CN103951206A

CN103951206A - Rare-earth-ion-doped BaGdBr5 microcrystalline glass and preparation method thereof

Info

Publication number: CN103951206A
Application number: CN201410197905.2A
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: CN103951206B

Abstract

The invention discloses a rare-earth-ion-doped BaGdBr5 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 40-50 mol% of B2O3, 15-25 mol% of Nb2O5, 22-25 mol% of BaGdBr5 and 5-8 mol% of LnBr3. The LnBr3 is CeBr3, EuBr3 or TbBr3. The preparation method comprises the following steps: preparing B2O3-Nb2O5-BaGdBr5-LnBr3 glass by a fusion process, and carrying out heat treatment to obtain the transparent BaGdBr5 microcrystalline glass. The BaGdBr5 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 BaGdBr 5devitrified 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 BaGdBr as scintillation material ₅devitrified 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.

BaGdBr ₅crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce ³⁺the BaGdBr of doping ₅it 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 BaGdBr ₅the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But BaGdBr ₅crystal is deliquescence very easily, and mechanical property is poor, easy 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 BaGdBr of temporal resolution ₅devitrified 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 BaGdBr ₅devitrified glass, its mole of percentage composition is:

B ₂O ₃：40-55mol％Nb ₂O ₅：15-25mol％

BaGdBr ₅：22-25mol％LnBr ₃：5-8mol％

LnBr wherein ₃for CeBr ₃, EuBr ₃, TbBr ₃in a kind of.

This flicker devitrified glass material component is: B ₂o ₃: 45mol%, Nb ₂o ₅: 25mol%, BaGdBr ₅: 25mol%, CeBr ₃: 5mol%.

This flicker devitrified glass material component is: B ₂o ₃: 55mol%, Nb ₂o ₅: 15mol%, BaGdBr ₅: 22mol%, EuBr ₃: 8mol%.

This flicker devitrified glass material component is: B ₂o ₃: 50mol%, Nb ₂o ₅: 20mol%, BaGdBr ₅: 25mol%, TbBr ₃: 5mol%.

Described rare earth ion doped BaGdBr ₅the preparation method of devitrified glass, comprises the steps:

(1) B ₂o ₃-Nb ₂o ₅-BaGdBr ₅-LnBr ₃be founding of glass:

By material component, take analytically pure each raw material, add the NH that accounts for raw material gross weight 5% ₄hBr ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1250-1350 ℃, 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 1 hour, 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) BaGdBr ₅devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near its first crystallization peak, heat-treated is 7～9 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 BaGdBr ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of bromine oxygen compound, short wavelength's through performance is good, has BaGdBr ₅the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome BaGdBr ₅single 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 BaGdBr ₅crystalline phase, the rare earth ion doped BaGdBr making ₅devitrified 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 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 the transmission electron microscope figure (TEM) of sample after embodiment mono-micritization thermal treatment.

Fig. 2 is the Ce:BaGdBr of embodiment mono-excitation of X-rays ₅the fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:BaGdBr of embodiment bis-excitation of X-rays ₅the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:BaGdBr of embodiment tri-excitation of X-rays ₅the 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 ₄hBr ₂after raw material is mixed, pour in quartz crucible and melt, 1250 ℃ 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, 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 711 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 730 ℃ of thermal treatments 7 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 BaGdBr of doping ₅devitrified glass sample.

BaGdBr to preparation ₅devitrified glass carries out transmission electron microscope test, obtain the transmission electron microscope picture of glass after micritization is processed 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 BaGdBr ₅phase, the material therefore obtaining is BaGdBr ₅the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping BaGdBr ₅as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion BaGdBr ₅devitrified glass light is output as 30000ph/MeV.

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 ₄hBr ₂after raw material is mixed, pour in corundum crucible and melt, 1300 ℃ 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, 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 717 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 732 ℃ of thermal treatments 9 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 BaGdBr of ion doping ₅devitrified glass.

BaGdBr to preparation ₅the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping BaGdBr ₅as shown in Figure 3, its result shows to produce Eu:BaGdBr after Overheating Treatment to the fluorescence spectrum of devitrified glass ₅crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:BaGdBr is described ₅the 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, by the formula in table 3, weigh 50 grams of analytical pure raw materials, and add 2.5 grams of NH ₄hBr ₂after raw material is mixed, pour in quartz crucible and melt, 1350 ℃ 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, 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 721 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 734 ℃ of thermal treatments 8 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 BaGdBr of ion doping ₅devitrified glass.

BaGdBr to preparation ₅the spectral quality test of devitrified glass, the Tb of excitation of X-rays ³⁺ion doping BaGdBr ₅as shown in Figure 4, its result shows to produce Tb:BaGdBr after Overheating Treatment to the fluorescence spectrum of devitrified glass ₅crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:BaGdBr is described ₅the luminosity of devitrified glass is better; The rare earth ion doped BaGdBr being obtained by above-mentioned preparation process ₅devitrified glass is transparent and physical and chemical performance is good.

Claims

1. a rare earth ion doped BaGdBr ₅devitrified glass, its mole of percentage composition is:

B ₂O ₃：40-55mol％Nb ₂O ₅：15-25mol％

BaGdBr ₅：22-25mol％LnBr ₃：5-8mol％

LnBr wherein ₃for CeBr ₃, EuBr ₃, TbBr ₃in a kind of.

2. rare earth ion doped BaGdBr claimed in claim 1 ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: B ₂o ₃: 45mol%, Nb ₂o ₅: 25mol%, BaGdBr ₅: 25mol%, CeBr ₃: 5mol%.

3. rare earth ion doped BaGdBr claimed in claim 1 ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: B ₂o ₃: 55mol%, Nb ₂o ₅: 15mol%, BaGdBr ₅: 22mol%, EuBr ₃: 8mol%.

4. rare earth ion doped BaGdBr claimed in claim 1 ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: B ₂o ₃: 50mol%, Nb ₂o ₅: 20mol%, BaGdBr ₅: 25mol%, TbBr ₃: 5mol%.

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

(1) B ₂o ₃-Nb ₂o ₅-Ba ₂gdBr ₅-LnBr ₃be founding of glass: by material component, take analytically pure each raw material, add the NH that accounts for raw material gross weight 5% ₄hBr ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1250-1350 (2, insulation 1-2 hour, melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, 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) BaGdBr ₅the preparation of devitrified glass: according to the thermal analysis experiment data of glass, the glass making is placed in near nitrogen fine annealing stove heat-treated 7～9 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 BaGdBr ₅devitrified glass.