CN103951259A - Rare-earth-ion-doped BaI2 microcrystalline glass and preparation method thereof - Google Patents
Rare-earth-ion-doped BaI2 microcrystalline glass and preparation method thereof Download PDFInfo
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- CN103951259A CN103951259A CN201410198522.7A CN201410198522A CN103951259A CN 103951259 A CN103951259 A CN 103951259A CN 201410198522 A CN201410198522 A CN 201410198522A CN 103951259 A CN103951259 A CN 103951259A
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- bai
- glass
- bao
- devitrified glass
- bai2
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Abstract
The invention discloses a rare-earth-ion-doped BaI2 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 65-75 mol% of TeO2, 5-10 mol% of ZnF2, 8-11 mol% of BaO, 10-15 mol% of BaI2 and 1-4 mol% of rare-earth iodide. The rare-earth iodide is EuI2, CeI3 or TbI3. The preparation method comprises the following steps: preparing TeO2-ZnF2-BaO-BaI2-LnI2 or TeO2-ZnF2-BaO-BaI2-LnI3 glass by a fusion process, and carrying out heat treatment to obtain the transparent BaI2 microcrystalline glass. The BaI2 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, and overcomes the defects of high tendency to deliquescence, poor mechanical properties, high tendency to flaking and the like in the iodide monocrystal. The preparation method of the microcrystalline glass is simple and lower in production cost.
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 BaI as scintillation material
2devitrified 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.
BaI
2crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Eu
2+the BaI of doping
2crystal 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.Ce
3+the BaI of doping
2crystal has High Light Output, the feature of fast decay, Tb
3+doping BaI
2crystal can be used for scintillation fluor screen.But BaI
2the crystal disadvantages affect such as very easily deliquescence, poor, the easy cleavage slabbing of mechanical property, 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 BaI of temporal resolution
2devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped BaI
2devitrified glass, its mole of percentage composition is:
TeO
2：65-75mol％ ZnF
2：5-10mol％ BaO：8-11mol％
BaI
2: 10-15mol% rare-earth iodide: 1-4mol%
Wherein rare-earth iodide is EuI
2, CeI
3, TbI
3in a kind of.
This flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 5mol%, BaO:11mol%, BaI
2: 10 mol%, EuI
2: 4mol%.
This flicker devitrified glass material component is: TeO
2: 65mol%, ZnF
2: 10mol%, BaO:9mol%, BaI
2: 15mol%, CeI
3: 1mol%.
This flicker devitrified glass material component is: TeO
2: 75mol%, ZnF
2: 5mol%, BaO:8mol%, BaI
2: 10mol%, TbI
3: 2mol%.
Described rare earth ion doped BaI
2the preparation method of devitrified glass, comprises the steps:
(1) TeO
2-ZnF
2-BaO-BaI
2-LnI
2, TeO
2-ZnF
2-BaO-BaI
2-LnI
3be founding of glass:
By material component, take analytically pure each raw material, respectively add the NH that accounts for raw material gross weight 5%
4hF
2, NH
4hI
2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 ℃, 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 2 hours, 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) BaI
2devitrified glass preparation:
According to heat analysis (DTA) experimental data of glass, the glass making is placed in near nitrogen 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, obtain transparent rare earth ion doped BaI
2devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of fluorine iodine oxygen compound, short wavelength's through performance is good, has BaI
2the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome BaI
2single 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 BaI
2crystalline phase, the rare earth ion doped BaI making
2devitrified 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 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 X-ray diffraction (XRD) figure of sample after embodiment mono-micritization thermal treatment.
Fig. 2 is the Eu:BaI of embodiment mono-excitation of X-rays
2the fluorescence spectrum of devitrified glass.
Fig. 3 is the Ce:BaI of embodiment bis-excitation of X-rays
2the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:BaI of embodiment tri-excitation of X-rays
2the 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
4hI
2after raw material is mixed, pour in corundum crucible and melt, 900 ℃ 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 2 hours, 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 480 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 499 ℃ 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
2+the BaI of ion doping
2devitrified glass.
BaI to preparation
2devitrified glass carries out X-ray diffraction test, obtains the XRD figure of glass after micritization is processed as shown in Figure 1, and its result is as follows: XRD diffraction peak and the BaI of the sample obtaining through Overheating Treatment
2the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtaining is BaI
2the devitrified glass of crystallization phase.And the Eu of excitation of X-rays
2+ion doping BaI
2as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Eu
2+ion BaI
2the output of devitrified glass light can reach 103000ph/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, 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
4hI
2after raw material is mixed, pour in quartz crucible and melt, 800 ℃ 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 2 hours, 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 475 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 492 ℃ 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 BaI of doping
2devitrified glass.
