CN103951252B - Rare earth ion doped LiBaI 3devitrified glass and preparation method thereof - Google Patents
Rare earth ion doped LiBaI 3devitrified glass and preparation method thereof Download PDFInfo
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- CN103951252B CN103951252B CN201410198462.9A CN201410198462A CN103951252B CN 103951252 B CN103951252 B CN 103951252B CN 201410198462 A CN201410198462 A CN 201410198462A CN 103951252 B CN103951252 B CN 103951252B
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- libai
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Abstract
The invention discloses a kind of rare earth ion doped LiBaI
3devitrified glass and preparation method thereof, its Mole percent consists of B
2o
3: 50-60mol%, BaF
2: 10-12mol%, NaF:8-13mol%, BaO:6-10mol%, LiBaI
3: 10-15mol%, LnI
3: 0.5-4mol%, wherein LnI
3for CeI
3, EuI
3, TbI
3in one, its preparation method first prepares B with scorification
2o
3-BaF
2-NaF-BaO-LiBaI
3-LnI
3be glass, after heat treatment obtain transparent LiBaI
3devitrified glass, LiBaI of the present invention
3devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution.The preparation method of this devitrified glass is simple, and production cost is lower.
Description
Technical field
The present invention relates to a kind of rare earth ion doped devitrified glass, especially relate to a kind of rare earth ion doped LiBaI being used as scintillation material
3devitrified glass and preparation method thereof.
Background technology
Scintillation material is a kind of lower optical function material that can send visible ray of exciting at energetic ray (as x-ray, gamma-rays) or other radioactive particle, is widely used in the fields such as the researchs of nuclear medicine diagnostic, high energy physics and nuclear physics experiment, industrial and geological prospecting.The requirement of difference to scintillator according to Application Areas is also not quite similar, but generally scintillation material should possess following properties: the features such as luminous efficiency is high, fluorescence decay is fast, density is comparatively large, cost is low and radiation resistance is good.Scintillation crystal generally has the advantage such as resistance to irradiation, fast decay, High Light Output, but scintillation crystal also exists following serious shortcoming: preparation difficulty, expensive.And although rare earth ion doped scintillation glass cost is low, easily prepare large-size glass, it is difficult compared with crystal in light output, multiplicity etc., and therefore its application is also very limited.
LiBaI
3crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce
3+the LiBaI of doping
3it is high that crystal has light output, decays soon, good energy resolution, temporal resolution and linear response, has than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, nuclear detection instrument efficiency can be made greatly to improve.Eu
3+, Tb
3+li doped BaI
3the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LiBaI
3crystal is deliquescence very easily, and mechanical property is poor, easy cleavage slabbing, large-size crystals growth difficulty, and expensively have impact on its practical application.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Deliquescence-resistant, good mechanical property, has extremely strong light output, fast decay, energy resolution and the good rare earth ion doped LiBaI of temporal resolution
3devitrified glass.Present invention also offers the preparation method of this flicker devitrified glass, it is simple that this preparation method has method, the advantage that cost is low.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped LiBaI
3devitrified glass, its Mole percent consists of:
B
2O
3：50-60mol％BaF
2：10-12mol％NaF：8-13mol％
BaO：6-10mol％LiBaI
3：10-15mol％LnI
3：0.5-4mol％
Wherein LnI
3for CeI
3, EuI
3, TbI
3in one.
This flicker devitrified glass material component is: B
2o
3: 60mol%, BaF
2: 8mol%, NaF:8mol%, BaO:10mol%, LiBaI
3: 12mol%, CeI
3: 2mol%.
This flicker devitrified glass material component is: B
2o
3: 50mol%, BaF
2: 12mol%, NaF:13mol%, BaO:6mol%, LiBaI
3: 15mol%, EuI
3: 4mol%.
This flicker devitrified glass material component is: B
2o
3: 59.5mol%, BaF
2: 10mol%, NaF:10mol%, BaO:10mol%, LiBaI
3: 10mol%, TbI
3: 0.5mol%.
Described rare earth ion doped LiBaI
3the preparation method of devitrified glass, comprises the steps:
(1) B
2o
3-BaF
2-NaF-BaO-LiBaI
3-LnI
3be founding of glass:
Take analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5%
4hF
2, NH
4hI
2raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 1350-1450 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 50 DEG C are cooled to the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment.
(2) LiBaI
3prepared by devitrified glass:
According to thermal analyses (DTA) experimental data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 4 ~ 6 hours near its first crystallization peak, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped LiBaI
3devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine iodine oxygen compound, the through performance of short wavelength is good, has LiBaI
3the feature that the superior scintillation properties of crystalline host material and the physical strength of oxide glass, stability and being easy to is processed, overcomes LiBaI
3single crystal is the shortcoming such as deliquescence, poor, the easy cleavage slabbing of mechanical property very easily; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped to LiBaI
3crystalline phase, obtained rare earth ion doped LiBaI
3devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution, can make nuclear detection instrument efficiency greatly improve.The preparation method of this devitrified glass is simple, and production cost is lower.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope figure (TEM) of sample after the thermal treatment of embodiment one micritization.
Fig. 2 is the Ce:LiBaI of embodiment one excitation of X-rays
3the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:LiBaI of embodiment two excitation of X-rays
3the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:LiBaI of embodiment three excitation of X-rays
3the fluorescence spectrum of devitrified glass.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment one: table 1 is glass formula and the first recrystallization temperature value of embodiment one.
