CN103951239B

CN103951239B - Rare earth ion doped LiLaCl4Devitrified glass and preparation method thereof

Info

Publication number: CN103951239B
Application number: CN201410198314.7A
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: Huzhou You Yan Intellectual Property Service Co., Ltd.
Priority date: 2014-05-08
Filing date: 2014-05-08
Publication date: 2016-06-08
Anticipated expiration: 2034-05-08
Also published as: CN103951239A

Abstract

The invention discloses a kind of rare earth ion doped LiLaCl₄Devitrified glass and preparation method thereof, its Mole percent consists of P₂O₅: 35-45mol%, Nb₂O₅: l5-23mol%, SrF₂: 16-24mol%, LiLaCl₄: 15-20mol%, LnCl₃: 1-4mol%, wherein LnCl₃It is CeCl₃��EuCl₃��TbCl₃��PrCl₃And NdCl₃In one, its preparation method is first to prepare P with fusion method₂O₅-Nb₂O₅-SrF₂-LiLaCl₄-LnCl₃It is glass, after heat treatment obtains transparent LiLaCl₄Devitrified glass, the LiLaCl of the present invention₄Devitrified glass, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate higher, there is stronger light output, decay soon, the performance such as good energy resolution and temporal resolution. The preparation method of this devitrified glass is simple, and production cost is relatively low.

Description

Rare earth ion doped LiLaCl4Devitrified 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 LiLaCl as scintillation material₄Devitrified glass and preparation method thereof.

Background technology

Scintillation material is a kind of optical function material that can send visible ray under high-energy ray (such as x-ray, gamma-rays) or the exciting of 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. The requirement of scintillator is also not quite similar by the difference according to application, but generally scintillation material should possess following properties: the features such as luminous efficiency is high, fluorescence decay fast, density is relatively big, 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 there is also following serious shortcoming: preparation difficulty, expensive. Although and rare earth ion doped scintillation glass cost is low, easily preparing large-size glass, but it is difficult compared with crystal in light output, number of repetition etc., therefore its application is also affected by considerable restraint.

LiLaCl₄Crystal be a kind of can the scintillation crystal substrate of doping with rare-earth ions, Ce³⁺The LiLaCl of doping₄Crystal has light output height, decays soon, and good energy resolution, temporal resolution and linear response have the luminous efficiency higher than rare earth ion doped crystal of fluoride and oxide crystal, scintillation detectors efficiency will be made to be greatly improved. Eu³⁺��Tb³⁺Doping LiLaCl₄The scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen. But LiLaCl₄Crystal is deliquescence very easily, and mechanical performance is poor, easy cleavage slabbing, large-size crystals growth difficulty, and expensive have impact on its practical application.

Summary of the invention

The technical problem to be solved in the present invention is in that to provide a kind of Deliquescence-resistant, good mechanical property, have the rare earth ion doped LiGdCl that stronger light output, fast decay, energy resolution and temporal resolution are good₄Devitrified glass. The preparation method that present invention also offers this flicker devitrified glass, it is simple that this preparation method has method, the advantage that cost is low.

This invention address that the technical scheme that above-mentioned technical problem adopts is: rare earth ion doped LiLaCl₄Devitrified glass, its Mole percent consists of:

P₂O₅: 35-45mol%Nb₂O₅: 15-23mol%SrF₂: 16-24mol%

LiLaCl₄: 15-20mol%LnCl₃: 1-4mol%

Wherein LnCl₃It is CeCl₃��EuCl₃��TbCl₃��PrCl₃And NdCl₃In one.

This flicker devitrified glass material component is: P₂O₅: 35mol%, Nb₂O₅: 23mol%, SrF₂: 23mol%, LiLaCl₄: 17mol%, CeCl₃: 2mol%.

This flicker devitrified glass material component is: P₂O₅: 40mol%, Nb₂O₅: 20mol%, SrF₂: 16mol%, LiLaCl₄: 20mol%, EuCl₃: 4mol%.

This flicker devitrified glass material component is: P₂O₅: 45mol%, Nb₂O₅: 15mol%, SrF₂: 24mol%, LiLaCl₄: 15mol%, TbCl₃: 1mol%.

Described rare earth ion doped LiLaCl₄The preparation method of devitrified glass, comprises the steps:

(1)P₂O₅-Nb₂O₅-SrF₂-LiLaCl₄-LnCl₃It is founding of glass:

Weigh analytically pure each raw material by material component, add the NH respectively accounting for raw material gross weight 6%₄HF₂��NH₄HCl₂By raw material mix homogeneously, it is then poured in silica crucible or corundum crucible and melts, fusion temperature 1300-1450 DEG C, it is incubated 1-2 hour, melt is poured in pig mold, be subsequently placed in Muffle furnace and be annealed, after glass transformation temperature Tg temperature 2 hours, it is cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle furnace power supply and be automatically cooled to room temperature, take out glass, for controlled micro crystallization heat treatment.

