CN103951215B

CN103951215B - Rare earth ion doped LuI 3devitrified glass and preparation method thereof

Info

Publication number: CN103951215B
Application number: CN201410198018.7A
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: 2016-04-27
Anticipated expiration: 2034-05-08
Also published as: CN103951215A

Abstract

The invention discloses a kind of rare earth ion doped LuI ₃devitrified glass and preparation method thereof, its Mole percent consists of P ₂o ₅: 30-40mol%, B ₂o ₃: 25-30mol%, BaF ₂: 7-15mol%, Lu ₂o ₃: 5-9mol%, LuI ₃: 15-20mol%, LnI ₃: 1-4mol%, wherein LnI ₃for CeI ₃, EuI ₃, TbI ₃, PrI ₃, NdI ₃in one, its preparation method first prepares P with scorification ₂o ₅-B ₂o ₃-BaF ₂-Lu ₂o ₃-LuI ₃-LnI ₃be glass, after heat treatment obtain transparent LuI ₃devitrified glass, LuI of the present invention ₃devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have extremely strong 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 LuI 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 LuI being used 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 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, industry 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.

LuI ₃crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce ³⁺the LuI 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, scintillation detectors efficiency can be made greatly to improve.Eu ³⁺, Tb ³⁺doping LuI ₃the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LuI 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 extremely strong light output, fast decay, energy resolution and the good rare earth ion doped LuI 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 LuI ₃devitrified glass, its Mole percent consists of:

P ₂O ₅：30-40mol％B ₂O ₃：25-30mol％BaF ₂：7-15mol％

Lu ₂O ₃：5-9mol％LuI ₃：15-20mol％LnI ₃：1-4mol％

Wherein LnI ₃for CeI ₃, EuI ₃, TbI ₃, PrI ₃, NdI ₃in one.

This flicker devitrified glass material component is: P ₂o ₅: 30mol%, B ₂o ₃: 30mol%, BaF ₂: 15mol%, Lu ₂o ₃: 5mol%, LuI ₃: 19mol%, CeI ₃: 1mol%.

This flicker devitrified glass material component is: P ₂o ₅: 35mol%, B ₂o ₃: 28mol%, BaF ₂: 7mol%, Lu ₂o ₃: 6mol%, LuI ₃: 20mol%, EuI ₃: 4mol%.

This flicker devitrified glass material component is: P ₂o ₅: 40mol%, B ₂o ₃: 25mol%, BaF ₂: 9mol%, Lu ₂o ₃: 9mol%, LuI ₃: 15mol%, TbI ₃: 2mol%.

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

(1) P ₂o ₅-B ₂o ₃-BaF ₂-Lu ₂o ₃-LuI ₃-LnI 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 ₄hI ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1200-1350 DEG C, be incubated and after 1-2 hour, glass melt poured in pig mold, then be placed in retort furnace to anneal, after 1 hour, 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 sample, for micritization thermal treatment.

(2) LuI ₃prepared by devitrified glass:

According to thermal analyses (DTA) experimental data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 4 ~ 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 LuI ₃devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine iodine oxygen compound, the through performance of short wavelength is good, has LuI 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 LuI 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 LuI ₃crystalline phase, obtained rare earth ion doped LuI ₃devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution, can make scintillation detectors efficiency greatly improve.The preparation method of this devitrified glass is simple, and it is lower that dirt produces cost.

Accompanying drawing explanation

Fig. 1 is X-ray diffraction (XRD) figure of sample after the thermal treatment of embodiment one micritization.

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

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

Fig. 4 is the Tb:LuI 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 ₄hI ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1200 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 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 670 DEG C, obtained glass is placed in fine annealing stove 690 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 LuI of doping ₃devitrified glass.

To the LuI of preparation ₃devitrified glass carries out X-ray diffraction test, and obtain the XRD figure of glass after micritization process as shown in Figure 1, its result is as follows: the XRD diffraction peak of the sample obtained through Overheating Treatment and LuI ₃the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is LuI ₃the devitrified glass of crystallization phase.And the Ce of excitation of X-rays ³⁺ion doping LuI ₃as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion LuI ₃devitrified glass light output can reach 45000ph/MeV, and fall time is 28ns, and its light output is high as seen, and fall time is short.

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 ₄hI ₂pour in corundum crucible after raw material is mixed and melt, temperature of fusion 1300 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 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 680 DEG C, obtained glass is placed in 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 Eu ³⁺the LuI of ion doping ₃devitrified glass.

To the LuI of preparation ₃the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping LuI ₃as shown in Figure 3, its result shows to produce Eu:LuI after Overheating Treatment the fluorescence spectrum of devitrified glass ₃crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LuI is described ₃the luminosity of devitrified glass is better; Be expected to very much the scintillator be used as in safety check.

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 ₄hI ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1350 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 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 690 DEG C, obtained glass is placed in nitrogen fine annealing stove 710 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 LuI of ion doping ₃devitrified glass.

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

Embodiment 4

Substantially the same manner as Example 1, difference is material component difference: P ₂o ₅: 40mol%, B ₂o ₃: 25mol%, BaF ₂: 9mol%, Lu ₂o ₃: 9mol%, LuI ₃: 15mol%, PrI ₃: 2mol%.

Embodiment 5

Substantially the same manner as Example 1, difference is material component difference: P ₂o ₅: 70mol%, BaF ₂: 10mol%, Lu ₂o ₃: 9mol%, LuI ₃: 10mol%, NdI ₃: 1mol%.

Embodiment 4,5 also can obtain LuI rare earth ion doped preferably ₃devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims

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

P ₂O ₅：30-40mol％B ₂O ₃：25-30mol％BaF ₂：7-15mol％

Lu ₂O ₃：5-9mol％LuI ₃：15-20mol％LnI ₃：1-4mol％

Wherein LnI ₃for CeI ₃, EuI ₃, TbI ₃, PrI ₃, NdI ₃in one.

2. rare earth ion doped LuI according to claim 1 ₃devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 30mol%, B ₂o ₃: 30mol%, BaF ₂: 15mol%, Lu ₂o ₃: 5mol%, LuI ₃: 19mol%, CeI ₃: 1mol%.

3. rare earth ion doped LuI according to claim 1 ₃devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 35mol%, B ₂o ₃: 28mol%, BaF ₂: 7mol%, Lu ₂o ₃: 6mol%, LuI ₃: 20mol%, EuI ₃: 4mol%.

4. rare earth ion doped LuI according to claim 1 ₃devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 40mol%, B ₂o ₃: 25mol%, BaF ₂: 9mol%, Lu ₂o ₃: 9mol%, LuI ₃: 15mol%, TbI ₃: 2mol%.

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

(1) P ₂o ₅-B ₂o ₃-BaF ₂-Lu ₂o ₃-LuI ₃-LnI 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 ₄hI ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1200-1350 DEG C, be incubated and after 1-2 hour, glass melt poured in pig mold, then be placed in retort furnace to anneal, after 1 hour, 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) LuI ₃the preparation of devitrified glass: according to the DTA thermal analysis experiment data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 4 ~ 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 LuI ₃devitrified glass.