CN103951214B - Rare earth ion doped LuBr 3devitrified glass and preparation method thereof - Google Patents
Rare earth ion doped LuBr 3devitrified glass and preparation method thereof Download PDFInfo
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- CN103951214B CN103951214B CN201410198017.2A CN201410198017A CN103951214B CN 103951214 B CN103951214 B CN 103951214B CN 201410198017 A CN201410198017 A CN 201410198017A CN 103951214 B CN103951214 B CN 103951214B
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Abstract
The invention discloses a kind of rare earth ion doped LuBr
3devitrified glass and preparation method thereof, its Mole percent consists of TeO
2: 65-75mol%, ZnF
2: 5-10mol%, Lu
2o
3: 8-11mol%, LuBr
3: 10-15mol%, LnBr
3: 1-4mol%, wherein LnBr
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in one, its preparation method first prepares TeO with scorification
2-ZnF
2-Lu
2o
3-LuBr
3-LnBr
3be glass, after heat treatment obtain transparent LuBr
3devitrified glass, LuBr of the present invention
3devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple photopermeability are good, 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
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 LuBr 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.
LuBr
3crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce
3+the LuBr 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+, Tb
3+doping LuBr
3the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LuBr
3crystal 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 LuBr 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 LuBr
3devitrified glass, its Mole percent consists of:
TeO
2：65-75mol％ZnF
2：5-10mol％Lu
2O
3：8-11mol％
LuBr
3：10-15mol％LnBr
3：1-4mol％
Wherein LnBr
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in one.
This flicker devitrified glass material component is: TeO
2: 65mol%, ZnF
2: 10mol%, Lu
2o
3: 9mol%, LuBr
3: 15mol%, CeBr
3: 1mol%.
This flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 5mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, EuBr
3: 4mol%.
This flicker devitrified glass material component is: TeO
2: 75mol%, ZnF
2: 5mol%, Lu
2o
3: 8mol%, LuBr
3: 10mol%, TbBr
3: 2mol%.
Described rare earth ion doped LuBr
3the preparation method of devitrified glass, comprises the steps:
(1) TeO
2-ZnF
2-Lu
2o
3-LuBr
3-LnBr
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
4hBr
2raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 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) LuBr
3prepared 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 LuBr
3devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine bromine oxygen compound, the through performance of short wavelength is good, has LuBr
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 LuBr
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 LuBr
3crystalline phase, obtained rare earth ion doped LuBr
3devitrified 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 scanning electron microscope diagram (SEM) 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 LuBr
3the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu of embodiment two excitation of X-rays
3+ion doping LuBr
3the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb of embodiment three excitation of X-rays
3+ion doping LuBr
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 NH4HF
2, 2.5 grams of NH
4hBr
2pour in quartz crucible after raw material is mixed and melt, temperature of fusion 800 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 455 DEG C, obtained glass is placed in nitrogen fine annealing stove 475 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 LuBr of doping
3devitrified glass.
To the LuBr of preparation
3devitrified glass carries out sem test, obtains the scanning electron microscope diagram of glass after micritization process as shown in Figure 1, and in particle shape in photo is the nano microcrystalline of separating out, and all the other are glassy phases.The test of X-ray diffraction shows that crystalline phase is LuBr
3phase, the material therefore obtained is LuBr
3the devitrified glass of crystallization phase.The Ce of excitation of X-rays
3 +ion doping LuBr
3as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LuBr
3devitrified glass light output can reach 24000ph/MeV, and fall time is 32ns, 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
4hBr
2pour in corundum crucible after raw material is mixed and melt, temperature of fusion 850 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 462 DEG C, obtained glass is placed in nitrogen fine annealing stove 480 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 LuBr of ion doping
3devitrified glass.
To the LuBr of preparation
3the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+ion doping LuBr
3as shown in Figure 3, its result shows to produce Eu:LuBr after Overheating Treatment the fluorescence spectrum of devitrified glass
3crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LuBr is described
3the luminosity of devitrified glass is better; Be expected to very much the scintillator be used as in safety check.
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
4hBr
2pour in quartz crucible after raw material is mixed and melt, temperature of fusion 900 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 471 DEG C, obtained glass is placed in fine annealing stove 490 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 LuBr of ion doping
3devitrified glass.
To the LuBr of preparation
3the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LuBr
3as shown in Figure 4, its result shows to produce Tb:LuBr after Overheating Treatment the fluorescence spectrum of devitrified glass
3crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:LuBr is described
3the luminosity of devitrified glass is better; The rare earth ion doped LuBr 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: this flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 8mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, PrBr
3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: this flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 8mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, NdBr
3: 1mol%.
Embodiment 4,5 also can obtain LuBr 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 LuBr
3devitrified glass, its Mole percent consists of:
TeO
2：65-75mol％ZnF
2：5-10mol％Lu
2O
3：8-11mol％
LuBr
3：10-15mol％LnBr
3：1-4mol％
Wherein LnBr
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in one.
2. rare earth ion doped LuBr according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: TeO
2: 65mol%, ZnF
2: 10mol%, Lu
2o
3: 9mol%, LuBr
3: 15mol%, CeBr
3: 1mol%.
3. rare earth ion doped LuBr according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 5mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, EuBr
3: 4mol%.
4. rare earth ion doped LuBr according to claim 1
3devitrified glass, is characterized in that this devitrified glass material component is: TeO
2: 75mol%, ZnF
2: 5mol%, Lu
2o
3: 8mol%, LuBr
3: 10mol%, TbBr
3: 2mol%.
5. rare earth ion doped LuBr according to claim 1
3the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) TeO
2-ZnF
2-Lu
2o
3-LuBr
3-LnBr
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
4hBr
2raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 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) LuBr
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 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 LuBr
3devitrified glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198017.2A CN103951214B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LuBr 3devitrified glass and preparation method thereof |
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|---|---|---|---|
| CN201410198017.2A CN103951214B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LuBr 3devitrified glass and preparation method thereof |
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|---|---|
| CN103951214A CN103951214A (en) | 2014-07-30 |
| CN103951214B true CN103951214B (en) | 2016-04-27 |
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