CN103951219B - Rare earth ion doped K 2laI 5devitrified glass and preparation method thereof - Google Patents

Rare earth ion doped K 2laI 5devitrified glass and preparation method thereof Download PDF

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CN103951219B
CN103951219B CN201410198075.5A CN201410198075A CN103951219B CN 103951219 B CN103951219 B CN 103951219B CN 201410198075 A CN201410198075 A CN 201410198075A CN 103951219 B CN103951219 B CN 103951219B
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lai
glass
devitrified glass
rare earth
earth ion
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CN103951219A (en
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欧阳绍业
张约品
夏海平
张为欢
王倩
杨斌
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Ningbo University
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Ningbo University
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Abstract

The invention discloses a kind of rare earth ion doped K 2laI 5devitrified glass and preparation method thereof, its Mole percent consists of TeO 2: 65-75mol%, Nb 2o 5: 8-11mol%, ZnF 2: 5-10mol%, K 2laI 5: 10-15mol%, LnI 3: 1-4mol%, wherein LnI 3for CeI 3, EuI 3, TbI 3, PrI 3and NdI 3in one, its preparation method first prepares TeO with scorification 2-Nb 2o 5-ZnF 2-K 2laI 5-LnI 3be glass, after heat treatment obtain transparent K 2laI 5devitrified glass, K of the present invention 2laI 5devitrified glass, energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution.The preparation method of this devitrified glass is simple, and production cost is lower.

