CN103951253B

CN103951253B - Rare earth ion doped LiGdCl 4devitrified glass and preparation method thereof

Info

Publication number: CN103951253B
Application number: CN201410198463.3A
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: 2016-02-10
Anticipated expiration: 2034-05-08
Also published as: CN103951253A

Abstract

The invention discloses a kind of rare earth ion doped LiGdCl ₄devitrified glass and preparation method thereof, its Mole percent consists of GeO ₂: 40-50mol%, AlF ₃: 18-21mol%, BaO:13-18mol%, LiGdCl ₄: 15-20mol%, LnCl ₃: 1-3mol%, wherein LnCl ₃for CeCl ₃, EuCl ₃, TbCl ₃in one, its preparation method first prepares GeO with scorification ₂-AlF ₃-BaO-LiGdCl ₄-LnCl ₃be glass, after heat treatment obtain transparent devitrified glass, LiGdCl of the present invention ₄devitrified 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 LiGdCl 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 LiGdCl being used as scintillation material ₄devitrified 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.

LiGdCl ₄crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce ³⁺the LiGdCl of doping ₄it 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⁺li doped GdCl ₄the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But LiGdCl ₄crystal 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 LiGdCl of temporal resolution ₄devitrified glass.Present invention also offers the preparation method of this flicker devitrified glass, 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 LiGdCl ₄devitrified glass, its Mole percent consists of:

GeO ₂：40-50mol％AlF ₃：18-21mol％BaO：13-18mol％

LiGdCl ₄：15-20mol％LnCl ₃：1-3mol％

Wherein LnCl ₃for CeCl ₃, EuCl ₃, TbCl ₃in one.

This flicker devitrified glass material component is: GeO ₂: 40mol%, AlF ₃: 20mol%, BaO:18mol%, LiGdCl ₄: 20mol%, CeCl ₃: 2mol%.

This flicker devitrified glass material component is: GeO ₂: 45mol%, AlF ₃: 18mol%, BaO:14mol%, LiGdCl ₄: 20mol%, EuCl ₃: 3mol%.

This flicker devitrified glass material component is: GeO ₂: 50mol%, AlF ₃: 21mol%, BaO:13mol%, LiGdCl ₄: 15mol%, TbCl ₃: 1mol%.

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

(1) GeO ₂-AlF ₃-BaO-LiGdCl ₄-LnCl ₃be founding of glass:

Take analytically pure each raw material by material component, then add the NH respectively accounting for raw material gross weight 5% ₄hF ₂, NH ₄hCl ₂, raw material is mixed, pours into after raw material is mixed in quartz crucible or corundum crucible and melt.Temperature of fusion 1300-1480 DEG C, insulation 1-2 hour, glass melt is 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) LiGdCl ₄prepared 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 LiGdCl ₄devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine chlorine oxonium compound, the through performance of short wavelength is good, has LiGdCl ₄the 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 LiGdCl 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 LiGdCl ₄crystalline phase, obtained rare earth ion doped LiGdCl ₄devitrified 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 X-ray diffraction (XRD) figure of sample after the thermal treatment of embodiment one micritization.

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

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

Fig. 4 is the Tb:LiGdCl of embodiment three excitation of X-rays ₄the 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, then adds 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hCl ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1300 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 701 DEG C, obtained glass is placed in nitrogen fine annealing stove 720 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 LiGdCl of doping ₄devitrified glass.

To the LiGdCl of preparation ₄devitrified 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 LiGdCl ₄the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is LiGdCl ₄the devitrified glass of crystallization phase.And the Ce of excitation of X-rays ³⁺ion doping LiGdCl ₄as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion LiGdCl ₄devitrified glass light output is 21000ph/MeV, and fall time is 60ns.

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, then adds 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hCl ₂pour in corundum crucible after raw material is mixed and melt, temperature of fusion 1480 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 705 DEG C, obtained glass is placed in nitrogen fine annealing stove 715 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 LiGdCl of ion doping ₄devitrified glass.

To the LiGdCl of preparation ₄the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping LiGdCl ₄as shown in Figure 3, its result shows to produce Eu:LiGdCl after Overheating Treatment the fluorescence spectrum of devitrified glass ₄crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LiGdCl is described ₄the 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, then adds 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hCl 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 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 710 DEG C, obtained glass is placed in nitrogen fine annealing stove 728 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 LiGdCl of ion doping ₄devitrified glass.

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

Claims

1. a rare earth ion doped LiGdCl ₄devitrified glass, its Mole percent consists of:

GeO ₂：40-50mol％AlF ₃：18-21mol％BaO：13-18mol％

LiGdCl ₄：15-20mol％LnCl ₃：1-3mol％

Wherein LnCl ₃for CeCl ₃, EuCl ₃, TbCl ₃in one.

2. rare earth ion doped LiGdCl according to claim 1 ₄devitrified glass, is characterized in that this devitrified glass material component is: GeO ₂: 40mol%, AlF ₃: 20mol%, BaO:18mol%, LiGdCl ₄: 20mol%, CeCl ₃: 2mol%.

3. rare earth ion doped LiGdCl according to claim 1 ₄devitrified glass, is characterized in that this devitrified glass material component is: GeO ₂: 45mol%, AlF ₃: 18mol%, BaO:14mol%, LiGdCl ₄: 20mol%, EuCl ₃: 3mol%.

4. rare earth ion doped LiGdCl according to claim 1 ₄devitrified glass, is characterized in that this devitrified glass material component is: GeO ₂: 50mol%, AlF ₃: 21mol%, BaO:13mol%, LiGdCl ₄: 15mol%, TbCl ₃: 1mol%.

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

(1) GeO ₂-AlF ₃-BaO-LiGdCl ₄-LnCl ₃be founding of glass: take analytically pure each raw material by material component, then add the NH respectively accounting for raw material gross weight 5% ₄hF ₂, NH ₄hCl ₂pour into after raw material is mixed in quartz crucible or corundum crucible and melt, temperature of fusion 1300-1480 DEG C, insulation 1-2 hour, pours into glass melt 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) LiGdCl ₄the 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 LiGdCl ₄devitrified glass.