CN103951249B - Rare earth ion doped Cs 2liGdI 6devitrified glass and preparation method thereof - Google Patents

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

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CN103951249B
CN103951249B CN201410198424.3A CN201410198424A CN103951249B CN 103951249 B CN103951249 B CN 103951249B CN 201410198424 A CN201410198424 A CN 201410198424A CN 103951249 B CN103951249 B CN 103951249B
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glass
devitrified glass
ligdi
rare earth
earth ion
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CN103951249A (en
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杨斌
张约品
夏海平
王倩
欧阳绍业
张为欢
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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 Cs 2liGdI 6devitrified glass and preparation method thereof, its Mole percent consists of P 2o 5: 30-40mol%, B 2o 3: 25-30mol%, BaF 2: 15-20mol%, Gd 2o 3: 5-9mol%, Cs 2liGd (1-x)ln xi 6: 11-15mol%, 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, its preparation method first prepares P with scorification 2o 5-B 2o 3-BaF 2-Gd 2o 3-Cs 2liGd (1-x)ln xi 6be glass, after heat treatment obtain transparent Cs 2liGdI 6devitrified glass, Cs of the present invention 2liGdI 6devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have stronger twinkling light luminescence 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 2liGdI 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 2liGdI 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 2liGdI 6crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce 3+the Cs of doping 2liGdI 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, nuclear detection instrument efficiency can be made greatly to improve.Eu 3+, Tb 3+doping Cs 2liGdI 6the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But Cs 2liGdI 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 2liGdI 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 2liGdI 6devitrified glass, its Mole percent consists of:
P 2O 5：30-40mol％B 2O 3：25-30mol％BaF 2：15-20mol％
Gd 2o 3: 5-9mol%Cs 2liGd (1-x)ln xi 6: 11-15mol%, 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: P 2o 5: 30mol%, B 2o 3: 30mol%, BaF 2: 20mol%, Gd 2o 3: 5mol%, Cs 2liGd 0.95ce 0.05i 6: 15mol%.
This flicker devitrified glass material component is: P 2o 5: 35mol%, B 2o 3: 28mol%, BaF 2: 17mol%, Gd 2o 3: 6mol%, Cs 2liGd 0.8eu 0.2i 6: 14mol%.
This flicker devitrified glass material component is P 2o 5: 40mol%, B 2o 3: 25mol%, BaF 2: 15mol%, Gd 2o 3: 9mol%, Cs 2liGd 0.9tb 0.1i 6: 11mol%.
Described rare earth ion doped Cs 2liGdI 6the preparation method of devitrified glass, comprises the steps:
(1) P 2o 5-B 2o 3-BaF 2-Gd 2o 3-Cs 2liGd (1-x)ln xi 6be founding of glass: Cs 2liGd (1-x)ln xi6 raw material is by CsI, LiI, GdI 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 1350-1450 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 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 2liGdI 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 2liGdI 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 2liGdI 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 2liGdI 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 2liGdI 6crystalline phase, obtained rare earth ion doped Cs 2liGdI 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 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:Cs of embodiment one excitation of X-rays 2liGdI 6the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:Cs of embodiment two excitation of X-rays 2liGdI 6the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:Cs of embodiment three excitation of X-rays 2liGdI 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 2liGd 0.95ce 0.05i 6raw material is by CsI, LiI, GdI 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 694 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 2liGdI 6devitrified glass sample.
To the Cs of preparation 2liGdI 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 2liGdI 6phase, the material therefore obtained is Cs 2liGdI 6the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping Cs 2liGdI 6as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion Cs 2liGdI 6devitrified glass light output is 32000ph/MeV, and fall time is 75ns.
