CN103951229A - Rare-earth-ion-doped Sr2LuCl7 microcrystalline glass and preparation method thereof - Google Patents

Rare-earth-ion-doped Sr2LuCl7 microcrystalline glass and preparation method thereof Download PDF

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CN103951229A
CN103951229A CN201410198214.4A CN201410198214A CN103951229A CN 103951229 A CN103951229 A CN 103951229A CN 201410198214 A CN201410198214 A CN 201410198214A CN 103951229 A CN103951229 A CN 103951229A
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lucl
glass
devitrified glass
rare earth
preparation
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CN103951229B (en
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欧阳绍业
张约品
夏海平
张为欢
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 rare-earth-ion-doped Sr2LuCl7 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 45-50 mol% of P2O5, 10-15 mol% of SiO2, 21-29 mol% of BaF2, 10-15 mol% of Sr2LuCl7 and 1-4 mol% of LnCl3. The LnCl3 is CeCl3, EuCl3, TbCl3, PrCl3 or NdCl3. The preparation method comprises the following steps: preparing P2O5-SiO2-BaF2-Sr2LuCl7-LnCl3 glass by a fusion process, and carrying out heat treatment to obtain the transparent Sr2LuCl7 microcrystalline glass. The Sr2LuCl7 microcrystalline glass has the advantages of deliquescence resistance, favorable mechanical properties, higher short-wavelength blue-violet light transmission rate, strong light output, quick attenuation, favorable energy resolution, favorable time resolution and the like. The preparation method of the microcrystalline glass is simple and lower in production cost.

