CN103951224B - Rare earth ion doped LiI devitrified glass and preparation method thereof - Google Patents
Rare earth ion doped LiI devitrified glass and preparation method thereof Download PDFInfo
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- CN103951224B CN103951224B CN201410198135.3A CN201410198135A CN103951224B CN 103951224 B CN103951224 B CN 103951224B CN 201410198135 A CN201410198135 A CN 201410198135A CN 103951224 B CN103951224 B CN 103951224B
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Abstract
The invention discloses a kind of rare earth ion doped LiI devitrified glass and preparation method thereof, its Mole percent consists of P
2o
5: 35-45mol%, GeO
2: 10-20mol%, NaF:15-23mol%, Li
2o:5-9mol%, LiI:15-20mol%, LnI
3: 1-4mol%, wherein LnI
3for CeI
3, EuI
3, TbI
3in one, its preparation method first prepares P with scorification
2o
5-GeO
2-NaF-Li
2o-LiI-LnI
3be glass, after heat treatment obtain transparent LiI devitrified glass, LiI devitrified glass of the present invention, 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
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 LiI devitrified glass as scintillation material 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.
LiI crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce
3+to have light output high for the LiI crystal of doping, 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+the scintillation properties of Li doped I crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LiI crystal very easily deliquescence, 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 LiI devitrified glass of temporal resolution and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped LiI devitrified glass, and its Mole percent consists of:
P
2O
5：35-45mol％GeO
2：10-20mol％NaF：15-23mol％
Li
2O：5-9mol％LiI：15-20mol％LnI
3：1-4mol％
Wherein LnI
3for CeI
3, EuI
3, TbI
3in one.
This flicker devitrified glass material component is: P
2o
5: 35mol%, GeO
2: 20mol%, NaF:23mol%, Li
2o:5mol%, LiI:15mol%, CeI
3: 2mol%.
This flicker devitrified glass material component is: P
2o
5: 40mol%, GeO
2: 15mol%, NaF:15mol%, Li
2o:6mol%, LiI:20mol%, EuI
3: 4mol%.
This flicker devitrified glass material component is: P
2o
5: 45mol%, GeO
2: 10mol%, NaF:20mol%, Li
2o:9mol%, LiI:15mol%, TbI
3: 1mol%.
The preparation method of described rare earth ion doped LiI devitrified glass, comprises the steps:
(1) P
2o
5-GeO
2-NaF-Li
2o-LiI-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
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, then glass is placed in retort furnace and anneals, in glass transformation temperature Tg temperature after 2 hours, 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) LiI devitrified glass preparation:
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 LiI devitrified 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, there is the physical strength of the superior scintillation properties of LiI crystalline host material and oxide glass, stability and be easy to the feature of processing, overcome the LiI single crystal very easily shortcoming such as deliquescence, poor, the easy cleavage slabbing of mechanical property; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped to LiI crystalline phase, obtained rare earth ion doped LiI devitrified glass is transparent, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, there is stronger light output, fast decay, 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 X-ray diffraction (XRD) figure of sample after the thermal treatment of embodiment one micritization.
Fig. 2 is the fluorescence spectrum of the Ce:LiI devitrified glass of embodiment one excitation of X-rays.
Fig. 3 is the fluorescence spectrum of the Eu:LiI devitrified glass of embodiment two excitation of X-rays.
Fig. 4 is the fluorescence spectrum of the Tb:LiI devitrified glass of embodiment three excitation of X-rays.
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 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 2 hours, 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 770 DEG C, obtained glass is placed in nitrogen fine annealing stove 790 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 LiI devitrified glass sample of doping.
X-ray diffraction test is carried out to the LiI devitrified glass of preparation, obtain the XRD figure of glass after micritization process as shown in Figure 1, its result is as follows: the XRD diffraction peak of sample obtained through Overheating Treatment all conforms to the main diffraction peak of the standard x RD figure of LiI crystalline phase, and the material therefore obtained is the devitrified glass of LiI crystallization phase.And the Ce of excitation of X-rays
3+as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of ion doping LiI devitrified glass.Mix Ce
3+ion LiI devitrified glass light output is 25000ph/MeV, and fall time is 60ns.
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 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 2 hours, 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 780 DEG C, obtained glass is placed in nitrogen fine annealing stove 800 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
2+the LiI devitrified glass of ion doping.
