CN103951244B - Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof - Google Patents

Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof Download PDF

Info

Publication number
CN103951244B
CN103951244B CN201410198382.3A CN201410198382A CN103951244B CN 103951244 B CN103951244 B CN 103951244B CN 201410198382 A CN201410198382 A CN 201410198382A CN 103951244 B CN103951244 B CN 103951244B
Authority
CN
China
Prior art keywords
glass
liyi
devitrified glass
rare earth
earth ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410198382.3A
Other languages
Chinese (zh)
Other versions
CN103951244A (en
Inventor
杨斌
张约品
夏海平
王倩
欧阳绍业
张为欢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo University
Original Assignee
Ningbo University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo University filed Critical Ningbo University
Priority to CN201410198382.3A priority Critical patent/CN103951244B/en
Publication of CN103951244A publication Critical patent/CN103951244A/en
Application granted granted Critical
Publication of CN103951244B publication Critical patent/CN103951244B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a kind of rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof, its Mole percent consists of GeO 2: 20-30mol%, B 2o 3: 25-35mol%, BaF 2: 20-25mol%, Y 2o 3: 2-7mol%, Cs 2liY (1-x)ln xi 6: 13-18mol%, in formula, x=0.05-0.2, Ln are Ce 3+, Eu 3+, Tb 3+, Pr 3+, Nd 3+in a kind of rare earth ion, its preparation method first prepares GeO with scorification 2-B 2o 3-BaF 2-Y 2o 3-Cs 2liY (1-x)ln xi 6be glass, after heat treatment obtain transparent Cs 2liYI 6devitrified glass, Cs of the present invention 2liYI 6devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have the luminescence of stronger twinkling light and export, the performances such as energy resolution is good.The preparation method of this devitrified glass is simple, and production cost is lower.

