CN103951205B - Rare earth ion doped SrGdCl5Devitrified glass and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of rare earth ion doped SrGdCl₅Devitrified glass and preparation method thereof, its mole of percentage composition is P₂O₅：50-60mol％、BaF₂：16-23mol％、Gd₂O₃：5-10mol％、SrGdCl₅：15-20mol％、LnCl₃: 1-3mol%, wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃In one, its preparation method is first to prepare P with fusion method₂O₅-BaF₂-Gd2O₃-SrGdCl₅-LnCl₃Be glass, after heat treatment obtain transparent SrGdCl₅Devitrified glass, SrGdCl of the present invention₅Devitrified 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 SrGdCl5Devitrified 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 SrGdCl as scintillation material₅Devitrified 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.

SrGdCl₅Crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce³⁺The SrGdCl of doping₅It 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, will make flash detection instrument efficiency greatly improve. Eu³⁺、Tb³⁺Doping SrGdCl₅The scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen. But SrGdCl₅Crystal 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 SrGdCl of temporal resolution₅Devitrified glass. The present invention also provides the preparation method of this flicker devitrified glass, and it is simple that this preparation method has method, the advantage that cost is low.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped SrGdCl₅Devitrified glass, its mole of percentage composition is:

P₂O₅：50-60mol％BaF₂：16-23mol％Gd₂O₃：5-10mol％

SrGdCl₅：15-20mol％LnCl₃：1-3mol％

Wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃In one.

This flicker devitrified glass material component is: P₂O₅：50mol％、BaF₂：23mol％、Gd₂O₃：10mol％、SrGdCl₅：15mol％、CeCl₃：2mol％。

This flicker devitrified glass material component is: P₂O₅：55mol％、BaF₂：16mol％、Gd₂O₃：6mol％、SrGdCl₅：20mol％、EuCl₃：3mol％。

This flicker devitrified glass material component is: P₂O₅：60mol％、BaF₂：19mol％、Gd₂O₃：5mol％、SrGdCl₅：15mol％、TbCl₃：1mol％。

Described rare earth ion doped SrGdCl₅The preparation method of devitrified glass, comprises the steps:

(1)P₂O₅-BaF₂-Gd₂O₃-SrGdCl₅-LnCl₃Be founding of glass: take analytically pure each raw material by material component, add the NH that respectively accounts for raw material gross weight 6%₄HF₂、NH₄HCl₂Raw material is mixed, then pour in silica crucible or corundum crucible and melt, fusion temperature 1350-1450 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 2 hours, 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)SrGdCl₅Devitrified glass preparation:

According to heat analysis (DTA) experimental data of glass, the glass making is placed in near nitrogen fine annealing stove 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, automatically be cooled to room temperature, obtain transparent rare earth ion doped SrGdCl₅Devitrified 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 SrGdCl₅The superior scintillation properties of crystalline host material and mechanical strength, the stability of oxide glass and be easy to processing feature, overcome SrGdCl₅Monocrystal 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 SrGdCl₅Crystalline phase, the rare earth ion doped SrGdCl making₅Devitrified 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 transmission electron microscope figure (TEM) of sample after embodiment mono-controlled micro crystallization heat treatment.

Fig. 2 is the Ce:SrGdCl of embodiment mono-excitation of X-rays₅The fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:SrGdCl of embodiment bis-excitation of X-rays₅The fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:SrGdCl of embodiment tri-excitation of X-rays₅The 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 2 and analyze pure raw material, add 3 grams of NH₄HF₂, 3 grams of NH₄HCl₂After raw material is mixed, pour in silica crucible and melt, 1350 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 2 hours, 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 732 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 757 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 SrGdCl of doping₅Devitrified glass sample.

To the SrGdCl of preparation₅Devitrified glass carries out transmission electron microscope test, obtain glass through controlled micro crystallization transmission electron microscope picture after treatment as shown in Figure 1, its result is as follows: in photo, glass basis seems more clearly with the nano microcrystalline of separating out, and the stain distributing in glass basis is microcrystal grain. X-ray diffraction test shows that crystalline phase is SrGdCl₅Phase, the material therefore obtaining is SrGdCl₅The devitrified glass of crystallization phase. The Ce of excitation of X-rays³⁺Ion doping SrGdCl₅As shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass. Mix Ce³⁺Ion SrGdCl₅Devitrified glass light is output as 25000ph/MeV.

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 1 and analyze pure raw material, add 3 grams of NH₄HF₂, 3 grams of NH₄HCl₂After raw material is mixed, pour in corundum crucible and melt, 1450 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 2 hours, 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 743 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 768 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 Eu²⁺The SrGdCl of ion doping₅Devitrified glass.

To the SrGdCl of preparation₅The spectral quality test of devitrified glass, the Eu of excitation of X-rays³⁺Ion doping SrGdCl₅As shown in Figure 3, its result shows to produce Eu:SrGdCl after Overheating Treatment to the fluorescence spectrum of devitrified glass₅Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:SrGdCl is described₅The 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 3 grams of NH₄HF₂, 3 grams of NH₄HCl₂After raw material is mixed, pour in silica crucible and melt, 1400 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 2 hours, 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 748 DEG C of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 785 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 SrGdCl of ion doping₅Devitrified glass.

To the SrGdCl of preparation₅The spectral quality test of devitrified glass, the Tb of excitation of X-rays³⁺Ion doping SrGdCl₅As shown in Figure 4, its result shows to produce Tb:SrGdCl after Overheating Treatment to the fluorescence spectrum of devitrified glass₅Crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:SrGdCl is described₅The luminosity of devitrified glass is better; The rare earth ion doped SrGdCl being obtained by above-mentioned preparation process₅Devitrified glass is transparent and physical and chemical performance is good.

Claims (5)

1. a rare earth ion doped SrGdCl₅Devitrified glass, its mole of percentage composition is:

P₂O₅：50-60mol％BaF₂：16-23mol％Gd₂O₃：5-10mol％

SrGdCl₅：15-20mol％LnCl₃：1-3mol％

Wherein LnCl₃For CeCl₃、EuCl₃、TbCl₃In one.

2. rare earth ion doped SrGdCl claimed in claim 1₅Devitrified glass, is characterized in that this devitrified glass raw material groupPart is: P₂O₅：50mol％、BaF₂：23mol％、Gd₂O₃：10mol％、SrGdCl₅：15mol％、CeCl₃：2mol％。

3. rare earth ion doped SrGdCl claimed in claim 1₅Devitrified glass, is characterized in that this devitrified glass raw material groupPart is: P₂O₅：55mol％、BaF₂：16mol％、Gd₂O₃：6mol％、SrGdCl₅：20mol％、EuCl₃：3mol％。

4. rare earth ion doped SrGdCl claimed in claim 1₅Devitrified glass, is characterized in that this devitrified glass raw material groupPart is: P₂O₅：60mol％、BaF₂：19mol％、Gd₂O₃：5mol％、SrGdCl₅：15mol％、TbCl₃：1mol％。

5. rare earth ion doped SrGdCl according to claim 1₅The preparation method of devitrified glass, is characterized in that bagDraw together following concrete steps:

(1)P₂O₅-BaF₂-Gd₂O₃-SrGdCl₅-LnCl₃Be founding of glass: take analytically pure each raw material by material component,Add the NH that respectively accounts for raw material gross weight 6%₄HF₂、NH₄HCl₂, raw material is mixed, then pour silica crucible or corundum crucible intoMiddle fusing, fusion temperature 1350-1450 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 2 hours, 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)SrGdCl₅The preparation of devitrified glass: according to the 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 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 SrGdCl₅Devitrified glass.