CN103951233B

CN103951233B - Rare earth ion doped LiYCl4Devitrified glass and preparation method thereof

Info

Publication number: CN103951233B
Application number: CN201410198259.1A
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: 2016-05-04
Anticipated expiration: 2034-05-08
Also published as: CN103951233A

Abstract

The invention discloses a kind of rare earth ion doped LiYCl₄Devitrified glass and preparation method thereof, its mole of percentage composition is SiO₂：50-55mol％、AlF₃：9-13mol％、NaF：15-20mol％、Y₂O₃：5-6mol％、LiYCl₄：10-15mol％、LnCl₃: 1-3mol%, wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃、PrCl₃、NdCl₃In one, its preparation method is first to prepare SiO with fusion method₂-AlF₃-NaF-Y₂O₃-LiYCl₄-LnCl₃Be glass, after heat treatment obtain transparent LiYCl₄Devitrified glass, LiYCl of the present invention₄Devitrified glass, can Deliquescence-resistant, the performance such as good mechanical property, short wavelength's royal purple light transmission rate be higher, has the luminous output of stronger passage of scintillation light, and energy resolution is good. The preparation method of this devitrified glass is simple, and production cost is lower.

Description

Rare earth ion doped LiYCl4Devitrified 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 LiYCl 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 the exciting of high-energy 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, 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 in aspect difficulties such as light output, numbers of repetition compared with crystal, and therefore its application is also very limited.

LiYCl₄Crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce³⁺The LiYCl of doping₄It 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. Eu³⁺、Tb³⁺Li doped YCl₄The scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen. But LiYCl₄Crystal is deliquescence very easily, and mechanical performance is poor, easily 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 LiYCl of temporal resolution₄Devitrified glass and preparation method thereof.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped LiYCl₄Devitrified glass, its mole of percentage composition is:

SiO₂：50-55mol％AlF₃：9-13mol％NaF：15-20mol％

Y₂O₃：5-6mol％LiYCl₄：10-15mol％LnCl₃：1-3mol％

Wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃、PrCl₃、NdCl₃In one.

This flicker devitrified glass material component is: SiO₂：50mol％、AlF₃：13mol％、NaF：20mol％、Y₂O₃：5mol％、LiYCl₄：11mol％、CeCl₃：1mol％。

This flicker devitrified glass material component is: SiO₂：52mol％、AlF₃：9mol％、NaF：15mol％、Y₂O₃：6mol％、LiYCl₄：15mol％、EuCl₃：3mol％。

This flicker devitrified glass material component is: SiO₂：55mol％、AlF₃：10mol％、NaF：18mol％、Y₂O₃：5mol％、LiYCl₄：10mol％、TbCl₃：2mol％。

Described rare earth ion doped LiYCl₄The preparation method of devitrified glass, comprises the steps:

(1)SiO₂-AlF₃-NaF-Y₂O₃-LiYCl₄-LnCl₃Be founding of glass:

Take analytically pure each raw material by material component, respectively add the NH that accounts for raw material gross weight 5%₄HF₂、NH₄HCl₂Raw material is mixed, then pour in silica crucible or corundum crucible and melt, fusion temperature 1400-1460 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, be 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)LiYCl₄Devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near heat treatment 4～6 hours its first crystallization peak, and then be cooled to 50 with the speed of 5 DEG C/h. DEG C, close fine annealing stove power supply, be automatically cooled to room temperature, obtain transparent rare earth ion doped LiYCl₄Devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine chlorine oxonium compound, short wavelength's through performance is good, has LiYCl₄The superior scintillation properties of crystalline host material and mechanical strength, the stability of oxide glass and be easy to processing feature, overcome LiYCl₄Monocrystal is the shortcoming such as deliquescence, poor, the easy cleavage slabbing of mechanical performance very easily; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped to LiYCl₄Crystalline phase, the rare earth ion doped LiYCl making₄Devitrified 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 good performance such as 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.

Brief description of the drawings

Fig. 1 is the scanning electron microscope diagram (SEM) of sample after embodiment mono-controlled micro crystallization heat treatment.

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

Fig. 3 is the Eu:LiYCl of embodiment bis-excitation of X-rays₄₅The fluorescence spectrum of devitrified glass.

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

Detailed description of the invention

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, and weigh 50 grams by the formula in table 1 and analyze pure raw material, add 2.5 grams of NH₄HF₂, 2.5 grams of NH₄HCl₂After raw material is mixed, pour in silica crucible and melt, 1400 DEG C of fusion temperatures, be incubated 2 hours, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, be 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; Second step, according to heat analysis (DTA) experimental data of glass, obtain 780 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 800 DEG C of heat 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 Ce³⁺The LiYCl of doping₄Devitrified glass sample.

To the LiYCl of preparation₄Devitrified glass carries out sem test, obtains glass through controlled micro crystallization scanning electron microscope diagram after treatment as shown in Figure 1, and what in photo, be grain shape is the nano microcrystalline of separating out, and particle gap is glassy phase. The test of X-ray diffraction shows that crystalline phase is LiYCl₄Phase, the material therefore obtaining is LiYCl₄The devitrified glass of crystallization phase. The Ce of excitation of X-rays³⁺Ion doping LiYCl₄As shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass. Mix Ce³⁺Ion LiYCl₄Devitrified glass light is output as 21000ph/MeV, and be 65ns die-away time.

