CN103951221B

CN103951221B - Rare earth ion doped CaI 2devitrified glass and preparation method thereof

Info

Publication number: CN103951221B
Application number: CN201410198131.5A
Authority: CN
Inventors: 王倩; 张约品; 夏海平; 杨斌; 张为欢; 欧阳绍业
Original assignee: Ningbo University
Current assignee: Ningbo University
Priority date: 2014-05-08
Filing date: 2014-05-08
Publication date: 2016-02-03
Anticipated expiration: 2034-05-08
Also published as: CN103951221A

Abstract

The invention discloses a kind of rare earth ion doped CaI ₂devitrified glass and preparation method thereof, its Mole percent consists of P ₂o ₅: 50-60mol%, BaF ₂: 10-14mol%, NaF:5-13mol%, CaO:5-10mol%, CaI ₂: 15-20mol%, rare-earth iodide: 1-4mol%, wherein rare-earth iodide is EuI ₂, CeI ₃, TbI ₃in one, its preparation method first prepares P with scorification ₂o ₅-BaF ₂-NaF-CaO-CaI ₂-LnI ₂, P ₂o ₅-BaF ₂-NaF-CaO-CaI ₂-LnI ₃be glass, after heat treatment obtain transparent CaI ₂devitrified glass, CaI of the present invention ₂devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have extremely strong twinkling light luminescence and export, the performances such as energy resolution is good.The preparation method of this devitrified glass is simple, and production cost is lower.

Description

Rare earth ion doped CaI 2devitrified 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 CaI being used as scintillation material ₂devitrified glass and preparation method thereof.

Background technology

Scintillation material is a kind of lower optical function material that can send visible ray of exciting at energetic ray (as x-ray, gamma-rays) or other radioactive particle, is widely used in the fields such as the researchs of nuclear medicine diagnostic, high energy physics and nuclear physics experiment, industrial and geological prospecting.The requirement of difference to scintillator according to Application Areas 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 comparatively large, cost is low and radiation resistance is good.Scintillation crystal generally has the advantage such as resistance to irradiation, fast decay, High Light Output, but scintillation crystal also exists following serious shortcoming: preparation difficulty, expensive.And although rare earth ion doped scintillation glass is with short production cycle, cost is low, easily prepare large-size glass, it is difficult compared with crystal in light output, multiplicity etc., and therefore its application is also very limited.

CaI ₂crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Eu ²⁺the CaI of doping ₂crystal has abnormal high light output, and good energy resolution, can be applicable in low energy physics and the field such as safety check, medical imaging.Ce ³⁺the CaI of doping ₂crystal has High Light Output, the feature of fast decay, Tb ³⁺doping CaI ₂crystal can be used for scintillation fluor screen.But CaI ₂crystal is deliquescence, poor, the easy cleavage slabbing of mechanical property, its practical application of the large-size crystals growth disadvantages affect such as difficult, expensive very easily.

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 CaI of temporal resolution ₂devitrified glass and preparation method thereof.

The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped CaI ₂devitrified glass, its Mole percent consists of:

P ₂O ₅：50-60mol％BaF ₂：10-14mol％NaF：5-13mol％

CaO:5-10mol%CaI ₂: 15-20mol% rare-earth iodide: 1-4mol%

Wherein rare-earth iodide is EuI ₂, CeI ₃, TbI ₃in one.

This flicker devitrified glass material component is: P ₂o ₅: 55mol%, BaF ₂: 10mol%, NaF:5mol%, CaO:6mol%, CaI ₂: 20mol%, EuI ₂: 4mol%.

This flicker devitrified glass material component is: P ₂o ₅: 50mol%, BaF ₂: 10mol%, NaF:13mol%, CaO:10mol%, CaI ₂: 15mol%, CeI ₃: 2mol%.

This flicker devitrified glass material component is: P ₂o ₅: 60mol%, BaF ₂: 14mol%, NaF:5mol%, CaO:5mol%, CaI ₂: 15mol%, TbI ₃: 1mol%.

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

(1) P ₂o ₅-BaF ₂-NaF-CaO-CaI ₂-LnI ₂, P ₂o ₅-BaF ₂-NaF-CaO-CaI ₂-LnI ₃be founding of glass: take analytically pure each raw material by material component, respectively add the NH accounting for raw material gross weight 5% ₄hF ₂, NH ₄hI ₂raw material is mixed, then pours in quartz crucible or corundum crucible and melt, temperature of fusion 1350-1450 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 50 DEG C are cooled to 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) CaI ₂prepared by devitrified glass:

According to thermal analyses (DTA) experimental data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 4 ~ 6 hours near 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 CaI ₂devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is made up of fluorine iodine oxygen compound, the through performance of short wavelength is good, has CaI ₂the feature that the superior scintillation properties of crystalline host material and the physical strength of oxide glass, stability and being easy to is processed, overcomes CaI ₂single 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 CaI ₂crystalline phase, obtained rare earth ion doped CaI ₂devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution, can make scintillation detectors efficiency greatly improve.The preparation method of this devitrified glass is simple, and production cost is lower.

