CN103951240A - Rare-earth-ion-doped Cs2LiLaCl6 microcrystalline glass and preparation method thereof - Google Patents

Rare-earth-ion-doped Cs2LiLaCl6 microcrystalline glass and preparation method thereof Download PDF

Info

Publication number
CN103951240A
CN103951240A CN201410198336.3A CN201410198336A CN103951240A CN 103951240 A CN103951240 A CN 103951240A CN 201410198336 A CN201410198336 A CN 201410198336A CN 103951240 A CN103951240 A CN 103951240A
Authority
CN
China
Prior art keywords
glass
lilacl
devitrified glass
rare earth
lila
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410198336.3A
Other languages
Chinese (zh)
Other versions
CN103951240B (en
Inventor
杨斌
张约品
夏海平
王倩
欧阳绍业
张为欢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo University
Original Assignee
Ningbo University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo University filed Critical Ningbo University
Priority to CN201410198336.3A priority Critical patent/CN103951240B/en
Publication of CN103951240A publication Critical patent/CN103951240A/en
Application granted granted Critical
Publication of CN103951240B publication Critical patent/CN103951240B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Glass Compositions (AREA)

Abstract

The invention discloses a rare-earth-ion-doped Cs2LiLaCl6 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 40-50 mol% of SiO2, 5-20 mol% of AlF3, 14-20 mol% of NaF, 5-8 mol% of La2O3 and 10-20 mol% of Cs2LiLa(1-x)LnxCl6, wherein x=0.01-0.2, and Ln is Ce<3+>, Eu<3+>, Tb<3+>, Pr<3+> or Nd<3+>. The preparation method comprises the following steps: preparing SiO2-AlF3-NaF-La2O3-Cs2LiLa(1-x)LnxCl6 glass by a fusion process, and carrying out heat treatment to obtain the transparent Cs2LiLaCl6 microcrystalline glass. The Cs2LiLaCl6 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