(2)LiLaCl₄Prepared by devitrified glass:

Heat according to glass analyzes (DTA) experimental data, prepared glass is placed in nitrogen fine annealing stove near its first crystallize peak temperature heat treatment 7��9 hours, then it is cooled to 50 DEG C with the speed of 5 DEG C/h again, close fine annealing stove power supply, automatically it is cooled to room temperature, obtains transparent rare earth ion doped LiLaCl₄Devitrified glass.

Compared with prior art, it is an advantage of the current invention that: this devitrified glass is made up of fluorine chlorine oxonium compound, the through performance of short wavelength is good, has LiLaCl₄The superior scintillation properties of crystalline host material and the mechanical strength of oxide glass, stability and be prone to the feature of processing, overcome LiLaCl₄The shortcomings such as monocrystal very easily deliquescence, mechanical performance cleavage slabbing poor, easy; The experiment proved that: by inventive formulation and preparation method, precipitate out rare earth ion doped to LiLaCl₄Crystalline phase, prepared rare earth ion doped LiLaCl₄Devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate higher, there is stronger light output, decay soon, the performance such as good energy resolution and temporal resolution, scintillation detectors efficiency can be made to be greatly improved. The preparation method of this devitrified glass is simple, and production cost is relatively low.

Accompanying drawing explanation

Fig. 1 is the transmission electron microscope figure (TEM) of sample after embodiment one controlled micro crystallization heat treatment.

Fig. 2 is the Ce:LiLaCl of embodiment one excitation of X-rays₄The fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:LiLaCl of embodiment two excitation of X-rays₄The fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:LiLaCl of embodiment three excitation of X-rays₄The fluorescence spectrum of devitrified glass.

Detailed description of the invention

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 3 grams of NH₄HF₂, 3 grams of NH₄HCl₂Melt pouring into after raw material mix homogeneously in silica crucible, fusion temperature 1300 DEG C, it is incubated 2 hours, glass melt is poured in pig mold, be subsequently placed in Muffle furnace and be annealed, after glass transformation temperature Tg temperature 2 hours, it is cooled to 50 DEG C with the speed of 10 DEG C/h, closes Muffle furnace power supply and be automatically cooled to room temperature, take out glass;Second step, heat according to glass analyzes (DTA) experimental data, obtain the first recrystallization temperature 715 DEG C, prepared glass is placed in nitrogen fine annealing stove 734 DEG C of heat treatments 7 hours, then it is cooled to 50 DEG C with the speed of 5 DEG C/h again, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce³⁺The LiLaCl of doping₄Devitrified glass.

LiLaCl to preparation₄Devitrified glass carries out transmission electron microscope test, obtain glass transmission electron microscope picture after controlled micro crystallization processes as shown in Figure 1, its result is as follows: in photo, the nano microcrystalline of glass basis and precipitation seems that comparison is clear, and in glass basis, the stain of distribution is microcrystal grain. X-ray diffraction test shows that crystalline phase is LiLaCl₄Phase, the material therefore obtained is LiLaCl₄The devitrified glass of crystallize phase. The Ce of excitation of X-rays³⁺Ion doping LiLaCl₄The fluorescence spectrum of devitrified glass is as in figure 2 it is shown, fluorescence peak intensity is very big. Mix Ce³⁺Ion LiLaCl₄Devitrified glass light is output as 28000ph/MeV, and die-away 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, adds 3 grams of NH₄HF₂, 3 grams of NH₄HCl₂Melt pouring into after raw material mix homogeneously in corundum crucible, fusion temperature 1450 DEG C, it is incubated 1 hour, glass melt is poured in pig mold, be subsequently placed in Muffle furnace and be annealed, after glass transformation temperature Tg temperature 2 hours, it is cooled to 50 DEG C with the speed of 10 DEG C/h, closes Muffle furnace power supply and be automatically cooled to room temperature, take out glass; Second step, heat according to glass analyzes (DTA) experimental data, obtain the first recrystallization temperature 717 DEG C, prepared glass is placed in nitrogen fine annealing stove 737 DEG C of heat treatments 9 hours, then it is cooled to 50 DEG C with the speed of 5 DEG C/h again, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu³⁺The LiLaCl of ion doping₄Devitrified glass.

