CN103951235B

CN103951235B - Rare earth ion doped K2LuI5Devitrified glass and preparation method thereof

Info

Publication number: CN103951235B
Application number: CN201410198282.0A
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: 2016-05-25
Anticipated expiration: 2034-05-08
Also published as: CN103951235A

Abstract

The invention discloses a kind of rare earth ion doped K₂LuI₅Devitrified glass and preparation method thereof, its mole of percentage composition is TeO₂：67-75moL％、P₂O₅：5-7moL％、ZnF₂：8-11moL％、K₂LuI₅：10-15moL％、LnI₃: 1-3moL%, wherein LnI₃For CeI₃、EuI₃、TbI₃、PrI₃And NdI₃In one, its preparation method is first to prepare TeO with fusion method₂-P₂O₅-ZnF₂-K₂LuI₅-LnI₃Be glass, after heat treatment obtain transparent K₂LuI₅Devitrified glass, K of the present invention₂LuI₅Devitrified glass, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has stronger light output, decay soon, the good performance such as energy resolution and temporal resolution. The preparation method of this devitrified glass is simple, and production cost is lower.

Description

Rare earth ion doped K2LuI5Devitrified 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 as scintillation materialThe K of ion doping₂LuI₅Devitrified glass and preparation method thereof.

Background technology

Scintillation material is that one can under the exciting of high-energy ray (as x ray, gamma-rays) or other radioactive particleSend the optical function material of visible ray, be widely used in nuclear medicine diagnostic, high-energy physics and nuclear physics experiment research, industry andThe fields such as geological prospecting. According to the difference of application, the requirement of scintillator is also not quite similar, but the material that generally glimmersMaterial 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. DodgeBright crystal generally has the advantages such as resistance to irradiation, fast decay, High Light Output, but scintillation crystal also exists following serious shortcoming: systemStandby difficulty, expensive. Although and rare earth ion doped scintillation glass cost is low, easily prepare large-size glass, it is at lightThe aspect difficulties such as output, number of repetition are compared with crystal, and therefore its application is also very limited.

K₂LuI₅Crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce³⁺The K of doping₂LuI₅Crystal has lightExport high, soon decay, good energy resolution, temporal resolution and linear response, have than rare earth ion doped fluorideThe luminous efficiency that crystal and oxide crystal are higher, can make flash detection instrument efficiency greatly improve. Eu³⁺、Tb³⁺Doping K₂LuI₅BrilliantThe scintillation properties of body is also more excellent, can be used for the field such as safety check, blinking screen. But K₂LuI₅Crystal is deliquescence very easily, mechanical performancePoor, easily cleavage slabbing, 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, have stronger light output,Fast decay, energy resolution and the good rare earth ion doped K of temporal resolution₂LuI₅Devitrified glass and preparation method thereof.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped K₂LuI₅Devitrified glass,Its mole of percentage composition is:

TeO₂：67-75moL％P₂O₅：5-7moL％

ZnF₂：8-11moL％K₂LuI₅：10-15moL％LnI₃：1-3moL％

Wherein LnI₃For CeI₃、EuI₃、TbI₃、PrI₃And NdI₃In one.

This flicker devitrified glass material component is: TeO₂：67moL％、P₂O₅：7moL％、ZnF₂：10moL％、K₂LuI₅：15moL％、CeI₃：1moL％。

This flicker devitrified glass material component is: TeO₂：70mol％、P₂O₅：6mol％、ZnF₂：11mol％、K₂LuI₅：10moL％、EuI₃：3moL％。

This flicker devitrified glass material component is: TeO₂：75mol％、P₂O₅：5mol％、ZnF₂：8mol％、K₂LuI₅：10mol％、TbI₃：2mol％。

Described rare earth ion doped K₂LuI₅The preparation method of devitrified glass, comprises the steps:

(1)TeO₂-P₂O₅-ZnF₂-K₂LuI₅-LnI₃Be 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、NH₄HI₂, raw material is mixedClose evenly, then pour in silica crucible or corundum crucible and melt, fusion temperature 800-900 DEG C, insulation 1-2 hour, by glassMelt is poured in pig mold, and be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, withThe speed of 10 DEG C/h is cooled to 50 DEG C, closes Muffle furnace power supply and is automatically cooled to room temperature, takes out glass, for crystallite heat-transmissionProcess.