Rare earth ion doped Cs 2liLaCl 6devitrified glass and preparation method thereof
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 Cs as scintillation material 2liLaCl 6devitrified 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 in aspect difficulties such as light output, multiplicity compared with crystal, and therefore its application is also very limited.
Cs 2liLaCl 6crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce 3+the Cs of doping 2liLaCl 6it 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 Cs 2liLaCl 6the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But Cs 2liLaCl 6crystal is deliquescence very easily, and mechanical property is poor, easily 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 Cs of temporal resolution 2liLaCl 6devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped Cs 2liLaCl 6devitrified glass, its mole of percentage composition is:
SiO 2：40-50mol％ AlF 3：15-20mol％ NaF：14-20mol％
La 2o 3: 5-8mol% Cs 2liLa (1-x)ln xcl 6: 10-20mol%, x=0.01-0.2 in formula, Ln is Ce 3+, Eu 3+, Tb 3+, Pr 3+, Nd 3+in a kind of rare earth ion.
This flicker devitrified glass material component is: SiO 2: 40mol%, AlF 3: 15mol%, NaF:20mol%, La 2o 3: 5mol%, Cs 2liLa 0.99ce 0.01cl 6: 20mol%.
This flicker devitrified glass material component is: SiO 2: 45mol%, AlF 3: 20mol%, NaF:14mol%, La 2o 3: 6mol%, Cs 2liLa 0.seu 0.2cl 6: 15mol%.
This flicker devitrified glass material component is: SiO 2: 50mol%, AlF 3: 15mol%, NaF:17mol%, La 2o 3: 8mol%, Cs 2liLa 09tb 0.1cl 6: 10mol%.
Described rare earth ion doped Cs 2liLaCl 6the preparation method of devitrified glass, comprises the steps:
(1) SiO 2-AlF 3-NaF-La 2o 3-Cs 2liLa (1-x)ln xcl 6be founding of glass:
Cs 2liLa (1-x)ln xcl 6raw material is by CsCl, LiCl, LaCl 3, LnCl 3mixed sintering forms, and takes analytically pure each raw material by material component, respectively adds the NH that accounts for raw material gross weight 5% 4hF 2, NH 4hCl 2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1350-1450 DEG C, 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 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment.
(2) Cs 2liLaCl 6devitrified 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 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped Cs 2liLaCl 6devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine chlorine oxonium compound, short wavelength's through performance is good, has Cs 2liLaCl 6the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome Cs 2liLaCl 6single 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 Cs 2liLaCl 6crystalline phase, the rare earth ion doped Cs making 2liLaCl 6devitrified 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 good performance such as energy resolution and temporal resolution, can make nuclear detection instrument efficiency greatly improve.The preparation method of this devitrified glass is simple, and production cost is lower.
Brief description of the drawings
Fig. 1 is the transmission electron microscope figure (TEM) of sample after embodiment mono-micritization thermal treatment.
Fig. 2 is the Ce:Cs of embodiment mono-excitation of X-rays 2liLaCl 6the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:Cs of embodiment bis-excitation of X-rays 2liLaCl 6the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:Cs of embodiment tri-excitation of X-rays 2liLaCl 6the 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, Cs 2liLa 0.99ce 0.01cI 6raw material is by CsCl, LiCl, LaCl 3, CeCl 3mixed sintering forms, and weighs 50 grams of analytical pure raw materials by the formula in table 1, adds 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hCl 2after raw material is mixed, pour in quartz crucible and melt, 1350 DEG C 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, be cooled to 50 DEG C with the speed of 10 DEG C/h, 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 656 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 675 DEG C of thermal treatments 6 hours, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce 3+the Cs of doping 2liLaCl 6devitrified glass sample.
To the Cs of preparation 2liLaCl 6devitrified glass carries out transmission electron microscope test, obtain glass through micritization transmission electron microscope picture after treatment as shown in Figure 1, its result is as follows: in photo, glass basis seems more clearly with the nano microcrystalline of separating out, and the stain distributing in glass basis is microcrystal grain.X-ray diffraction test shows that crystalline phase is Cs 2liLaCl 6phase, the material therefore obtaining is Cs 2liLaCl 6the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping Cs 2liLaCl 6as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion Cs 2liLaCl 6the output of devitrified glass light can reach 33000ph/MeV, and be 90ns 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, Cs 2liLa 0.seu 0.2cl 6raw material is by CsCl, LiCI, LaCl 3, EuCl 3mixed sintering forms, and weighs 50 grams of analytical pure raw materials by the formula in table 2, adds 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hCl 2after raw material is mixed, pour in corundum crucible and melt, 1400 DEG C 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, be cooled to 50 DEG C with the speed of 10 DEG C/h, 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 673 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 690 DEG C of thermal treatments 4 hours, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu 3+the Cs of ion doping 2liLaCl 6devitrified glass.
