CN103951218B

CN103951218B - Rare earth ion doped K2LaBr5Devitrified glass and preparation method thereof

Info

Publication number: CN103951218B
Application number: CN201410198065.1A
Authority: CN
Inventors: 欧阳绍业; 张约品; 夏海平; 张为欢; 王倩; 杨斌
Original assignee: Ningbo University
Current assignee: Ningbo University
Priority date: 2014-05-08
Filing date: 2014-05-08
Publication date: 2016-06-15
Anticipated expiration: 2034-05-08
Also published as: CN103951218A

Abstract

The invention discloses a kind of rare earth ion doped K₂LaBr₅Devitrified glass and preparation method thereof, its Mole percent consists of B₂O₃: 40-50mol%, Nb₂O₅: 5-15mol%, BaF₂: 10-24mol%, La₂O₃: 5-6mol%, K₂LaBr₅: 15-25mol%, LnBr₃: 1-4mol%, wherein LnBr₃For CeBr₃、EuBr₃、TbBr₃、PrBr₃And NdBr₃In one, its preparation method is first to prepare B with fusion method₂O₃-Nb₂O₅-BaF₂-La₂O₃-K₂LaBr₅-LnBr₃It is glass, after heat treatment obtains transparent K₂LaBr₅Devitrified glass, the K of the present invention₂LaBr₅Devitrified 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 K2LaBr5Devitrified 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 K as scintillation material₂LaBr₅Devitrified 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.

K₂LaBr₅Crystal be a kind of can the scintillation crystal substrate of doping with rare-earth ions, Ce³⁺The K of doping₂LaBr₅Crystal 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 can be made to be greatly improved. Eu³⁺The K of doping₂LaBr₅Crystal and Tb³⁺The K of doping₂LaBr₅The scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen. But K₂LaBr₅The shortcomings such as the growth of crystal very easily deliquescence, mechanical performance cleavage slabbing poor, easy, large-size crystals is difficult, 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 K that stronger light output, fast decay, energy resolution and temporal resolution are good₂LaBr₅Devitrified glass and preparation method thereof.

This invention address that the technical scheme that above-mentioned technical problem adopts is: rare earth ion doped K₂LaBr₅Devitrified glass, its Mole percent consists of:

B₂O₃: 40-50mol%Nb₂O₅: 5-15mol%BaF₂: 10-24mol%

La₂O₃: 5-6mol%K₂LaBr₅: 15-25mol%LnBr₃: 1-4mol%

Wherein LnBr₃For CeBr₃、EuBr₃、TbBr₃、PrBr₃In one.

This flicker devitrified glass material component is: B₂O₃: 40mol%, Nb₂O₅: 15mol%, BaF₂: 24mol%, La₂O₃: 5mol%, K₂LaBr₅: 15mol%, CeBr₃: 1mol%.

This flicker devitrified glass material component is: B₂O₃: 45mol%, Nb₂O₅: 10mol%, BaF₂: 10mol%, La₂O₃: 6mol%, K₂LaBr₅: 25mol%, EuBr₃: 4mol%.

This flicker devitrified glass material component is: B₂O₃: 50mol%, Nb₂O₅: 5mol%, BaF₂: 17mol%, La₂O₃: 6mol%, K₂LaBr₅: 20mol%, TbBr₃: 2mol%.

Described rare earth ion doped K₂LaBr₅The preparation method of devitrified glass, comprises the steps:

(1)B₂O₃-Nb₂O₅-BaF₂-La₂O₃-K₂LaBr₅-LnBr₃It is founding of glass:

Weigh analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5%₄HF₂、NH₄HBr₂By raw material mix homogeneously, it is then poured in silica crucible or corundum crucible and melts, fusion temperature 1250-1350 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 1 hour, 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)K₂LaBr₅Prepared by devitrified glass:

Heat according to glass analyzes (DTA) experimental data, prepared glass is placed in nitrogen fine annealing stove, temperature heat treatment 7～9 hours near its first crystallize peak, 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 K₂LaBr₅Devitrified glass.

Compared with prior art, it is an advantage of the current invention that: this devitrified glass is made up of fluorine bromine oxygen compound, and the through performance of short wavelength is good, has K₂LaBr₅The superior scintillation properties of crystalline host material and the mechanical strength of oxide glass, stability and be prone to the feature of processing, overcome K₂LaBr₅The 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 K₂LaBr₅Crystalline phase, prepared rare earth ion doped K₂LaBr₅Devitrified 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 X-ray diffraction (XRD) figure of sample after embodiment one controlled micro crystallization heat treatment.

Fig. 2 is the Ce:K of embodiment one excitation of X-rays₂LaBr₅The fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:K of embodiment two excitation of X-rays₂LaBr₅The fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:K of embodiment three excitation of X-rays₂LaBr₅The 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 2.5 grams of NH₄HF₂, 2.5 grams of NH₄HBr₂Melt pouring into after raw material mix homogeneously in silica crucible, fusion temperature 1250 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 1 hour, 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 701 DEG C, prepared glass is placed in nitrogen fine annealing stove 720 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 K of doping₂LaBr₅Devitrified glass sample.

