CN103951251A

CN103951251A - Rare-earth-ion-doped LiBaBr3 microcrystalline glass and preparation method thereof

Info

Publication number: CN103951251A
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: 2014-07-30
Anticipated expiration: 2034-05-08
Also published as: CN103951251B

Abstract

The invention discloses a rare-earth-ion-doped LiBaBr3 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 55-60 mol% of P2O5, 15-20 mol% of AlF3, 7-14 mol% of BaO, 10-15 mol% of LiBaBr3 and 1-3 mol% of LnBr3. The LnBr3 is CeBr3, EuBr3 or TbBr3. The preparation method comprises the following steps: preparing P2O5-AlF3-BaO-LiBaBr3-LnBr3 glass by a fusion process, and carrying out heat treatment to obtain the transparent LiBaBr3 microcrystalline glass. The LiBaBr3 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

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 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 in aspect difficulties such as light output, multiplicity compared with crystal, and therefore its application is also very limited.

LiBaBr ₃crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce ³⁺the LiBaBr 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 nuclear detection instrument efficiency greatly 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, 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 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 of percentage composition is:

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 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 DEG C, 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, 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) LiBaBr ₃devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near heat-treated 3～6 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 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, short wavelength's through performance is good, has LiBaBr ₃the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome 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, the rare earth ion doped LiBaBr making ₃devitrified 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:LiBaBr of embodiment mono-excitation of X-rays ₃the fluorescence spectrum of devitrified glass.

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

Fig. 4 is the Tb:LiBaBr of embodiment tri-excitation of X-rays 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, weigh 50 grams of analytical pure raw materials by the formula in table 1, 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 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 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 heat analysis (DTA) experimental data of glass, obtain 657 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 LiBaBr of doping ₃devitrified glass sample.

To the LiBaBr of preparation ₃devitrified 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 LiBaBr ₃phase, the material therefore obtaining 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 is output as 26000ph/MeV, and be 55ns 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, weigh 50 grams of analytical pure raw materials by the formula in table 2, 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 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 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 heat analysis (DTA) experimental data of glass, obtain 658 DEG C of the first recrystallization temperatures, the glass making is placed in to 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 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, weigh 50 grams of analytical pure raw materials by the formula in table 3, 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 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 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 heat analysis (DTA) experimental data of glass, obtain 661 DEG C of the first recrystallization temperatures, the glass making is placed in to 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 to 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 being obtained by above-mentioned preparation process ₃devitrified glass is transparent and physical and chemical performance is good.

Claims

1. a rare earth ion doped LiBaBr ₃devitrified glass, its mole of percentage composition is:

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 claimed in claim 1 ₃devitrified glass, is characterized in that this flicker 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 claimed in claim 1 ₃devitrified glass, is characterized in that this flicker 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 claimed in claim 1 ₃devitrified glass, is characterized in that this flicker 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 that accounts for raw material gross weight 5% ₄hF ₂, NH ₄hBr ₂, raw 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 being placed in retort furnace anneals, after glass transformation temperature Tg temperature is incubated 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, for micritization thermal treatment;

(2) LiBaBr 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 heat-treated 3～6 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 LiBaBr ₃devitrified glass.