CN103951238A - Rare-earth-ion-doped RbGd2I7 microcrystalline glass and preparation method thereof - Google Patents

Rare-earth-ion-doped RbGd2I7 microcrystalline glass and preparation method thereof Download PDF

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CN103951238A
CN103951238A CN201410198313.2A CN201410198313A CN103951238A CN 103951238 A CN103951238 A CN 103951238A CN 201410198313 A CN201410198313 A CN 201410198313A CN 103951238 A CN103951238 A CN 103951238A
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rbgd
glass
devitrified glass
rare earth
preparation
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CN103951238B (en
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欧阳绍业
张约品
夏海平
张为欢
王倩
杨斌
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Ningbo University
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Ningbo University
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Abstract

The invention discloses a rare-earth-ion-doped RbGd2I7 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, 8-11 mol% of BaF2, 5-10 mol% of ZnF2, 10-15 mol% of RbGd2I7 and 1-4 mol% of LnI3. The LnI3 is CeI3, EuI3, TbI3, PrI3 or NdI3. The preparation method comprises the following steps: preparing TeO2-BaF2-ZnF2-RbGd2I7-LnI3 glass by a fusion process, and carrying out heat treatment to obtain the transparent RbGd2I7 microcrystalline glass. The RbGd2I7 microcrystalline glass has the advantages of deliquescence resistance, favorable mechanical properties, higher short-wavelength blue-violet light transmission rate, superhigh light output, quick attenuation, favorable energy resolution, favorable time resolution and the like. The preparation method of the microcrystalline glass is simple and lower in production cost.