Description

Rare earth ion doped Sr 2luCl 7devitrified 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 Sr as scintillation material 2luCl 7devitrified glass and preparation method thereof.
Background technology
Scintillation material is a kind of optical function material that can send visible ray under the exciting of energetic ray (as x ray, gamma-rays) or other radioactive particle, is widely used in the fields such as nuclear medicine diagnostic, high energy physics and nuclear physics experiment research, industry and geological prospecting.According to the difference of Application Areas, the requirement of scintillator 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 large, cost is low and radiation resistance is good.Scintillation crystal generally has the advantages such as resistance to irradiation, fast decay, High Light Output, but scintillation crystal also exists following serious shortcoming: preparation difficulty, and expensive.Although and rare earth ion doped scintillation glass cost is low, easily prepare large-size glass, it is compared with crystal in aspect difficulties such as light output, multiplicity, so its application is also very limited.
Sr 2luCl 7crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce 3+the Sr of doping 2luCl 7it is high that crystal has light output, decay soon, and good energy resolution, temporal resolution and linear response, have than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, can make flash detection instrument efficiency greatly improve.Eu 3+, Tb 3+doping Sr 2luCl 7the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But Sr 2luCl 7crystal is deliquescence very easily, and mechanical property is poor, easy cleavage slabbing, and large-size crystals growth difficulty, and expensively affected 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 Sr of temporal resolution 2luCl 7devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped Sr 2luCl 7devitrified glass, its mole of percentage composition is:
P 2O 5：45-50mol％ SiO 2：10-15mol％ BaF 2：21-29mol％
Sr 2LuCl 7：10-15mol％ LnCl 3：1-4mol％
LnCl wherein 3for CeCl 3, EuCl 3, TbCl 3, PrCl 3and NdCl 3in a kind of.
This flicker devitrified glass material component is: P 2o 5: 45mol%, SiO 2: 15mol%, BaF 2: 28mol%, Sr 2luCl 7: 10mol%, CeCl 3: 2mol%.
This flicker devitrified glass material component is: P 2o:48mol%, SiO 2: 12mol%, BaF 2: 21mol%, Sr 2luCl 7: 15mol%, EuCl 3: 4mol%.
This flicker devitrified glass material component is: P 2o 5: 50mol%, SiO 2: 10mol%, BaF 2: 29mol%, Sr 2luCl 7: 10mol%, TbCl 3: 1mol%.
Described rare earth ion doped Sr 2luCl 7the preparation method of devitrified glass, comprises the steps:
(1) P 2o 5-SiO 2-BaF 2-Sr 2luCl 7-LnCl 3be founding of glass:
By material component, take analytically pure each raw material, add the NH that respectively accounts for raw material gross weight 5% 4hF 2, NH 4hCl 2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1410-1450 ℃, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment.
(2) Sr 2luCl 7devitrified glass preparation:
According to heat analysis (DTA) experimental data of glass, the glass making is placed in near fine annealing stove heat-treated 4～6 hours its first crystallization peak, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply, automatically be cooled to room temperature, finally can obtain transparent rare earth ion doped Sr 2luCl 7devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of fluorine chlorine oxonium compound, short wavelength's through performance is good, has Sr 2luCl 7the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome Sr 2luCl 7single 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 Sr 2luCl 7crystalline phase, the rare earth ion doped Sr making 2luCl 7devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has stronger light output, and decay soon, the performances such as good energy resolution and temporal resolution, can make flash 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 embodiment mono-micritization thermal treatment.
Fig. 2 is the Ce:Sr of embodiment mono-excitation of X-rays 2luCl 7the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:Sr of embodiment bis-excitation of X-rays 2luCl 7the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:Sr of embodiment tri-excitation of X-rays 2luCl 7the fluorescence spectrum of devitrified glass.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment mono-: table 1 is glass formula and the first recrystallization temperature value of embodiment mono-.
Table 1
Concrete preparation process is as follows: the first step, by the formula in table 1, weigh 50 grams of analytical pure raw materials, and add 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hCl 2after raw material is mixed, pour in quartz crucible and melt, 1410 ℃ of temperature of fusion, be incubated 2 hours, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass; Second step, according to heat analysis (DTA) experimental data of glass, obtain 725 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 737 ℃ of thermal treatments 6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce 3+the Sr of doping 2luCl 7devitrified glass.
Sr to preparation 2luCl 7devitrified glass carries out transmission electron microscope test, obtain the transmission electron microscope picture of glass after micritization is processed as shown in Figure 1, its result is as follows: in photo, glass basis seems more clearly with the nano microcrystalline of separating out, and the stain distributing in glass basis is microcrystal grain.X-ray diffraction test shows that crystalline phase is Sr 2luCl 7phase, the material therefore obtaining is Sr 2luCl 7the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping Sr 2luCl 7as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion Sr 2luCl 7devitrified glass light is output as 18000ph/MeV, and be 46ns fall time.
Embodiment bis-: table 2 is glass formula and the first recrystallization temperature value of embodiment bis-.
Table 2
