CN103951209A - Rare-earth-ion-doped LaI3 microcrystalline glass and preparation method thereof - Google Patents
Rare-earth-ion-doped LaI3 microcrystalline glass and preparation method thereof Download PDFInfo
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- CN103951209A CN103951209A CN201410197933.4A CN201410197933A CN103951209A CN 103951209 A CN103951209 A CN 103951209A CN 201410197933 A CN201410197933 A CN 201410197933A CN 103951209 A CN103951209 A CN 103951209A
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- lai
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Abstract
The invention discloses a rare-earth-ion-doped LaI3 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 40-60 mol% of GeO2, 5-15 mol% of BaF2, 5-10 mol% of KF, 5-18 mol% of La2O3, 15-25 mol% of LaI3 and 2-5 mol% of LnI3. The LnI3 is CeI3, EuI3, TbI3, PrI3 or NdI3. The preparation method comprises the following steps: preparing GeO2-BaF2-KF-La2O3-LaI3-LnI3 glass by a fusion process, and carrying out heat treatment to obtain the transparent LaI3 microcrystalline glass. The LaI3 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
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 LaI 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.
LaI
3crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce
3+the LaI 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+the LaI of doping
3crystal and Tb
3+the LaI of doping
3the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But LaI
3the 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 LaI 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 LaI
3devitrified glass, its mole of percentage composition is:
GeO
2：40-60mol％ BaF
2：5-15mol％ KF：5-10mol％
La
2O
3：5-18mol％ LaI
3：15-25mol％ LnI
3：2-5mol％
LnI wherein
3for CeI
3, EuI
3, TbI
3, PrI
3, NdI
3in a kind of.
This flicker devitrified glass material component is: GeO
2: 40mol%, BaF
2: 10mol%, KF:10mol%, La
2o
3: 18mol%, LaI
3: 20mol%, CeI
3: 2mol%.
This flicker devitrified glass material component is: GeO
2: 45mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, EuI
3: 5mol%.
This flicker devitrified glass material component is: GeO
2: 60mol%, BaF
2: 5mol%, KF:5mol%, La
2o
3: 13mol%, LaI
3: 15mol%, TbI
3: 2mol%.
Described rare earth ion doped LaI
3the preparation method of devitrified glass, comprises the steps:
(1) GeO
2-BaF
2-KF-La
2o
3-LaI
3-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
2after raw material is mixed, pour in quartz crucible or corundum crucible and melt, temperature of fusion 1300-1480 ℃, insulation 1-2 hour, pours glass melt in pig mold into, then being placed in retort furnace anneals, in the insulation of glass transformation temperature Tg temperature, after 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 sample, for micritization thermal treatment.
(2) LaI
3devitrified glass preparation:
According to heat analysis (DTA) experimental data of glass, the glass making is placed in near nitrogen fine annealing stove heat-treated 3～6 hours its first crystallization peak, 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 rare earth ion doped LaI
3devitrified glass sample.
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 LaI
3the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome LaI
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 LaI
3crystalline phase, the rare earth ion doped LaI making
3devitrified 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 Ce of embodiment mono-excitation of X-rays
3+ion doping LaI
3the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu of embodiment bis-excitation of X-rays
3+ion doping LaI
3the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb of embodiment tri-excitation of X-rays
3+ion doping LaI
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 NH
4hF
2, 2.5 grams of NH
4hI
2after raw material is mixed, pour in quartz crucible and melt, 1300 ℃ 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 675 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 690 ℃ 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 LaI of doping
3devitrified glass.
LaI to preparation
3devitrified 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 LaI of the sample obtaining through Overheating Treatment
3the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtaining is mainly LaI
3the devitrified glass of crystallization phase.And the Ce of excitation of X-rays
3+ion doping LaI
3as shown in Figure 2, glow peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LaI
3the output of devitrified glass light can reach 58000ph/MeV, and be 30ns 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
4hI
2after raw material is mixed, pour in corundum crucible and melt, 1480 ℃ 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 680 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 695 ℃ of thermal treatments 3 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 LaI of ion doping
3devitrified glass.
LaI to preparation
3the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+ion doping LaI
3as shown in Figure 3, its result shows to produce Eu:LaI after Overheating Treatment to the fluorescence spectrum of devitrified glass
3crystallite is significantly improved than luminous intensity with corresponding glass matrix phase, and Eu:LaI is described
3the 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, 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 690 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 710 ℃ 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 Tb
3+the LaI of ion doping
3devitrified glass.
LaI to preparation
3the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LaI
3as shown in Figure 4, its result shows to produce Tb:LaI 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:LaI is described
3the luminosity of devitrified glass is better; The rare earth ion doped LaI 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: 49mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, PrI
3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: 49mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, TbI
3: 1mol%.
