CN103951255A

CN103951255A - Rare-earth-ion-doped LiGdI4 microcrystalline glass and preparation method thereof

Info

Publication number: CN103951255A
Application number: CN201410198491.5A
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: 2014-07-30
Anticipated expiration: 2034-05-08
Also published as: CN103951255B

Abstract

The invention discloses a rare-earth-ion-doped LiGdI4 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 70-75 mol% of TeO2, 13-18 mol% of ZnF2, 10-11 mol% of LiGdI4 and 1-3 mol% of LnI3. The LnI3 is CeI3, EuI3 or TbI3. The preparation method comprises the following steps: preparing TeO2-ZnF2-LiGdI4-LnI3 glass by a fusion process, and carrying out heat treatment to obtain the transparent LiGdI4 microcrystalline glass. The LiGdI4 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 LiGdI 4devitrified 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 LiGdI as scintillation material ₄devitrified 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.

LiGdI ₄crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce ³⁺the LiGdI of doping ₄it 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⁺li doped GdI ₄the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But LiGdI ₄crystal 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 LiGdI of temporal resolution ₄devitrified 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 LiGdI ₄devitrified glass, its mole of percentage composition is:

TeO ₂：70-75mol％ ZnF ₂：13-18mol％

LiGdI ₄：10-11mol％ LnI ₃：1-3mol％

LnI wherein ₃for CeI ₃, EuI ₃, TbI ₃in a kind of.

This flicker devitrified glass material component is: TeO ₂: 70mol%, ZnF ₂: 18mol%, LiGdI ₄: 11mol%, CeI ₃: 1mol%.

This flicker devitrified glass material component is: TeO ₂: 70mol%, ZnF ₂: 17mol%, LiGdI ₄: 10mol%, EuI ₃: 3mol%.

This flicker devitrified glass material component is: TeO ₂: 75mol%, ZnF ₂: 13mol%, LiGdI ₄: 10mol%, TbI ₃: 2mol%.

Described rare earth ion doped LiGdI ₄the preparation method of devitrified glass, comprises the steps:

(1) TeO ₂-ZnF ₂-LiGdI ₄-LnI ₃be founding of glass: by material component, take analytically pure each raw material, add the NH that respectively 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 ℃, 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) LiGdI ₄devitrified glass preparation: 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 LiGdI ₄devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of iodine fluorine oxide, short wavelength's through performance is good, has LiGdI ₄the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome LiGdI ₄single 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 LiGdI ₄crystalline phase, the rare earth ion doped LiGdI making ₄devitrified 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:LiGdI of embodiment mono-excitation of X-rays ₄the fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:LiGdI of embodiment bis-excitation of X-rays ₄the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:LiGdI of embodiment tri-excitation of X-rays ₄the 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 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 ℃ 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 445 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 470 ℃ 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 LiGdI of doping ₄devitrified glass sample.

LiGdI to preparation ₄devitrified 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 LiGdI ₄phase, the material therefore obtaining is LiGdI ₄the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping LiGdI ₄as shown in Figure 2, fluorescence peak intensity is larger for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion LiGdI ₄devitrified glass light is output as 32000ph/MeV, and be 55ns 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, by the formula in table 2, weigh 50 grams of analytical pure raw materials, 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, 850 ℃ 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 450 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 470 ℃ 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 LiGdI of ion doping ₄devitrified glass.

LiGdI to preparation ₄the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping LiGdI ₄as shown in Figure 3, its result shows to produce Eu:LiGdI after Overheating Treatment to the fluorescence spectrum of devitrified glass ₄crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:LiGdI is described ₄the 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 2.5 grams of NH ₄hF ₂, 2.5 grams of NH ₄hI ₂after raw material is mixed, pour in quartz crucible and melt, 900 ℃ 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 453 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 472 ℃ 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 LiGdI of ion doping ₄devitrified glass.

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

Claims

1. a rare earth ion doped LiGdI ₄devitrified glass, its mole of percentage composition is:

TeO ₂：70-75mol％ ZnF ₂：13-18mol％

LiGdI ₄：10-11mol％ LnI ₃：1-3mol％

LnI wherein ₃for CeI ₃, EuI ₃, TbI ₃in a kind of.

2. rare earth ion doped LiGdI claimed in claim 1 ₄devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO ₂: 70mol%, ZnF ₂: 18mol%, LiGdI ₄: 11mol%, CeI ₃: 1mol%.

3. rare earth ion doped LiGdI claimed in claim 1 ₄devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO ₂: 70mol%, ZnF ₂: 17mol%, LiGdI ₄: 10mol%, EuI ₃: 3mol%.

4. rare earth ion doped LiGdI claimed in claim 1 ₄devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO ₂: 75mol%, ZnF ₂: 13mol%, LiGdI ₄: 10mol%, TbI ₃: 2mol%.

5. rare earth ion doped LiGdI according to claim 1 ₄the preparation method of devitrified glass, is characterized in that comprising following concrete steps:

(1) TeO ₂-ZnF ₂-LiGdI ₄-LnI ₃be founding of glass: by material component, take analytically pure each raw material, add the NH that respectively 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 ℃, 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) LiGdI ₄the preparation of devitrified glass: according to the thermal analysis experiment 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, obtain transparent rare earth ion doped LiGdI ₄devitrified glass.