CN115231824B - Rare earth element Tm doped fluoborate luminescent glass and preparation method thereof - Google Patents
Rare earth element Tm doped fluoborate luminescent glass and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 115
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 229910004261 CaF 2 Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 17
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 230000008646 thermal stress Effects 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 12
- 230000005855 radiation Effects 0.000 abstract description 11
- 238000005266 casting Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000891 luminescent agent Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000007578 melt-quenching technique Methods 0.000 description 5
- -1 rare earth ions Chemical class 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000335574 Narayana Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- MMNGZONHBQOVCH-UHFFFAOYSA-N [Bi].B(F)(F)F Chemical compound [Bi].B(F)(F)F MMNGZONHBQOVCH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YISOXLVRWFDIKD-UHFFFAOYSA-N bismuth;borate Chemical compound [Bi+3].[O-]B([O-])[O-] YISOXLVRWFDIKD-UHFFFAOYSA-N 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005383 fluoride glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to the technical field of luminescent material preparation, and discloses a rare earth element Tm doped fluoborate luminescent glass and a preparation method thereof, wherein the luminescent glass is prepared from CaF as a raw material 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、BaCO 3 Composition of CaF 2 5‑15％，ZnO 5‑15％，H 3 BO 3 5‑60％，Li 2 CO 3 5‑15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.05-2%. Accurately weighing the raw materials according to a certain stoichiometric ratio, grinding and mixing, heating to 1000-1200 ℃ at 2-10 ℃/min, and preserving heat for 1-5 hours to enable the raw materials to be fully melted; casting the melt onto a copper template at 400-500 ℃ to solidify into glass, and maintaining the temperature for 2-12 hours to sufficiently remove thermal stress; and then cooled to room temperature at 1-5 deg.c/min. The invention relates to a fluoborate luminescent glass which takes fluoborate as a matrix and rare earth element Tm as a luminescent agent, and the optical performance of the fluoborate luminescent glass is adjusted by the proportion of raw materials. The fluoborate luminescent glass prepared by the technical scheme can be used for preparing solid blue laser and transparent radiation shielding devices.
Description
Technical Field
The invention relates to a luminescent material and a preparation method thereof, in particular to a fluoborate luminescent glass doped with a rare earth element Tm and a preparation method thereof.
Background
Borate oxide glass is a matrix very suitable for doping rare earth ions, and can obtain effective luminescence in electromagnetic spectrum; in rare earth ions, tm element has stronger luminescence at 453nm, corresponding to 1 D 2 → 3 F 4 A transition; the Tm ion doped glass also has strong luminescence at 1528nm in the near infrared band.
Harmful radiation (gamma and x-rays) exists in the places such as cancer treatment centers, nuclear power stations, medical examination centers and some research laboratories, and human beings are often exposed to the harmful radiation to damage human organs and even harm human lives, so that it is necessary to shield the radiation to protect the health and safety of human beings.
At present, a Chinese patent with publication number of CN100344565C discloses a kind ofYtterbium-doped bismuth borate glass has a melt quenching time as long as 13 hours, and also requires stirring rods made of platinum to continuously stir the melt at a rate of 30 revolutions per minute, and the preparation process is complicated because the wide application thereof is limited. The Tm doped alkaline bismuth boron fluoride glass up-conversion luminescent material published by Chinese patent with publication number CN104059650A can be used as a blue light luminescent material, but the melt quenching temperature is 1200 ℃, and the casting temperature of a model is up to 700 ℃, so that the industrial technical economy is lower, and the application and development of the material are not facilitated. The Chinese patent publication No. CN106497558B discloses a borate-based rare earth ion doped visible-ultraviolet up-conversion luminescent material which generates ultraviolet light for sterilization under the irradiation of sunlight, but two or more doping ions are needed, and the temperature needed for preparing a completely molten glass mixture is 1200 ℃, so that the technical economy is poor. Rare earth ion doped YCl of Chinese patent with publication number CN105314871A 3 The microcrystalline glass has higher blue-violet light transmittance and high up-conversion efficiency, and can be used for preparing up-conversion lasers, but the preparation process is complicated.
