CN103951212A - Rare earth ion doped LaBr3 glass ceramics and preparation method thereof - Google Patents
Rare earth ion doped LaBr3 glass ceramics and preparation method thereof Download PDFInfo
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- CN103951212A CN103951212A CN201410198005.XA CN201410198005A CN103951212A CN 103951212 A CN103951212 A CN 103951212A CN 201410198005 A CN201410198005 A CN 201410198005A CN 103951212 A CN103951212 A CN 103951212A
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Abstract
The invention discloses rare earth ion doped LaBr3 glass ceramics and a preparation method thereof. The rare earth ion doped LaBr3 glass ceramics comprises the following components by molar percent: 50-70mol% of B2O3, 4-10mol% of AlF3, 3-15mol% of NaF, 1-15mol% of La2O3, 5-20mol% of LaBr3, and 0.5-10mol% of LnBr3, wherein LnBr3 is one of CeBr3, EuBr3, TbBr3, PrBr3 and NdBr3. The preparation method comprises the steps of firstly preparing B2O3-AlF3-NaF-La2O3-LaBr3-LnBr3 glass through a fusion method, and carrying out thermal processing so as to obtain the transparent LaBr3 glass ceramics. The LaBr3 glass ceramics prepared by the method can resist deliquescence, has good mechanical property, short wavelength and relatively high transmittance of blue violet light, and has the properties like very strong light output, rapid attenuation, good energy resolution and time resolution; the preparation method of the glass ceramics is simple and low 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 LaBr 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.
LaBr
3crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce
3+the LaBr 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 LaBr
3the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But LaBr
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 LaBr 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 LaBr
3devitrified glass, its mole of percentage composition is:
B
2O
3：50-70mol％ AlF
3：4-10mol％ NaF：3-15mol％
La
2O
3：1-15mol％ LaBr
3：5-20mol％ LnBr
3：0.5-10mol％
LnBr wherein
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
ain a kind of.
This flicker devitrified glass material component is: B
2o
3: 70mol%, AlF
3: 10mol%, NaF:3mol%, La
2o
3: 10mol%, LaBr
3: 5mol%, CeBr
3: 2mol%.
This flicker devitrified glass material component is: B
2o
3: 50mol%, AlF
3: 4mol%, NaF:15mol%, La
2o
3: 1mol%, LaBr
3: 20mol%, EuBr
3: 10mol%.
This flicker devitrified glass material component is: B
2o
3: 60.5mol%, AlF
3: 4mol%, NaF:10mol%, La
2o
3: 15mol%, LaBr
3: 10mol%, TbBr
3: 0.5mol%.
Described rare earth ion doped LaBr
3the preparation method of devitrified glass, comprises the steps:
(1) B
2o
3-AlF
3-NaF-La
2o
3-LaBr
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 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 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) LaBr
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 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 LaBr
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 LaBr
3the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome LaBr
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 LaBr
3crystalline phase, the rare earth ion doped LaBr 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 LaBr
3the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu of embodiment bis-excitation of X-rays
3+ion doping LaBr
3the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb of embodiment tri-excitation of X-rays
3+ion doping LaBr
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
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 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 655 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 675 ℃ 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 LaBr of doping
3devitrified glass sample.
LaBr 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 LaBr 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 LaBr
3the devitrified glass of crystallization phase.And the Ce of excitation of X-rays
3+ion doping LaBr
3as shown in Figure 2, glow peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce
3+ion LaBr
3the output of devitrified glass light can reach between 58000ph/MeV, and be 35ns 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 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 662 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 680 ℃ 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 LaBr of ion doping
3devitrified glass.
LaBr to preparation
3the spectral quality test of devitrified glass, the Eu of excitation of X-rays
3+ion doping LaBr
3as shown in Figure 3, its result shows to produce Eu:LaBr 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:LaBr is described
3the luminosity of devitrified glass is better, and luminous intensity obviously improves.
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 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 671 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 690 ℃ 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 LaBr of ion doping
3devitrified glass.
LaBr to preparation
3the spectral quality test of devitrified glass, the Tb of excitation of X-rays
3+ion doping LaBr
3as shown in Figure 4, its result shows to produce Tb:LaBr 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:LaBr is described
3the luminosity of devitrified glass is better, and luminous intensity obviously improves; The rare earth ion doped LaBr being obtained by above-mentioned preparation process
3devitrified glass is transparent and physical and chemical performance is good.
Claims (5)
1. a rare earth ion doped LaBr
3devitrified glass, its mole of percentage composition is:
B
2O
3：50-70mol％ AlF
3：4-10mol％ NaF：3-15mol％
La
2O
3：1-15mol％ LaBr
3：5-20mol％ LnBr
3：0.5-10mol％
LnBr wherein
3for CeBr
3, EuBr
3, TbBr
3, PrBr
3, NdBr
3in a kind of.
2. rare earth ion doped LaBr claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: B
2o
3: 70mol%, AlF
3: 10mol%, NaF:3mol%, La
2o
3: 10mol%, LaBr
3: 5mol%, CeBr
3: 2mol%.
3. rare earth ion doped LaBr claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: B
2o
3: 50mol%, AlF
3: 4mol%, NaF:15mol%, La
2o
3: 1mol%, LaBr
3: 20mol%, EuBr
3: 10mol%.
4. rare earth ion doped LaBr claimed in claim 1
3devitrified glass, is characterized in that this flicker devitrified glass material component is: B
2o
3: 60.5mol%, AlF
3: 4mol%, NaF:10mol%, La
2o
3: 15mol%, LaBr
3: 10mol%, TbBr
3: 0.5mol%.
5. rare earth ion doped LaBr according to claim 1
3the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) B
2o
3-AlF
3-NaF-La
2o
3-LaBr
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 quartz crucible into or corundum crucible is added a cover fusing, 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 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) LaBr
3the preparation of devitrified glass: according to the thermal analysis experiment 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 LaBr
3devitrified glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198005.XA CN103951212B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LaBr3Devitrified glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198005.XA CN103951212B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LaBr3Devitrified glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951212A true CN103951212A (en) | 2014-07-30 |
| CN103951212B CN103951212B (en) | 2016-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410198005.XA Expired - Fee Related CN103951212B (en) | 2014-05-08 | 2014-05-08 | Rare earth ion doped LaBr3Devitrified glass and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271801A (en) * | 2015-11-16 | 2016-01-27 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystalline |
| CN105314859A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped LaBr3 glass ceramics and preparation method thereof |
| CN105314873A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion-doped CeBr3 microcrystalline glass and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060021285A1 (en) * | 2004-07-29 | 2006-02-02 | 3M Innovative Properties Company | Ceramics, and methods of making and using the same |
| 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 CN201410198005.XA patent/CN103951212B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060021285A1 (en) * | 2004-07-29 | 2006-02-02 | 3M Innovative Properties Company | Ceramics, and methods of making and using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271801A (en) * | 2015-11-16 | 2016-01-27 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystalline |
| CN105314859A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion doped LaBr3 glass ceramics and preparation method thereof |
| CN105314873A (en) * | 2015-11-27 | 2016-02-10 | 宁波大学 | Rare earth ion-doped CeBr3 microcrystalline glass and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103951212B (en) | 2016-05-25 |
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