To the spectral quality test of the LiI devitrified glass of preparation, the Eu of excitation of X-rays
3+as shown in Figure 3, its result shows that after Overheating Treatment, produce Eu:LiI crystallite luminous intensity compared with corresponding glass basis is significantly improved, and illustrates that the luminosity of Eu:LiI crystallite is better to the fluorescence spectrum of ion doping LiI devitrified glass.
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 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 2 hours, 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 790 DEG C, obtained glass is placed in nitrogen fine annealing stove 810 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 LiI devitrified glass of ion doping.
To the spectral quality test of the LiI devitrified glass of preparation, the Tb of excitation of X-rays
3+as shown in Figure 4, its result shows that after Overheating Treatment, produce Tb:LiI crystallite luminous intensity compared with corresponding glass basis is significantly improved, and illustrates that the luminosity of Tb:LiI crystallite is better to the fluorescence spectrum of ion doping LiI devitrified glass; The rare earth ion doped LiI devitrified glass obtained by above-mentioned preparation process is transparent and physical and chemical performance is excellent.
Claims (5)
1. a rare earth ion doped LiI devitrified glass, its Mole percent consists of:
P
2O
5：35-45mol％GeO
2：10-20mol％NaF：15-23mol％
Li
2O：5-9mol％LiI：15-20mol％LnI
3：1-4mol％
Wherein LnI
3for CeI
3, EuI
3, TbI
3in one.
2. rare earth ion doped LiI devitrified glass according to claim 1, is characterized in that this devitrified glass material component is: P
2o
5: 35mol%, GeO
2: 20mol%, NaF:23mol%, Li
2o:5mol%, LiI:15mol%, CeI
3: 2mol%.
3. rare earth ion doped LiI devitrified glass according to claim 1, is characterized in that this devitrified glass material component is: P
2o
5: 40mol%, GeO
2: 15mol%, NaF:15mol%, Li
2o:6mol%, LiI:20mol%, EuI
3: 4mol%.
4. rare earth ion doped LiI devitrified glass according to claim 1, is characterized in that this devitrified glass material component is: P
2o
5: 45mol%, GeO
2: 10mol%, NaF:20mol%, Li
2o:9mol%, LiI:15mol%, TbI
3: 1mol%.
5. the preparation method of rare earth ion doped LiI devitrified glass according to claim 1, is characterized in that comprising following concrete steps:
(1) P
2o
5-GeO
2-NaF-Li
2o-LiI-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
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 2 hours, 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) preparation of LiI 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 LiI devitrified glass.
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|---|---|---|---|
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|---|---|---|---|
| CN201410198135.3A CN103951224B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LiI devitrified glass and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103951224A CN103951224A (en) | 2014-07-30 |
| CN103951224B true CN103951224B (en) | 2016-04-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293943A (en) * | 2015-11-16 | 2016-02-03 | 宁波大学 | Glass film containing rare-earth-ion-doped lithium iodide microcrystalline and preparation method thereof |
| CN111499204A (en) * | 2020-04-21 | 2020-08-07 | 中国工程物理研究院材料研究所 | Ce3+Silicate-doped scintillation glass and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599284A (en) * | 1985-10-01 | 1986-07-08 | Union Carbide Corporation | Vitreous phosphorus oxide-sulfide solid lithium electrolyte |
| CN1952689A (en) * | 2005-10-19 | 2007-04-25 | 原子高科股份有限公司 | scintillation activity meter |
| CN101811829A (en) * | 2010-03-31 | 2010-08-25 | 武汉理工大学 | Chalcogenide microcrystalline glass material with function of lithium ion conductor and preparation method thereof |
-
2014
- 2014-05-08 CN CN201410198135.3A patent/CN103951224B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599284A (en) * | 1985-10-01 | 1986-07-08 | Union Carbide Corporation | Vitreous phosphorus oxide-sulfide solid lithium electrolyte |
| CN1952689A (en) * | 2005-10-19 | 2007-04-25 | 原子高科股份有限公司 | scintillation activity meter |
| CN101811829A (en) * | 2010-03-31 | 2010-08-25 | 武汉理工大学 | Chalcogenide microcrystalline glass material with function of lithium ion conductor and preparation method thereof |
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