Bashter et al prepared concrete materials for radiation resistance, while concrete had opacity, thus limiting its application and development (Bashter: ann. Nucl. Energy,1997, 24:1389-1401; DOI: info: DOI/10.1016/S0306-4549 (97) 00003-0). The Shalma et al prepares Tm ion doped ZnPbWTE glass, and 1mol percent of Tm ion doping is most suitable for manufacturing deep red emission photoelectronic devices and lasers, but the system is added with PbO, so that the system does not accord with the green environmental protection concept. (Shalma R: J.non-Cryst. Solids,2019, 516:82-88; DOI: 10.1016/j.jnoncrysol.2019.04.032). Tellurate glass prepared by Venkatelwarlu et al, found that 0.5mol% of Tm ion doped glass was most suitable for bright visible red emission and near infrared lasers at 650 and 800nm, respectively, but the system added PbF 2 The method also does not accord with the green environmental protection concept, so the application is limited. (Venkateswarlu M.: J.Lumin,2016, 175:225-231; DOI: 10.1016/j.jlumin.2016.03.006). Tm-doped multicomponent borosilicate glass prepared by Lakshm Narayana et al has optical absorption and radiation resistance properties, but has various components and is quenchedThe temperature requirement is high and reaches 1400 ℃, so the technical economy is lower in the preparation process. (Lakshminarayana G: appl. Phys. A,2018, 378:124-139; DOI:10.1007/s 00339-018-1801-4). Therefore, the luminescent glass with blue emission and radiation resistance has few reports, so the luminescent glass has wide application prospect in solid blue laser and radiation shielding devices.
The invention provides a rare earth element Tm doped fluoborate luminescent glass and a preparation method thereof. Compared with the prior art or products, the invention has stable physical and chemical properties, blue light emitting and ray shielding functions and higher light emitting efficiency; the preparation process is simple and has high technical economy.
Disclosure of Invention
The invention aims to provide the fluoborate luminescent glass doped with the rare earth element Tm and the preparation method thereof, so as to overcome the defects of the prior art, and the glass prepared by the method has the advantages of improved thermal stress and luminous efficiency, simple preparation method and easy realization of industrialization.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a kind of rare earth element Tm doped fluoborate luminescent glass and its preparation method, which is characterized in that: the raw material of the luminescent glass is CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.05-2%.
A kind of rare earth element Tm doped fluoborate luminescent glass and its preparation method, including the following steps:
(1) Raw material weight: weighing glass raw materials and rare earth oxide respectively, wherein the glass raw materials are prepared from CaF 2 、ZnO、H 3 BO 3 、 Li 2 CO 3 、BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.05-2%.
(2) Preparing a glass premix: accurately weighing according to the stoichiometric ratio of a target product, and then grinding in an agate mortar to uniformly mix the target product;
(3) Preparing a completely molten glass frit: pouring the glass premix into a pre-cleaned alumina crucible, placing the crucible in a muffle furnace, heating to 1000-1200 ℃ at the speed of 2-10 ℃/min, and preserving the heat for 1-5 hours to enable the raw materials to be completely melted;
(4) Preparing luminescent glass: pouring the melt onto a copper template at 400-500 ℃ to solidify into glass, maintaining the temperature for 2-12 hours to eliminate thermal stress, and then cooling to room temperature at 1-5 ℃ per minute to obtain the luminescent glass.
The invention relates to a glass doped with Tm of rare earth element, li 2 CO 3 Is added to make sp 2 Plane BO 3 Conversion of units to sp 3 Tetrahedral BO 4 Units, thereby potentially generating more non-bridging oxygen while increasing glass transition temperature, refractive index, rare earth ion solubility, and glass density; znO can increase the strength, mechanical strength and thermal stability of the glass. BaCO 3 The addition of (2) can improve the gamma-ray attenuation performance, and the addition of fluoride can reduce non-radiative emission to the greatest extent. The method for preparing the rare earth element Tm doped fluoborate glass by adopting the melt quenching method has the advantages of quick reaction and high efficiency, belongs to a safe and effective glass preparation method, and can reduce the preparation cost while ensuring the quality of the glass.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention uses fluoborate as glass matrix, uses rare earth element Tm as luminescent agent, adopts melt quenching method to prepare fluoborate luminescent glass doped with rare earth element Tm, and improves the thermal stress and luminous efficiency of the glass by adjusting the types and concentration of glass raw materials. The melt quenching method adopted by the invention has simple preparation process and low cost, and is easy to realize industrialization; the prepared fluoborate glass has stable physical and chemical properties, blue emission and radiation shielding functions and high luminous efficiency, and can be applied to manufacturing solid blue laser and transparent radiation shielding devices.
