CN103951235A

CN103951235A - Rare-earth-ion-doped K2LuI5 microcrystalline glass and preparation method thereof

Info

Publication number: CN103951235A
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: 2014-07-30
Anticipated expiration: 2034-05-08
Also published as: CN103951235B

Abstract

The invention discloses a rare-earth-ion-doped K2LuI5 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 67-75 mol% of TeO2, 5-7 mol% of P2O5, 8-11 mol% of ZnF2, 10-15 mol% of K2LuI5 and 1-3 mol% of LnI3. The LnI3 is CeI3, EuI3, TbI3, PrI3 or NdI3. The preparation method comprises the following steps: preparing TeO2-P2O5-ZnF2-K2LuI5-LnI3 glass by a fusion process, and carrying out heat treatment to obtain the transparent K2LuI5 microcrystalline glass. The K2LuI5 microcrystalline glass has the advantages of deliquescence resistance, favorable mechanical properties, higher short-wavelength blue-violet light transmission rate, strong light output, quick attenuation, favorable energy resolution, favorable time resolution and the like. The preparation method of the microcrystalline glass is simple and lower in production cost.

Description

Rare earth ion doped K 2luI 5devitrified 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 material ₂luI ₅devitrified 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 energetic 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 Areas, 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, multiplicity compared with crystal, and therefore its application is also very limited.

K ₂luI ₅crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce ³⁺the K of doping ₂luI ₅it 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.Eu ³⁺, Tb ³⁺doping K ₂luI ₅the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But K ₂luI ₅crystal is deliquescence very easily, and mechanical property 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 K of temporal resolution ₂luI ₅devitrified glass and preparation method thereof.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped K ₂luI ₅devitrified glass, its mole of percentage composition is:

TeO ₂：67-75moL％ P ₂O ₅：5-7moL％

ZnF ₂：8-11moL％ K ₂LuI ₅：10-15moL％LnI ₃：1-3moL％

Wherein LnI ₃for CeI ₃, EuI ₃, TbI ₃, PrI ₃and NdI ₃in one.

This flicker devitrified glass material component is: TeO ₂: 67moL%, P ₂o ₅: 7moL%, ZnF ₂: 10moL%, K ₂luI ₅: 15moL%, CeI ₃: 1moL%.

This flicker devitrified glass material component is: TeO ₂: 70mol%, P ₂o ₅: 6mol%, ZnF ₂: 11mol%, K ₂luI ₅: 10moL%, EuI ₃: 3moL%.

This flicker devitrified glass material component is: TeO ₂: 75mol%, P ₂o ₅: 5mol%, ZnF ₂: 8mol%, K ₂luI ₅: 10mol%, TbI ₃: 2mol%.

Described rare earth ion doped K ₂luI ₅the preparation method of devitrified glass, comprises the steps:

(1) TeO ₂-P ₂o ₅-ZnF ₂-K ₂luI ₅-LnI ₃be founding of glass:

Take analytically pure each raw material by material component, respectively add the NH that accounts for raw material gross weight 5% ₄hF ₂, NH ₄hI ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort 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 retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment.

(2) K ₂luI ₅devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near heat-treated 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, automatically be cooled to room temperature, obtain transparent rare earth ion doped K ₂luI ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine iodine oxygen compound, short wavelength's through performance is good, has K ₂luI ₅the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome K ₂luI ₅single 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 K ₂luI ₅crystalline phase, the rare earth ion doped K making ₂luI ₅devitrified 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-micritization thermal treatment.

Fig. 2 is the Ce:K of embodiment mono-excitation of X-rays ₂luI ₅the fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:K of embodiment bis-excitation of X-rays ₂luI ₅the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:K of embodiment tri-excitation of X-rays ₂luI ₅the fluorescence spectrum of devitrified glass.

Embodiment

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, weigh 50 grams of analytical pure raw materials by the formula in table 1, and add 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂after raw material is mixed, pour in quartz crucible and melt, 800 DEG C of temperature of fusion, be incubated 2 hours, glass melt is poured in pig mold, be then placed in retort 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 retort 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 450 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 465 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 K of doping ₂luI ₅devitrified glass.