Concrete preparation process is as follows: the first step, by the formula in table 2, weigh 50 grams of analytical pure raw materials, and add 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hCl 2after raw material is mixed, pour in corundum crucible and melt, 1450 ℃ of temperature of fusion, be incubated 1 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass; Second step, according to heat analysis (DTA) experimental data of glass, obtain 739 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 760 ℃ of thermal treatments 4 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu 3+the Sr of ion doping 2luCl 7devitrified glass.
Sr to preparation 2luCl 7the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping Sr 2luCl 7as shown in Figure 3, its result shows to produce Eu:Sr after Overheating Treatment to the fluorescence spectrum of devitrified glass 2luCl 7crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:Sr is described 2luCl 7the luminosity of devitrified glass is better.
Embodiment tri-: table 3 is glass formula and the first recrystallization temperature value of embodiment tri-.
Table 3
Concrete preparation process is as follows: the first step, by the formula in table 3, weigh 50 grams of analytical pure raw materials, and add 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hCl 2after raw material is mixed, pour in quartz crucible and melt, 1430 ℃ of temperature of fusion, be incubated 1.5 hours, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass.Second step, according to heat analysis (DTA) experimental data of glass, obtain 753 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 780 ℃ of thermal treatments 5 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb 3+the Sr of ion doping 2luCl 7devitrified glass.
Sr to preparation 2luCl 7the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping Sr 2luCl 7as shown in Figure 4, its result shows to produce Tb:Sr after Overheating Treatment to the fluorescence spectrum of devitrified glass 2luCl 7crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:Sr is described 2luCl 7the luminosity of devitrified glass is better; The rare earth ion doped Sr being obtained by above-mentioned preparation process 2luCl 7devitrified glass is transparent and physical and chemical performance is good.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: P 2o 5: 50mol%, SiO 2: 10mol%, BaF 2: 29mol%, Sr 2luCl 7: 10mol%, PrCl 3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: P 2o 5: 50mol%, SiO 2: 10mol%, BaF 2: 29mol%, Sr 2luCl 7: 10mol%, NdCl 3: 1mol%.
Embodiment 4,5 also can obtain rare earth ion doped Sr preferably 2luCl 7devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped Sr 2luCl 7devitrified glass, its mole of percentage composition is:
P 2O 5：45-50mol％ SiO 2：10-15mol％ BaF 2：21-29mol％
Sr 2LuCl 7：10-15mol％ LnCl 3：1-4mol％
LnCl wherein 3for CeCl 3, EuCl 3, TbCl 3, PrCl 3and NdCl 3in a kind of.
2. rare earth ion doped Sr claimed in claim 1 2luCl 7devitrified glass, is characterized in that this flicker devitrified glass material component is: P 2o 5: 45mol%, SiO 2: 15mol%, BaF 2: 28mol%, Sr 2luCl 7: 10mol%, CeCl 3: 2mol%.
3. rare earth ion doped Sr claimed in claim 1 2luCl 7devitrified glass, is characterized in that this flicker devitrified glass material component is: P 2o:48mol%, SiO 2: 12mol%, BaF 2: 21mol%, Sr 2luCl 7: 15mol%, EuCl 3: 4mol%.
4. rare earth ion doped Sr claimed in claim 1 2luCl 7devitrified glass, is characterized in that this flicker devitrified glass material component is P 2o 5: 50mol%, SiO 2: 10mol%, BaF 2: 29mol%, Sr 2luCl 7: 10mol%, TbCl 3: 1mol%.
5. rare earth ion doped Sr according to claim 1 2luCl 7the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) P 2o 5-SiO 2-BaF 2-Sr 2luCl 7-LnCl 3be founding of glass: by material component, take analytically pure each raw material, add the NH that respectively accounts for raw material gross weight 5% 4hF 2, NH 4hCl 2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1410-1450 ℃, insulation 1-2 hour, glass melt is poured on pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;
(2) Sr 2luCl 7the preparation of devitrified glass: according to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near its first crystallization peak, heat-treated is 4～6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped Sr 2luCl 7devitrified glass.
CN201410198214.4A 2014-05-08 2014-05-08 Rare earth ion doped Sr 2luCl 7devitrified glass and preparation method thereof Expired - Fee Related CN103951229B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271776A (en) * 2015-11-27 2016-01-27 宁波大学 Rare-earth-ion-doped Cs2LuCl5 microcrystalline glass and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1004899A1 (en) * 1998-01-12 2000-05-31 Jury Dmitrievich Zavartsev Scintillating substance and scintillating wave-guide element
CN1715230A (en) * 2004-06-10 2006-01-04 通用电气公司 Compositions and methods for scintillator arrays
EP1760049A1 (en) * 2005-08-31 2007-03-07 Ohara Inc. Glass or fluorescent glass
JP2007197249A (en) * 2006-01-26 2007-08-09 Ohara Inc Glass ceramic and method for producing glass ceramic
CN101054522A (en) * 2007-06-01 2007-10-17 北京玻璃研究院 Cerium activated rare earth halide bromide scintillator and preparing method thereof
EP2308949A1 (en) * 2009-10-09 2011-04-13 Schott AG Scintillator materials with low oxygen content and method for producing same
CN103011592A (en) * 2012-11-29 2013-04-03 宁波大学 Europium-ion-doped gadolinium lutetium oxyfluoride scintillation glass and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1004899A1 (en) * 1998-01-12 2000-05-31 Jury Dmitrievich Zavartsev Scintillating substance and scintillating wave-guide element
CN1715230A (en) * 2004-06-10 2006-01-04 通用电气公司 Compositions and methods for scintillator arrays
EP1760049A1 (en) * 2005-08-31 2007-03-07 Ohara Inc. Glass or fluorescent glass
JP2007197249A (en) * 2006-01-26 2007-08-09 Ohara Inc Glass ceramic and method for producing glass ceramic
CN101054522A (en) * 2007-06-01 2007-10-17 北京玻璃研究院 Cerium activated rare earth halide bromide scintillator and preparing method thereof
EP2308949A1 (en) * 2009-10-09 2011-04-13 Schott AG Scintillator materials with low oxygen content and method for producing same
CN103011592A (en) * 2012-11-29 2013-04-03 宁波大学 Europium-ion-doped gadolinium lutetium oxyfluoride scintillation glass and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271776A (en) * 2015-11-27 2016-01-27 宁波大学 Rare-earth-ion-doped Cs2LuCl5 microcrystalline glass and preparation method thereof

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