BaI to preparation
2the spectral quality test of devitrified glass, the Ce of excitation of X-rays
3+ion doping BaI
2as shown in Figure 3, its result shows to produce Ce:BaI after Overheating Treatment to the fluorescence spectrum of devitrified glass
2crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Ce:BaI is described
2the 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
4hI
2after raw material is mixed, pour in quartz crucible and melt, 850 ℃ 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 2 hours, 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 485 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 505 ℃ 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 BaI of ion doping
2devitrified glass.
BaI to preparation
2the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping BaI
2as shown in Figure 4, its result shows to produce Tb:BaI after Overheating Treatment to the fluorescence spectrum of devitrified glass
2crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:BaI is described
2the luminosity of devitrified glass is better; The rare earth ion doped BaI being obtained by above-mentioned preparation process
2devitrified glass is transparent and physical and chemical performance is good.
Claims (5)
1. a rare earth ion doped BaI
2devitrified glass, its mole of percentage composition is:
TeO
2：65-75mol％ ZnF
2：5-10mol％ BaO：8-11mol％
BaI
2: 10-15mol% rare-earth iodide: 1-4mol%
Wherein rare-earth iodide is EuI
2, CeI
3, TbI
3in a kind of.
2. rare earth ion doped BaI claimed in claim 1
2devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 5mol%, BaO:11mol%, BaI
2: 10mol%, EuI
2: 4mol%.
3. rare earth ion doped BaI claimed in claim 1
2devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO
2: 65mol%, ZnF
2: 10mol%, BaO:9mol%, BaI
2: 15mol%, CeI
3: 1mol%.
4. rare earth ion doped BaI claimed in claim 1
2devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO
2: 75mol%, ZnF
2: 5mol%, BaO:8mol%, BaI
2: 10mol%, TbI
3: 2mol%.
5. rare earth ion doped BaI according to claim 1
2the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) TeO
2-ZnF
2-BaO-BaI
2-LnI
2, TeO
2-ZnF
2-BaO-BaI
2-LnI
3be founding of glass: by material component, take analytically pure each raw material, respectively add the NH that accounts for raw material gross weight 5%
4hF
2, NH
4hI
2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 ℃, 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 2 hours, 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) BaI
2the preparation of devitrified glass: according to the thermal analysis experiment data of glass, the glass making is placed in near nitrogen 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, obtain transparent rare earth ion doped BaI
2devitrified glass.
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|---|---|---|---|
| CN201410198522.7A CN103951259B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped BaI2devitrified glass and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103951259A true CN103951259A (en) | 2014-07-30 |
| CN103951259B CN103951259B (en) | 2016-09-14 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384343A (en) * | 2015-11-16 | 2016-03-09 | 宁波大学 | Preparation method of glass film containing rare-earth ion doped barium iodide microcrystals |
| CN107162413A (en) * | 2017-05-09 | 2017-09-15 | 中国科学院西安光学精密机械研究所 | A kind of fluorotellurite glass and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913767A (en) * | 2010-08-03 | 2010-12-15 | 宁波大学 | Rare-earth doped oxyfluoride tellurate scintillation glass and preparation method thereof |
| US20130175475A1 (en) * | 2011-11-24 | 2013-07-11 | Vladimir Ouspenski | Luminescent material and a process of forming the same |
-
2014
- 2014-05-08 CN CN201410198522.7A patent/CN103951259B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913767A (en) * | 2010-08-03 | 2010-12-15 | 宁波大学 | Rare-earth doped oxyfluoride tellurate scintillation glass and preparation method thereof |
| US20130175475A1 (en) * | 2011-11-24 | 2013-07-11 | Vladimir Ouspenski | Luminescent material and a process of forming the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384343A (en) * | 2015-11-16 | 2016-03-09 | 宁波大学 | Preparation method of glass film containing rare-earth ion doped barium iodide microcrystals |
| CN107162413A (en) * | 2017-05-09 | 2017-09-15 | 中国科学院西安光学精密机械研究所 | A kind of fluorotellurite glass and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103951259B (en) | 2016-09-14 |
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