in an oxide glass matrix2O4Eu and Dy microcrystal; the glass component of the glass matrix of the microcrystalline glass is as follows: p2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3And Sb2O3(ii) a The glass component content of the glass matrix of the microcrystalline glass is P2O5+SiO2:40-80mol％；BaO+SrO+CaO:3-15mol％；ZnO+Al2O3+La2O3:5-20mol％；Na2O+Li2O:5-15mol％；B2O3+Bi2O3+Sb2O35-20 mol%; the sum of the contents of the components is 100mol percent.
2. The transparent long-afterglow microcrystalline glass according to claim 1, wherein: SrAl in the microcrystalline glass2O4The content of Eu, Dy long afterglow powder is 1-15 wt% of glass matrix.
3. The transparent long-afterglow microcrystalline glass according to claim 2, wherein: SrAl in the microcrystalline glass2O4Eu and Dy long afterglow powder in 2-10 wt% of the glass base.
4. The transparent long-afterglow microcrystalline glass according to claim 3, wherein: SrAl in the microcrystalline glass2O4The content of Eu and Dy long afterglow powder is 3-8 wt% of glass matrix.
5. A preparation method of transparent long afterglow microcrystalline glass is characterized in that: the glass-ceramic is based on a transparent long-afterglow glass-ceramic as claimed in claim 1 or 2; the method comprises a two-step melt quenching method, and comprises the following steps:
step (1) adding P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3Weighing the powder raw materials according to the component proportion, heating and preserving heat to melt the powder raw materials to obtain blocky precursor glass;
step (2) will stepGrinding the precursor glass obtained in the step (1) into powder, and adding SrAl2O4Eu and Dy long afterglow powder is further ground, heated and heat preserved to melt to obtain block microcrystal glass.
6. The method for preparing transparent long-afterglow microcrystalline glass according to claim 5, wherein: the method specifically comprises the following steps:
(1) will P2O5、SiO2、BaO、SrO、CaO、ZnO、Al2O3、La2O3、Na2O、Li2O、B2O3、Bi2O3、Sb2O3Weighing the powder raw materials according to the component proportion, grinding and uniformly mixing the raw materials, placing the mixture into a crucible, placing the crucible into a heating furnace, heating the mixture to the temperature of 900-1100 ℃, preserving heat for 1 hour to melt the mixture, and then taking out the glass melt and rapidly cooling the glass melt to obtain precursor glass;
(2) grinding the precursor glass obtained in the step (1) into powder, and adding SrAl2O4Eu and Dy long afterglow powder is further ground and set inside crucible, and the crucible is heated in electric furnace to 850 deg.c and maintained for 1 hr to melt, and the molten glass is taken out and fast poured into mold to form block microcrystal glass.
7. The method for preparing transparent long-afterglow microcrystalline glass according to claim 5, wherein: SrAl in the microcrystalline glass2O4Eu and Dy long afterglow powder in 2-10 wt% of the glass base.
8. The method for preparing transparent long-afterglow microcrystalline glass according to claim 5, wherein: SrAl in the microcrystalline glass2O4The content of Eu and Dy long afterglow powder is 3-8 wt% of glass matrix.
CN201910388917.6A 2019-05-10 2019-05-10 Transparent long-afterglow microcrystalline glass and preparation method thereof Active CN110156332B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910388917.6A CN110156332B (en) 2019-05-10 2019-05-10 Transparent long-afterglow microcrystalline glass and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910388917.6A CN110156332B (en) 2019-05-10 2019-05-10 Transparent long-afterglow microcrystalline glass and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110156332A CN110156332A (en) 2019-08-23
CN110156332B true CN110156332B (en) 2021-12-07

Family

ID=67634116

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910388917.6A Active CN110156332B (en) 2019-05-10 2019-05-10 Transparent long-afterglow microcrystalline glass and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110156332B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114479859B (en) * 2022-01-05 2023-08-15 浙江大学 Multicolor adjustable germanate fluorescent glass ceramic and preparation method thereof
CN115583792B (en) * 2022-09-13 2023-12-22 昆明理工大学 Coordinated luminous color-changing glass and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820660A (en) * 1986-12-26 1989-04-11 Central Glass Company, Limited Light transmitting calcium phosphate glass-ceramics
JP2002053343A (en) * 2000-06-28 2002-02-19 Ivoclar Vivadent Ag Low-temperature sinterable apatite glass ceramic
CN1546405A (en) * 2003-12-16 2004-11-17 中国科学院长春应用化学研究所 Process for preparing rare-earth green long-lasting luminescent glass
CN103183473A (en) * 2013-04-10 2013-07-03 中国科学院福建物质结构研究所 Ce:YAG microcrystalline glass used for white light LED and preparation method of Ce:YAG microcrystalline glass
CN104986953A (en) * 2015-05-22 2015-10-21 杭州电子科技大学 Preparation method of blue-green long-afterglow luminescent glass
CN107129154A (en) * 2017-07-02 2017-09-05 桂林电子科技大学 Transparent glass ceramics material and preparation method for fluorescence temperature probe

