CN103951251B

CN103951251B - Rare earth ion doped LiBaBr 3devitrified glass and preparation method thereof

Info

Publication number: CN103951251B
Application number: CN201410198460.XA
Authority: CN
Inventors: 张为欢; 张约品; 夏海平; 欧阳绍业; 王倩; 杨斌
Original assignee: Ningbo University
Current assignee: Ningbo University
Priority date: 2014-05-08
Filing date: 2014-05-08
Publication date: 2016-03-30
Anticipated expiration: 2034-05-08
Also published as: CN103951251A

Abstract

The invention discloses a kind of rare earth ion doped LiBaBr ₃devitrified glass and preparation method thereof, its Mole percent consists of P ₂o ₅: 55-60mol%, AlF ₃: 15-20mol%, BaO:7-14mol%, LiBaBr ₃: 10-15mol%, LnBr ₃: 1-3mol%, wherein LnBr ₃for CeBr ₃, EuBr ₃, TbBr ₃in one, its preparation method first prepares P with scorification ₂o ₅-AlF ₃-BaO-LiBaBr ₃-LnBr ₃be glass, after heat treatment obtain transparent LiBaBr ₃devitrified glass, LiBaBr of the present invention ₃devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have stronger light output, decay soon, the performances such as good energy resolution and temporal resolution.The preparation method of this devitrified glass is simple, and production cost is lower.

Description

Rare earth ion doped LiBaBr 3devitrified 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 LiBaBr being used as scintillation material ₃devitrified glass and preparation method thereof.

Background technology

Scintillation material is a kind of lower optical function material that can send visible ray of exciting at energetic ray (as x-ray, gamma-rays) or other radioactive particle, is widely used in the fields such as the researchs of nuclear medicine diagnostic, high energy physics and nuclear physics experiment, industrial and geological prospecting.The requirement of difference to scintillator according to Application Areas 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 comparatively large, cost is low and radiation resistance is good.Scintillation crystal generally has the advantage such as resistance to irradiation, fast decay, High Light Output, but scintillation crystal also exists following serious shortcoming: preparation difficulty, expensive.And although rare earth ion doped scintillation glass cost is low, easily prepare large-size glass, it is difficult compared with crystal in light output, multiplicity etc., and therefore its application is also very limited.

LiBaBr ₃crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce ³⁺the LiBaBr of doping ₃it is high that crystal has light output, decays soon, good energy resolution, temporal resolution and linear response, has than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, nuclear detection instrument efficiency can be made greatly to improve.Eu ³⁺, Tb ³⁺li doped BaBr ₃the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LiBaBr ₃crystal is deliquescence very easily, and mechanical property is poor, easy cleavage slabbing, large-size crystals growth difficulty, and expensively have impact on 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 LiBaBr 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 LiBaBr ₃devitrified glass, its Mole percent consists of:

P ₂O ₅：55-60mol％AlF ₃：15-20mol％BaO：7-14mol％

LiBaBr ₃：10-15mol％LnBr ₃：1-3mol％

Wherein LnBr ₃for CeBr ₃, EuBr ₃, TbBr ₃one.

This flicker devitrified glass material component is: P ₂o ₅: 55mol%, AlF ₃: 20mol%, BaO:8mol%, LiBaBr ₃: 15mol%, CeBr ₃: 2mol%.

This flicker devitrified glass material component is: P ₂o ₅: 60mol%, AlF ₃: 15mol%, BaO:7mol%, LiBaBr ₃: 15mol%, EuBr ₃: 3mol%.

This flicker devitrified glass material component is: P ₂o ₅: 60mol%, AlF ₃: 15mol%, BaO:14mol%, LiBaBr ₃: 10mol%, TbBr ₃: 1mol%.

Described rare earth ion doped LiBaBr ₃the preparation method of devitrified glass, comprises the steps:

(1) P ₂o ₅-AlF ₃-BaO-LiBaBr ₃-LnBr ₃be founding of glass:

Take analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5% ₄hF ₂, NH ₄hBr ₂raw material is mixed, then pours 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, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 50 DEG C are cooled to 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) LiBaBr ₃prepared by devitrified glass:

According to thermal analyses (DTA) experimental data of glass, obtained glass is placed in nitrogen fine annealing stove, heat-treated 3 ~ 6 hours near 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 and be automatically cooled to room temperature, obtain transparent rare earth ion doped LiBaBr ₃devitrified glass sample.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine bromine oxygen compound, the through performance of short wavelength is good, has LiBaBr ₃the feature that the superior scintillation properties of crystalline host material and the physical strength of oxide glass, stability and being easy to is processed, overcomes LiBaBr 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 LiBaBr ₃crystalline phase, obtained rare earth ion doped LiBaBr ₃devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have stronger light output, decay soon, the performances such as good 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.