Detailed Description
A rare earth element Tm doped fluoborate luminescent glass and a preparation method thereof, wherein the raw material of the rare earth element Tm doped fluoborate luminescent glass is CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％， H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.05-2%.
A kind of rare earth element Tm doped fluoborate luminescent glass and its preparation method, including the following steps:
the raw material of the luminescent glass is CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、BaCO 3 Composition of CaF 2 5-15％， ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the preparation method of the luminescent glass comprises the steps of weighing raw materials, ball milling and mixing, high-temperature melting of the raw materials, casting of a model and thermal insulation annealing.
The invention is described in further detail below with reference to examples:
example 1
The preparation method of the fluoborate luminescent glass doped with the rare earth element Tm comprises the following steps:
(1) Weighting raw materials, respectively weighing glass raw materials and rare earth oxide, wherein the glass raw materials are prepared from CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、 BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.05%;
(2) Preparing a glass premix, accurately weighing according to the stoichiometric ratio of a target product, and grinding in an agate mortar to uniformly mix the glass premix;
(3) Preparing a glass frit in a complete molten state, pouring the glass frit into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1100 ℃ at a speed of 4 ℃/min, and preserving heat for 1 hour to enable the raw materials to be completely molten;
(4) Preparing luminous glass, pouring the melt on a copper template at 450 ℃ to solidify into glass, maintaining at the temperature for 8 hours to eliminate thermal stress, and cooling to room temperature at 1-5 ℃ per minute to obtain the luminous glass
Example two
The preparation method of the fluoborate luminescent glass doped with the rare earth element Tm comprises the following steps:
(1) Weighting raw materials, respectively weighing glass raw materials and rare earth oxide, wherein the glass raw materials are prepared from CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、 BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.3%;
(2) Preparing a glass premix, accurately weighing according to the stoichiometric ratio of a target product, and grinding in an agate mortar to uniformly mix the glass premix;
(3) Preparing a glass frit in a complete molten state, pouring the glass frit into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1100 ℃ at a speed of 4 ℃/min, and preserving heat for 1 hour to enable the raw materials to be completely molten;
(4) Luminescent glass is prepared by casting the above melt onto a copper template at 450 ℃ to solidify into glass, and maintaining at that temperature for 8 hours to relieve thermal stress, followed by cooling to room temperature at 1-5 ℃/min.
Example III
The preparation method of the fluoborate luminescent glass doped with the rare earth element Tm comprises the following steps:
(1) Weighting raw materials, respectively weighing glass raw materials and rare earth oxide, wherein the glass raw materials are prepared from CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、 BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.5%;
(2) Preparing a glass premix, accurately weighing according to the stoichiometric ratio of a target product, and grinding in an agate mortar to uniformly mix the glass premix;
(3) Preparing a glass frit in a complete molten state, pouring the glass frit into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1100 ℃ at a speed of 4 ℃/min, and preserving heat for 1 hour to enable the raw materials to be completely molten;
(4) Luminescent glass is prepared by casting the above melt onto a copper template at 450 ℃ to solidify into glass, and maintaining at that temperature for 8 hours to relieve thermal stress, followed by cooling to room temperature at 1-5 ℃/min.
