CN103951204B - Rare earth ion doped BaLu 2cl 8devitrified glass and preparation method thereof - Google Patents

Rare earth ion doped BaLu 2cl 8devitrified glass and preparation method thereof Download PDF

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Publication number
CN103951204B
CN103951204B CN201410197885.9A CN201410197885A CN103951204B CN 103951204 B CN103951204 B CN 103951204B CN 201410197885 A CN201410197885 A CN 201410197885A CN 103951204 B CN103951204 B CN 103951204B
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balu
glass
devitrified glass
rare earth
earth ion
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CN103951204A (en
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张为欢
张约品
夏海平
欧阳绍业
王倩
杨斌
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Ningbo University
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Ningbo University
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Abstract

The invention discloses a kind of rare earth ion doped BaLu 2cl 8devitrified glass and preparation method thereof, its Mole percent consists of SiO 2: 45-50mol%, Al 2o 3: 18-20mol%, BaF 2: 19-25mol%, BaLu 2cl 8: 10-12mol%, LnCl 3: 1-2mol%, wherein LnCl 3for CeCl 3, EuCl 3, TbCl 3, PrCl 3and NdCl 3in one, its preparation method first prepares SiO with scorification 2-Al 2o 3-BaF 2-BaLu 2cl 8-LnCl 3be glass, after heat treatment obtain transparent BaLu 2cl 8devitrified glass, BaLu of the present invention 2cl 8devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have stronger 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