(2)K₂LuI₅Devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, itsNear heat treatment 4～6 hours one crystallization peak, and then be cooled to 50 DEG C with the speed of 5 DEG C/h, close fine annealingStove power supply, is cooled to room temperature automatically, obtains transparent rare earth ion doped K₂LuI₅Devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine iodine oxygen compound, short wavelength'sThrough performance is good, has K₂LuI₅The superior scintillation properties of crystalline host material and the mechanical strength of oxide glass, stability andThe feature that is easy to processing, has overcome K₂LuI₅Monocrystal is the shortcoming such as deliquescence, poor, the easy cleavage slabbing of mechanical performance very easily; Through realityVerify bright: by formula of the present invention and preparation method, separate out rare earth ion doped to K₂LuI₅Crystalline phase, what make is rare earth ion dopedK₂LuI₅Devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has stronger light defeatedGo out, decay soon, the good performance such as energy resolution and temporal resolution, can make flash detection instrument efficiency greatly improve. This crystalliteThe preparation method of 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:K of embodiment mono-excitation of X-rays₂LuI₅The fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:K of embodiment bis-excitation of X-rays₂LuI₅The fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:K of embodiment tri-excitation of X-rays₂LuI₅The 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 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 NH₄HI₂, after raw material is mixed, to pour in silica crucible and melt, 800 DEG C of fusion temperatures, are incubated 2 hours, by glassMelt is poured in pig mold, and be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, withThe speed of 10 DEG C/h is cooled to 50 DEG C, closes Muffle furnace power supply and is automatically cooled to room temperature, takes out glass; Second step, according to glassHeat analysis (DTA) experimental data of glass, obtains 450 DEG C of the first recrystallization temperatures, and the glass making is placed in to nitrogen fine annealing stoveIn 465 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 automaticBe cooled to room temperature, obtain transparent Ce³⁺The K of doping₂LuI₅Devitrified glass.

To the K of preparation₂LuI₅Devitrified glass carries out sem test, obtains glass through controlled micro crystallization scanning electricity after treatmentAs shown in Figure 1, what in photo, be grain shape is the nano microcrystalline of separating out to sub-microscope figure, and remainder is glassy phase. X rayThe test of diffraction shows that crystalline phase is K₂LuI₅Phase, the material therefore obtaining is K₂LuI₅The devitrified glass of crystallization phase. Excitation of X-raysCe³⁺Ion doping K₂LuI₅As shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass. Mix Ce³⁺Ion K₂LuI₅Devitrified glass light is output as 25000ph/MeV, and be 45ns 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 NH₄HI₂, after raw material is mixed, to pour in corundum crucible and melt, 900 DEG C of fusion temperatures, are incubated 1 hour, by glassMelt is poured in pig mold, and be then placed in Muffle furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, withThe speed of 10 DEG C/h is cooled to 50 DEG C, closes Muffle furnace power supply and is automatically cooled to room temperature, takes out glass; Second step, according to glassHeat analysis (DTA) experimental data of glass, obtains 455 DEG C of the first recrystallization temperatures, and the glass making is placed in to nitrogen fine annealing stoveIn 470 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 automaticBe cooled to room temperature, obtain transparent Eu³⁺The K of ion doping₂LuI₅Devitrified glass.

To the K of preparation₂LuI₅The spectral quality test of devitrified glass, the Eu of excitation of X-rays³⁺Ion doping K₂LuI₅CrystalliteAs shown in Figure 3, its result shows to produce Eu:K after Overheating Treatment to the fluorescence spectrum of glass₂LuI₅Crystallite and corresponding glass-basedBody is compared luminous intensity and is significantly improved, and Eu:K is described₂LuI₅The 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 NH₄HI₂, after raw material is mixed, to pour in silica crucible and melt, 850 DEG C of fusion temperatures, are incubated 1.5 hours, by glassGlass melt is poured in pig mold, and 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 toHeat analysis (DTA) experimental data of glass, obtains 458 DEG C of the first recrystallization temperatures, and the glass making is placed in to nitrogen fine annealingIn stove, 473 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 fromMove and be cooled to room temperature, obtain transparent Tb³⁺The K of ion doping₂LuI₅Devitrified glass.