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 2liGd 0.8eu 0.2i 6raw material is by CsI, LiI, GdI 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 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 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 682 DEG C, obtained glass is placed in nitrogen fine annealing stove 695 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 2liGdI 6devitrified glass.
To the Cs of preparation 2liGdI 6the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping Cs 2liGdI 6as shown in Figure 3, its result shows to produce Eu:Cs after Overheating Treatment the fluorescence spectrum of devitrified glass 2liGdI 6crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:Cs is described 2liGdI 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 table 1
Concrete preparation process is as follows: the first step, Cs 2liGd 0.9tb 0.1i 6raw material is by CsI, LiI, GdI 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 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 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 689 DEG C, obtained glass is placed in nitrogen fine annealing stove 720 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 Cs of ion doping 2liGdI 6devitrified glass.
To the Cs of preparation 2liGdI 6the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping Cs 2liGdI 6as shown in Figure 4, its result shows to produce Cs after Overheating Treatment the fluorescence spectrum of devitrified glass 2liGdI 6crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:Cs is described 2liGdI 6the luminosity of devitrified glass is better; The rare earth ion doped Cs obtained by above-mentioned preparation process 2liGdI 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: P 2o 5: 30mol%, B 2o 3: 30mol%, BaF 2: 20mol%, Gd 2o 3: 5mol%, Cs 2liGd 0.95pr 0.05i 6: 15mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: P 2o 5: 30mol%, B 2o 3: 30mol%, BaF 2: 20mol%, Gd2O 3: 5mol%, Cs 2liGd 0.95nd 0.05i 6: 15mol%.
Embodiment 4,5 also can obtain Cs rare earth ion doped preferably 2liGdI 6devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped Cs 2liGdI 6devitrified glass, its Mole percent consists of:
P 2O 5：30-40mol％B 2O 3：25-30mol％BaF 2：15-20mol％
Gd 2o 3: 5-9mol%Cs 2liGd (1-x)ln xi 6: 11-15mol%, 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.
2. rare earth ion doped Cs according to claim 1 2liGdI 6devitrified glass, is characterized in that this devitrified glass material component is: P 2o 5: 30mol%, B 2o 3: 30mol%, BaF 2: 20mol%, Gd 2o 3: 5mol%, Cs 2liGd 0.95ce 0.05i 6: 15mol%.
3. rare earth ion doped Cs according to claim 1 2liGdI 6devitrified glass, is characterized in that this devitrified glass material component is: P 2o 5: 35mol%, B 2o 3: 28mol%, BaF 2: 17mol%, Gd 2o 3: 6mol%, Cs 2liGd 0.8eu 0.2i 6: 14mol%.
4. rare earth ion doped Cs according to claim 1 2liGdI 6devitrified glass, is characterized in that this devitrified glass material component is: P 2o 5: 40mol%, B 2o 3: 25mol%, BaF 2: 15mol%, Gd 2o 3: 9mol%, Cs 2liGd 0.9tb 0.1i 6: 11mol%.
5. rare earth ion doped Cs according to claim 1 2liGdI 6the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) P 2o 5-B 2o 3-BaF 2-Gd 2o 3-Cs 2liGd (1-x)ln xi 6be founding of glass: Cs 2liGd (1-x)ln xi 6raw material is by CsI, LiI, GdI 3, LnI 3mixed sintering forms, and takes analytically pure each raw material by the material component of devitrified glass, adds the NH accounting for devitrified glass raw material gross weight 5% 4hF 2, add the NH accounting for devitrified glass raw material gross weight 5% 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 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 2liGdI 6the 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 Cs 2liGdI 6devitrified glass.
CN201410198424.3A 2014-05-08 2014-05-08 Rare earth ion doped Cs 2liGdI 6devitrified glass and preparation method thereof Expired - Fee Related CN103951249B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1251564A (en) * 1997-04-03 2000-04-26 康宁股份有限公司 Transparent apatite glass-ceramics
US8153982B1 (en) * 2008-06-25 2012-04-10 Radiation Monitoring Devices, Inc. Yttrium-containing scintillator compositions, devices and methods

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1251564A (en) * 1997-04-03 2000-04-26 康宁股份有限公司 Transparent apatite glass-ceramics
US8153982B1 (en) * 2008-06-25 2012-04-10 Radiation Monitoring Devices, Inc. Yttrium-containing scintillator compositions, devices and methods

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