CN103951222A - Rare-earth-ion-doped SrBr2 microcrystalline glass and preparation method thereof - Google Patents
Rare-earth-ion-doped SrBr2 microcrystalline glass and preparation method thereof Download PDFInfo
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- CN103951222A CN103951222A CN201410198132.XA CN201410198132A CN103951222A CN 103951222 A CN103951222 A CN 103951222A CN 201410198132 A CN201410198132 A CN 201410198132A CN 103951222 A CN103951222 A CN 103951222A
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- srbr
- glass
- rare earth
- sro
- devitrified glass
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Abstract
The invention discloses a rare-earth-ion-doped SrBr2 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 30-40 mol% of P2O5, 25-30 mol% of B2O3, 7-15 mol% of BaF2, 5-9 mol% of SrO, 15-20 mol% of SrBr2 and 1-4 mol% of rare-earth bromide. The rare-earth bromide is EuBr2, CeBr3 or TbBr3. The preparation method comprises the following steps: preparing P2O5-B2O3-BaF2-SrO-SrBr2-LnBr2 or P2O5-B2O3-BaF2-SrO-SrBr2-LnBr3 glass by a fusion process, and carrying out heat treatment to obtain the transparent SrBr2 microcrystalline glass. The SrBr2 microcrystalline glass has the advantages of deliquescence resistance, favorable mechanical properties, higher short-wavelength blue-violet light transmission rate, high flare light emission output, favorable energy resolution and the like. 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 SrBr 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 is with short production cycle, cost is low, be easy to batch production, can realize large size in preparation technology, it is compared with crystal in aspect difficulties such as light output, multiplicity, so its application is also very limited.
SrBr
2crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Eu
2+the SrBr 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 SrBr of doping
2crystal has High Light Output, the feature of fast decay, Tb
3+doping SrBr
2crystal can be used for scintillation fluor screen.But SrBr
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 stronger light output, fast decay, energy resolution and the good rare earth ion doped SrBr 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 SrBr
2devitrified glass, its mole of percentage composition is:
P
2O
5：30-40mol％ B
2O
3：25-30mol％ BaF
2：7-15mol％
SrO:5-9mol% SrBr
2: 15-20mol% rare earth bromide: 1-4mol%
Wherein rare earth bromide is EuBr
2, CeBr
3, TbBr
3in a kind of.
This flicker devitrified glass material component is: P
2o
5: 35mol%, B
2o
3: 28mol%, BaF
2: 7mol%, SrO:6mol%, SrBr
2: 20mol%, EuBr
2: 4mol%.
This flicker devitrified glass material component is: P
2o
5: 30mol%, B
2o
3: 30mol%, BaF
2: 15mol%, SrO:5mol%, SrBr
2: 19mol%, CeBr
3: 1mol%.
This flicker devitrified glass material component is: P
2o
5: 40mol%, B
2o
3: 25mol%, BaF
2: 9mol%, SrO:9mol%, SrBr
2: 15mol%, TbBr
3: 2mol%.
Described rare earth ion doped SrBr
2the preparation method of devitrified glass, comprises the steps:
(1) P
2o
5-B
2o
3-BaF
2-SrO-SrBr
2-LnBr
2, P
2o
5-B
2o
3-NaF-SrO-SrBr
2-LnBr
3be founding of glass:
By material component, take analytically pure each raw material, raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1360-1460 ℃, 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) SrBr
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 SrBr
2devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of fluorine bromine oxygen compound, short wavelength's through performance is good, has SrBr
2the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome SrBr
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 SrBr
2crystalline phase, the rare earth ion doped SrBr 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:SrBr of embodiment bis-excitation of X-rays
2the fluorescence spectrum of devitrified glass.
Fig. 3 is the Ce:SrBr of embodiment mono-excitation of X-rays
2the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:SrBr 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
4hBr
2after raw material is mixed, pour in corundum crucible and melt, 1460 ℃ 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 715 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 735 ℃ 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 SrBr of ion doping
2devitrified glass.
SrBr 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 SrBr 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 SrBr
2the devitrified glass of crystallization phase.The Eu of excitation of X-rays
2+ion doping SrBr
2as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Eu
2+ion SrBr
2the output of devitrified glass light can reach 94000ph/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
4hBr
2after raw material is mixed, pour in quartz crucible and melt, 1360 ℃ 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 705 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 725 ℃ 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 SrBr of doping
2devitrified glass.
SrBr to preparation
2the spectral quality test of devitrified glass, the Ce of excitation of X-rays
3+ion doping SrBr
2as shown in Figure 3, its result shows to produce Ce:SrBr 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:SrBr is described
2the luminosity of crystallite 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
4hBr
2after raw material is mixed, pour in quartz crucible and melt, 1410 ℃ 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 723 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 756 ℃ 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 SrBr of ion doping
2devitrified glass.
SrBr to preparation
2the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping SrBr
2as shown in Figure 4, its result shows to produce Tb:SrBr2 crystallite after Overheating Treatment to be compared luminous intensity with corresponding glass basis and is significantly improved the fluorescence spectrum of devitrified glass, and Tb:SrBr is described
2the luminosity of crystallite is better; The rare earth ion doped SrBr 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 SrBr
2devitrified glass, its mole of percentage composition is:
P
2O
5：30-40mol％ B
2O
3：25-30mol％ BaF
2：7-15mol％
SrO:5-9mol% SrBr
2: 15-20mol% rare earth bromide: 1-4mol%
Wherein rare earth bromide is EuBr
2, CeBr
3, TbBr
3in a kind of.