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820660A (en) * 1986-12-26 1989-04-11 Central Glass Company, Limited Light transmitting calcium phosphate glass-ceramics
JP2002053343A (en) * 2000-06-28 2002-02-19 Ivoclar Vivadent Ag Low-temperature sinterable apatite glass ceramic
CN1546405A (en) * 2003-12-16 2004-11-17 中国科学院长春应用化学研究所 Process for preparing rare-earth green long-lasting luminescent glass
CN103183473A (en) * 2013-04-10 2013-07-03 中国科学院福建物质结构研究所 Ce:YAG microcrystalline glass used for white light LED and preparation method of Ce:YAG microcrystalline glass
CN104986953A (en) * 2015-05-22 2015-10-21 杭州电子科技大学 Preparation method of blue-green long-afterglow luminescent glass
CN107129154A (en) * 2017-07-02 2017-09-05 桂林电子科技大学 Transparent glass ceramics material and preparation method for fluorescence temperature probe

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘鸣等.基于两种载体合成发光玻璃的实验研究.《沈阳建筑大学学报》.2007,第23卷(第4期),615-619页. *
基于两种载体合成发光玻璃的实验研究;刘鸣等;《沈阳建筑大学学报》;20070731;第23卷(第4期);第615-619页 *

Also Published As

Publication number Publication date
CN110156332A (en) 2019-08-23

Similar Documents

Publication Publication Date Title
CN110194593B (en) Method for promoting crystallization of all-inorganic perovskite quantum dots in glass by adding fluoride
CN103183473A (en) Ce:YAG microcrystalline glass used for white light LED and preparation method of Ce:YAG microcrystalline glass
JP5696965B2 (en) Rare earth ion doped silicate luminescent glass and its preparation method
CN102121591B (en) White LED light source and manufacturing method of phosphor thereof
CN102730975B (en) Glass-ceramic and preparation method thereof
CN104193346A (en) Semitransparent fluorescent powder/glass composite luminescent ceramic wafer and preparation method thereof
CN109592907B (en) Boron bismuthate glass-based Ce: YAG glass ceramic for white light LED and preparation method thereof
CN106587641A (en) Low-melting-point glass powder and laser-illumination glass ceramic made from low-melting-point glass powder
CN102674693A (en) Full-color emission glass phosphor and preparation method thereof
CN104529166A (en) Ce: YAG microcrystalline glass and application thereof in white-light LED
CN110156332B (en) Transparent long-afterglow microcrystalline glass and preparation method thereof
CN101381204A (en) CaO-MgO-SiO2 series fluorescent glass-ceramics and preparation method thereof
CN101723593A (en) Luminous glass ceramic used for LED white-light illumination and preparation method thereof
CN101209898A (en) Erbium-doped barium-yttrium-fluoride-nanocrystalline containing transparent oxyfluoride glass ceramic and preparation thereof
Liu et al. Crystallization behavior and enhanced fluorescence properties of Yb3+/Ho3+/Tb3+ co-doped transparent glass-ceramics containing oxyapatite-type Na3YSi2O7 crystals
CN104986953A (en) Preparation method of blue-green long-afterglow luminescent glass
CN113620599A (en) Novel long-afterglow luminescent glass-ceramic and preparation method thereof
CN110117160B (en) Microcrystalline glass and preparation method and application thereof
CN102849953A (en) Luminescent glass ceramic doped with multiple rare earth ions and capable of up and down-conversion to ultraviolet light and preparation method thereof
WO2014166085A1 (en) Ce:yag microcrystalline glass for white light led and preparation method therefor
CN107827354B (en) Red fluorescent glass and preparation method and application thereof
CN108409148B (en) Infrared incoherent LED excited upconversion NaLuF4Glass-ceramic and method for producing the same
CN102503139B (en) A kind of up-conversion luminous transparent glass ceramic and preparation method thereof
CN105819696A (en) Low temperature glass-phosphor composite material and preparation method thereof
CN109437590A (en) A kind of preparation method of the glass fluorescent plate for warm white LED

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant