CN103951236B - Rare earth ion doped RbGd2Cl7Devitrified glass and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of rare earth ion doped RbGd₂Cl₇Devitrified glass and preparation method thereof, its mole of percentage composition is P₂O₅：45-50mol％、SiO₂：10-15mol％、NaF：15-23mol％、Gd₂O₃：5-9mol％、RbGd₂Cl₇：10-15mol％、LnCl₃: 1-4mol%, wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃、PrCl₃And NdCl₃In one, its preparation method is first to prepare P with fusion method₂O₅-SiO₂-NaF-Gd₂O₃-RbGd₂Cl₇-LnCl₃Be glass, after heat treatment obtain transparent RbGd₂Cl₇Devitrified glass, RbGd of the present invention₂Cl₇Devitrified 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 RbGd2Cl7Devitrified 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 RbGd of ion doping₂Cl₇Devitrified 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.

RbGd₂Cl₇Crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce³⁺The RbGd of doping₂Cl₇Crystal toolThere is light output high, decay soon, good energy resolution, temporal resolution and linear response, have than rare earth ion doped fluorineThe luminous efficiency that compound crystal and oxide crystal are higher, can make flash detection instrument efficiency greatly improve. Eu³⁺、Tb³⁺DopingRbGd₂Cl₇The scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen. But RbGd₂Cl₇Crystal very easilyDeliquescence, mechanical performance is poor, easily cleavage slabbing, large-size crystals growth difficulty, and expensively affected its actual answeringWith.

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 RbGd of temporal resolution₂Cl₇Devitrified glass and preparation method thereof.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped GdCl₃Devitrified glass,Its mole of percentage composition is:

P₂O₅：45-50mol％SiO₂：10-15mol％NaF：15-23mol％

Gd₂O₃：5-9mol％RbGd₂Cl₇：10-15mol％LnCl₃：1-4mol％

Wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃、PrCl₃And NdCl₃In one.

This flicker devitrified glass material component is: P₂O₅：45mol％、SiO₂：15mol％、NaF：23mol％、Gd₂O₃：5mol％、RbGd₂Cl₇：10mol％、CeCl₃：2mol％。

This flicker devitrified glass material component is: P₂O₅：48mol％、SiO₂：12mol％、NaF：15mol％、Gd₂O₃：6mol％、RbGd₂Cl₇：15mol％、EuCl₃：4mol％。

This flicker devitrified glass material component is: P₂O₅：50mol％、SiO₂：10mol％、NaF：20mol％、Gd₂O₃：9mol％、RbGd₂Cl₇：10mol％、TbCl₃：1mol％。

Described rare earth ion doped RbGd₂Cl₇The preparation method of devitrified glass, comprises the steps:

(1)P₂O₅-SiO₂-NaF-Gd₂O₃-RbGd₂Cl₇-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, by raw materialMix, then pour in silica crucible or corundum crucible and melt, fusion temperature 1410-1450 DEG C, insulation 1-2 hour, willGlass melt is poured in pig mold, is then placed in Muffle furnace and anneals, in glass transformation temperature Tg temperature insulation 1 hourAfter, 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 crystalliteHeat-transmission processing.

(2)RbGd₂Cl₇Devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, by the glass making be placed in 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, finally can obtain transparent rare earth ion doped RbGd₂Cl₇Devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine chlorine oxonium compound, short wavelength'sThrough performance is good, has RbGd₂Cl₇The superior scintillation properties of crystalline host material and mechanical strength, the stability of oxide glassFeature with being easy to processing, has overcome RbGd₂Cl₇Monocrystal 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 RbGd₂Cl₇Crystalline phase, the rare earth making fromSon doping RbGd₂Cl₇Devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has strongerLight output, 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:RbGd of embodiment mono-excitation of X-rays₂Cl₇The fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:RbGd of embodiment bis-excitation of X-rays₂Cl₇The fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:RbGd of embodiment tri-excitation of X-rays₂Cl₇The 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 NH₄HCl₂, after raw material is mixed, to pour in silica crucible and melt, 1410 DEG C of fusion temperatures, are incubated 2 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 715 DEG C of the first recrystallization temperatures, and the glass making is placed in to nitrogen fine annealingIn stove, 730 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 fromMove and be cooled to room temperature, obtain transparent Ce³⁺The RbGd of doping₂Cl₇Devitrified glass sample.

To the RbGd of preparation₂Cl₇Devitrified glass carries out sem test, obtains glass through controlled micro crystallization scanning after treatmentAs shown in Figure 1, what in photo, be grain shape is the nano microcrystalline of separating out to electron microscope picture, and remainder is glassy phase. X penetratesThe test of line diffraction shows that crystalline phase is RbGd₂Cl₇Phase, the material therefore obtaining is RbGd₂Cl₇The devitrified glass of crystallization phase. X penetratesThe Ce that line excites³⁺Ion doping RbGd₂Cl₇As shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass. Mix Ce³⁺FromSub-RbGd₂Cl₇The output of devitrified glass light can reach 46000ph/MeV, and be 32ns die-away time, and its light output is high as seen, die-away timeShort.

