CN118851567B - Luminescent microcrystalline glass containing nanocrystals and core-shell structure and preparation method thereof - Google Patents
Luminescent microcrystalline glass containing nanocrystals and core-shell structure and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 62
- 239000011258 core-shell material Substances 0.000 title claims abstract description 34
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 229910001597 celsian Inorganic materials 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910016495 ErF3 Inorganic materials 0.000 claims abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910009520 YbF3 Inorganic materials 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001632 barium fluoride Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- QGJSAGBHFTXOTM-UHFFFAOYSA-K trifluoroerbium Chemical compound F[Er](F)F QGJSAGBHFTXOTM-UHFFFAOYSA-K 0.000 claims abstract 4
- 239000002241 glass-ceramic Substances 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 16
- 229910015999 BaAl Inorganic materials 0.000 claims description 14
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 11
- 230000005284 excitation Effects 0.000 abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000006121 base glass Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000000156 glass melt Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000010431 corundum Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 239000002419 bulk glass Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- -1 rare earth ion Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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
- 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
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- 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
- C03C10/16—Halogen containing crystalline phase
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
本发明公开了含有纳米晶及核壳结构的发光微晶玻璃及其制备方法，涉及稀土发光材料技术领域。本发明以特定摩尔百分含量的SiO2、Al2O3、Na2O、ErF3、YbF3和BaF2为原料组分，经熔融、成型、退火处理，得到绿色发光基础玻璃，之后对基础玻璃进行一定温度的热处理析出Ba0.625Er0.375F2.375纳米晶，进一步提高热处理温度得到含有Ba0.625Er0.375F2.375@BaAl2Si2O8核壳结构的发光微晶玻璃。本发明提供的微晶玻璃在紫外光的激发下可以表现出强烈的红色发光，作为新型发光材料可以作为红光发光材料应用于LED照明等领域。
The present invention discloses a luminescent microcrystalline glass containing nanocrystals and a core-shell structure and a preparation method thereof, and relates to the technical field of rare earth luminescent materials. The present invention uses SiO2 , Al2O3 , Na2O , ErF3 , YbF3 and BaF2 with specific molar percentage as raw material components, and obtains green luminescent basic glass through melting, molding and annealing treatment, and then heat - treats the basic glass at a certain temperature to precipitate Ba0.625Er0.375F2.375 nanocrystals, and further increases the heat treatment temperature to obtain a luminescent microcrystalline glass containing Ba0.625Er0.375F2.375@BaAl2Si2O8 core - shell structure . The microcrystalline glass provided by the present invention can show strong red luminescence under the excitation of ultraviolet light, and as a new type of luminescent material, it can be used as a red luminescent material in the fields of LED lighting.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to luminescent microcrystalline glass containing nanocrystalline and a core-shell structure and a preparation method thereof.
Background
In order to further expand the application scene and the luminous performance of the rare earth luminous material, a matrix material with good physical and chemical properties and suitable for rare earth ion doping needs to be found. The fluoride-oxygen microcrystalline glass is a composite material composed of fluoride nanocrystals and oxide glass, has the advantages of low phonon energy of the fluoride nanocrystals, good physical and chemical properties of the oxide glass and easy molding, and is an ideal rare earth ion luminescent matrix material.
The core-shell structure material is a material with a special structure formed by interconnecting a core layer material and a shell layer material through physical or chemical action. The rare earth doped core-shell structure luminescent material has unique structural characteristics, can integrate the properties of two materials, supplement the respective defects, for example, the core layer material has good luminescent performance, and the shell layer has the effects of keeping the stability of the core material, preventing the agglomeration of internal particles and controlling the interface reaction of particles, thereby expanding the application range of the rare earth doped nano material. The traditional oxyfluoride microcrystalline glass is characterized in that single fluoride nanocrystalline is separated out in a glass matrix by regulating and controlling glass components and a heat treatment process, and the microcrystalline glass with a core-shell structure needs to be further researched. Therefore, by designing special glass components and a preparation process, the fluorescent microcrystalline glass with the core-shell structure is expected to further improve the luminescent performance of rare earth ions and expand the application scene of the rare earth doped microcrystalline glass.
Disclosure of Invention
The invention aims to provide luminescent microcrystalline glass with a core-shell structure and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides green luminous glass, which comprises the following raw materials in mole percent:
SiO240~60mol%、Al2O3 10-25mol%、Na2O 5-15mol%、ErF31-5mol%、YbF3 1-5mol%、BaF215-20mol%;
the preparation method of the green luminescent glass comprises the following steps:
And mixing the raw materials, melting, shaping the obtained melt, and annealing at 450-500 ℃ to obtain the green luminescent glass.
