CN103951207B - Rare earth ion doped BaGdI 5devitrified glass and preparation method thereof - Google Patents

Rare earth ion doped BaGdI 5devitrified glass and preparation method thereof Download PDF

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CN103951207B
CN103951207B CN201410197914.1A CN201410197914A CN103951207B CN 103951207 B CN103951207 B CN 103951207B CN 201410197914 A CN201410197914 A CN 201410197914A CN 103951207 B CN103951207 B CN 103951207B
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bagdi
glass
devitrified glass
rare earth
earth ion
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CN103951207A (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 BaGdI 5devitrified glass and preparation method thereof, its Mole percent consists of P 2o 5: 33-40mol%, Nb 2o 5: 19-23mol%, BaF 2: 21-25mol%, BaGdI 5: 15-20mol%, LnI 3: 1-4mol%, wherein LnI 3ceI 3, EuI 3, TbI 3, PrI 3and NdI 3in one, its preparation method first prepares P with scorification 2o 5-Nb 2o 5-BaF 2-BaGdI 5-LnI 3be glass, after heat treatment obtain transparent BaGdI 5devitrified glass, BaGdI of the present invention 5devitrified 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 BaGdI 5devitrified 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 BaGdI being used as scintillation material 5devitrified 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.
BaGdI 5crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce 3+the BaGdI of doping 5it 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 oxidizing materials body, scintillation detectors efficiency can be made greatly to improve.Eu 3+, Tb 3+doping BaGdI 5the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But BaGdI 5crystal 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 BaGdI of temporal resolution 5devitrified 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 BaGdI 5devitrified glass, its Mole percent consists of:
P 2O 5：33-40mol％Nb 2O 5：19-23mol％BaF 2：21-25mol％
BaGdI 5：15-20mol％LnI 3：1-4mol％
Wherein LnI 3ceI 3, EuI 3, TbI 3, PrI 3and NdI 3in one.
This flicker devitrified glass material component is: P 2o 5: 33mol%, Nb 2o 5: 23mol%, BaF 2: 25mol%, BaGdI 5: 17mol%, CeI 3: 2mol%.
This flicker devitrified glass material component is: P 2o 5: 35mol%, Nb 2o 5: 20mol%, BaF 2: 21mol%, BaGdI 5: 20mol%, EuI 3: 4mol%.
This flicker devitrified glass material component is: P 2o 5: 40mol%, Nb 2o 5: 19mol%, BaF 2: 25mol%, BaGdI 5: 15mol%, TbI 3: 1mol%.
Described rare earth ion doped BaGdI 5the preparation method of devitrified glass, comprises the steps:
(1) P 2o 5-Nb 2o 5-BaF 2-BaGdI 5-LnI 3be founding of glass:
Take analytically pure each raw material by material component, add the NH respectively 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 1300-1450 DEG C, insulation 1-2 hour, 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) BaGdI 5prepared by devitrified glass:
According to thermal analyses (DTA) experimental data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 7 ~ 9 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 BaGdI 5devitrified 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 BaGdI 5the 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 BaGdI 5single 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 BaGdI 5crystalline phase, obtained rare earth ion doped BaGdI 5devitrified 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 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:BaGdI of embodiment one excitation of X-rays 5the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:BaGdI of embodiment two excitation of X-rays 5the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:BaGdI of embodiment three excitation of X-rays 5the 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 1300 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 722 DEG C, obtained glass is placed in nitrogen fine annealing stove 739 DEG C of thermal treatments 7 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 BaGdI of doping 5devitrified glass sample.
To the BaGdI of preparation 5devitrified 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 BaGdI 5phase, the material therefore obtained is BaGdI 5the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping BaGdI 5as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion BaGdI 5devitrified glass light output is 42000ph/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 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 1450 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 725 DEG C, obtained glass is placed in nitrogen fine annealing stove 742 DEG C of thermal treatments 9 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 BaGdI of ion doping 5devitrified glass.
