CN103951254A

CN103951254A - Rare-earth-ion-doped LiGdBr4 microcrystalline glass and preparation method thereof

Info

Publication number: CN103951254A
Application number: CN201410198465.2A
Authority: CN
Inventors: 王倩; 张约品; 夏海平; 杨斌; 张为欢; 欧阳绍业
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: CN103951254B

Abstract

The invention discloses a rare-earth-ion-doped LiGdBr4 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 30-40 mol% of P2O5, 25-30 mol% of B2O3, 18-20 mol% of AlF3, 15-19 mol% of LiGdBr4 and 1-4 mol% of LnBr3. The LnBr3 is CeBr3, EuBr3 or TbBr3. The preparation method comprises the following steps: preparing P2O5-B2O3-AlF3-LiGdBr4-LnBr3 glass by a fusion process, and carrying out heat treatment to obtain the transparent LiGdBr4 microcrystalline glass. The LiGdBr4 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 LiGdBr 4devitrified 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 LiGdBr as scintillation material ₄devitrified 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.

LiGdBr ₄crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce ³⁺the LiGdBr of doping ₄it 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⁺li doped GdBr ₄the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LiGdBr ₄crystal 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 LiGdBr of temporal resolution ₄devitrified glass.The present invention also provides the preparation method of this flicker devitrified glass, and it is simple that this preparation method has method, the advantage that cost is low.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped LiGdBr ₄devitrified glass, its mole of percentage composition is:

P ₂O ₅：30-40mol％ B ₂O ₃：25-30mol％AlF ₃：18-20mol％

LiGdBr ₄：15-19mol％ LnBr ₃：1-4mol％

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

This flicker devitrified glass material component is: P ₂o ₅: 30mol%, B ₂o ₃: 30mol%, AlF ₃: 20mol%, LiGdBr ₄: 19mol%, CeBr ₃: 1mol%.

This flicker devitrified glass material component is: P ₂o ₅: 35mol%, B ₂o ₃: 28mol%, AlF ₃: 18mol%, LiGdBr ₄: 15mol%, EuBr ₃: 4mol%.

This flicker devitrified glass material component is: P ₂o ₅: 40mol%, B ₂o ₃: 25mol%, AlF ₃: 18mol%, LiGdBr ₄: 15mol%, TbBr ₃: 2mol%.

Described rare earth ion doped LiGdBr ₄the preparation method of devitrified glass, comprises the steps:

(1) P ₂o ₅-B ₂o ₃-AlF ₃-LiGdBr ₄-LnBr ₃be founding of glass:

Take analytically pure each raw material by material component, add the NH that respectively 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 1200-1350 DEG C, is incubated and after 1-2 hour, glass melt is poured in pig mold, then being placed in retort furnace anneals, after 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h in the insulation of glass transformation temperature Tg temperature, close retort furnace power supply and be automatically cooled to room temperature, take out glass sample, for micritization thermal treatment.

(2) LiGdBr ₄devitrified 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 LiGdBr4 devitrified glass.

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 LiGdBr ₄the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome LiGdBr ₄single 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 LiGdBr ₄crystalline phase, the rare earth ion doped LiGdBr making ₄devitrified 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 flash 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 scanning electron microscope diagram (SEM) of sample after embodiment mono-micritization thermal treatment.

Fig. 2 is the Ce:LiGdBr of embodiment mono-excitation of X-rays ₄the fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:LiGdBr of embodiment bis-excitation of X-rays ₄the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:LiGdBr of embodiment tri-excitation of X-rays ₄the 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, 1200 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 the first recrystallization temperature 667 glass making is placed in to nitrogen fine annealing stove 689 processing 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 LiGdBr of doping ₄devitrified glass.

To the LiGdBr of preparation ₄devitrified glass carries out sem test, obtains glass through micritization scanning electron microscope diagram after treatment as shown in Figure 1, and what in photo, be particle shape is the nano microcrystalline of separating out, and particle gap is glassy phase.The test of X-ray diffraction shows that crystalline phase is LiGdBr ₄phase, the material therefore obtaining is LiGdBr ₄the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping LiGdBr ₄as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion LiGdBr ₄devitrified glass light is output as between 26000ph/MeV, and be 65ns 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, 1300 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 678 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 699 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 Eu ³⁺the LiGdBr of ion doping ₄devitrified glass.

To the LiGdBr of preparation ₄the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping LiGdBr ₄as shown in Figure 3, its result shows to produce Eu:LiGdBr after Overheating Treatment to the fluorescence spectrum of devitrified glass ₄crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LiGdBr is described ₄the 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, 1350 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 the first recrystallization temperature 693, the glass making is placed in to nitrogen fine annealing stove 711 thermal treatment 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 LiGdBr of ion doping ₄devitrified glass.

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

Claims

1. a rare earth ion doped LiGdBr ₄devitrified glass, its mole of percentage composition is:

P ₂O ₅：30-40mol％ B ₂O ₃：25-30mol％ AlF ₃：18-20mol％

LiGdBr ₄：15-19mol％ LnBr ₃：1-4mol％

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

2. rare earth ion doped LiGdBr claimed in claim 1 ₄devitrified glass, is characterized in that this flicker devitrified glass material component is: P ₂o ₅: 30mol%, B ₂o ₃: 30mol%, AlF ₃: 20mol%, LiGdBr ₄: 19mol%, CeBr ₃: 1mol%.

3. rare earth ion doped LiGdBr claimed in claim 1 ₄devitrified glass, is characterized in that this flicker devitrified glass material component is: P ₂o ₅: 35mol%, B ₂o ₃: 28mol%, AlF ₃: 18mol%, LiGdBr4:15mol%, EuBr ₃: 4mol%.

4. rare earth ion doped LiGdBr claimed in claim 1 ₄devitrified glass, is characterized in that this flicker devitrified glass material component is: P ₂o ₅: 40mol%, B ₂o ₃: 25mol%, AlF ₃: 18mol%, LiGdBr ₄: 15mol%, TbBr ₃: 2mol%.

5. rare earth ion doped LiGdBr according to claim 1 ₄the preparation method of devitrified glass, is characterized in that comprising following concrete steps:

(1) P ₂o ₅-B ₂o ₃-AlF ₃-LiGdBr ₄-LnBr ₃be founding of glass: take analytically pure each raw material by material component, add the NH that respectively 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 1200-1350 DEG C, is incubated and after 1-2 hour, glass melt is poured in pig mold, then being placed in retort furnace anneals, after 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h in the insulation of 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) LiGdBr ₄the preparation of devitrified glass: 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 LiGdBr ₄devitrified glass.