To the Cs of preparation 2liLaCl 6the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping Cs 2liLa Cl 6as shown in Figure 3, its result shows to produce Eu:Cs after Overheating Treatment to the fluorescence spectrum of devitrified glass 2liLaCl 6crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:Cs is described 2liLaCl 6the 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, Cs 2liLa 0.9tb 0.1cl 6raw material is by CsCl, LiCl, LaCl 3, TbCl 3mixed sintering forms, and weighs 50 grams of analytical pure raw materials by the formula in table 3, adds 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hCl 2after raw material is mixed, pour in quartz crucible and melt, 1450 DEG C 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, be cooled to 50 DEG C with the speed of 10 DEG C/h, 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 678 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 695 DEG C of thermal treatments 5 hours, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb 3+the Cs of ion doping 2liLaCl 6devitrified glass.
To the Cs of preparation 2liLaCl 6the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping Cs 2liLa Cl 6as shown in Figure 4, its result shows to produce Tb:Cs after Overheating Treatment to the fluorescence spectrum of devitrified glass 2liLaCl 6crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:Cs is described 2liLaCl 6the luminosity of devitrified glass is better; The rare earth ion doped Cs being obtained by above-mentioned preparation process 2liLaCl 6devitrified glass is transparent and physical and chemical performance is good.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: SiO 2: 50mol%, AlF 3: 15mol%, NaF:17mol%, La 2o 3: 8mol%, Cs 2liLa 0.9pr 0.1cl 6: 10mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: SiO 2: 50mol%, AlF 3: 15mol%, NaF:17mol%, La 2o 3: 8mol%, Cs 2liLa 0.9nd 0.1cl 6: 10mol%.
Embodiment 4,5 also can obtain rare earth ion doped Cs preferably 2liLaCl 6devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped Cs 2liLaCl 6devitrified glass, its mole of percentage composition is:
SiO 2：40-50mol％ AlF 3：15-20mol％ NaF：14-20mol％
La 2o 3: 5-8mol% Cs 2liLa (1-x)ln xcl 6: 10-20mol%, x=0.01-0.2 in formula, Ln is Ce 3+, Eu 3+, Tb 3+, Pr 3+, Nd 3+in a kind of rare earth ion.
2. rare earth ion doped Cs claimed in claim 1 2liLaCl 6devitrified glass, is characterized in that this flicker devitrified glass material component is: SiO 2: 40mol%, AlF 3: 15mol%, NaF:20mol%, La 2o 3: 5mol%, Cs 2liLa 0.99ce 0.01cl 6: 20mol%.
3. rare earth ion doped Cs claimed in claim 1 2liLaCl 6devitrified glass, is characterized in that this flicker devitrified glass material component is: SiO 2: 45mol%, AlF 3: 20mol%, NaF:14mol%, La 2o 3: 6mol%, Cs 2liLa 0.seu 0.2cl 6: 15mol%.
4. rare earth ion doped Cs claimed in claim 1 2liLaCl 6devitrified glass, is characterized in that this flicker devitrified glass material component is: SiO 2: 50mol%, AlF 3: 15mol%, NaF:17mol%, La 2o 3: 8mol%, Cs 2liLa 0.9tb 0.1cl 6: 10mol%.
5. rare earth ion doped Cs according to claim 1 2liLaCl 6the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) SiO 2-AlF 3-NaF-La 2o 3-Cs 2liLa (1-x)ln xcl 6be founding of glass: Cs 2liLa (1-x)ln xcl 6raw material is by CsCl, LiCl, LaCl 3, LnCl 3mixed sintering forms, and takes analytically pure each raw material by material component, respectively adds the NH that accounts for raw material gross weight 5% 4hF 2, NH 4hCl 2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1350-1450 DEG C, 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 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;
(2) Cs 2liLaCl 6the 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 heat-treated 4～6 hours its first crystallization peak, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped Cs 2liLaCl 6devitrified glass.
CN201410198336.3A 2014-05-08 2014-05-08 Rare earth ion doped Cs2liLaCl6devitrified glass and preparation method thereof Expired - Fee Related CN103951240B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410198336.3A CN103951240B (en) 2014-05-08 2014-05-08 Rare earth ion doped Cs2liLaCl6devitrified glass and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410198336.3A CN103951240B (en) 2014-05-08 2014-05-08 Rare earth ion doped Cs2liLaCl6devitrified glass and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103951240A true CN103951240A (en) 2014-07-30
CN103951240B CN103951240B (en) 2016-09-14