LiLaCl to preparation₄The spectral quality test of devitrified glass, the Eu of excitation of X-rays³⁺Ion doping LiLaCl₄The fluorescence spectrum of devitrified glass is as it is shown on figure 3, its result shows generation Eu:LiLaCl after Overheating Treatment₄Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LiLaCl is described₄The 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, adds 3 grams of NH₄HF₂, 3 grams of NH₄HCl₂Melt pouring into after raw material mix homogeneously in silica crucible, fusion temperature 1400 DEG C, it is incubated 1.5 hours, glass melt is poured in pig mold, be subsequently placed in Muffle furnace and be annealed, after glass transformation temperature Tg temperature 2 hours, it is cooled to 50 DEG C with the speed of 10 DEG C/h, closes Muffle furnace power supply and be automatically cooled to room temperature, take out glass. Second step, heat according to glass analyzes (DTA) experimental data, obtain the first recrystallization temperature 721 DEG C, prepared glass is placed in nitrogen fine annealing stove 734 DEG C of heat treatments 8 hours, then it is cooled to 50 DEG C with the speed of 5 DEG C/h again, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb³⁺The LiLaCl of ion doping₄Devitrified glass.

LiLaCl to preparation₄The spectral quality test of devitrified glass, the Tb of excitation of X-rays³⁺Ion doping LiLaCl₄As shown in Figure 4, its result shows generation Tb:LiLaCl after Overheating Treatment to the fluorescence spectrum of devitrified glass₄Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and illustrates that the luminosity of Tb:LiLaCl4 devitrified glass is better;The rare earth ion doped LiLaCl obtained by above-mentioned preparation process₄Devitrified glass is transparent and physical and chemical performance is excellent.

Embodiment 4

Substantially the same manner as Example 1, different simply material components is different: P₂O₅: 36mol%, Nb₂O₅: 23mol%, SrF₂: 23mol%, LiLaCl₄: 17mol%, PrCl₃: 1mol%.

Embodiment 5

Substantially the same manner as Example 1, different simply material components is different: P₂O₅: 36mol%, Nb₂O₅: 23mol%, SrF₂: 23mol%, LiLaCl₄: 17mol%, NdCl₃: 1mol%.

Embodiment 4,5 also can obtain LiLaCl rare earth ion doped preferably₄Devitrified glass, concrete flicker devitrified glass light is composed and is not provided one by one.

Claims

1. LiLaCl one kind rare earth ion doped₄Devitrified glass, its Mole percent consists of:

P₂O₅: 35-45mol%Nb₂O₅: 15-23mol%SrF₂: 16-24mol%

LiLaCl₄: 15-20mol%LnCl₃: 1-4mol%

2. the rare earth ion doped LiLaCl described in claim 1₄Devitrified glass, it is characterised in that this devitrified glass material component is: P₂O₅: 35mol%, Nb₂O₅: 23mol%, SrF₂: 23mol%, LiLaCl₄: 17mol%, CeCl₃: 2mol%.

3. the rare earth ion doped LiLaCl described in claim 1₄Devitrified glass, it is characterised in that this devitrified glass material component is: P₂O₅: 40mol%, Nb₂O₅: 20mol%, SrF₂: 16mol%, LiLaCl₄: 20mol%, EuCl₃: 4mol%.

4. the rare earth ion doped LiLaCl described in claim 1₄Devitrified glass, it is characterised in that this devitrified glass material component is: P₂O₅: 45mol%, Nb₂O₅: 15mol%, SrF₂: 24mol%, LiLaCl₄: 15mol%, TbCl₃: 1mol%.

5. the preparation method of rare earth ion doped LiLaCl4 devitrified glass according to claim 1, it is characterised in that include following concrete steps:

(1)P₂O₅-Nb₂O₅-SrF₂-LiLaCl₄-LnCl₃It is founding of glass: weigh analytically pure each raw material by material component, add the NH respectively accounting for raw material gross weight 6%₄HF₂��NH₄HCl₂By raw material mix homogeneously, it is then poured in silica crucible or corundum crucible and melts, fusion temperature 1300-1450 DEG C, it is incubated 1-2 hour, glass melt is poured in pig mold, be subsequently placed in Muffle furnace and be annealed, after glass transformation temperature Tg temperature 2 hours, it is cooled to 50 DEG C with the speed of 10 DEG C/h, close Muffle furnace power supply and be automatically cooled to room temperature, take out glass, for controlled micro crystallization heat treatment;

(2)LiLaCl₄The preparation of devitrified glass: the thermal analysis experiment data according to glass, prepared glass is placed in the close annealing furnace of nitrogen near its first crystallize peak temperature heat treatment 7��9 hours, then it is cooled to 50 DEG C with the speed of 5 DEG C/h again, close fine annealing stove power supply, automatically it is cooled to room temperature, obtains transparent rare earth ion doped LiLaCl₄Devitrified glass.