The second technical scheme of the invention is to provide red luminescent microcrystalline glass containing Ba 0.625Er0.375F2.375 nanocrystalline, which comprises the following raw materials in mole percent:
SiO240~60mol%、Al2O3 10-25mol%、Na2O 5-15mol%、ErF31-5mol%、YbF3 1-5mol%、BaF215-20mol%;
The preparation method of the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375 nanocrystalline comprises the following steps:
Mixing and melting raw materials, forming the obtained melt, and then sequentially annealing and heat-treating to obtain the red luminescent microcrystalline glass containing Ba 0.625Er0.375F2.375 nano-crystals;
the annealing temperature is 450-500 ℃, and the heat treatment temperature is more than or equal to 580 ℃ and less than 710 ℃.
As a further preferable mode, when the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375 nanocrystalline is prepared, the melting temperature is 1400-1600 ℃, the melting time is 45-60 min, and the heat treatment time is 2-5h. More preferably, the melting further comprises a step of maintaining the temperature for 30-60 min.
The third technical scheme of the invention is to provide red luminescent microcrystalline glass containing a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure, which comprises the following raw materials in mole percent:
SiO240~60mol%、Al2O3 10-25mol%、Na2O 5-15mol%、ErF31-5mol%、YbF3 1-5mol%、BaF215-20mol%;
The preparation method of the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure comprises the following steps:
mixing and melting raw materials, forming the obtained melt, and then sequentially annealing and heat-treating to obtain the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure;
The annealing temperature is 450-500 ℃, and the heat treatment temperature is 710-750 ℃.
As a further preferable mode, when the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure is prepared, the melting temperature is 1400-1600 ℃, the melting time is 45-60 min, and the heat treatment time is 2-5h. More preferably, the melting further comprises a step of maintaining the temperature for 30-60 min.
As a further preferred aspect of the present invention, the core-shell structure uses Ba 0.625Er0.375F2.375 as a crystal nucleus and BaAl 2Si2O8 as a shell layer.
As a further preferred aspect of the present invention, ba 0.625Er0.375F2.375 is a nano-scale tetragonal phase crystal and BaAl 2Si2O8 is a micro-scale hexagonal phase crystal.
In the microcrystalline glass raw material component, na 2 O serves as a network exosome in the glass structure and is used for adjusting the glass structure and does not participate in crystallization.
The fourth technical scheme of the invention is to provide the application of the green luminescent glass as a luminescent material in the field of illumination.
The fifth technical scheme of the invention is to provide the application of the red luminescent microcrystalline glass containing Ba 0.625Er0.375F2.375 nanocrystalline as a luminescent material in the field of illumination.
The sixth technical scheme of the invention is to provide the application of the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure as a luminescent material in the field of illumination.
In the invention, the rare earth ion Er 3+ is not only the constituent element of the nanocrystalline, but also the luminescence center. In the base glass which is not subjected to heat treatment, the luminous color of Er 3+ under ultraviolet light excitation is green, ba 0.625Er0.375F2.375 nanocrystalline is separated out through heat treatment at a certain temperature, the luminous color of Er 3+ under ultraviolet light excitation is changed from green to red, hexagonal phase BaAl 2Si2O8 microcrystals are separated out by taking the Ba 0.625Er0.375F2.375 nanocrystalline as a nucleus when the heat treatment temperature is further increased, a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure is formed, and the red luminescence of Er 3+ is further enhanced.
According to the invention, the oxyfluoride silicate glass is used as base glass, and Ba 0.625Er0.375F2.375 nano-crystal or Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure crystal is separated out from the glass through constant temperature heat treatment. The core-shell structure takes tetragonal phase Ba 0.625Er0.375F2.375 as a crystal nucleus and hexagonal phase BaAl 2Si2O8 as a shell layer, tetragonal phase Ba 0.625Er0.375F2.375 is evolved from BaF 2, and Er 3+ randomly occupies three-eighths of positive ion lattice sites.
Yb 3+ is used as a sensitizer to be doped into Ba 0.625Er0.375F2.375 nanocrystalline, and due to the special crystal structure, a cross relaxation process occurs between Yb 3+ and Er 3+, so that red luminescence of Er 3+ is greatly enhanced, and the microcrystalline glass is enabled to emit red light.
The microcrystalline glass with the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure has simple preparation method, emits strong red light under ultraviolet excitation, and is a novel red luminescent material.