2. rare earth ion doped SrBr claimed in claim 1
2devitrified glass, is characterized in that this flicker devitrified glass material component is: P
2o
5: 35mol%, B
2o
3: 28mol%, BaF
2: 7mol%, SrO:6mol%, SrBr
2: 20mol%, EuBr
2: 4mol%.
3. rare earth ion doped SrBr claimed in claim 1
2devitrified glass, is characterized in that this flicker devitrified glass material component is: P
2o
5: 30mol%, B
2o
3: 30mol%, BaF
2: 15mol%, SrO:5mol%, SrBr
2: 19mol%, CeBr
3: 1mol%.
4. rare earth ion doped SrBr claimed in claim 1
2devitrified glass, is characterized in that this flicker devitrified glass material component is: P
2o
5: 40mol%, B
2o
3: 25mol%, BaF
2: 9mol%, SrO:9mol%, SrBr
2: 15mol%, TbBr
3: 2mol%.
5. rare earth ion doped SrBr according to claim 1
2the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) P
2o
5-B
2o
3-BaF
2-SrO-SrBr
2-LnBr
2, P
2o
5-B
2o
3-BaF
2-SrO-SrBr
2-LnBr
3be founding of glass: by material component, take analytically pure each raw material, raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1360-1460 ℃, insulation 1-2 hour, glass melt is poured in pig mold, then glass is placed in to retort furnace and anneals, 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) SrBr
2the preparation of devitrified glass: 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 SrBr
2devitrified glass.
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|---|---|---|---|
| CN201410198132.XA CN103951222B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped SrBr 2devitrified glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198132.XA CN103951222B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped SrBr 2devitrified glass and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103951222A true CN103951222A (en) | 2014-07-30 |
| CN103951222B CN103951222B (en) | 2016-04-06 |
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|---|---|---|---|
| CN201410198132.XA Expired - Fee Related CN103951222B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped SrBr 2devitrified glass and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384344A (en) * | 2015-11-16 | 2016-03-09 | 宁波大学 | Preparation method of glass film containing rare-earth ion doped barium bromide microcrystals |
| CN105461230A (en) * | 2015-11-16 | 2016-04-06 | 宁波大学 | Glass film containing divalent europium ion doped strontium bromide microcrystals and preparation method thereof |
| CN108840571A (en) * | 2018-07-03 | 2018-11-20 | 中国科学院福建物质结构研究所 | A kind of twin crystal phase glass ceramics and preparation method thereof for fluorescence temperature probe |
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| US20090190214A1 (en) * | 2008-01-29 | 2009-07-30 | Nicholas Francis Borrelli | Polarizing photorefractive glass |
| JP2010150132A (en) * | 2008-11-27 | 2010-07-08 | Nihon Yamamura Glass Co Ltd | Polarizing glass having high extinction ratio |
| CN101786792A (en) * | 2008-09-04 | 2010-07-28 | Hoya株式会社 | Fluorophosphate glass, and manufacture method thereof and use thereof |
| CN102557458A (en) * | 2012-01-11 | 2012-07-11 | 宁波大学 | Microcrystalline glass containing rare earth mixing yttrium aluminum garnet (YAG) phase and preparation method thereof |
-
2014
- 2014-05-08 CN CN201410198132.XA patent/CN103951222B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090190214A1 (en) * | 2008-01-29 | 2009-07-30 | Nicholas Francis Borrelli | Polarizing photorefractive glass |
| CN101786792A (en) * | 2008-09-04 | 2010-07-28 | Hoya株式会社 | Fluorophosphate glass, and manufacture method thereof and use thereof |
| JP2010150132A (en) * | 2008-11-27 | 2010-07-08 | Nihon Yamamura Glass Co Ltd | Polarizing glass having high extinction ratio |
| CN102557458A (en) * | 2012-01-11 | 2012-07-11 | 宁波大学 | Microcrystalline glass containing rare earth mixing yttrium aluminum garnet (YAG) phase and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384344A (en) * | 2015-11-16 | 2016-03-09 | 宁波大学 | Preparation method of glass film containing rare-earth ion doped barium bromide microcrystals |
| CN105461230A (en) * | 2015-11-16 | 2016-04-06 | 宁波大学 | Glass film containing divalent europium ion doped strontium bromide microcrystals and preparation method thereof |
| CN108840571A (en) * | 2018-07-03 | 2018-11-20 | 中国科学院福建物质结构研究所 | A kind of twin crystal phase glass ceramics and preparation method thereof for fluorescence temperature probe |
| CN108840571B (en) * | 2018-07-03 | 2020-12-29 | 中国科学院福建物质结构研究所 | Double-crystal-phase glass ceramic for fluorescent temperature probe and preparation method thereof |
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|---|---|
| CN103951222B (en) | 2016-04-06 |
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Granted publication date: 20160406 Termination date: 20190508 |