K to preparation₂LaBr₅Devitrified glass carries out X-ray diffraction test, obtains glass XRD figure after controlled micro crystallization processes as it is shown in figure 1, its result is as follows: pass through XRD diffraction maximum and the K of the sample being thermally treated resulting in₂LaBr₅The main diffraction peak of the standard x RD figure of crystalline phase is all consistent, and the material therefore obtained is pure K₂LaBr₅The devitrified glass of crystallize phase. And the Ce of excitation of X-rays³⁺Ion doping K₂LaBr₅The fluorescence spectrum of devitrified glass is as in figure 2 it is shown, fluorescence peak intensity is very big. Mix Ce³⁺Ion K₂LaBr₅Devitrified glass light exports up to 38000ph/MeV.

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 NH₄HF₂, 2.5 grams of NH₄HBr₂Melt pouring into after raw material mix homogeneously in corundum crucible, fusion temperature 1300 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 1 hour, 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 705 DEG C, prepared glass is placed in nitrogen fine annealing stove 725 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 K of ion doping₂LaBr₅Devitrified glass.

K to preparation₂LaBr₅The spectral quality test of devitrified glass, the Eu of excitation of X-rays³⁺Ion doping K₂LaBr₅The fluorescence spectrum of devitrified glass is as it is shown on figure 3, its result shows generation Eu:K after Overheating Treatment₂LaBr₅Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:K is described₂LaBr₅The 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 2.5 grams of NH₄HF₂, 2.5 grams of NH₄HBr₂Melt pouring into after raw material mix homogeneously in silica crucible, fusion temperature 1350 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 1 hour, 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 712 DEG C, prepared glass is placed in nitrogen fine annealing stove 730 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 K of ion doping₂LaBr₅Devitrified glass.

K to preparation₂LaBr₅The spectral quality test of devitrified glass, the Tb of excitation of X-rays³⁺Ion doping K₂LaBr₅As shown in Figure 4, its result shows generation Tb:K after Overheating Treatment to the fluorescence spectrum of devitrified glass₂LaBr₅Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:K is described₂LaBr₅The luminosity of devitrified glass is better;The rare earth ion doped K obtained by above-mentioned preparation process₂LaBr₅Devitrified 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: B₂O₃: 40mol%, Nb₂O₅: 15mol%, BaF₂: 24mol%, La₂O₃: 5mol%, K₂LaBr₅: 15mol%, PrBr₃: 1mol%.

Embodiment 5

Substantially the same manner as Example 1, different simply material components is different: B₂O₃: 40mol%, Nb₂O₅: 15mol%, BaF₂: 24mol%, La₂O₃: 5mol%, K₂LaBr₅: 15mol%, NdBr₃: 1mol%

Embodiment 4,5 also can obtain K rare earth ion doped preferably₂LaBr₅Devitrified glass, concrete flicker devitrified glass light is composed and is not provided one by one.

Claims

1. K one kind rare earth ion doped₂LaBr₅Devitrified glass, its Mole percent consists of:

B₂O₃: 40-50mol%Nb₂O₅: 5-15mol%BaF₂: 10-24mol%

La₂O₃: 5-6mol%K₂LaBr₅: 15-25mol%LnBr₃: 1-4mol%

Wherein LnBr₃For CeBr₃、EuBr₃、TbBr₃、PrBr₃And NdBr₃In one.

2. the rare earth ion doped K described in claim 1₂LaBr₅Devitrified glass, it is characterised in that this devitrified glass material component is: B₂O₃: 40mol%, Nb₂O₅: 15mol%, BaF₂: 24mol%, La₂O₃: 5mol%, K₂LaBr₅: 15mol%, CeBr₃: 1mol%.

3. the rare earth ion doped K described in claim 1₂LaBr₅Devitrified glass, it is characterised in that this devitrified glass material component is: B₂O₃: 45mol%, Nb₂O₅: 10mol%, BaF₂: 10mol%, La₂O₃: 6mol%, K₂LaBr₅: 25mol%, EuBr₃: 4mol%.

4. the rare earth ion doped K described in claim 1₂LaBr₅Devitrified glass, it is characterised in that this devitrified glass material component is: B₂O₃: 50mol%, Nb₂O₅: 5mol%, BaF₂: 17mol%, La₂O₃: 6mol%, K₂LaBr₅: 20mol%, TbBr₃: 2mol%.

5. rare earth ion doped K according to claim 1₂LaBr₅The preparation method of devitrified glass, it is characterised in that include following concrete steps:

(1)B₂O₃-Nb₂O₅-BaF₂-La₂O₃-K₂LaBr₅-LnBr₃It is founding of glass: weigh analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5%₄HF₂、NH₄HBr₂By raw material mix homogeneously, it is then poured in silica crucible or corundum crucible and melts, fusion temperature 1250-1350 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 1 hour, 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)K₂LaBr₅The preparation of devitrified glass: the thermal analysis experiment data according to glass, 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 K₂LaBr₅Devitrified glass.