Description

Rare earth ion doped Cs 2liYI 6devitrified 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 Cs being used as scintillation material 2liYI 6devitrified 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.
Cs 2liYI 6crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce 3+the Cs of doping 2liYI 6it 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 Cs 2liYI 6the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But Cs 2liYI 6crystal 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 Cs of temporal resolution 2liYI 6devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped Cs 2liYI 6devitrified glass, its Mole percent consists of:
GeO 2：20-30mol％B 2O 3：25-35mol％BaF 2：20-25mol％
Y 2o 3: 2-7mol%Cs 2liY (1-x)ln xi 6: 13-18mol%, in formula, x=0.05-0.2, Ln are Ce 3+, Eu 3+, Tb 3+, Pr 3+and Nd 3+in a kind of rare earth ion.
This flicker devitrified glass material component is: GeO 2: 30mol%, B 2o 3: 25mol%, BaF 2: 25mol%, Y 2o 3: 7mol%, Cs 2liY 0.95ce 0.05i 6: 13mol%.
This flicker devitrified glass material component is: GeO 2: 25mol%, B 2o 3: 35mol%, BaF 2: 20mol%, Y 2o 3: 5mol%, Cs 2liY 0.8eu 0.2i 6: 15mol%.
This flicker devitrified glass material component is: GeO 2: 20mol%, B 2o 3: 35mol%, BaF 2: 25mol%, Y 2o 3: 2mol%, Cs 2liY 0.9tb 0.ii 6: 18mol%.
Described rare earth ion doped YI 3the preparation method of devitrified glass, comprises the steps:
(1) GeO 2-B 2o 3-BaF 2-Y 2o 3-Cs 2liY (1-x)ln xi 6be founding of glass:
Cs 2liY (1-x)ln xi 6raw material is by CsI, LiI, YI 3, LnI 3mixed sintering forms, and takes analytically pure each raw material, respectively add the NH accounting for raw material gross weight 5% by material component 4hF 2, NH 4hI 2raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 1350-1480 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 1 hour, 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) Cs 2liYI 6prepared 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 Cs 2liYI 6devitrified 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 Cs 2liYI 6the 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 Cs 2liYI 6single 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 Cs 2liYI 6crystalline phase, obtained rare earth ion doped Cs 2liYI 6devitrified 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:Cs of embodiment one excitation of X-rays 2liYI 6the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:Cs of embodiment two excitation of X-rays 2liYI 6the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:Cs of embodiment three excitation of X-rays 2liYI 6the 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, Cs 2liY 0.95ce 0.05i 6raw material is by CsI, LiI, YI 3, CeI 3mixed sintering forms, and 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 1 hour, 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 680 DEG C, obtained glass is placed in nitrogen fine annealing stove 695 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 Cs of doping 2liYI 6devitrified glass.
To the Cs of preparation 2liYI 6devitrified 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 Cs 2liYI 6phase, the material therefore obtained is Cs 2liYI 6the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping Cs 2liYI 6as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion Cs 2liYI 6devitrified glass light output is 33000ph/MeV, and fall time is 50ns.
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, Cs 2liY 0.8eu 0.2i 6raw material is by CsI, LiI, YI 3, EuI 3mixed sintering forms, and 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 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 1 hour, 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 690 DEG C, obtained glass is placed in nitrogen fine annealing stove 705 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 Cs of ion doping 2liYI 6devitrified glass.
To the Cs of preparation 2liYI 6the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping Cs 2liYI 6as shown in Figure 3, its result shows to produce Eu: Cs after Overheating Treatment the fluorescence spectrum of devitrified glass 2liYI 6crystallite luminous intensity compared with corresponding glass basis is significantly improved, and illustrates Eu: Cs 2liYI 6the 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, Cs 2liY 0.95ce 0.05i 6raw material is by CsI, LiI, YI 3, TbI 3mixed sintering forms, and 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 1 hour, 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 695 DEG C, obtained glass is placed in nitrogen fine annealing stove 715 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 Tb 3+the Cs of ion doping 2liYI 6devitrified glass.
To the Cs of preparation 2liYI 6the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping Cs 2liYI 6as shown in Figure 4, its result shows to produce Tb: Cs after Overheating Treatment the fluorescence spectrum of devitrified glass 2liYI 6crystallite luminous intensity compared with corresponding glass basis is significantly improved, and illustrates Tb: Cs 2liYI 6the luminosity of devitrified glass is better; The rare earth ion doped Cs obtained by above-mentioned preparation process 2liYI 6devitrified glass is transparent and physical and chemical performance is excellent.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: GeO 2: 20mol%, B 2o 3: 35mol%, BaF 2: 25mol%, Y 2o 3: 2mol%, Cs 2liY 0.9pr 0.1i 6: 18mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: GeO 2: 20mol%, B 2o 3: 35mol%, BaF 2: 25mol%, Y 2o 3: 2mol%, Cs 2liY 0.9nd 0.1i 6: 18mol%.
Embodiment 4,5 also can obtain Cs rare earth ion doped preferably 2liYI 6devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped Cs 2liYI 6devitrified glass, its Mole percent consists of:
GeO 2：20-30mol％B 2O 3：25-35mol％BaF 2：20-25mol％
Y 2o 3: 2-7mol%Cs 2liY (1-x)ln xi 6: 13-18mol%, in formula, x=0.05-0.2, Ln are Ce 3+, Eu 3+, Tb 3+, Pr 3+, Nd 3+in a kind of rare earth ion.
2. rare earth ion doped Cs according to claim 1 2liYI 6devitrified glass, is characterized in that this devitrified glass material component is: GeO 2: 30mol%, B 2o 3: 25mol%, BaF 2: 25mol%, Y 2o 3: 7mol%, Cs 2liY 0.95ce 0.05i 6: 13mol%.
3. rare earth ion doped Cs according to claim 1 2liYI 6devitrified glass, is characterized in that this devitrified glass material component is: GeO 2: 25mol%, B 2o 3: 35mol%, BaF 2: 20mol%, Y 2o 3: 5mol%, Cs 2liY 0.8eu 0.2i 6: 15mol%.
4. rare earth ion doped Cs according to claim 1 2liYI 6devitrified glass, is characterized in that this devitrified glass material component is: GeO 2: 20mol%, B 2o 3: 35mol%, BaF 2: 25mol%, Y 2o 3: 2mol%, Cs 2liY 0.9tb 0.1i 6: 18mol%.
5. rare earth ion doped Cs according to claim 1 2liYI 6the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) GeO 2-B 2o 3-BaF 2-Y 2o 3-Cs 2liY (1-x)ln xi 6be founding of glass: Cs 2liY (1-x)ln xi 6raw material is by CsI, LiI, YI 3, LnI 3mixed sintering forms, by GeO 2-B 2o 3-BaF 2-Y 2o 3-Cs 2liY (1-x)ln xi 6be that the material component of glass takes analytically pure each raw material, 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 1350-1480 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 1 hour, 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) Cs 2liYI 6the 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 Cs 2liYI 6devitrified glass.
CN201410198382.3A 2014-05-08 2014-05-08 Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof Expired - Fee Related CN103951244B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410198382.3A CN103951244B (en) 2014-05-08 2014-05-08 Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410198382.3A CN103951244B (en) 2014-05-08 2014-05-08 Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103951244A CN103951244A (en) 2014-07-30
CN103951244B true CN103951244B (en) 2016-01-13