To the BaGdI of preparation 5the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping BaGdI 5as shown in Figure 3, its result shows to produce Eu:BaGdI after Overheating Treatment the fluorescence spectrum of devitrified glass 5crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:BaGdI is described 5the 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 1400 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 728 DEG C, obtained glass is placed in nitrogen fine annealing stove 748 DEG C of thermal treatments 8 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 BaGdI of ion doping 5devitrified glass.
To the BaGdI of preparation 5the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping BaGdI 5as shown in Figure 4, its result shows to produce Tb:BaGdI after Overheating Treatment the fluorescence spectrum of devitrified glass 5crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:BaGdI is described 5the luminosity of devitrified glass is better; The rare earth ion doped BaGdI obtained by above-mentioned preparation process 5devitrified glass is transparent and physical and chemical performance is excellent.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: P 2o 5: 40mol%, Nb 2o 5: 19mol%, BaF 2: 25mol%, BaGdI 5: 15mol%, PrI 3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: P 2o 5: 40mol%, Nb 2o 5: 19mol%, BaF 2: 25mol%, BaGdI 5: 15mol%, NdI 3: 1mol%.
Embodiment 4,5 also can obtain BaGdI rare earth ion doped preferably 5devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped BaGdI 5devitrified glass, its Mole percent consists of:
P 2O 5：33-40mol％Nb 2O 5：19-23mol％BaF 2：21-25mol％
BaGdI 5：15-20mol％LnI 3：1-4mol％
Wherein LnI 3ceI 3, EuI 3, TbI 3, PrI 3and NdI 3in one.
2. rare earth ion doped BaGdI according to claim 1 5devitrified glass, is characterized in that this devitrified glass material component is: P 2o 5: 33mol%, Nb 2o 5: 23mol%, BaF 2: 25mol%, BaGdI 5: 17mol%, CeI 3: 2mol%.
3. rare earth ion doped BaGdI according to claim 1 5devitrified glass, is characterized in that this devitrified glass material component is: P 2o 5: 35mol%, Nb 2o 5: 20mol%, BaF 2: 21mol%, BaGdI 5: 20mol%, EuI 3: 4mol%.
4. rare earth ion doped BaGdI according to claim 1 5devitrified glass, is characterized in that this devitrified glass material component is: P 2o 5: 40mol%, Nb 2o 5: 19mol%, BaF 2: 25mol%, BaGdI 5: 15mol%, TbI 3: 1mol%.
5. rare earth ion doped BaGdI according to claim 1 5the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) P 2o 5-Nb 2o 5-BaF 2-BaGdI 5-LnI 3be founding of glass: take analytically pure each raw material by material component, add the NH respectively 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 1300-1450 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) BaGdI 5the preparation of devitrified glass: according to the thermal analysis experiment data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 7 ~ 9 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 BaGdI 5devitrified glass.
CN201410197914.1A 2014-05-08 2014-05-08 Rare earth ion doped BaGdI 5devitrified glass and preparation method thereof Expired - Fee Related CN103951207B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1636910A (en) * 2004-12-09 2005-07-13 中国科学院上海光学精密机械研究所 Transparent scintillating glass ceramic and preparation method thereof
JP2007197249A (en) * 2006-01-26 2007-08-09 Ohara Inc Glass ceramic and method for producing glass ceramic
CN103265177A (en) * 2013-05-17 2013-08-28 沈阳化工大学 P2O5-BaO-Na2O-K2O-Gd2O3-Eu2O3 glass ceramic and preparation method thereof
CN103666475A (en) * 2013-12-11 2014-03-26 昆明理工大学 Rare earth doped glass frequency conversion luminous material and preparation method thereof
CN103723925A (en) * 2012-10-10 2014-04-16 株式会社小原 Crystallized glass and method for manufacturing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1636910A (en) * 2004-12-09 2005-07-13 中国科学院上海光学精密机械研究所 Transparent scintillating glass ceramic and preparation method thereof
JP2007197249A (en) * 2006-01-26 2007-08-09 Ohara Inc Glass ceramic and method for producing glass ceramic
CN103723925A (en) * 2012-10-10 2014-04-16 株式会社小原 Crystallized glass and method for manufacturing same
CN103265177A (en) * 2013-05-17 2013-08-28 沈阳化工大学 P2O5-BaO-Na2O-K2O-Gd2O3-Eu2O3 glass ceramic and preparation method thereof
CN103666475A (en) * 2013-12-11 2014-03-26 昆明理工大学 Rare earth doped glass frequency conversion luminous material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
铈/铽掺杂高钆镥闪烁玻璃能量传递机理;杨斌等;《中国激光》;20130531;第40卷(第5期);0506001-1-0506001-5 *

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