Example IV
The preparation method of the fluoborate luminescent glass doped with the rare earth element Tm comprises the following steps:
(1) Weighting raw materials, respectively weighing glass raw materials and rare earth oxide, wherein the glass raw materials are prepared from CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、 BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 1%;
(2) Preparing a glass premix, accurately weighing according to the stoichiometric ratio of a target product, and grinding in an agate mortar to uniformly mix the glass premix;
(3) Preparing a glass frit in a complete molten state, pouring the glass frit into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1100 ℃ at a speed of 4 ℃/min, and preserving heat for 1 hour to enable the raw materials to be completely molten;
(4) Luminescent glass is prepared by casting the above melt onto a copper template at 450 ℃ to solidify into glass, and maintaining at that temperature for 8 hours to relieve thermal stress, followed by cooling to room temperature at 1-5 ℃/min.
Example five
The preparation method of the fluoborate luminescent glass doped with the rare earth element Tm comprises the following steps:
(1) Weighting raw materials, respectively weighing glass raw materials and rare earth oxide, wherein the glass raw materials are prepared from CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、 BaCO 3 Composition of CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 5-60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 2%;
(2) Preparing a glass premix, accurately weighing according to the stoichiometric ratio of a target product, and grinding in an agate mortar to uniformly mix the glass premix;
(3) Preparing a glass frit in a complete molten state, pouring the glass frit into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1100 ℃ at a speed of 4 ℃/min, and preserving heat for 1 hour to enable the raw materials to be completely molten;
(4) Luminescent glass is prepared by casting the above melt onto a copper template at 450 ℃ to solidify into glass, and maintaining at that temperature for 8 hours to relieve thermal stress, followed by cooling to room temperature at 1-5 ℃/min.
The doping obtained in the above examples was 0.05%,0.3%,0.5%,1% and 2% tm 2 O 3 The fluoroborate glasses of (a) are noted as 0.05TmBLCZFB,0.3TmBLCZFB,0.5TmBLCZFB,1TmBLCZFB and 2TmBLCZFB, respectively.
Drawings
FIG. 1 shows the doping concentration Tm of the material according to an embodiment of the present invention 2 O 3 Visible light emission of the fluoroborate luminescent glass of (2)An emission spectrum;
FIG. 2 shows the doping concentration Tm of the material according to the embodiment of the present invention 2 O 3 Near infrared emission spectrum of the fluoroborate luminescent glass;
FIG. 3 shows the doping concentration Tm of the material according to the embodiment of the present invention 2 O 3 The mass attenuation coefficient of the fluoroborate luminescent glass to photons with the irradiation energy of 15keV-15MeV is shown in the illustration as a linear attenuation coefficient;
FIG. 4 shows the doping concentration Tm of the material according to the embodiment of the present invention 2 O 3 The thickness required for halving the photon energy in the energy range of 15keV-15 MeV-half-value layer, the illustration is the thickness of the glass layer required for the remaining tenth of the photon energy;
FIG. 5 shows the doping concentration Tm of the material according to the embodiment of the present invention 2 O 3 The chromaticity coordinates of the emission color of the fluoroborate luminescent glass in the CIE diagram (1931).
Description of the attached tables
TABLE 1 doping with various concentrations Tm as provided in the examples of the invention 2 O 3 Is composed of fluoborate luminous glass
TABLE 2 doping with respective concentrations Tm provided in the examples of the invention 2 O 3 Physical properties of the fluoroborate luminescent glass
FIG. 1 is a luminescence spectrum of a fluoroborate glass, a visible emission spectrum of the glass showing high intensity emission at 453nm, corresponding to 1 D 2 → 3 F 4 And (5) transition.
FIG. 2 is a near infrared emission spectrum of fluoroborate glass, shown at 1528nm (6544 cm -1 ) There is a wide emission corresponding to 3 H 4 → 3 F 4 And (5) transition.
FIG. 3 is a plot of mass attenuation coefficient of a sample versus incident gamma ray photon energy. The mass attenuation coefficient is one of the basic parameters for the measurement of the shielding gamma radiation. It can be seen that the mass attenuation coefficient decreases rapidly with increasing photon energy. The inset of fig. 3 shows the linear attenuation coefficient versus the incident photon energy, which also decreases rapidly as the photon energy increases.