Family

ID=51328636

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410198382.3A Expired - Fee Related CN103951244B (en) 2014-05-08 2014-05-08 Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103951244B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384350A (en) * 2015-11-16 2016-03-09 宁波大学 Glass film containing rare-earth ion doped Cs2LiScI6 microcrystals and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5955388A (en) * 1997-01-02 1999-09-21 Corning Incorporated Transparent oxyflouride glass-ceramic composition and process of making
CN1415693A (en) * 2002-12-05 2003-05-07 苏州大学 Infrared upward rotating marking material and its prepn. method
CN101669189A (en) * 2007-04-20 2010-03-10 皇家飞利浦电子股份有限公司 The metal halide lamp that comprises ionogenic salt filling

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5955388A (en) * 1997-01-02 1999-09-21 Corning Incorporated Transparent oxyflouride glass-ceramic composition and process of making
CN1415693A (en) * 2002-12-05 2003-05-07 苏州大学 Infrared upward rotating marking material and its prepn. method
CN101669189A (en) * 2007-04-20 2010-03-10 皇家飞利浦电子股份有限公司 The metal halide lamp that comprises ionogenic salt filling

Also Published As

Publication number Publication date
CN103951244A (en) 2014-07-30

Similar Documents

Publication Publication Date Title
CN103951209B (en) Rare earth ion doped LaI 3devitrified glass and preparation method thereof
CN103951215B (en) Rare earth ion doped LuI 3devitrified glass and preparation method thereof
CN103951197B (en) Rare earth ion doped Cs2LiYBr6Devitrified glass and preparation method thereof
CN103951222B (en) Rare earth ion doped SrBr 2devitrified glass and preparation method thereof
CN103951246B (en) Rare earth ion doped Cs 2liLuBr 6devitrified glass and preparation method thereof
CN103951224B (en) Rare earth ion doped LiI devitrified glass and preparation method thereof
CN103951244B (en) Rare earth ion doped Cs 2liYI 6devitrified glass and preparation method thereof
CN103951199B (en) Rare earth ion doped LiLuI 4devitrified glass and preparation method thereof
CN103951251B (en) Rare earth ion doped LiBaBr 3devitrified glass and preparation method thereof
CN103951256B (en) Rare earth ion doped LiLuCl 4devitrified glass and preparation method thereof
CN103951229B (en) Rare earth ion doped Sr 2luCl 7devitrified glass and preparation method thereof
CN103951216B (en) Rare earth ion doped GdI 3devitrified glass and preparation method thereof
CN103951214B (en) Rare earth ion doped LuBr 3devitrified glass and preparation method thereof
CN103951198A (en) Rare-earth-ion-doped Cs2LiGdBr6 microcrystalline glass and preparation method thereof
CN103951201B (en) Rare earth ion doped LiLaI 4devitrified glass and preparation method thereof
CN103951219B (en) Rare earth ion doped K 2laI 5devitrified glass and preparation method thereof
CN103951234B (en) Rare earth ion doped K 2luBr 5devitrified glass and preparation method thereof
CN103951241B (en) Rare earth ion doped Cs2LiLaBr6Devitrified glass and preparation method thereof
CN103951247B (en) Rare earth ion doped Cs2LiLuI6Devitrified glass and preparation method thereof
CN103951255B (en) Rare earth ion doped LiGdI 4devitrified glass and preparation method thereof
CN103951200B (en) Rare earth ion doped LiLaBr4Devitrified glass and preparation method thereof
CN103951249B (en) Rare earth ion doped Cs 2liGdI 6devitrified glass and preparation method thereof
CN103951252B (en) Rare earth ion doped LiBaI 3devitrified glass and preparation method thereof
CN103951248B (en) Rare earth ion doped Cs 2liGdCl 6devitrified glass and preparation method thereof
CN103951207B (en) Rare earth ion doped BaGdI 5devitrified glass and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160113

Termination date: 20180508