CN103951257A - Rare-earth-ion-doped LiLuBr4 microcrystalline glass and preparation method thereof - Google Patents
Rare-earth-ion-doped LiLuBr4 microcrystalline glass and preparation method thereof Download PDFInfo
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- CN103951257A CN103951257A CN201410198495.3A CN201410198495A CN103951257A CN 103951257 A CN103951257 A CN 103951257A CN 201410198495 A CN201410198495 A CN 201410198495A CN 103951257 A CN103951257 A CN 103951257A
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Abstract
The invention discloses a rare-earth-ion-doped LiLuBr4 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 20-30 mol% of GeO2, 25-35 mol% of B2O3, 22-25 mol% of BaF2, 20-22 mol% of LiLuBr4 and 1-5 mol% of LnBr3. The LnBr3 is CeBr3, EuBr3, TbBr3, PrBr3 or NdBr3. The preparation method comprises the following steps: preparing GeO2-B2O3-BaF2-LiLuBr4-LnBr3 glass by a fusion process, and carrying out heat treatment to obtain the transparent LiLuBr4 microcrystalline glass. The LiLuBr4 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 LiLuBr as scintillation material
4devitrified 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.
LiLuBr
4crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce
3+the LiLuBr of doping
4it 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+li doped LuBr
4the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But LiLuBr
4crystal 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 LiLuBr of temporal resolution
4devitrified 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 LiLuBr
4devitrified glass, its mole of percentage composition is:
GeO
2：20-30mol％ B
2O
3：25-35mol％ BaF
2：22-25mol％
LiLuBr
4：20-22mol％ LnBr
3：1-5mol％
LnBr wherein
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in a kind of.
This flicker devitrified glass material component is: GeO
2: 30mol%, B
2o
3: 25mol%, BaF
2: 22mol%, LiLuBr
4: 22mol%, CeBr
3: 1mol%.
This flicker devitrified glass material component is: GeO
2: 20mol%, B
2o
3: 30mol%, BaF
2: 25mol%, LiLuBr
4: 20mol%, EuBr
3: 5mol%.
This flicker devitrified glass material component is: GeO
2: 20mol%, B
2o
3: 35mol%, BaF
2: 23mol%, LiLuBr
4: 20mol%, TbBr
3: 2mol%.
Described rare earth ion doped LiLuBr
4the preparation method of devitrified glass, comprises the steps:
(1) GeO
2-B
2o
3-BaF
2-LiLuBr
4-LnBr
3be founding of glass:
By material component, take analytically pure each raw material, add the NH that respectively 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 1350-1450 ℃, 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) LiLuBr
4devitrified 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 LiLuBr
4devitrified 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 LiLuBr
4the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome LiLuBr
4the single crystal shortcoming such as very easily deliquescence, poor, the easy cleavage of mechanical property be in blocks; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped to LiLuBr
4crystalline phase, the rare earth ion doped LiLuBr making
4devitrified 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 it is lower that dirt produces cost.
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:LiLuBr of embodiment mono-excitation of X-rays
4the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:LiLuBr of embodiment bis-excitation of X-rays
4the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:LiLuBr of embodiment tri-excitation of X-rays
4the 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 quartz crucible and melt, 1350 ℃ 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 723 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 740 ℃ 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 LiLuBr of doping
4devitrified glass.
LiLuBr to preparation
4devitrified 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 rest part is glassy phase.The test of X-ray diffraction shows that crystalline phase is LiLuBr
4phase, the material therefore obtaining is LiLuBr
4the devitrified glass of crystallization phase.The Ce of excitation of X-rays
3+ion doping LiLuBr
4as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LiLuBr
4devitrified glass light is output as between 15000ph/MeV, and be 45ns 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
4hBr
2after raw material is mixed, pour in corundum crucible and melt, 1400 ℃ 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 730 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 748 ℃ 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 LiLuBr of ion doping
4devitrified glass.
LiLuBr to preparation
4the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+as shown in Figure 3, its result shows to produce Eu:LiLuBr after Overheating Treatment to the fluorescence spectrum of ion doping LiLuBr4 devitrified glass
4crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:LiLuBr is described
4the 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
4hBr
2after raw material is mixed, pour in quartz crucible and melt, 1450 ℃ 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 742 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 760 ℃ 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 LiLuBr of ion doping
4devitrified glass.
LiLuBr to preparation
4the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LiLuBr
4as shown in Figure 4, its result shows to produce Tb:LiLuBr after Overheating Treatment to the fluorescence spectrum of devitrified glass
4crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:LiLuBr is described
4the luminosity of devitrified glass is better; The rare earth ion doped LiLuBr being obtained by above-mentioned preparation process
4devitrified glass is transparent and physical and chemical performance is good.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: GeO
2: 30mol%, B
2o
3: 25mol%, BaF
2: 22mol%, LiLuBr
4: 22mol%, PrBr
3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: GeO
2: 30mol%, B
2o
3: 25mol%, BaF
2: 22mol%, LiLuBr4:22mol%, NdBr
3: 1mol%.
Embodiment 4,5 also can obtain rare earth ion doped LiLuBr preferably
4devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.
Claims (5)
1. a rare earth ion doped LiLuBr
4devitrified glass, its mole of percentage composition is:
GeO
2：20-30mol％ B
2O
3：25-35mol％ BaF
2：22-25mol％
LiLuBr
4：20-22mol％ LnBr
3：1-5mol％
LnBr wherein
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in a kind of.
2. rare earth ion doped LiLuBr claimed in claim 1
4devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO
2: 30mol%, B
2o
3: 25mol%, BaF
2: 22mol%, LiLuBr
4: 22mol%, CeBr
3: 1mol%.
3. rare earth ion doped LiLuBr claimed in claim 1
4devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO
2: 20mol%, B
2o
3: 30mol%, BaF
2: 25mol%, LiLuBr
4: 20mol%, EuBr
3: 5mol%.
4. rare earth ion doped LiLuBr claimed in claim 1
4devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO
2: 20mol%, B
2o
3: 35mol%, BaF
2: 23mol%, LiLuBr
4: 20mol%, TbBr
3: 2mol%.
5. rare earth ion doped LiLuBr according to claim 1
4the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) GeO
2-B
2o
3-BaF
2-LiLuBr
4-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 1350-1450 ℃, 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) LiLuBr
4the 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 LiLuBr
4devitrified glass.
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|---|---|---|---|
| CN201410198495.3A CN103951257B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LiLuBr 4devitrified glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198495.3A CN103951257B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LiLuBr 4devitrified glass and preparation method thereof |
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|---|---|
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| CN103951257B CN103951257B (en) | 2016-04-27 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884166A (en) * | 2006-07-12 | 2006-12-27 | 中国科学院上海光学精密机械研究所 | Visible and mid-infrared transparent germanate gallate glass |
| JP2007197249A (en) * | 2006-01-26 | 2007-08-09 | Ohara Inc | Glass ceramic and method for producing glass ceramic |
| CN101265028A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Rare earth doping LiYF4 microcrystalline glass and preparation method thereof |
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2014
- 2014-05-08 CN CN201410198495.3A patent/CN103951257B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197249A (en) * | 2006-01-26 | 2007-08-09 | Ohara Inc | Glass ceramic and method for producing glass ceramic |
| CN1884166A (en) * | 2006-07-12 | 2006-12-27 | 中国科学院上海光学精密机械研究所 | Visible and mid-infrared transparent germanate gallate glass |
| CN101265028A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Rare earth doping LiYF4 microcrystalline glass and preparation method thereof |
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