Embodiment 4,5 also can obtain rare earth ion doped LaI preferably
3devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.
Claims (5)
1. a rare earth ion doped LaI
3devitrified glass, its mole of percentage composition is:
GeO
2：40-60mol％ BaF
2：5-15mol％ KF：5-10mol％
La
2O
3：5-18mol％ LaI
3：15-25mol％ LnI
3：2-5mol％
LnI wherein
3for CeI
3, EuI
3, TbI
3, PrI
3, NdI
3in a kind of.
2. rare earth ion doped LaI claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO
2: 40mol%, BaF
2: 10mol%, KF:10mol%, La
2o
3: 18mol%, LaI
3: 20mol%, CeI
3: 2mol%.
3. rare earth ion doped LaI claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO
2: 45mol%, BaF
2: 15mol%, KF:5mol%, La
2o
3: 5mol%, LaI
3: 25mol%, EuI
3: 5mol%.
4. rare earth ion doped LaI claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO
2: 60mol%, BaF
2: 5mol%, KF:5mol%, La
2o
3: 13mol%, LaI
3: 15mol%, TbI
3: 2mol%.
5. rare earth ion doped LaI according to claim 1
3the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) GeO
2-BaF
2-KF-La
2o
3-LaI
3-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
2after raw material is mixed, pour in quartz crucible or corundum crucible and melt, temperature of fusion 1300-1480 ℃, insulation 1-2 hour, pours glass melt in pig mold into, then being placed in retort furnace anneals, in the insulation of glass transformation temperature Tg temperature, after 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) LaI
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 3～6 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 LaI
3devitrified glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410197933.4A CN103951209B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LaI 3devitrified glass and preparation method thereof |
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|---|---|---|---|
| CN201410197933.4A CN103951209B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LaI 3devitrified glass and preparation method thereof |
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|---|---|
| CN103951209A true CN103951209A (en) | 2014-07-30 |
| CN103951209B CN103951209B (en) | 2016-02-10 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293925A (en) * | 2015-11-27 | 2016-02-03 | 宁波大学 | Rare earth ion doped GdI3 glass ceramic and preparation method thereof |
| CN105314854A (en) * | 2015-11-16 | 2016-02-10 | 宁波大学 | Glass containing rare earth ion doped lutetium iodide micro-crystals and preparation method of glass film |
| CN105314872A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped CeI3 glass ceramics and preparation method thereof |
| CN105314858A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped LaI3 glass ceramics and preparation method thereof |
| CN105461229A (en) * | 2015-11-16 | 2016-04-06 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystals |
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| CN1239936A (en) * | 1997-01-02 | 1999-12-29 | 康宁股份有限公司 | Transparent oxyfluoride glass-ceramic composition and process for making the same |
| US20030020044A1 (en) * | 2001-07-30 | 2003-01-30 | General Electric Company | Scintillator compositions of alkali and rare-earth tungstates |
| CN1785870A (en) * | 2005-10-28 | 2006-06-14 | 宁波大学 | Rare earth ion doped YAG micro crystalline glass and its preparation method |
| US20090190214A1 (en) * | 2008-01-29 | 2009-07-30 | Nicholas Francis Borrelli | Polarizing photorefractive glass |
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2014
- 2014-05-08 CN CN201410197933.4A patent/CN103951209B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239936A (en) * | 1997-01-02 | 1999-12-29 | 康宁股份有限公司 | Transparent oxyfluoride glass-ceramic composition and process for making the same |
| US20030020044A1 (en) * | 2001-07-30 | 2003-01-30 | General Electric Company | Scintillator compositions of alkali and rare-earth tungstates |
| CN1785870A (en) * | 2005-10-28 | 2006-06-14 | 宁波大学 | Rare earth ion doped YAG micro crystalline glass and its preparation method |
| US20090190214A1 (en) * | 2008-01-29 | 2009-07-30 | Nicholas Francis Borrelli | Polarizing photorefractive glass |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314854A (en) * | 2015-11-16 | 2016-02-10 | 宁波大学 | Glass containing rare earth ion doped lutetium iodide micro-crystals and preparation method of glass film |
| CN105461229A (en) * | 2015-11-16 | 2016-04-06 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystals |
| CN105293925A (en) * | 2015-11-27 | 2016-02-03 | 宁波大学 | Rare earth ion doped GdI3 glass ceramic and preparation method thereof |
| CN105314872A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped CeI3 glass ceramics and preparation method thereof |
| CN105314858A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped LaI3 glass ceramics and preparation method thereof |
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| Publication number | Publication date |
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| CN103951209B (en) | 2016-02-10 |
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