Description

Rare earth ion doped K 2laI 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 K being used as scintillation material 2laI 5devitrified 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 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.
K 2laI 5crystal be a kind of can the scintillation crystal matrix of doping with rare-earth ions, Ce 3+the K of doping 2laI 5it is high that crystal has light output, decays soon, good energy resolution, temporal resolution and linear response, has than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, scintillation detectors efficiency can be made greatly to improve.Eu 3+, Tb 3+doping K 2laI 5the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But K 2laI 5crystal is deliquescence very easily, and mechanical property is poor, easy cleavage slabbing, large-size crystals growth difficulty, and expensively have impact on 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 extremely strong light output, fast decay, energy resolution and the good rare earth ion doped K of temporal resolution 2laI 5devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped K 2laI 5devitrified glass, its Mole percent consists of:
TeO 2：65-75mol％Nb 2O 5：8-11mol％
ZnF 2：5-10mol％K 2LaI 5：10-15mol％LnI 3：1-4mol％
Wherein LnI 3for CeI 3, EuI 3, TbI 3, PrI 3and NdI 3in one.
This flicker devitrified glass material component is: TeO 2: 65mol%, Nb 2o 5: 9mol%, ZnF 2: 10mol%, K 2laI 5: 15mol%, CeI 3: 1mol%.
This flicker devitrified glass material component is: TeO 2: 70mol%, Nb 2o 5: 11mol%, ZnF 2: 5mol%, K 2laI 5: 10mol%, EuI 3: 4mol%.
This flicker devitrified glass material component is: TeO 2: 75mol%, Nb 2o 5: 8mol%, ZnF 2: 5mol%, K 2laI 5: 10mol%, TbI 3: 2mol%.
Described rare earth ion doped K 2laI 5the preparation method of devitrified glass, comprises the steps:
(1) TeO 2-Nb 2o 5-ZnF 2-K 2laI 5-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 800-900 DEG C, insulation 1-2 hour after fusing, glass melt is poured in pig mold, be then placed in retort furnace and anneal, in glass transformation temperature Tg temperature after 1 hour, 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) K 2laI 5prepared 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 K 2laI 5devitrified 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 K 2laI 5the 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 K 2laI 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 K 2laI 5crystalline phase, obtained rare earth ion doped K 2laI 5devitrified 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 Ce:K of embodiment one excitation of X-rays 2laI 5the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:K of embodiment two excitation of X-rays 2laI 5the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:K of embodiment three excitation of X-rays 2laI 5the 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 quartz crucible after raw material is mixed and melt, temperature of fusion 800 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 1 hour, 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 445 DEG C, obtained glass is placed in nitrogen fine annealing stove 452 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 K of doping 2laI 5devitrified glass.
To the K of preparation 2laI 5devitrified 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 K 2laI 5the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is K 2laI 5the devitrified glass of crystallization phase.And the Ce of excitation of X-rays 3+ion doping K 2laI 5as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion K 2laI 5devitrified glass light output can reach 55000ph/MeV, and fall time is 24ns.
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 corundum crucible after raw material is mixed and melt, temperature of fusion 900 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 1 hour, 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 451 DEG C, obtained glass is placed in nitrogen fine annealing stove 470 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 3+the K of ion doping 2laI 5devitrified glass.
To the K of preparation 2laI 5the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping K 2laI 5as shown in Figure 3, its result shows to produce Eu:K after Overheating Treatment the fluorescence spectrum of devitrified glass 2laI 5crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Eu:K is described 2laI 5the 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 850 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 1 hour, 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 455 DEG C, obtained glass is placed in nitrogen fine annealing stove 475 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 K of ion doping 2laI 5devitrified glass.
To the K of preparation 2laI 5the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping K 2laI 5as shown in Figure 4, its result shows to produce Tb:K after Overheating Treatment the fluorescence spectrum of devitrified glass 2laI 5crystallite luminous intensity compared with corresponding glass basis is significantly improved, and Tb:K is described 2laI 5the luminosity of devitrified glass is better; The rare earth ion doped K obtained by above-mentioned preparation process 2laI 5devitrified glass is transparent and physical and chemical performance is excellent.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: TeO 2: 70mol%, Nb 2o 5: 11mol%, ZnF 2: 8mol%, K 2laI 5: 10mol%, PrI 3: 1mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: TeO 2: 70mol%, Nb 2o 5: 11mol%, ZnF 2: 8mol%, K 2laI 5: 10mol%, NdI 3: 1mol%.
Embodiment 4,5 also can obtain K rare earth ion doped preferably 2laI 5devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped K 2laI 5devitrified glass, its Mole percent consists of:
TeO 2：65-75mol％Nb 2O 5：8-11mol％
ZnF 2：5-10mol％K 2LaI 5：10-15mol％LnI 3：1-4mol％
Wherein LnI 3for CeI 3, EuI 3, TbI 3, PrI 3and NdI 3in one.
2. rare earth ion doped K according to claim 1 2laI 5devitrified glass, is characterized in that this devitrified glass material component is: TeO 2: 65mol%, Nb 2o 5: 9mol%, ZnF 2: 10mol%, K 2laI 5: 15mol%, CeI 3: 1mol%.
3. rare earth ion doped K according to claim 1 2laI 5devitrified glass, is characterized in that this devitrified glass material component is: TeO 2: 70mol%, Nb 2o 5: 11mol%, ZnF 2: 5mol%, K 2laI 5: 10mol%, EuI 3: 4mol%.
4. rare earth ion doped K according to claim 1 2laI 5devitrified glass, is characterized in that this devitrified glass material component is: TeO 2: 75mol%, Nb 2o 5: 8mol%, ZnF 2: 5mol%, K 2laI 5: 10mol%, TbI 3: 2mol%.
5. rare earth ion doped K according to claim 1 2laI 5the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) TeO 2-Nb 2o 5-ZnF 2-K 2laI 5-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 800-900 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 1 hour, 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) K 2laI 5the 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 K 2laI 5devitrified glass.
CN201410198075.5A 2014-05-08 2014-05-08 Rare earth ion doped K 2laI 5devitrified glass and preparation method thereof Expired - Fee Related CN103951219B (en)

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CN101265028A (en) * 2008-04-18 2008-09-17 中国计量学院 Rare earth doping LiYF4 microcrystalline glass and preparation method thereof
CN101723594A (en) * 2009-12-17 2010-06-09 苏州恒仓红外光学材料研发中心有限责任公司 Rare earth iron-doped transparent oxygen fluorine germanate microcrystalline glass and preparation method thereof

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CN101597138B (en) * 2009-07-23 2012-07-04 中国计量学院 Microcrystal glass with precipitation of LiAl5O8 nanocrystal and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101265028A (en) * 2008-04-18 2008-09-17 中国计量学院 Rare earth doping LiYF4 microcrystalline glass and preparation method thereof
CN101723594A (en) * 2009-12-17 2010-06-09 苏州恒仓红外光学材料研发中心有限责任公司 Rare earth iron-doped transparent oxygen fluorine germanate microcrystalline glass and preparation method thereof

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