CN103951214A - Rare-earth-ion-doped LuBr3 microcrystalline glass and preparation method thereof - Google Patents
Rare-earth-ion-doped LuBr3 microcrystalline glass and preparation method thereof Download PDFInfo
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- CN103951214A CN103951214A CN201410198017.2A CN201410198017A CN103951214A CN 103951214 A CN103951214 A CN 103951214A CN 201410198017 A CN201410198017 A CN 201410198017A CN 103951214 A CN103951214 A CN 103951214A
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Abstract
The invention discloses a rare-earth-ion-doped LuBr3 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 Lu2O3, 10-15 mol% of LuBr3 and 1-4 mol% of LnBr3. The LnBr3 is CeBr3, EuBr3, TbBr3, PrBr3 or NdBr3. The preparation method comprises the following steps: preparing TeO2-ZnF2-Lu2O3-LuBr3-LnBr3 glass by a fusion process, and carrying out heat treatment to obtain the transparent LuBr3 microcrystalline glass. The LuBr3 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. 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 LuBr as scintillation material
3devitrified 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.
LuBr
3crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce
3+the LuBr of doping
3it 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 LuBr
3the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But LuBr
3crystal 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 stronger light output, fast decay, energy resolution and the good rare earth ion doped LuBr of temporal resolution
3devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped LuBr
3devitrified glass, its mole of percentage composition is:
TeO
2：65-75mol％ ZnF
2：5-10mol％Lu
2O
3：8-11mol％
LuBr
3：10-15mol％ LnBr
3：1-4mol％
LnBr wherein
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in a kind of.
This flicker devitrified glass material component is: TeO
2: 65mol%, ZnF
2: 10mol%, Lu
2o
3: 9mol%, LuBr
3: 15mol%, CeBr
3: 1mol%.
This flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 5mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, EuBr
3: 4mol%.
This flicker devitrified glass material component is: TeO
2: 75mol%, ZnF
2: 5mol%, Lu
2o
3: 8mol%, LuBr
3: 10mol%, TbBr
3: 2mol%.
Described rare earth ion doped LuBr
3the preparation method of devitrified glass, comprises the steps:
(1) TeO
2-ZnF
2-Lu
2o
3-LuBr
3-LnBr
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
4hBr
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) LuBr
3devitrified glass preparation: 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 LuBr
3devitrified 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 LuBr
3the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome LuBr
3single 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 LuBr
3crystalline phase, the rare earth ion doped LuBr making
3devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has stronger 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 of embodiment mono-excitation of X-rays
3+ion doping LuBr
3the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu of embodiment bis-excitation of X-rays
3+ion doping LuBr
3the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb of embodiment tri-excitation of X-rays
3+ion doping LuBr
3the 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 NH4HF
2, 2.5 grams of NH
4hBr
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 455 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 475 ℃ 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 LuBr of doping
3devitrified glass.
LuBr to preparation
3devitrified 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 all the other are glassy phases.The test of X-ray diffraction shows that crystalline phase is LuBr
3phase, the material therefore obtaining is LuBr
3the devitrified glass of crystallization phase.The Ce of excitation of X-rays
3+ion doping LuBr
3as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LuBr
3the output of devitrified glass light can reach 24000ph/MeV, and be 32ns fall time, and its light output is high as seen, and fall time is short.
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 corundum crucible and melt, 850 ℃ 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 462 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 480 ℃ 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 LuBr of ion doping
3devitrified glass.
LuBr to preparation
3the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+ion doping LuBr
3as shown in Figure 3, its result shows to produce Eu:LuBr after Overheating Treatment to the fluorescence spectrum of devitrified glass
3crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:LuBr is described
3the luminosity of devitrified glass is better; Be expected to very much be used as the scintillator in safety check.
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, 900 ℃ 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 471 ℃ of the first recrystallization temperatures, the glass making is placed in to 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 LuBr of ion doping
3devitrified glass.
LuBr to preparation
3the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LuBr
3as shown in Figure 4, its result shows to produce Tb:LuBr after Overheating Treatment to the fluorescence spectrum of devitrified glass
3crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:LuBr is described
3the luminosity of devitrified glass is better; The rare earth ion doped LuBr being obtained by above-mentioned preparation process
3devitrified glass is transparent and physical and chemical performance is good.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: this flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 8mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, PrBr
3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: this flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 8mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, NdBr
3: 1mol%.
Embodiment 4,5 also can obtain rare earth ion doped LuBr preferably
3devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.
Claims (5)
1. a rare earth ion doped LuBr
3devitrified glass, its mole of percentage composition is:
TeO
2：65-75mol％ ZnF
2：5-10mol％ Lu
2O
3：8-11mol％
LuBr
3：10-15mol％ LnBr
3：1-4mol％
LnBr wherein
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in a kind of.
2. rare earth ion doped LuBr claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO
2: 65mol%, ZnF
2: 10mol%, Lu
2o
3: 9mol%, LuBr
3: 15mol%, CeBr
3: 1mol%.
3. rare earth ion doped LuBr claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO
2: 70mol%, ZnF
2: 5mol%, Lu
2o
3: 11mol%, LuBr
3: 10mol%, EuBr
3: 4mol%.
4. rare earth ion doped LuBr claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO
2: 75mol%, ZnF
2: 5mol%, Lu
2o
3: 8mol%, LuBr
3: 10mol%, TbBr
3: 2mol%.
5. rare earth ion doped LuBr according to claim 1
3the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) TeO
2-ZnF
2-Lu
2o
3-LuBr
3-LnBr
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
4hBr
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) LuBr
3the 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 LuBr
3devitrified glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198017.2A CN103951214B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LuBr 3devitrified glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198017.2A CN103951214B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LuBr 3devitrified glass and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103951214A true CN103951214A (en) | 2014-07-30 |
| CN103951214B CN103951214B (en) | 2016-04-27 |
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|---|---|---|---|
| CN201410198017.2A Expired - Fee Related CN103951214B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LuBr 3devitrified glass and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314855A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped GdBr3 glass ceramics and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1137088A1 (en) * | 1983-07-22 | 1985-01-30 | Предприятие П/Я Р-6681 | Glass |
| CN1653010A (en) * | 2002-03-15 | 2005-08-10 | 株式会社小原 | SBN glass ceramic system |
| CN1852869A (en) * | 2003-09-18 | 2006-10-25 | 3M创新有限公司 | Ceramics comprising Ai2o3, Reo, Zro2 and/or Hfo2, and Nb2o5 and/or Ta2o5 and methods of making the same |
-
2014
- 2014-05-08 CN CN201410198017.2A patent/CN103951214B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1137088A1 (en) * | 1983-07-22 | 1985-01-30 | Предприятие П/Я Р-6681 | Glass |
| CN1653010A (en) * | 2002-03-15 | 2005-08-10 | 株式会社小原 | SBN glass ceramic system |
| CN1852869A (en) * | 2003-09-18 | 2006-10-25 | 3M创新有限公司 | Ceramics comprising Ai2o3, Reo, Zro2 and/or Hfo2, and Nb2o5 and/or Ta2o5 and methods of making the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314855A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped GdBr3 glass ceramics and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103951214B (en) | 2016-04-27 |
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Granted publication date: 20160427 Termination date: 20190508 |