Rare earth ion doped BaLu 2cl 8devitrified glass and preparation method thereof
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 BaLu being used as scintillation material 2cl 8devitrified 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.
BaLu 2cl 8crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce 3+the BaLu of doping 2cl 8it 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, scintillation detectors efficiency can be made greatly to improve.Eu 3+, Tb 3+doping BaLu 2cl 8the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But BaLu 2cl 8crystal 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 stronger light output, fast decay, energy resolution and the good rare earth ion doped BaLu of temporal resolution 2cl 8devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped BaLu 2cl 8devitrified glass, its Mole percent consists of:
SiO 2：45-50mol％Al 2O 3：18-20mol％BaF 2：19-25mol％
BaLu 2Cl 8：10-12mol％LnCl 3：1-2mol％
Wherein LnCl 3for CeCl 3, EuCl 3, TbCl 3, PrCl 3and NdCl 3in one.
This flicker devitrified glass material component is: SiO 2: 45mol%, Al 2o 3: 18mol%, BaF 2: 25mol%, BaLu 2cl 8: 11mol%, CeCl 3: 1mol%.
This flicker devitrified glass material component is: SiO 2: 45mol%, Al 2o 3: 20mol%, BaF 2: 21mol%, BaLu 2cl 8: 12mol%, EuCl 3: 2mol%.
This flicker devitrified glass material component is: SiO 2: 50mol%, Al 2o 3: 20mol%, BaF 2: 19mol%, BaLu 2cl 8: 10mol%, TbCl 3: 1mol%.
Described rare earth ion doped BaLu 2cl 8the preparation method of devitrified glass, comprises the steps:
(1) SiO 2-Al 2o 3-BaF 2-BaLu 2cl 8-LnCl 3be founding of glass:
Take analytically pure each raw material by material component, add the NH respectively accounting for raw material gross weight 6% 4hF 2, NH 4hCl 2raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 1430-1480 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 hyaloid, for micritization thermal treatment.
(2) BaLu 2cl 8prepared 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 BaLu 2cl 8devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine chlorine oxonium compound, the through performance of short wavelength is good, has BaLu 2cl 8the 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 BaLu 2cl 8single 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 BaLu 2cl 8crystalline phase, obtained rare earth ion doped BaLu 2cl 8devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have stronger light output, decay soon, the performances such as good energy resolution and temporal resolution, can make scintillation detectors 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:BaLu of embodiment one excitation of X-rays 2cl 8the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:BaLu of embodiment two excitation of X-rays 2cl 8the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:BaLu of embodiment three excitation of X-rays 2cl 8the 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 3 grams of NH 4hF 2, 3 grams of NH 4hCl 2pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1430 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 805 DEG C, obtained glass is placed in nitrogen fine annealing stove 822 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 BaLu of doping 2cl 8devitrified glass sample.
To the BaLu of preparation 2cl 8devitrified 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 BaLu 2cl 8phase, the material therefore obtained is BaLu 2cl 8the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping BaLu 2cl 8as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion BaLu 2cl 8devitrified glass light output is 35000ph/MeV.
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 3 grams of NH 4hF 2, 3 grams of NH 4hCl 2pour in corundum crucible after raw material is mixed and melt, temperature of fusion 1480 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 807 DEG C, obtained glass is placed in nitrogen atmosphere fine annealing stove 835 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 BaLu of ion doping 2cl 8devitrified glass.
To the BaLu of preparation 2cl 8the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping BaLu 2cl 8as shown in Figure 3, its result shows to produce Eu:BaLu after Overheating Treatment the fluorescence spectrum of devitrified glass 2cl 8crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:BaLu is described 2cl 8the 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 3 grams of NH 4hF 2, 3 grams of NH 4hCl 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 812 DEG C, obtained glass is placed in nitrogen fine annealing stove 830 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 BaLu of ion doping 2cl 8devitrified glass.
To the BaLu of preparation 2cl 8the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping BaLu 2cl 8as shown in Figure 4, its result shows to produce Tb:BaLu after Overheating Treatment the fluorescence spectrum of devitrified glass 2cl 8crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:BaLu is described 2cl 8the luminosity of devitrified glass is better; The rare earth ion doped BaLu obtained by above-mentioned preparation process 2cl 8devitrified glass is transparent and physical and chemical performance is excellent.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: SiO 2: 45mol%, Al 2o 3: 18mol%, BaF 2: 25mol%, BaLu 2cl 8: 11mol%, PrCl 3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: SiO 2: 45mol%, Al 2o 3: 18mol%, BaF 2: 25mol%, BaLu 2cl 8: 11mol%, NdCl 3: 1mol%.
Embodiment 4,5 also can obtain BaLu rare earth ion doped preferably 2cl 8devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped BaLu 2cl 8devitrified glass, its Mole percent consists of:
SiO 2：45-50mol％Al 2O 3：18-20mol％BaF 2：19-25mol％
BaLu 2Cl 8：10-12mol％LnCl 3：1-2mol％
Wherein LnCl 3for CeCl 3, EuCl 3, TbCl 3, PrCl 3and NdCl 3in one.
2. rare earth ion doped BaLu according to claim 1 2cl 8devitrified glass, is characterized in that this devitrified glass material component is: SiO 2: 45mol%, Al 2o 3: 18mol%, BaF 2: 25mol%, BaLu 2cl 8; 11mol%, CeCl 3: 1mol%.
3. rare earth ion doped BaLu according to claim 1 2cl 8devitrified glass, is characterized in that this devitrified glass material component is: SiO 2: 45mol%, Al 2o 3: 20mol%, BaF 2: 21mol%, BaLu 2cl 8: 12mol%, EuCl 3: 2mol%.
4. rare earth ion doped BaLu according to claim 1 2cl 8devitrified glass, is characterized in that this devitrified glass material component is: SiO 2: 50mol%, Al 2o 3: 20mol%, BaF 2: 19mol%, BaLu 2cl 8: 10mol%, TbCl 3: 1mol%.
5. rare earth ion doped BaLu according to claim 1 2cl 8the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) SiO 2-Al 2o 3-BaF 2-BaLu 2cl 8-LnCl 3be founding of glass: take analytically pure each raw material by material component, add the NH respectively accounting for raw material gross weight 6% 4hF 2, NH 4hCl 2raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 1430-1480 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) BaLu 2cl 8the preparation of 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 BaLu 2cl 8devitrified glass.
CN201410197885.9A 2014-05-08 2014-05-08 Rare earth ion doped BaLu 2cl 8devitrified glass and preparation method thereof Expired - Fee Related CN103951204B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006321689A (en) * 2005-05-19 2006-11-30 Kyoto Univ Crystallized glass composite body
CN101265026A (en) * 2008-04-18 2008-09-17 中国计量学院 Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof
CN101328019A (en) * 2008-07-29 2008-12-24 昆明理工大学 Rare earth doping metal halogenide photostimulable phosphor glass and preparation thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006321689A (en) * 2005-05-19 2006-11-30 Kyoto Univ Crystallized glass composite body
CN101265026A (en) * 2008-04-18 2008-09-17 中国计量学院 Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof
CN101328019A (en) * 2008-07-29 2008-12-24 昆明理工大学 Rare earth doping metal halogenide photostimulable phosphor glass and preparation thereof

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