To the K of preparation ₂luI ₅devitrified glass carries out sem test, obtains glass through micritization scanning electron microscope diagram after treatment as shown in Figure 1, and what in photo, be particle shape is the nano microcrystalline of separating out, and rest part is glassy phase.The test of X-ray diffraction shows that crystalline phase is K ₂luI ₅phase, the material therefore obtaining is K ₂luI ₅the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping K ₂luI ₅as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion K ₂luI ₅devitrified glass light is output as 25000ph/MeV, and be 45ns fall 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, weigh 50 grams of analytical pure raw materials by the formula in table 2, and add 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂after raw material is mixed, pour in corundum crucible and melt, 900 DEG C of temperature of fusion, be incubated 1 hour, glass melt is poured in pig mold, be then placed in retort 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 retort 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 455 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 470 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 Eu ³⁺the K of ion doping ₂luI ₅devitrified glass.

To the K of preparation ₂luI ₅the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping K ₂luI ₅as shown in Figure 3, its result shows to produce Eu:K after Overheating Treatment to the fluorescence spectrum of devitrified glass ₂luI ₅crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:K is described ₂luI ₅the 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, weigh 50 grams of analytical pure raw materials by the formula in table 3, and add 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂after raw material is mixed, pour in quartz crucible and melt, 850 DEG C of temperature of fusion, be incubated 1.5 hours, glass melt is poured in pig mold, be then placed in retort 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 retort 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 458 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 473 DEG C of thermal 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 Tb ³⁺the K of ion doping ₂luI ₅devitrified glass.

To the K of preparation ₂luI ₅the spectral quality test of devitrified glass, the Tb of excitation of X-rays ³⁺ion doping K ₂luI ₅as shown in Figure 4, its result shows to produce Tb:K after Overheating Treatment to the fluorescence spectrum of devitrified glass ₂luI ₅crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:K is described ₂luI ₅the luminosity of devitrified glass is better; The rare earth ion doped K being obtained by above-mentioned preparation process ₂luI ₅devitrified glass is transparent and physical and chemical performance is good.

Embodiment 4

Substantially the same manner as Example 1, difference is material component difference: TeO ₂: 72moL%, P ₂o ₅: 6moL%, ZnF ₂: 11moL%, K ₂luI ₅: 10moL%, PrI ₃: 1moL%.

Embodiment 5

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

TeO ₂：72moL％、P ₂O ₅：6moL％、ZnF ₂：11moL％、K ₂LuI ₅：10moL％、NdI ₃：1moL％。

Embodiment 4,5 also can obtain rare earth ion doped K preferably ₂luI ₅devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims

1. a rare earth ion doped K ₂luI ₅devitrified glass, its mole of percentage composition is:

TeO ₂：67-75moL％ P ₂O ₅：5-7moL％ ZnF ₂：8-11moL％

K ₂LuI ₅：10-15moL％ LnI ₃：1-3moL％

Wherein LnI ₃for CeI ₃, EuI ₃, TbI ₃, PrI ₃and NdI ₃in one.

2. rare earth ion doped K claimed in claim 1 ₂luI ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO ₂: 67moL%, P ₂o ₅: 7moL%, ZnF ₂: 10moL%, K ₂luI ₅: 15moL%, CeI ₃: 1moL%.

3. rare earth ion doped K claimed in claim 1 ₂luI ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO ₂: 70moL%, P ₂o ₅: 6moL%, ZnF ₂: 11moL%, K ₂luI ₅: 10moL%, EuI ₃: 3moL%.

4. rare earth ion doped K claimed in claim 1 ₂luI ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO ₂: 75moL%, P ₂o ₅: 5moL%, ZnF ₂: 8moL%, K ₂luI ₅: 10moL%, TbI ₃: 2moL%.

5. rare earth ion doped K according to claim 1 ₂luI ₅the preparation method of devitrified glass, is characterized in that comprising following concrete steps:

(1) TeO ₂-P ₂o ₅-ZnF ₂-K ₂luI ₅-LnI ₃be founding of glass: take analytically pure each raw material by material component, respectively add the NH that accounts for raw material gross weight 5% ₄hF ₂, NH ₄hI ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort 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 retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;

(2) K ₂luI ₅the preparation of devitrified glass: according to heat analysis (DTA) experimental data of glass, the glass making is placed in near nitrogen fine annealing stove heat-treated 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, automatically be cooled to room temperature, obtain transparent rare earth ion doped K ₂luI ₅devitrified glass.