Description

Rare earth ion doped RbGd 2i 7devitrified glass and preparation method thereof
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 RbGd as scintillation material 2i 7devitrified 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.
RbGd 2i 7crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce 3+the RbGd of doping 2i 7it is high that crystal has light output, decay soon, and good energy resolution, temporal resolution and linear response, have than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, can make flash detection instrument efficiency greatly improve.Eu 3+, Tb 3+doping RbGd 2i 7the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But RbGd 2i 7crystal is deliquescence very easily, and mechanical property is poor, easy cleavage slabbing, and large-size crystals growth difficulty, and expensively affected 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 RbGd of temporal resolution 2i 7devitrified glass.The present invention also provides the preparation method of this flicker devitrified glass, and it is simple that this preparation method has method, the advantage that cost is low.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped RbGd 2i 7devitrified glass, its mole of percentage composition is:
TeO 2：65-75mol％ BaF 2：8-11mol％ ZnF 2：5-10mol％
RbGd 2I 7：10-15mol％ LnI 3：1-4mol％
LnI wherein 3for CeI 3, EuI 3, TbI 3, PrI 3and NdI 3in a kind of.
This flicker devitrified glass material component is TeO 2: 65mol%, BaF 2: 9mol%, ZnF 2: 10mol%, RbGd 2i 7: 15mol%, CeI 3: 1mol%.
This flicker devitrified glass material component is: TeO 2: 70mol%, BaF 2: 11mol%, ZnF 2: 5mol%, RbGd 2i 7: 10mol%, EuI 3: 4mol%.
This flicker devitrified glass material component is: TeO 2: 75mol%, BaF 2: 8mol%, ZnF 2: 5mol%, RbGd 2i 7: 10mol%, TbI 3: 2mol%.
Described rare earth ion doped RbGd 2i 7the preparation method of devitrified glass, comprises the steps:
(1) TeO 2-BaF 2-ZnF 2-RbGd 2i 7-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 1 hour, 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) RbGd 2i 7devitrified 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 RbGd 2i 7devitrified 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 RbGd 2i 7the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome RbGd 2i 7single 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 RbGd 2i 7crystalline phase, the rare earth ion doped RbGd making 2i 7devitrified 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 the scanning electron microscope diagram (SEM) of sample after embodiment mono-micritization thermal treatment.
Fig. 2 is the Ce:RbGd of embodiment mono-excitation of X-rays 2i 7the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:RbGd of embodiment bis-excitation of X-rays 2i 7the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:RbGd of embodiment tri-excitation of X-rays 2i 7the 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 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 1 hour, 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 450 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 467 ℃ 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 RbGd of doping 2i 7devitrified glass.
RbGd to preparation 2i 7devitrified glass carries out sem test, obtains the scanning electron microscope diagram of glass after micritization is processed as shown in Figure 1, and what in photo, be particle shape is the nano microcrystalline of separating out, and particle gap is glassy phase.The test of X-ray diffraction shows that crystalline phase is RbGd 2i 7phase, the material therefore obtaining is RbGd 2i 7the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping RbGd 2i 7as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion RbGd 2i 7the output of devitrified glass light can reach 81000ph/MeV, and be 46ns fall time.
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 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 1 hour, 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 456 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 475 ℃ 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 3+the RbGd of ion doping 2i 7devitrified glass.
RbGd to preparation 2i 7the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping RbGd 2i 7as shown in Figure 3, its result shows to produce Eu:RbGd after Overheating Treatment to the fluorescence spectrum of devitrified glass 2i 7crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:RbGd is described 2i 7the 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 1 hour, 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 470 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 490 ℃ 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 RbGd of ion doping 2i 7devitrified glass.
RbGd to preparation 2i 7the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping RbGd 2i 7as shown in Figure 4, its result shows to produce Tb:RbGd after Overheating Treatment to the fluorescence spectrum of devitrified glass 2i 7crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:RbGd is described 2i 7the luminosity of devitrified glass is better; The rare earth ion doped RbGd being obtained by above-mentioned preparation process 2i 7devitrified glass is transparent and physical and chemical performance is good.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: TeO 2: 70mol%, BaF2:11mol%, ZnF 2: 8mol%, RbGd 2i 7: 10mol%, PrI 3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: TeO 2: 70mol%, BaF2:11mol%, ZnF 2: 8mol%, RbGd 2i 7: 10mol%, NdI 3: 1mol%.
Embodiment 4,5 also can obtain rare earth ion doped RbGd preferably 2i 7devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped RbGd 2i 7devitrified glass, its mole of percentage composition is:
TeO 2：65-75mol％ BaF 2：8-11mol％ ZnF 2：5-10mol％
RbGd 2I 7：10-15mol％ LnI 3：1-4mol％
LnI wherein 3for CeI 3, EuI 3, TbI 3, PrI 3and NdI 3in a kind of.
2. rare earth ion doped RbGd claimed in claim 1 2i 7devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO 2: 65mol%, BaF 2: 9mol%, ZnF 2: 10mol%, RbGd 2i 7: 15mol%, CeI 3: 1mol%.
3. rare earth ion doped RbGd claimed in claim 1 2i 7devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO 2: 70mol%, BaF 2: 11mol%, ZnF 2: 5mol%, RbGd 2i 7: 10mol%, EuI 3: 4mol%.
4. rare earth ion doped RbGd claimed in claim 1 2i 7devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO 2: 75mol%, BaF 2: 8mol%, ZnF 2: 5mol%, RbGd 2i 7: 10mo1%, TbI 3: 2mo1%.
5. rare earth ion doped RbGd according to claim 1 2i 7the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) TeO 2-BaF 2-ZnF 2-RbGd 2i 7-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 1 hour, 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) RbGd 2i 7the preparation of devitrified glass: according to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near its first crystallization peak, heat-treated is 4～6 hours, 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 RbGd 2dI 7devitrified glass.
CN201410198313.2A 2014-05-08 2014-05-08 Rare earth ion doped RbGd2i7devitrified glass and preparation method thereof Expired - Fee Related CN103951238B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105293919A (en) * 2015-11-16 2016-02-03 宁波大学 Glass film containing rare-earth-ion-doped Cs2LiLaI6 microcrystalline and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105293919A (en) * 2015-11-16 2016-02-03 宁波大学 Glass film containing rare-earth-ion-doped Cs2LiLaI6 microcrystalline and preparation method thereof

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