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 NH₄HCl₂, after raw material is mixed, to pour in corundum crucible and melt, 1450 DEG C of fusion temperatures, are incubated 1 hour, 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 733 DEG C of the first recrystallization temperatures, and the glass making is placed in to nitrogen fine annealingIn stove, 760 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 fromMove and be cooled to room temperature, obtain transparent Eu³⁺The RbGd of ion doping₂Cl₇Devitrified glass.

To the RbGd of preparation₂Cl₇The spectral quality test of devitrified glass, the Eu of excitation of X-rays³⁺Ion doping RbGd₂Cl₇As shown in Figure 3, its result shows to produce Eu:RbGd after Overheating Treatment to the fluorescence spectrum of devitrified glass₂Cl₇Crystallite is with correspondingGlass basis is compared luminous intensity and is significantly improved, and Eu:RbGd is described₂Cl₇The 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 NH₄HCl₂, after raw material is mixed, to pour in silica crucible and melt, 1430 DEG C of fusion temperatures, are incubated 1.5 hours, willGlass melt is poured in pig mold, is then placed in Muffle furnace and anneals, in glass transformation temperature Tg temperature insulation 1 hourAfter, 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 742 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen precisionIn annealing furnace, 777 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 electricitySource automatic is cooled to room temperature, obtains transparent Tb³⁺The RbGd of ion doping₂Cl₇Devitrified glass.

To the RbGd of preparation₂Cl₇The spectral quality test of devitrified glass, the Tb of excitation of X-rays³⁺Ion doping RbGd₂Cl₇As shown in Figure 4, its result shows to produce Tb:RbGd after Overheating Treatment to the fluorescence spectrum of devitrified glass₂Cl₇Crystallite is with correspondingGlass basis is compared luminous intensity and is significantly improved, and Tb:RbGd is described₂Cl₇The luminosity of devitrified glass is better; By upperState the rare earth ion doped RbGd that preparation process obtains₂Cl₇Devitrified glass is transparent and physical and chemical performance is good.

Embodiment 4

Substantially the same manner as Example 1, difference is material component difference: P₂O₅：50mol％、SiO₂：10mol％、NaF：20mol％、Gd₂O₃：9mol％、RbGd₂Cl₇：10mol％、PrCl₃：1mol％。

Embodiment 5

Substantially the same manner as Example 1, difference is material component difference: P₂O₅：50mol％、SiO₂：10mol％、NaF：20mol％、Gd₂O₃：9mol％、RbGd₂Cl₇：10mol％、NdCl₃：1mol％。

Embodiment 4,5 also can obtain rare earth ion doped RbGd preferably₂Cl₇Devitrified glass, concrete flicker is micro-Crystal glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped RbGd₂Cl₇Devitrified glass, its mole of percentage composition is:

P₂O₅：45-50mol％SiO₂：10-15mol％NaF：15-23mol％

Gd₂O₃：5-9mol％RbGd₂Cl₇：10-15mol％LnCl₃：1-4mol％

Wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃、PrCl₃And NdCl₃In one.

2. rare earth ion doped RbGd claimed in claim 1₂Cl₇Devitrified glass, is characterized in that this devitrified glass raw material groupPart is: P₂O₅：45mol％、SiO₂：15mol％、NaF：23mol％、Gd₂O₃：5mol％、RbGd₂Cl₇：10mol％、CeCl₃：2mol％。

3. rare earth ion doped RbGd claimed in claim 1₂Cl₇Devitrified glass, is characterized in that this devitrified glass raw material groupPart is: P₂O₅：48mol％、SiO₂：12mol％、NaF：15mol％、Gd₂O₃：6mol％、RbGd₂Cl₇：15mol％、EuCl₃：4mol％。

4. rare earth ion doped RbGd claimed in claim 1₂Cl₇Devitrified glass, is characterized in that this devitrified glass raw material groupPart is: P₂O₅：50mol％、SiO₂：10mol％、NaF：20mol％、Gd₂O₃：9mol％、RbGd₂Cl₇：10mol％、TbCl₃：1mol％。

5. according to the rare earth ion doped RbGd described in claim l₂Cl₇The preparation method of devitrified glass, is characterized in that bagDraw together following concrete steps:

(1)P₂O₅-SiO₂-NaF-Gd₂O₃-RbGd₂Cl₇-LnCl₃Be founding of glass: take analytically pure each former by material componentMaterial, respectively adds 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 1410-1450 DEG C, insulation 1-2 hour, pours glass melt on 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, close horseNot stove power supply is cooled to room temperature automatically, takes out glass, for controlled micro crystallization heat treatment;

(2)RbGd₂Cl₇The preparation of devitrified glass: according to the DTA thermal analysis experiment data of glass, the glass making is placed in to nitrogenIn fine annealing stove, near heat treatment 4～6 hours its first crystallization peak, and then lower the temperature with the speed of 5 DEG C/hTo 50 DEG C, close fine annealing stove power supply, be automatically cooled to room temperature, obtain transparent rare earth ion doped RbGd₂Cl₇CrystalliteGlass.