The invention discloses the following technical effects:
(1) Under the excitation of ultraviolet light, the red light of Er 3+ is greatly enhanced due to the special crystal structure and the cross relaxation process between rare earth ions, so that the glass ceramics sample shows strong red luminescence. The microcrystalline glass with the core-shell structure can be used as a red light luminescent material in the fields of LED illumination and the like.
(2) Compared with the traditional core-shell structure nanocrystalline, the microcrystalline glass with the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure provided by the invention has the advantages of simple preparation method, easiness in forming and capability of mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows XRD patterns of the base glass prepared in example 1 of the present invention and the glass ceramics obtained by different heat treatments.
FIG. 2 is a microscopic magnification of the surface of the glass ceramics obtained by different heat treatments according to example 1 of the present invention, wherein (a) is glass ceramics prepared by heat treatment at 640 ℃, (b) is glass ceramics prepared by heat treatment at 710 ℃, and (C) is glass ceramics prepared by heat treatment at 750 ℃.
FIG. 3 is a TEM image of the glass ceramics obtained by different heat treatments according to example 1 of the present invention, wherein (a) is glass ceramics obtained by heat treatment at 640 ℃, (b) is glass ceramics obtained by heat treatment at 710 ℃, and (C) is glass ceramics obtained by heat treatment at 750 ℃.
FIG. 4 is an emission spectrum of the base glass of example 1 and the glass ceramics obtained by different heat treatments under the excitation of 378 nm ultraviolet light.
FIG. 5 is an XRD pattern of a glass ceramic sample obtained in comparative example 1;
FIG. 6 is an emission spectrum of the base glass and glass-ceramic samples prepared in comparative example 1 under excitation of 378 nm ultraviolet light.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In the following examples of the present invention, siO 2 had a purity of 99.99%.
Example 1
The raw material components were weighed according to the mole percentages in table 1, and the total weight of the raw material components was 20g.
TABLE 1
(1) Mixing and melting raw materials, namely fully grinding all raw material components in a mortar, uniformly mixing, pouring the obtained mixture into a corundum crucible, and melting for 45min in a high-temperature falling furnace at 1500 ℃;
(2) Pouring the obtained glass melt liquid onto a room-temperature iron plate rapidly, and pressing the glass melt liquid into a block of glass by using another iron plate;
(3) Annealing, namely putting the obtained bulk glass into a muffle furnace at 500 ℃ for annealing for 2 hours, and cooling to obtain base glass;
(4) And (3) heat treatment, namely, respectively placing the obtained base glass in muffle furnaces at 640 ℃, 710 ℃ and 750 ℃ for heat treatment for 2 hours to obtain the corresponding microcrystalline glass product.
XRD of the base glass prepared in example 1 and the glass ceramics obtained by different heat treatments is shown in FIG. 1.
The base glass is of an amorphous structure, ba 0.625Er0.375F2.375 nano-crystals are precipitated in the glass after heat treatment at 640 ℃, ba 0.625Er0.375F2.375 is taken as a crystal nucleus in the glass when the heat treatment temperature is increased to 710 ℃, baAl 2Si2O8 is precipitated, and when the heat treatment temperature is 750 ℃, the grain size of BaAl 2Si2O8 reaches a micron level and is far larger than that of nano-scale Ba 0.625Er0.375F2.375, so that the XRD pattern mainly shows hexagonal phase BaAl 2Si2O8.
FIG. 2 is a microscopic magnification of the surface of the glass ceramics obtained by the different heat treatments of example 1, wherein (a) is glass ceramics prepared by the heat treatment at 640 ℃, (b) is glass ceramics prepared by the heat treatment at 710 ℃, and (C) is glass ceramics prepared by the heat treatment at 750 ℃.
Since the grain size of Ba 0.625Er0.375F2.375 precipitated at the time of heat treatment at 640 ℃ is nano-scale as shown in (a) of fig. 2, no obvious grain is seen in a microphotograph of the glass-ceramic surface, micro-scale BaAl 2Si2O8 crystals are precipitated with Ba 0.625Er0.375F2.375 nanocrystals as crystal nuclei at the time of heat treatment at 710 ℃ as shown in (b) of fig. 2, and the crystallinity of BaAl 2Si2O8 is further improved when the heat treatment temperature reaches 750 ℃ as shown in (C) of fig. 2, so that a clear grain boundary can be seen in a microphotograph of the glass-ceramic surface.
FIG. 3 is a TEM image of glass ceramics obtained by different heat treatments of example 1.