Accompanying drawing explanation

Fig. 1 is X-ray diffraction (XRD) figure of sample after the thermal treatment of embodiment one micritization.

Fig. 2 is the Eu:CaI of embodiment two excitation of X-rays ₂the fluorescence spectrum of devitrified glass.

Fig. 3 is the Ce:CaI of embodiment one excitation of X-rays ₂the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:CaI of embodiment three excitation of X-rays ₂the fluorescence spectrum of devitrified glass.

Embodiment

Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.

Embodiment one: table 1 is glass formula and the first recrystallization temperature value of embodiment one.

Table 1

Concrete preparation process is as follows: the first step, weighs 50 grams of analytical pure raw materials by the formula in table 1, adds 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂pour in corundum crucible after raw material is mixed and melt, temperature of fusion 1450 DEG C, be incubated 1 hour, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 737 DEG C, obtained glass is placed in nitrogen fine annealing stove 761 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 ²⁺the CaI of ion doping ₂devitrified glass.

To the CaI of preparation ₂devitrified glass carries out X-ray diffraction test, and obtain the XRD figure of glass after micritization process as shown in Figure 1, its result is as follows: the XRD diffraction peak of the sample obtained through Overheating Treatment and CaI ₂the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is CaI ₂the devitrified glass of crystallization phase.And the Eu of excitation of X-rays ²⁺ion doping CaI ₂as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Eu ²⁺ion CaI ₂devitrified glass light output can reach 110000ph/MeV.

Embodiment two: table 2 is glass formula and the first recrystallization temperature value of embodiment two.

Table 2

Concrete preparation process is as follows: the first step, weighs 50 grams of analytical pure raw materials by the formula in table 2, adds 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1350 DEG C, be incubated 2 hours, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 731 DEG C, obtained glass is placed in nitrogen fine annealing stove 751 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 CaI of doping ₂devitrified glass sample.

To the CaI of preparation ₂the spectral quality test of devitrified glass, the Ce of excitation of X-rays ³⁺ion doping CaI ₂as shown in Figure 3, its result shows to produce Ce:CaI after Overheating Treatment the fluorescence spectrum of devitrified glass ₂crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Ce:CaI is described ₂the luminosity of devitrified glass is better.

Embodiment three: table 3 is glass formula and the first recrystallization temperature value of embodiment three.

Table 3

Concrete preparation process is as follows: the first step, weighs 50 grams of analytical pure raw materials by the formula in table 3, adds 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂pour in quartz crucible after raw material is mixed and melt, temperature of fusion 1400 DEG C, be incubated 1.5 hours, glass melt poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 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 thermal analyses (DTA) experimental data of glass, obtain the first recrystallization temperature 742 DEG C, obtained glass is placed in nitrogen fine annealing stove 785 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 CaI of ion doping ₂devitrified glass.

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

Claims

1. a rare earth ion doped CaI ₂devitrified glass, its feed molar percentage composition is:

P ₂O ₅：50-60mol％BaF ₂：10-14mol％NaF：5-13mol％

CaO:5-10mol%CaI ₂: 15-20mol% rare-earth iodide: 1-4mol%

Wherein rare-earth iodide is EuI ₂, CeI ₃, TbI ₃in one.

2. rare earth ion doped CaI according to claim 1 ₂devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 55mol%, BaF ₂: 10mol%, NaF:5mol%, CaO:6mol%, CaI ₂: 20mol%, EuI ₂: 4mol%.

3. rare earth ion doped CaI according to claim 1 ₂devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 50mol%, BaF ₂: 10mol%, NaF:13mol%, CaO:10mol%, CaI ₂: 15mol%, CeI ₃: 2mol%.

4. rare earth ion doped CaI according to claim 1 ₂devitrified glass, is characterized in that this devitrified glass material component is: P ₂o ₅: 60mol%, BaF ₂: 14mol%, NaF:5mol%, CaO:5mol%, CaI ₂: 15mol%, TbI ₃: 1mol%.

5. a rare earth ion doped CaI ₂the preparation method of devitrified glass, is characterized in that comprising following concrete steps:

(1) P ₂o ₅-BaF ₂-NaF-CaO-CaI ₂-LnI ₂, P ₂o ₅-BaF ₂-NaF-CaO-CaI ₂-LnI ₃be founding of glass: be: P by feed molar percentage composition ₂o ₅: 50-60mol%, BaF ₂: 10-14mol%, NaF:5-13mol%, CaO:5-10mol%, CaI ₂: 15-20mol%, rare-earth iodide: 1-4mol%, wherein rare-earth iodide is EuI ₂, CeI ₃, TbI ₃in one; Take analytically pure each raw material, respectively add the NH accounting for raw material gross weight 5% ₄hF ₂, NH ₄hI ₂mix, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 1350-1450 DEG C, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 2 hours, 50 DEG C are cooled to 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) CaI ₂the preparation of devitrified glass: according to the thermal analysis experiment data of glass, obtained glass is placed in nitrogen fine annealing stove heat-treated 4 ~ 6 hours near 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 CaI ₂devitrified glass.