CN103951209B - Rare earth ion doped LaI 3devitrified glass and preparation method thereof - Google Patents
Rare earth ion doped LaI 3devitrified glass and preparation method thereof Download PDFInfo
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- CN103951209B CN103951209B CN201410197933.4A CN201410197933A CN103951209B CN 103951209 B CN103951209 B CN 103951209B CN 201410197933 A CN201410197933 A CN 201410197933A CN 103951209 B CN103951209 B CN 103951209B
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- lai
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- devitrified glass
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Abstract
The invention discloses a kind of rare earth ion doped LaI
3devitrified glass and preparation method thereof, its Mole percent consists of GeO
2: 40-60mol%, BaF
2: 5-15mol%, KF:5-10mol%, La
2o
3: 5-18mol%, LaI
3: 15-25mol%, LnI
3: 2-5mol%, wherein LnI
3for CeI
3, EuI
3, TbI
3, PrI
3, NdI
3in one, its preparation method first prepares GeO with scorification
2-BaF
2-KF-La
2o
3-LaI
3-LnI
3be glass, after heat treatment obtain transparent LaI
3devitrified glass, LaI of the present invention
3devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have extremely strong 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
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 LaI being used as scintillation material
3devitrified 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.
LaI
3crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce
3+the LaI of doping
3it 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+the LaI of doping
3crystal and Tb
3+the LaI of doping
3the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LaI
3crystal is deliquescence, poor, the easy cleavage slabbing of mechanical property, its practical application of the large-size crystals growth disadvantages affect such as difficult, expensive very easily.
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 extremely strong light output, fast decay, energy resolution and the good rare earth ion doped LaI of temporal resolution
3devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped LaI
3devitrified glass, its Mole percent consists of:
GeO
2：40-60mol％BaF
2：5-15mol％KF：5-10mol％
La
2O
3：5-18mol％LaI
3：15-25mol％LnI
3：2-5mol％
Wherein LnI
3for CeI
3, EuI
3, TbI
3, PrI
3, NdI
3in one.
This flicker devitrified glass material component is: GeO
2: 40mol%, BaF
2: 10mol%, KF:10mol%, La
2o
3: 18mol%, LaI
3: 20mol%, CeI
3: 2mol%.
This flicker devitrified glass material component is: GeO
2: 45mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, EuI
3: 5mol%.
This flicker devitrified glass material component is: GeO
2: 60mol%, BaF
2: 5mol%, KF:5mol%, La
2o
3: 13mol%, LaI
3: 15mol%, TbI
3: 2mol%.
Described rare earth ion doped LaI
3the preparation method of devitrified glass, comprises the steps:
(1) GeO
2-BaF
2-KF-La
2o
3-LaI
3-LnI
3be founding of glass:
Take analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5%
4hF
2, NH
4hI
2pour into after raw material is mixed in quartz crucible or corundum crucible and melt, temperature of fusion 1300-1480 DEG C, insulation 1-2 hour, pours into glass melt in pig mold, then be placed in retort furnace to anneal, after 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h in glass transformation temperature Tg temperature, close retort furnace power supply and be automatically cooled to room temperature, take out glass sample, for micritization thermal treatment.
(2) LaI
3prepared by devitrified glass:
According to thermal analyses (DTA) experimental data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 3 ~ 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 and be automatically cooled to room temperature, obtain transparent rare earth ion doped LaI
3devitrified glass sample.
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 LaI
3the 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 LaI
3single 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 LaI
3crystalline phase, obtained rare earth ion doped LaI
3devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have extremely strong 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 X-ray diffraction (XRD) figure of sample after the thermal treatment of embodiment one micritization.
Fig. 2 is the Ce of embodiment one excitation of X-rays
3+ion doping LaI
3the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu of embodiment two excitation of X-rays
3+ion doping LaI
3the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb of embodiment three excitation of X-rays
3+ion doping LaI
3the 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 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 675 DEG C, obtained glass is placed in nitrogen fine annealing stove 690 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 LaI of doping
3devitrified glass.
To the LaI of preparation
3devitrified glass carries out X-ray diffraction test, and obtain the XRD figure of glass after micritization process as shown in Figure 1, its result is as follows: the XRD diffraction peak of the sample obtained through Overheating Treatment and LaI
3the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, the material therefore obtained mainly LaI
3the devitrified glass of crystallization phase.And the Ce of excitation of X-rays
3+ion doping LaI
3as shown in Figure 2, glow peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LaI
3devitrified glass light output can reach 58000ph/MeV, and fall time is 30ns, and its light output is high as seen, and fall time is short.
