CN103951258B - Rare earth ion doped SrI2Devitrified glass and preparation method thereof - Google Patents
Rare earth ion doped SrI2Devitrified glass and preparation method thereof Download PDFInfo
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- CN103951258B CN103951258B CN201410198513.8A CN201410198513A CN103951258B CN 103951258 B CN103951258 B CN 103951258B CN 201410198513 A CN201410198513 A CN 201410198513A CN 103951258 B CN103951258 B CN 103951258B
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Abstract
The invention discloses a kind of rare earth ion doped SrI2Devitrified glass and preparation method thereof, its mole of percentage composition is B2O3：55-70mol％、BaF2：5-10mol％、NaF：5-13mol％、SrO：1-5mol％、SrI2: 10-20mol%, rare-earth iodide: 1-4mol%, wherein rare-earth iodide is EuI2、CeI3、TbI3In one, its preparation method is first to prepare B with fusion method2O3-BaF2-NaF-SrO-SrI2-LnI2With B2O3-BaF2-NaF-SrO-SrI2-LnI3Be glass, after heat treatment obtain transparent SrI2Devitrified glass, SrI of the present invention2Devitrified glass, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has extremely strong light output, fast decay, the good performance such as 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 SrI as scintillation material2Devitrified 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 high-energy 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, 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 in aspect difficulties such as light output, numbers of repetition compared with crystal, and therefore its application is also very limited.
SrI2Crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Eu2+The SrI of doping2Crystal has abnormal high light output, and good energy resolution, can be applicable in the fields such as low energy physics and safety check, medical imaging. Ce3+The SrI of doping2Crystal has High Light Output, the feature of fast decay, Tb3+Doping SrI2Crystal can be used for scintillation fluor screen. But SrI2The crystal disadvantages affect such as very easily deliquescence, poor, the easy cleavage slabbing of mechanical performance, large-size crystals growth be difficult, expensive 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 extremely strong light output, fast decay, energy resolution and the good rare earth ion doped SrI of temporal resolution2Devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped SrI2Devitrified glass, its mole of percentage composition is:
B2O3：55-70mol％BaF2：5-10mol％NaF：5-13mol％
SrO：1-5mol％SrI2: 10-20mol% rare-earth iodide: 1-4mol%
Wherein rare-earth iodide is EuI2、CeI3、TbI3In one.
This flicker devitrified glass material component is: B2O3：60mol％、BaF2：5mol％、NaF：10mol％、SrO：1mol％、SrI2：20mol％、EuI2：4mol％。
This flicker devitrified glass material component is: B2O3：55mol％、BaF2：10mol％、NaF：13mol％、SrO：5mol％、SrI2：15mol％、CeI3：2mol％。
This flicker devitrified glass material component is: B2O3：70mol％、BaF2：9mol％、NaF：5mol％、SrO：5mol％、SrI2：10mol％、TbI3：1mol％。
Described rare earth ion doped SrI2The preparation method of devitrified glass, comprises the steps:
(1)B2O3-BaF2-NaF-SrO-SrI2-LnI2、B2O3-BaF2-NaF-SrO-SrI2-LnI3Be founding of glass:
Take analytically pure each raw material by material component, respectively add the NH that accounts for raw material gross weight 5%4HF2、NH4HI2Raw material is mixed, then pour in silica crucible or corundum crucible and melt, fusion temperature 1200-1350 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle furnace power supply and be automatically cooled to room temperature, take out glass, for controlled micro crystallization heat treatment.
(2)SrI2Devitrified glass preparation:
According to heat analysis (DTA) experimental data of glass, the glass making is placed in near nitrogen fine annealing stove heat treatment 4～6 hours 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 SrI2Devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine iodine oxygen compound, short wavelength's through performance is good, has SrI2The superior scintillation properties of crystalline host material and mechanical strength, the stability of oxide glass and be easy to processing feature, overcome SrI2Monocrystal is the shortcoming such as deliquescence, poor, the easy cleavage slabbing of mechanical performance very easily; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped to SrI2Crystalline phase, the rare earth ion doped SrI making2Devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has extremely strong light output, and decay soon, the good performance such as 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.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of sample after embodiment mono-controlled micro crystallization heat treatment.
Fig. 2 is the Eu:SrI of embodiment mono-excitation of X-rays2The fluorescence spectrum of devitrified glass.
Fig. 3 is the Ce:SrI of embodiment bis-excitation of X-rays2The fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:SrI of embodiment tri-excitation of X-rays2The fluorescence spectrum of devitrified glass.
Detailed description of the invention
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, and weigh 50 grams by the formula in table 1 and analyze pure raw material, add 2.5 grams of NH4HF2, 2.5 grams of NH4HI2After raw material is mixed, pour in corundum crucible and melt, 1350 DEG C of fusion temperatures, be incubated 1 hour, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle 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 730 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 760 DEG C of heat 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 Eu2+The SrI of ion doping2Devitrified glass.