Family

ID=51328632

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410198336.3A Expired - Fee Related CN103951240B (en) 2014-05-08 2014-05-08 Rare earth ion doped Cs2liLaCl6devitrified glass and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103951240B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107366018A (en) * 2017-07-12 2017-11-21 宁波大学 A kind of rare earth halide mixing scintillation crystal and preparation method thereof
CN108531988A (en) * 2018-05-09 2018-09-14 宁波大学 A kind of preparation method of rare earth halide scintillation crystal and application
CN114958331A (en) * 2022-05-05 2022-08-30 闽都创新实验室 Double perovskite crystal and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101913766A (en) * 2010-08-04 2010-12-15 宁波大学 Rare earth ion doped oxyhalogen silicate glass and preparation method thereof
US20130175475A1 (en) * 2011-11-24 2013-07-11 Vladimir Ouspenski Luminescent material and a process of forming the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101913766A (en) * 2010-08-04 2010-12-15 宁波大学 Rare earth ion doped oxyhalogen silicate glass and preparation method thereof
US20130175475A1 (en) * 2011-11-24 2013-07-11 Vladimir Ouspenski Luminescent material and a process of forming the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107366018A (en) * 2017-07-12 2017-11-21 宁波大学 A kind of rare earth halide mixing scintillation crystal and preparation method thereof
CN107366018B (en) * 2017-07-12 2019-05-21 宁波大学 A kind of rare earth halide mixing scintillation crystal and preparation method thereof
CN108531988A (en) * 2018-05-09 2018-09-14 宁波大学 A kind of preparation method of rare earth halide scintillation crystal and application
CN114958331A (en) * 2022-05-05 2022-08-30 闽都创新实验室 Double perovskite crystal and preparation method and application thereof
CN114958331B (en) * 2022-05-05 2024-01-02 闽都创新实验室 Double perovskite crystal and preparation method and application thereof

Also Published As

Publication number Publication date
CN103951240B (en) 2016-09-14

Similar Documents

Publication Publication Date Title
CN103951243B (en) Rare earth ion doped Cs2LiYCl6Devitrified glass and preparation method thereof
CN103951197A (en) Rare-earth-ion-doped Cs2LiYBr6 microcrystalline glass and preparation method thereof
CN103951221B (en) Rare earth ion doped CaI 2devitrified glass and preparation method thereof
CN103951240A (en) Rare-earth-ion-doped Cs2LiLaCl6 microcrystalline glass and preparation method thereof
CN103951246A (en) Rare-earth-ion-doped Cs2LiLuBr6 microcrystalline glass and preparation method thereof
CN103951206A (en) Rare-earth-ion-doped BaGdBr5 microcrystalline glass and preparation method thereof
CN103951236B (en) Rare earth ion doped RbGd2Cl7Devitrified glass and preparation method thereof
CN103951233B (en) Rare earth ion doped LiYCl4Devitrified glass and preparation method thereof
CN103951245A (en) Rare-earth-ion-doped Cs2LiLuCl6 microcrystalline glass and preparation method thereof
CN103951198A (en) Rare-earth-ion-doped Cs2LiGdBr6 microcrystalline glass and preparation method thereof
CN103951253A (en) Rare-earth-ion-doped LiGdCl4 microcrystalline glass and preparation method thereof
CN103951224A (en) Rare-earth-ion-doped LiI microcrystalline glass and preparation method thereof
CN103951213A (en) Rare-earth-ion-doped LuCl3 microcrystalline glass and preparation method thereof
CN103951250B (en) Rare earth ion doped LiBaCl 3devitrified glass and preparation method thereof
CN103951254B (en) Rare earth ion doped LiGdBr4Devitrified glass and preparation method thereof
CN103951241A (en) Rare-earth-ion-doped Cs2LiLaBr6 microcrystalline glass and preparation method thereof
CN103951205B (en) Rare earth ion doped SrGdCl5Devitrified glass and preparation method thereof
CN103951248B (en) Rare earth ion doped Cs 2liGdCl 6devitrified glass and preparation method thereof
CN103951251A (en) Rare-earth-ion-doped LiBaBr3 microcrystalline glass and preparation method thereof
CN103951244A (en) Rare-earth-ion-doped Cs2LiYI6 microcrystalline glass and preparation method thereof
CN103951247A (en) Rare-earth-ion-doped Cs2LiLuI6 microcrystalline glass and preparation method thereof
CN103951249B (en) Rare earth ion doped Cs 2liGdI 6devitrified glass and preparation method thereof
CN103951252B (en) Rare earth ion doped LiBaI 3devitrified glass and preparation method thereof
CN103951235A (en) Rare-earth-ion-doped K2LuI5 microcrystalline glass and preparation method thereof
CN103951204B (en) Rare earth ion doped BaLu 2cl 8devitrified glass and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160914

Termination date: 20190508

CF01 Termination of patent right due to non-payment of annual fee