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 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 680 DEG C, obtained glass is placed in nitrogen fine annealing stove 695 DEG C of thermal treatments 3 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 LaI of ion doping
3devitrified glass.
To the LaI of preparation
3the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+ion doping LaI
3as shown in Figure 3, its result shows to produce Eu:LaI after Overheating Treatment the fluorescence spectrum of devitrified glass
3crystallite is significantly improved than luminous intensity with corresponding glass matrix phase, and Eu:LaI is described
3the 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 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 690 DEG C, obtained glass is placed in nitrogen fine annealing stove 710 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 LaI of ion doping
3devitrified glass.
To the LaI of preparation
3the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LaI
3as shown in Figure 4, its result shows to produce Tb:LaI after Overheating Treatment the fluorescence spectrum of devitrified glass
3crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:LaI is described
3the luminosity of devitrified glass is better; The rare earth ion doped LaI obtained by above-mentioned preparation process
3devitrified glass is transparent and physical and chemical performance is excellent.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: 49mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, PrI
3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: 49mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, TbI
3: 1mol%.
Embodiment 4,5 also can obtain LaI rare earth ion doped preferably
3devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.
Claims (5)
1. a rare earth ion doped LaI
3devitrified glass, its Mole percent consists of:
GeO
2：40-60mol％BaF
2：5-15mol％KF：5-10mol％
La
2O
3：5-18mol％LaI
3：15-25mol％LnI
3：2-5mol％
Wherein LnI
3for CeI
3, EuI
3, TbI
3, PrI
3, NdI
3in one.
2. rare earth ion doped LaI according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: GeO
2: 40mol%, BaF
2: 10mol%, KF:10mol%, La
2o
3: 18mol%, LaI
3: 20mol%, CeI
3: 2mol%.
3. rare earth ion doped LaI according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: GeO
2: 45mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, EuI
3: 5mol%.
4. rare earth ion doped LaI according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: GeO
2: 60mol%, BaF
2: 5mol%, KF:5mol%, La
2o
3: 13mol%, LaI
3: 15mol%, TbI
3: 2mol%.
5. rare earth ion doped LaI according to claim 1
3the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) GeO
2-BaF
2-KF-La
2o
3-LaI
3-LnI
3be founding of glass: take analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5%
4hF
2, NH
4hI
2pour into after raw material is mixed in quartz crucible or corundum crucible and melt, temperature of fusion 1300-1480 DEG C, insulation 1-2 hour, pours into glass melt in pig mold, then be placed in retort furnace to anneal, after 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h in glass transformation temperature Tg temperature, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;
(2) LaI
3the preparation of devitrified glass: according to the thermal analysis experiment data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 3 ~ 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 LaI
3devitrified glass.
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|---|---|---|---|
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|---|---|---|---|
| CN201410197933.4A CN103951209B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LaI 3devitrified glass and preparation method thereof |
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|---|---|
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| CN103951209B true CN103951209B (en) | 2016-02-10 |
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| CN105461229A (en) * | 2015-11-16 | 2016-04-06 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystals |
| CN105314854A (en) * | 2015-11-16 | 2016-02-10 | 宁波大学 | Glass containing rare earth ion doped lutetium iodide micro-crystals and preparation method of glass film |
| CN105314872A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped CeI3 glass ceramics and preparation method thereof |
| CN105314858A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped LaI3 glass ceramics and preparation method thereof |
| CN105293925A (en) * | 2015-11-27 | 2016-02-03 | 宁波大学 | Rare earth ion doped GdI3 glass ceramic and preparation method thereof |
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| US5955388A (en) * | 1997-01-02 | 1999-09-21 | Corning Incorporated | Transparent oxyflouride glass-ceramic composition and process of making |
| US6585913B2 (en) * | 2001-07-30 | 2003-07-01 | General Electric Company | Scintillator compositions of alkali and rare-earth tungstates |
| CN1326790C (en) * | 2005-10-28 | 2007-07-18 | 宁波大学 | Rare earth ion doped YAG micro crystalline glass and its preparation method |
| US20090190214A1 (en) * | 2008-01-29 | 2009-07-30 | Nicholas Francis Borrelli | Polarizing photorefractive glass |
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