Accompanying drawing explanation

Fig. 1 is the transmission electron microscope figure (TEM) of sample after the thermal treatment of embodiment one micritization.

Fig. 2 is the Ce:LiBaBr of embodiment one excitation of X-rays ₃the fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:LiBaBr of embodiment two excitation of X-rays ₃the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:LiBaBr of embodiment three excitation of X-rays ₃the fluorescence spectrum of devitrified glass.

Embodiment

Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.

Embodiment one: table 1 is glass formula and the first recrystallization temperature value of embodiment one.

Table 1

Concrete preparation process is as follows: the first step, 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 ₄hBr ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1350 DEG C, be incubated 2 hours, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 657 DEG C, obtained glass is placed in 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 LiBaBr of doping ₃devitrified glass sample.

To the LiBaBr of preparation ₃devitrified glass carries out transmission electron microscope test, obtain the transmission electron microscope picture of glass after micritization process as shown in Figure 1, its result is as follows: in photo, the nano microcrystalline of glass basis and precipitation seems more clearly, and the stain distributed in glass basis is microcrystal grain.X-ray diffraction test shows that crystalline phase is LiBaBr ₃phase, the material therefore obtained is LiBaBr ₃the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping LiBaBr ₃as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion LiBaBr ₃devitrified glass light output is 26000ph/MeV, and fall time is 55ns.

Embodiment two: table 2 is glass formula and the first recrystallization temperature value of embodiment two.

Table 2

Concrete preparation process is as follows: the first step, 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 ₄hBr ₂pour in corundum crucible after raw material is mixed and melt, temperature of fusion 1400 DEG C, be incubated 1 hour, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 658 DEG C, obtained glass is placed in nitrogen fine annealing stove 672 DEG C of thermal treatments 3 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 LiBaBr of ion doping ₃devitrified glass.

To the LiBaBr of preparation ₃the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping LiBaBr ₃as shown in Figure 3, its result shows Eu:LiBaBr after Overheating Treatment to the fluorescence spectrum of devitrified glass ₃crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LiBaBr is described ₃the luminosity of devitrified glass is better.

Embodiment three: table 3 is glass formula and the first recrystallization temperature value of embodiment three.

Table 3

Concrete preparation process is as follows: the first step, 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 ₄hBr ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1450 DEG C, be incubated 1.5 hours, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 661 DEG C, obtained glass is placed in nitrogen fine annealing stove 682 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 Tb ³⁺the LiBaBr of ion doping ₃devitrified glass.

To the LiBaBr of preparation ₃the spectral quality test of devitrified glass, the Tb of excitation of X-rays ³⁺ion doping LiBaBr ₃as shown in Figure 4, its result shows to produce Tb:LiBaBr after Overheating Treatment the fluorescence spectrum of devitrified glass ₃crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:LiBaBr is described ₃the luminosity of devitrified glass is better; The rare earth ion doped LiBaBr obtained by above-mentioned preparation process ₃devitrified glass is transparent and physical and chemical performance is excellent.

Claims

1. a rare earth ion doped LiBaBr ₃devitrified glass, its Mole percent consists of:

P ₂O ₅：55-60mol％AlF ₃：15-20mol％BaO：7-14mol％

LiBaBr ₃：10-15mol％LnBr ₃：1-3mol％

Wherein LnBr ₃for CeBr ₃, EuBr ₃, TbBr ₃in one.

2. rare earth ion doped LiBaBr according to claim 1 ₃devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 55mol%, AlF ₃: 20mol%, BaO:8mol%, LiBaBr ₃: 15mol%, CeBr ₃: 2mol%.

3. rare earth ion doped LiBaBr according to claim 1 ₃devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 60mol%, AlF ₃: 15mol%, BaO:7mol%, LiBaBr ₃: 15mol%, EuBr ₃: 3mol%.

4. rare earth ion doped LiBaBr according to claim 1 ₃devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 60mol%, AlF ₃: 15mol%, BaO:14mol%, LiBaBr ₃: 10mol%, TbBr ₃: 1mol%.

5. rare earth ion doped LiBaBr according to claim 1 ₃the preparation method of devitrified glass, is characterized in that comprising following concrete steps:

(1) P ₂o ₅-AlF ₃-BaO-LiBaBr ₃-LnBr ₃be founding of glass: take analytically pure each raw material by material component, respectively add the NH accounting 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 DEG C, after insulation 1-2 is little, glass melt is poured in pig mold, then be placed in retort furnace to anneal, after 2 hours, be cooled to 50 DEG C with the speed of 10 DEG C/h in glass transformation temperature Tg temperature, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;

(2) LiBaBr ₃the preparation of devitrified glass: according to the thermal analysis experiment data of glass, obtained glass is placed in nitrogen fine annealing stove, heat-treated 3 ~ 6 hours near 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 LiBaBr ₃devitrified glass.