CN103951202A

CN103951202A - Rare-earth-ion-doped BaYCl5 microcrystalline glass and preparation method thereof

Info

Publication number: CN103951202A
Application number: CN201410197840.1A
Authority: CN
Inventors: 张为欢; 张约品; 夏海平; 欧阳绍业; 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

Abstract

The invention discloses a rare-earth-ion-doped BaYCl5 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 50-55 mol% of P2O5, 15-20 mol% of SiO2, 20-25 mol% of BaYCl5 and 5-10 mol% of LnCl3. The LnCl3 is CeCl3, EuCl3, TbCl3, PrCl3 or NdCl3. The preparation method comprises the following steps: preparing P2O5-SiO2-BaYCl5-LnCl3 glass by a fusion process, and carrying out heat treatment to obtain the transparent BaYCl5 microcrystalline glass. The BaYCl5 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 other properties, overcomes the defects of high tendency to deliquescence, poor mechanical properties, high tendency to flaking and the like in the BaYCl5 monocrystal, and thus, has favorable comprehensive properties. The preparation method of the microcrystalline glass is simple and lower in production cost.

Description

Rare earth ion doped BaYCl 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 BaYCl as scintillation material 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 compared with crystal in aspect difficulties such as light output, multiplicity, so its application is also very limited.

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

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

P ₂O ₅：50-55mol％ SiO ₂：15-20mol％

BaYCl ₅：20-25mol％ LnCl ₃：5-10mol％

LnCl wherein ₃for CeCl ₃, EuCl ₃, TbCl ₃, PrCl ₃and NdCl ₃in a kind of.

This flicker devitrified glass material component is: P ₂o ₅: 50mol%SiO ₂: 20mol%, BaYCl ₅: 25mol%, CeCl ₃: 5mol%.

This flicker devitrified glass material component is: P ₂o ₅: 53mol%, SiO ₂: 17mol%, BaYCl ₅: 20mol%, EuCl ₃: 10mol%.

This flicker devitrified glass material component is: P ₂o ₅: 55mol%, SiO ₂: 15mol%, BaYCl ₅: 25mol%, TbCl ₃: 5mol%.

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

(1) P ₂o ₅-SiO ₂-BaYCl ₅-LnCl ₃be founding of glass:

By material component, take analytically pure each raw material, add the NH that accounts for raw material gross weight 6% ₄hCl ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1410-1450 ℃, 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, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment.

(2) BaYCl ₅devitrified glass preparation:

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 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply, automatically be cooled to room temperature, finally can obtain transparent rare earth ion doped BaYCl ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of chlorine oxonium compound, short wavelength's through performance is good, has BaYCl ₅the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome BaYCl 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 BaYCl ₅crystalline phase, the rare earth ion doped BaYCl making 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 performances such as good energy resolution and temporal resolution, can make nuclear detection instrument efficiency greatly improve.The preparation method of this devitrified glass is simple, and production cost is lower.

Accompanying drawing explanation

Fig. 1 is the transmission electron microscope figure (TEM) of sample after embodiment mono-micritization thermal treatment.

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

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

Fig. 4 is the Tb:BaYCl of embodiment tri-excitation of X-rays 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

Concrete preparation process is as follows: the first step, by the formula in table 1, weigh 50 grams of analytical pure raw materials, and add 3 grams of NH ₄hCl ₂after raw material is mixed, pour in quartz crucible and melt, 1410 ℃ 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, with the speed of 10 ℃/h, be cooled to 50 ℃, 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 713 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 728 ℃ of thermal treatments 6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce ³⁺the B of doping _ayCl ₅devitrified glass sample.

BaYCl to preparation ₅devitrified glass carries out transmission electron microscope test, obtain the transmission electron microscope picture of glass after micritization is processed 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 BaYCl ₅phase, the material therefore obtaining is BaYCl ₅the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping BaYCl ₅as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion BaYCl ₅devitrified glass light is output as 23000ph/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, by the formula in table 2, weigh 50 grams of analytical pure raw materials, and add 3 grams of NH ₄hCl ₂after raw material is mixed, pour in corundum crucible and melt, 1450 ℃ 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, with the speed of 10 ℃/h, be cooled to 50 ℃, 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 723 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 740 ℃ of thermal treatments 4 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu ³⁺the BaYCl of ion doping ₅devitrified glass.

BaYCl to preparation ₅the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping BaYCl ₅as shown in Figure 3, its result shows to produce Eu:BaYCl after Overheating Treatment to the fluorescence spectrum of devitrified glass ₅crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:BaYCl is described 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, by the formula in table 3, weigh 50 grams of analytical pure raw materials, and add 3 grams of NH ₄hCl ₂after raw material is mixed, pour in quartz crucible and melt, 1430 ℃ 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, with the speed of 10 ℃/h, be cooled to 50 ℃, 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 732 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 760 ℃ of thermal treatments 5 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb ³⁺the BaYCl of ion doping ₅devitrified glass.

BaYCl to preparation ₅the spectral quality test of devitrified glass, the Tb of excitation of X-rays ³⁺ion doping BaYCl ₅as shown in Figure 4, its result shows to produce Tb:BaYCl after Overheating Treatment to the fluorescence spectrum of devitrified glass ₅crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:BaYCl is described ₅the luminosity of devitrified glass is better; The rare earth ion doped BaYCl being obtained by above-mentioned preparation process 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: P ₂o ₅: 50mol%SiO ₂: 20mol%, BaYCl ₅: 25mol%, PrCl ₃: 5mol%.

Embodiment 5

Substantially the same manner as Example 1, difference is material component difference: P ₂o ₅: 50mol%SiO ₂: 20mol%, BaYCl ₅: 25mol%, NdCl ₃: 5mol%.

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

Claims

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

P ₂O ₅：50-55mol％ SiO ₂：15-20mol％

BaYCl ₅：20-25mol％ LnCl ₃：5-10mol％

2. rare earth ion doped BaYCl claimed in claim 1 ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: P ₂o ₅: 50mol%SiO ₂: 20mol%, BaYCl ₅: 25mol%, CeCl ₃: 5mol%.

3. rare earth ion doped BaYCl claimed in claim 1 ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: P ₂o ₅: 53mol%, SiO ₂: 17mol%, BaYCl ₅: 20mol%, EuCl ₃: 10mol%.

4. rare earth ion doped BaYCl claimed in claim 1 ₅devitrified glass, is characterized in that this flicker devitrified glass material component is: P ₂o ₅: 55mol%, SiO ₂: 15mol%, BaYCl ₅: 25mol%, TbCl ₃: 5mol%.

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

(1) P ₂o ₅-SiO ₂-BaYCl ₅-LnCl ₃be founding of glass: by material component, take analytically pure each raw material, add the NH that accounts for raw material gross weight 6% ₄hCl ₂raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1410-1450 ℃, insulation 1-2 hour, glass melt is poured on pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;

(2) BaYCl ₅the preparation of devitrified glass: according to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near its first crystallization peak, heat-treated is 4～6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped BaYCl ₅devitrified glass.