Table 1
Concrete preparation process is as follows: the first step, weighs 50 grams of analytical pure raw materials by the formula in table 1, adds 2.5 grams of NH
4hF
2, 2.5 grams of NH
4hI
2pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1350 DEG C, be incubated 2 hours, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass; Second step, according to thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 665 DEG C, obtained glass is placed in nitrogen fine annealing stove 680 DEG C of thermal treatments 6 hours, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce
3+the LiBaI of doping
3devitrified glass.
To the LiBaI of preparation
3devitrified glass carries out transmission electron microscope test, obtain the transmission electron microscope picture of glass after micritization process as shown in Figure 1, its result is as follows: in photo, the nano microcrystalline of glass basis and precipitation seems more clearly, and the stain distributed in glass basis is microcrystal grain.X-ray diffraction test shows that crystalline phase is LiBaI
3phase, the material therefore obtained is LiBaI
3the devitrified glass of crystallization phase.The Ce of excitation of X-rays
3+ion doping LiBaI
3as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LiBaI
3devitrified glass light output is 32000ph/MeV, and fall time is 70ns.
Embodiment two: table 2 is glass formula and the first recrystallization temperature value of embodiment two.
Table 2
Concrete preparation process is as follows: the first step, weighs 50 grams of analytical pure raw materials by the formula in table 2, adds 2.5 grams of NH
4hF
2, 2.5 grams of NH
4hI
2pour in corundum crucible after raw material is mixed and melt, temperature of fusion 1400 DEG C, be incubated 1 hour, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass; Second step, according to thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 669 DEG C, obtained glass is placed in nitrogen fine annealing stove 690 DEG C of thermal treatments 4 hours, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu
3+the LiBaI of ion doping
3devitrified glass.
To the LiBaI of preparation
3the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+ion doping LiBaI
3as shown in Figure 3, its result shows to produce Eu:LiBaI after Overheating Treatment the fluorescence spectrum of devitrified glass
3crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LiBaI is described
3the luminosity of devitrified glass is better.
Embodiment three: table 3 is glass formula and the first recrystallization temperature value of embodiment three.
Table 3
Concrete preparation process is as follows: the first step, weighs 50 grams of analytical pure raw materials by the formula in table 3, adds 2.5 grams of NH
4hF
2, 2.5 grams of NH
4hI
2pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1450 DEG C, be incubated 1.5 hours, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass.Second step, according to thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 674 DEG C, obtained glass is placed in but nitrogen fine annealing stove 692 DEG C of thermal treatments 5 hours, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb
3+the LiBaI of ion doping
3devitrified glass.
To the LiBaI of preparation
3the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LiBaI
3as shown in Figure 4, its result shows to produce Tb:LiBaI after Overheating Treatment the fluorescence spectrum of devitrified glass
3crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:LiBaI is described
3the luminosity of devitrified glass is better; The rare earth ion doped LiBaI obtained by above-mentioned preparation process
3devitrified glass is transparent and physical and chemical performance is excellent.
Claims (4)
1. a rare earth ion doped LiBaI
3devitrified glass, its feed molar percentage composition is:
B
2O
3：50-60mol％BaF
2：10-12mol％NaF：8-13mol％
BaO：6-10mol％LiBaI
3：10-15mol％LnI
3：0.5-4mol％
Wherein LnI
3for CeI
3, EuI
3, TbI
3in one.
2. rare earth ion doped LiBaI according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: B
2o
3: 50mol%, BaF
2: 12mol%, NaF:13mol%, BaO:6mol%, LiBaI
3: 15mol%, EuI
3: 4mol%.
3. rare earth ion doped LiBaI according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: B
2o
3: 59.5mol%, BaF
2: 10mol%, NaF:10mol%, BaO:10mol%, LiBaI
3: 10mol%, TbI
3: 0.5mol%.
4. a rare earth ion doped LiBaI
3the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) B
2o
3-BaF
2-NaF-BaO-LiBaI
3-LnI
3be founding of glass: be B by feed molar percentage composition
2o
3: 50-60mol%, BaF
2: 10-12mol%, NaF:8-13mol%, BaO:6-10mol%, LiBaI
3: 10-15mol%, LnI
3: 0.5-4mol%, wherein LnI
3for CeI
3, EuI
3, TbI
3in one; Take analytically pure each raw material, respectively add the NH accounting for raw material gross weight 5%
4hF
2, NH
4hI
2mix, then pour fusing in quartz crucible or corundum crucible into, temperature of fusion 1350-1450 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 50 DEG C are cooled to the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;
(2) LiBaI
3the preparation of devitrified glass: according to the thermal analysis experiment data of glass, obtained glass is placed in nitrogen fine annealing stove, heat-treated 4 ~ 6 hours near its first crystallization peak, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped LiBaI
3devitrified glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198462.9A CN103951252B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LiBaI 3devitrified glass and preparation method thereof |
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|---|---|---|---|
| CN201410198462.9A CN103951252B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LiBaI 3devitrified glass and preparation method thereof |
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|---|---|
| CN103951252A CN103951252A (en) | 2014-07-30 |
| CN103951252B true CN103951252B (en) | 2016-03-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3222567C2 (en) * | 1982-06-16 | 1986-06-05 | Schott Glaswerke, 6500 Mainz | Colorless barium silicate glass containing cerium and phosphorus with good scintillation properties |
| JP4358713B2 (en) * | 2004-09-09 | 2009-11-04 | 株式会社住田光学ガラス | Solid state device |
| CN101799609B (en) * | 2009-02-11 | 2012-12-19 | 中国科学院理化技术研究所 | Nonlinear optical crystal BaZnBO3F, preparation method and application thereof |
| CN102337586B (en) * | 2010-07-20 | 2013-11-27 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof |
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