To the SrI of preparation2Devitrified glass carries out X-ray diffraction test, obtains glass and schemes as shown in Figure 1 through controlled micro crystallization XRD after treatment, and its result is as follows: XRD diffraction maximum and the SrI of the sample obtaining through Overheating Treatment2The main diffraction maximum of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtaining is SrI2The devitrified glass of crystallization phase. And the Eu of excitation of X-rays2+Ion doping SrI2As shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass. Mix Eu2+Ion SrI2The output of devitrified glass light can reach 110000ph/MeV.
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, and weigh 50 grams by the formula in table 2 and analyze pure raw material, add 2.5 grams of NH4HF2, 2.5 grams of NH4HI2After raw material is mixed, pour in silica crucible and melt, 1200 DEG C of fusion temperatures, be incubated 2 hours, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle 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 720 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 750 DEG C of heat 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 Ce3+The SrI of doping2Devitrified glass sample.
To the SrI of preparation2The spectral quality test of devitrified glass, the Ce of excitation of X-rays3+Ion doping SrI2As shown in Figure 3, its result shows to produce Ce:SrI after Overheating Treatment to the fluorescence spectrum of devitrified glass2Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Ce:SrI is described2The 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, and weigh 50 grams by the formula in table 3 and analyze pure raw material, add 2.5 grams of NH4HF2, 2.5 grams of NH4HI2After raw material is mixed, pour in silica crucible and melt, 1300 DEG C of fusion temperatures, be incubated 1.5 hours, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle 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 745 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 780 DEG C of heat 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 Tb3+The SrI of ion doping2Devitrified glass.
To the SrI of preparation2The spectral quality test of devitrified glass, the Tb of excitation of X-rays3+Ion doping SrI2As shown in Figure 4, its result shows to produce Tb:SrI after Overheating Treatment to the fluorescence spectrum of devitrified glass2Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:SrI is described2The luminosity of devitrified glass is better; The rare earth ion doped SrI being obtained by above-mentioned preparation process2Devitrified glass is transparent and physical and chemical performance is good.
Claims (5)
1. a rare earth ion doped SrI2Devitrified glass, its mole of percentage composition is:
B2O3：55-70mol％BaF2：5-10mol％NaF：5-13mol％
SrO：1-5mol％SrI2: 10-20mol% rare-earth iodide: 1-4mol%
Wherein rare-earth iodide is EuI2、CeI3、TbI3In one.
2. rare earth ion doped SrI claimed in claim 12Devitrified glass, is characterized in that this devitrified glass material component is:B2O3：60mol％、BaF2：5mol％、NaF：10mol％、SrO：1mol％、SrI2：20mol％、EuI2：4mol％。
3. rare earth ion doped SrI claimed in claim 12Devitrified glass, is characterized in that this devitrified glass material component is:B2O3：55mol％、BaF2：10mol％、NaF：13mol％、SrO：5mol％、SrI2：15mol％、CeI3：2mol％。
4. rare earth ion doped SrI claimed in claim 12Devitrified glass, is characterized in that this devitrified glass material component is:B2O3：70mol％、BaF2：9mol％、NaF：5mol％、SrO：5mol％、SrI2：10mol％、TbI3：1mol％。
5. rare earth ion doped SrI according to claim 12The preparation method of devitrified glass, under it is characterized in that comprisingRow concrete steps:
(1)B2O3-BaF2-NaF-SrO-SrI2-rare-earth iodide is founding of glass, and wherein rare-earth iodide is EuI2、CeI3、TbI3In one: take analytically pure each raw material by material component, respectively add the NH that accounts for raw material gross weight 5%4HF2、NH4HI2，Raw material is mixed, then pour in silica crucible or corundum crucible and melt, fusion temperature 1200-1350 DEG C, 1-2 is little in insulationTime, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, in glass transformation temperature Tg temperature insulation 2After hour, be cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle furnace power supply and be automatically cooled to room temperature, take out glass, useIn controlled micro crystallization heat treatment;
(2)SrI2The preparation of devitrified glass: according to the thermal analysis experiment data of glass, the glass making is placed in to nitrogen precision and moves backIn stove, near heat treatment 4～6 hours 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, be automatically cooled to room temperature, obtain transparent rare earth ion doped SrI2Devitrified glass.
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| CN105778900B (en) * | 2014-12-24 | 2018-03-16 | 有研稀土新材料股份有限公司 | Inorganic scintillation material |
| CN105293941A (en) * | 2015-11-16 | 2016-02-03 | 宁波大学 | Preparation method for glass film containing divalent-europium-ion-doped strontium iodide microcrystalline |
| CN105330163A (en) * | 2015-11-27 | 2016-02-17 | 宁波大学 | Rare earth ion doped SrI2 microcrystalline glass and preparation method thereof |
| CN105314864A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare-earth ion doping SrBr2 glass ceramics and preparation method thereof |
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