Fig. 4 shows the half-value layers of all glasses, and it can be seen that all glasses are nearly identical in the low energy region (< 0.1 MeV) but then increase rapidly in the high energy region half-value layer. The inset is the thickness of the glass layer required for one tenth of the radiant photon energy remaining.
As shown in fig. 5, the luminescent chromaticity coordinates of the fluoroborate glass prepared in the examples of the present invention all fall in the blue region of the CIE (international commission on luminescence) 1931 chromaticity diagram, which demonstrates that the prepared fluoroborate glass can be used in solid-state blue lasers.
Table 1 shows the compositions of the fluoroborate glasses of the examples of the present invention.
Table 2 lists the density, refractive index, etc. parameters of the glass samples of the examples of the present invention.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (2)
1. A kind of rare earth element Tm doped fluoborate luminescent glass, characterized by: the raw material of the luminescent glass is CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、BaCO 3 Is composed of and doped with rare earth oxide, wherein CaF 2 5-15％，ZnO 5-15％，H 3 BO 3 60％，Li 2 CO 3 5-15％，BaCO 3 5-15%; the rare earth oxide is Tm 2 O 3 The mass percentage is 0.05-2%.
2. The rare earth element according to claim 1The preparation method of the plain Tm doped fluoborate luminescent glass is characterized by comprising the following steps of: the raw material CaF 2 、ZnO、H 3 BO 3 、Li 2 CO 3 、BaCO 3 And Tm 2 O 3 Accurately weighing according to the stoichiometric ratio of a target product, and then grinding in an agate mortar to uniformly mix the target product; pouring the glass premix into a ceramic crucible which is cleaned in advance, placing the ceramic crucible into a muffle furnace, heating to 1000-1200 ℃ at the speed of 2-10 ℃/min, and preserving the heat for 1-5 hours to enable the raw materials to be completely melted; the melt is poured onto a copper template at 400-600 ℃ to be solidified into glass, and kept at the temperature for 2-12 hours to eliminate thermal stress, and then cooled to room temperature at 1-5 ℃ per minute, so that the rare earth element Tm-doped fluoborate luminescent glass is prepared.
Priority Applications (1)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514489A (en) * | 2008-02-22 | 2009-08-26 | 中国科学院理化技术研究所 | Fluoborate and crystal containing rare earth ions, growing method and application of crystal |
| CN104059650A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Thulium doped basic bismuth fluoborate glass up-conversion luminescent material, preparation method and application thereof |
| CN104529166A (en) * | 2014-12-16 | 2015-04-22 | 温州大学 | Ce: YAG microcrystalline glass and application thereof in white-light LED |
| CN111139069A (en) * | 2020-01-07 | 2020-05-12 | 湖北大学 | Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder |
| CN112144119A (en) * | 2020-08-19 | 2020-12-29 | 中国科学院福建物质结构研究所 | Rare earth doped barium calcium fluoborate laser crystal, preparation method thereof and method for realizing laser |
-
2021
- 2021-04-22 CN CN202110433550.2A patent/CN115231824B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514489A (en) * | 2008-02-22 | 2009-08-26 | 中国科学院理化技术研究所 | Fluoborate and crystal containing rare earth ions, growing method and application of crystal |
| CN104059650A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Thulium doped basic bismuth fluoborate glass up-conversion luminescent material, preparation method and application thereof |
| CN104529166A (en) * | 2014-12-16 | 2015-04-22 | 温州大学 | Ce: YAG microcrystalline glass and application thereof in white-light LED |
| CN111139069A (en) * | 2020-01-07 | 2020-05-12 | 湖北大学 | Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder |
| CN112144119A (en) * | 2020-08-19 | 2020-12-29 | 中国科学院福建物质结构研究所 | Rare earth doped barium calcium fluoborate laser crystal, preparation method thereof and method for realizing laser |
Non-Patent Citations (2)
| Title |
|---|
| 周张健.无机非金属材料工艺学.北京：中国轻工业出版社,2010,第350页. * |
| 陈照峰.无机非金属材料学.西安：西北工业大学出版社,2016,第84-85页. * |
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