In fig. 3, (a) a TEM image of a glass ceramic prepared by heat treatment at 640 ℃ showed that the crystal lattice fringes corresponding to the crystal plane of Ba 0.625Er0.375F2.375 nanocrystalline (101) were observed, indicating that Ba 0.625Er0.375F2.375 nanocrystalline was successfully precipitated at this temperature, (b) a TEM image of a glass ceramic prepared by heat treatment at 710 ℃ showed that the crystal lattice fringes corresponding to the crystal plane of Ba 0.625Er0.375F2.375 (112) and the crystal plane of BaAl 2Si2O8 (102) were observed, indicating that BaAl 2Si2O8 crystal was successfully precipitated with Ba 0.625Er0.375F2.375 as a crystal nucleus, and (C) a TEM image of a glass ceramic prepared by heat treatment at 740 ℃ showed that only the crystal lattice fringes and crystal boundaries corresponding to the crystal planes of BaAl 2Si2O8 (104), (102) and (100) were observed, indicating that the degree of crystallinity of heat treatment of BaAl 2Si2O8 was higher at this temperature. The TEM test results are consistent with the XRD and glass-ceramic surface photomicrographs.
FIG. 4 is an emission spectrum of the base glass of example 1 and the glass ceramics obtained by different heat treatments under the excitation of 378 nm ultraviolet light.
Under the excitation of ultraviolet light, the green luminous intensity of Er 3+ in the base glass is far higher than the red light intensity, so the base glass is green. And after heat treatment, red light is greatly enhanced, and the ratio of red to green luminous intensity is further increased along with the increase of the heat treatment temperature.
Example 2
The raw material components were weighed according to the mole percentages in table 2, and the total weight of the raw material components was 20g.
TABLE 2
(1) Mixing and melting raw materials, namely fully grinding all raw material components in a mortar, uniformly mixing, pouring the obtained mixture into a corundum crucible, and melting for 50min in a high-temperature lifting furnace at 1450 ℃;
(2) Pouring the obtained glass melt liquid onto a room-temperature iron plate rapidly, and pressing the glass melt liquid into a block of glass by using another iron plate;
(3) Annealing, namely putting the obtained bulk glass into a muffle furnace at 500 ℃ for annealing for 2 hours, and cooling to obtain base glass;
(4) And (3) heat treatment, namely placing the obtained base glass in a muffle furnace at 700 ℃ for heat treatment for 5 hours to obtain the red luminescent microcrystalline glass with the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure.
Example 3
The raw material components were weighed according to the mole percentages in table 3, and the total weight of the raw material components was 20g.
TABLE 3 Table 3
(1) Mixing and melting raw materials, namely fully grinding all raw material components in a mortar, uniformly mixing, pouring the obtained mixture into a corundum crucible, and placing the corundum crucible into a high-temperature lifting furnace at 1550 ℃ to melt for 60min;
(2) Pouring the obtained glass melt liquid onto a room-temperature iron plate rapidly, and pressing the glass melt liquid into a block of glass by using another iron plate;
(3) Annealing, namely putting the obtained bulk glass into a muffle furnace at 500 ℃ for annealing for 2 hours, and cooling to obtain base glass;
(4) And (3) heat treatment, namely placing the obtained base glass in a muffle furnace at 720 ℃ for heat treatment for 4 hours to obtain the red luminescent microcrystalline glass with the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure.
Example 4
The raw material components were weighed according to the mole percentages in table 4, and the total weight of the raw material components was 20g.
TABLE 4 Table 4
(1) Mixing and melting raw materials, namely fully grinding all raw material components in a mortar, uniformly mixing, pouring the obtained mixture into a corundum crucible, and melting for 45min in a high-temperature falling furnace at 1480 ℃;
(2) Pouring the obtained glass melt liquid onto a room-temperature iron plate rapidly, and pressing the glass melt liquid into a block of glass by using another iron plate;
(3) Annealing, namely putting the obtained bulk glass into a muffle furnace at 500 ℃ for annealing for 2 hours, and cooling to obtain base glass;
(4) And (3) heat treatment, namely placing the obtained base glass in a muffle furnace at 750 ℃ for heat treatment for 3 hours to obtain the red luminescent microcrystalline glass with the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure.
Comparative example 1
The raw material components were weighed according to the mole percentages in table 5, and the total weight of the raw material components was 20g.