To the K of preparation₂LuI₅The spectral quality test of devitrified glass, the Tb of excitation of X-rays³⁺Ion doping K₂LuI₅CrystalliteAs shown in Figure 4, its result shows to produce Tb:K after Overheating Treatment to the fluorescence spectrum of glass₂LuI₅Crystallite and corresponding glass-basedBody is compared luminous intensity and is significantly improved, and Tb:K is described₂LuI₅The luminosity of devitrified glass is better; Prepared by above-mentionedThe rare earth ion doped K that journey obtains₂LuI₅Devitrified glass is transparent and physical and chemical performance is good.

Embodiment 4

Substantially the same manner as Example 1, difference is material component difference: TeO₂：72moL％、P₂O₅：6moL％、ZnF₂：11moL％、K₂LuI₅：10moL％、PrI₃：1moL％。

Embodiment 5

Substantially the same manner as Example 1, difference is material component difference:

TeO₂：72moL％、P₂O₅：6moL％、ZnF₂：11moL％、K₂LuI₅：10moL％、NdI₃：1moL％。

Embodiment 4,5 also can obtain rare earth ion doped K preferably₂LuI₅Devitrified glass, concrete flicker crystalliteGlass light is composed and is not done to provide one by one.

Claims

1. a rare earth ion doped K₂LuI₅Devitrified glass, its mole of percentage composition is:

TeO₂：67-75mol％P₂O₅：5-7mol％ZnF₂：8-11mol％

K₂LuI₅：10-15mol％LnI₃：1-3mol％

Wherein LnI₃For CeI₃、EuI₃、TbI₃、PrI₃And NdI₃In one.

2. rare earth ion doped K claimed in claim 1₂LuI₅Devitrified glass, is characterized in that this devitrified glass material componentFor: TeO₂：67mol％、P₂O₅：7mol％、ZnF₂：10mol％、K₂LuI₅：15mol％、CeI₃：1mol％。

3. rare earth ion doped K claimed in claim 1₂LuI₅Devitrified glass, is characterized in that this devitrified glass material componentFor: TeO₂：70mol％、P₂O₅：6mol％、ZnF₂：11mol％、K₂LuI₅：10mol％、EuI₃：3mol％。

4. rare earth ion doped K claimed in claim 1₂LuI₅Devitrified glass, is characterized in that this devitrified glass material componentFor: TeO₂：75mol％、P₂O₅：5mol％、ZnF₂：8mol％、K₂LuI₅：10mol％、TbI₃：2mol％。

5. rare earth ion doped K according to claim 1₂LuI₅The preparation method of devitrified glass, is characterized in that comprisingFollowing concrete steps:

(1)TeO₂-P₂O₅-ZnF₂-K₂LuI₅-LnI₃Be founding of glass: take analytically pure each raw material by material component, respectively addAccount for the NH of raw material gross weight 5%₄HF₂、NH₄HI₂, raw material is mixed, then pour in silica crucible or corundum crucible and melt,Fusion temperature 800-900 DEG C, insulation 1-2 hour, pours glass melt in pig mold into, is then placed in Muffle furnace and moves backFire, after 1 hour, is cooled to 50 DEG C with the speed of 10 DEG C/h in the insulation of glass transformation temperature Tg temperature, closes Muffle furnace power supplyAutomatically be cooled to room temperature, take out glass, for controlled micro crystallization heat treatment;

(2)K₂LuI₅The preparation of devitrified glass: according to the DTA thermal analysis experiment data of glass, the glass making is placed in to nitrogen essenceIn close annealing furnace near its first crystallization peak heat treatment 4～6 hours, and then be cooled to 50 with the speed of 5 DEG C/hDEG C, close fine annealing stove power supply, be automatically cooled to room temperature, obtain transparent rare earth ion doped K₂LuI₅Devitrified glass.