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, and weigh 50 grams by the formula in table 2 and analyze pure raw material, add 2.5 grams of NH₄HF₂, 2.5 grams of NH₄HCl₂After raw material is mixed, pour in corundum crucible and melt, 1460 DEG C of fusion temperatures, be incubated 1 hour, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, be 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; Second step, according to heat analysis (DTA) experimental data of glass, obtain 790 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 810 DEG C of heat 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 Eu³⁺The LiYCl of ion doping₄Devitrified glass.

To the LiYCl of preparation₄The spectral quality test of devitrified glass, the Eu of excitation of X-rays³⁺Ion doping LiYCl₄As shown in Figure 3, its result shows to produce Eu:LiYCl after Overheating Treatment to the fluorescence spectrum of devitrified glass₄Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:LiYCl is described₄The 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, and weigh 50 grams by the formula in table 3 and analyze pure raw material, add 2.5 grams of NH₄HF₂, 2.5 grams of NH₄HCl₂After raw material is mixed, pour in silica crucible and melt, 1440 DEG C of fusion temperatures, be incubated 1.5 hours, glass melt is poured in pig mold, be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, be 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. Second step, according to heat analysis (DTA) experimental data of glass, obtain 800 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 830 DEG C of heat 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 Tb³⁺The LiYCl of ion doping₄Devitrified glass.

To the LiYCl of preparation₄The spectral quality test of devitrified glass, the Tb of excitation of X-rays³⁺Ion doping LiYCl₄As shown in Figure 4, its result shows to produce Tb:LiYCl after Overheating Treatment to the fluorescence spectrum of devitrified glass₄Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:LiYCl is described₄The luminosity of devitrified glass is better; The rare earth ion doped LiYCl being obtained by above-mentioned preparation process₄Devitrified glass is transparent and physical and chemical performance is good.

Embodiment 4

Substantially the same manner as Example 1, difference is material component difference: SiO₂：55mol％、AlF₃：10mol％、NaF：19mol％、Y₂O₃：5mol％、LiYCl₄：10mol％、PrCl₃：1mol％。

Embodiment 5

Substantially the same manner as Example 1, difference is material component difference: SiO₂：55mol％、AlF₃：10mol％、NaF：19mol％、Y₂O₃：5mol％、LiYCl₄：10mol％、NdCl₃：1mol％。

Embodiment 4,5 also can obtain rare earth ion doped LiYCl preferably₄Devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims

1. a rare earth ion doped LiYCl₄Devitrified glass, its mole of percentage composition is:

SiO₂：50-55mol％AlF₃：9-13mol％NaF：15-20mol％

Y₂O₃：5-6mol％LiYCl₄：10-15mol％LnCl₃：1-3mol％

Wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃、PrCl₃、NdCl₃In one.

2. rare earth ion doped LiYCl claimed in claim 1₄Devitrified glass, is characterized in that this devitrified glass material componentFor: SiO₂：50mol％、AlF₃：13mol％、NaF：20mol％、Y₂O₃：5mol％、LiYCl₄：11mol％、CeCl₃：1mol％。

3. rare earth ion doped LiYCl claimed in claim 1₄Devitrified glass, is characterized in that this devitrified glass material componentFor: SiO₂：52mol％、AlF₃：9mol％、NaF：15mol％、Y₂O₃：6mol％、LiYCl₄：15mol％、EuCl₃：3mol％。

4. rare earth ion doped LiYCl claimed in claim 1₄Devitrified glass, is characterized in that this devitrified glass material componentFor: SiO₂：55mol％、AlF₃：10mol％、NaF：18mol％、Y₂O₃：5mol％、LiYCl₄：10mol％、TbCl₃：2mol％。

5. rare earth ion doped LiYCl according to claim 1₄The preparation method of devitrified glass, is characterized in that comprisingFollowing concrete steps:

(1)SiO₂-AlF₃-NaF-Y₂O₃-LiYCl₄-LnCl₃Be founding of glass: take analytically pure each raw material by material component,Respectively add the NH that accounts for raw material gross weight 5%₄HF₂、NH₄HCl₂, raw material is mixed, then pour silica crucible or corundum crucible intoMiddle fusing, fusion temperature 1400-1460 DEG C, insulation 1-2 hour, pours glass melt in pig mold into, is then placed in Muffle furnaceIn anneal, after glass transformation temperature Tg temperature insulation 1 hour, be cooled to 50 DEG C with the speed of 10 DEG C/h, closeMuffle furnace power supply is cooled to room temperature automatically, takes out glass, for controlled micro crystallization heat treatment;

(2)LiYCl₄The preparation of devitrified glass: according to the thermal analysis experiment data of glass, the glass making is placed in to nitrogen precisionIn annealing furnace, near heat treatment 4～6 hours 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, be automatically cooled to room temperature, obtain transparent rare earth ion doped LiYCl₄Devitrified glass.