TABLE 5
(1) Mixing and melting raw materials, namely fully grinding all raw material components in a mortar, uniformly mixing, pouring the obtained mixture into a corundum crucible, and melting the mixture in a 1470 ℃ high-temperature falling furnace for 45min;
(2) Pouring the obtained glass melt liquid onto a room-temperature iron plate rapidly, and pressing the glass melt liquid into a block of glass by using another iron plate;
(3) Annealing, namely putting the obtained bulk glass into a muffle furnace at 500 ℃ for annealing for 2 hours, and cooling to obtain base glass;
(4) And (3) heat treatment, namely placing the obtained base glass in a muffle furnace at 640 ℃ for heat treatment for 3 hours to obtain the microcrystalline glass containing Ba 0.625Er0.375F2.37 nano crystals.
FIG. 5 shows the XRD pattern of the glass-ceramic sample obtained in comparative example 1, indicating that Ba 0.625Er0.375F2.375 nanocrystals can still be successfully precipitated from the glass matrix without the incorporation of Yb 3+. FIG. 6 shows the emission spectra of the base glass and glass-ceramic samples prepared in comparative example 1 under excitation by ultraviolet light 378 nm. In comparison with example 1, although Ba 0.625Er0.375F2.375 nanocrystals were precipitated, since Yb 3+ was not doped, there was no cross relaxation of Yb 3+ and Er 3+, resulting in a spectral red-green ratio of only 0.21 and 0.13 for the base glass and the glass ceramic samples, exhibiting green emission color.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The green luminescent glass is characterized by comprising the following raw materials in percentage by mole:
SiO2 40~60mol%、Al2O3 10-25mol%、Na2O 5-15mol%、ErF3 1-5mol%、YbF3 1-5mol%、BaF2 15-20mol%;
the preparation method of the green luminescent glass comprises the following steps:
And mixing the raw materials, melting, shaping the obtained melt, and annealing at 450-500 ℃ to obtain the green luminescent glass.
2. A red luminescent microcrystalline glass containing Ba 0.625Er0.375F2.375 nanocrystalline is characterized by comprising the following raw materials in percentage by mole:
SiO2 40~60mol%、Al2O3 10-25mol%、Na2O 5-15mol%、ErF3 1-5mol%、YbF3 1-5mol%、BaF2 15-20mol%;
The preparation method of the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375 nanocrystalline comprises the following steps:
Mixing and melting raw materials, forming the obtained melt, and then sequentially annealing and heat-treating to obtain the red luminescent microcrystalline glass containing Ba 0.625Er0.375F2.375 nano-crystals;
the annealing temperature is 450-500 ℃, and the heat treatment temperature is more than or equal to 580 ℃ and less than 710 ℃.
3. The red luminescent glass ceramic containing Ba 0.625Er0.375F2.375 nano-crystals according to claim 2, wherein the melting temperature is 1400-1600 ℃, and the heat treatment time is 2-5h.
4. A red luminescent microcrystalline glass containing a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure is characterized by comprising the following raw materials in percentage by mole:
SiO2 40~60mol%、Al2O3 10-25mol%、Na2O 5-15mol%、ErF3 1-5mol%、YbF3 1-5mol%、BaF2 15-20mol%;
The preparation method of the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure comprises the following steps:
mixing and melting raw materials, forming the obtained melt, and then sequentially annealing and heat-treating to obtain the red luminescent microcrystalline glass containing the Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure;
The annealing temperature is 450-500 ℃, and the heat treatment temperature is 710-750 ℃.
5. The red luminescent glass ceramic containing a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure according to claim 4, wherein the melting temperature is 1400-1600 deg.C, and the heat treatment time is 2-5h.
6. The red luminescent glass ceramic containing a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure according to claim 4, wherein said core-shell structure uses Ba 0.625Er0.375F2.375 as crystal nucleus and BaAl 2Si2O8 as shell layer.
7. The red luminescent glass ceramic containing a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure according to claim 6, wherein said Ba 0.625Er0.375F2.375 is a nano-scale tetragonal phase crystal and said BaAl 2Si2O8 is a micro-scale hexagonal phase crystal.
8. Use of the green luminescent glass according to claim 1 as luminescent material in the field of lighting.
9. The use of a red luminescent glass ceramic containing Ba 0.625Er0.375F2.375 nanocrystals as claimed in claim 2 as luminescent material in the field of lighting.
10. The use of a red luminescent glass ceramic containing a Ba 0.625Er0.375F2.375@BaAl2Si2O8 core-shell structure according to claim 4 as luminescent material in the field of lighting.
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| CN109437572A (en) * | 2018-12-20 | 2019-03-08 | 中国计量大学 | A kind of precipitation BaTbF5Nanocrystalline germanium silicate glass-ceramics and preparation method thereof |
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