CN111825332A - High-transparency microcrystalline glass scintillator and preparation method and application thereof - Google Patents

High-transparency microcrystalline glass scintillator and preparation method and application thereof Download PDF

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CN111825332A
CN111825332A CN202010729404.XA CN202010729404A CN111825332A CN 111825332 A CN111825332 A CN 111825332A CN 202010729404 A CN202010729404 A CN 202010729404A CN 111825332 A CN111825332 A CN 111825332A
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scintillator
laf
transparency
glass
microcrystalline
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徐旭辉
唐海涛
吴涛
房昭会
杨泽
章皓
余雪
邱建备
周大成
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/12Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16Halogen containing crystalline phase
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21KTECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K4/00Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens

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Abstract

The invention discloses a high-transparency microcrystalline glass scintillator and a preparation method and application thereof, and belongs to the technical field of microcrystalline glass. The transmittance of the high-transparency microcrystalline glass scintillator in a visible light waveband, namely a 380-760 nm waveband, is not lower than 89%, and the microcrystalline scintillator has a chemical formula of Ba2LaF7:Tb3+. Mixing high-purity Na2CO3、SiO2、Al2O3、BaF2、LaF3And TbF3Grinding to obtain mixed powder; the mixed powder is placed in an air atmosphere at the temperature of 1400-1500 ℃ for melting treatment for 30-60 min, poured onto a preheating lining plate and cooled and formed to obtain precursor glass; performing high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in sequence to obtain Ba2LaF7:Tb3+High transparencyBright microcrystalline glass scintillator. Inventive Ba2LaF7:Tb3+The high-transparency microcrystalline glass scintillator has excellent luminescence performance under the excitation of X rays (the tube voltage is 50KV, the tube current is 100 muA), and the transmittance of a visible light wave band (380-760 nm) reaches 89%, so that a clear image can be formed under the X rays, and an X-ray imaging fluorescent screen can be prepared.

Description

High-transparency microcrystalline glass scintillator and preparation method and application thereof
Technical Field
The invention relates to a high-transparency microcrystalline glass scintillator and a preparation method and application thereof, belonging to the technical field of microcrystalline glass.
Background
Scintillators are capable of absorbing high energy X-ray photons and converting the absorbed energy into low energy visible photons, which are critical for X-ray imaging, radiation exposure monitoring, security inspection, and X-ray astronomy applications. At present, the traditional scintillator materials (CsI: Tl, NaI: Tl and the like) and perovskite scintillator materials have the following defects: (1) the material contains elements with high toxicity such as Pb, Tl and the like, and the chemical stability and the mechanical property of the material are insufficient; (2) the plastic scintillator is easy to dissolve in solvents such as ketones, ethanol, dilute acid, dilute alkalinity and the like, and the application in the imaging field is limited due to the insufficient luminous intensity; (3) because the traditional scintillator materials are all powder materials, the mismatching of the refractive indexes of the powder materials and the cladding materials and the incompatibility of the powder materials and the cladding materials cause that the transparent scintillator materials with fixed shapes are difficult to obtain, and the application in the aspect of X-ray imaging is restricted.
Therefore, it is necessary to research a stable X-ray scintillator with high brightness and high transparency and a preparation method thereof,
disclosure of Invention
Aiming at the technical problem of the existing X-ray imaging fluorescent screen, the invention provides a high-transparency microcrystalline glass scintillator and a preparation method and application thereofOf Ba2LaF7:Tb3+The microcrystalline glass scintillator material has strong luminous intensity, and the transmittance in a visible light band (380-760 nm) is more than 89%.
A high-transparency microcrystal glass scintillator with Ba as chemical formula2LaF7:Tb3+The transmittance of the high-transparency glass-ceramic scintillator in a visible light band, namely a 380-760 nm band, is not lower than 89%.
A preparation method of a high-transparency microcrystalline glass scintillator comprises the following specific steps:
(1) mixing high-purity Na2CO3、SiO2、Al2O3、BaF2、LaF3And TbF3Grinding to obtain mixed powder;
(2) melting the mixed powder in the step (1) in an air atmosphere at 1400-1500 ℃ for 30-60 min, pouring the melted mixed powder onto a preheating lining plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain Ba2LaF7:Tb3+High transparent microcrystalline glass scintillator.
The step (1) Na2CO3、SiO2And Al2O3Being a glass matrix, BaF2、LaF3And TbF3Is a microcrystalline material.
In terms of mole fraction, Na in the mixed powder in the step (1)2 CO 310~15%、SiO 240~50%、Al2O310~20%、BaF218~23%、LaF34 to 7% and TbF31~3%。
The temperature of the high-temperature stress relief treatment in the step (3) is 400-450 ℃, and the stress relief time is 5-10 h.
The temperature of the high-temperature heat treatment in the step (3) is 500-700 ℃, and the heat treatment time is 2-5 h.
The high-transparency microcrystalline glass scintillator is used for preparing a fluorescent screen for X-ray imaging.
The basic principle of the X-ray imaging of the high-transparency glass-ceramic scintillator comprises the following steps: since different objects have different attenuation to X-rays due to differences in density, thickness, and the like, images composed of dots of different brightness can be formed on the screen. If the projection thickness is constant, the dark place on the screen shows that the density of the corresponding object is high, the X-ray absorption is high, the bright place shows that the density is low, and the X-ray absorption is low. The inspector can judge the attributes of the article by observing the shape of each object on the fluorescent screen in combination with the density of different substances.
The invention has the beneficial effects that:
(1) inventive Ba2LaF7:Tb3+The high-transparency microcrystalline glass scintillator has the characteristics of high brightness, high stability and high transparency, has excellent luminous performance under the excitation of X rays (the tube voltage is 50KV, the tube current is 100 muA), and has the transmittance of a visible light wave band (380-760 nm) of 89 percent, so that clear images can be formed under the X rays, and an X-ray imaging fluorescent screen can be prepared;
(2) microcrystalline scintillator Ba of the invention2LaF7:Tb3+The scintillator material is protected by an inert aluminosilicate glass matrix, so that the scintillator material has good chemical stability and high mechanical property, and is not easy to damage in the practical application process; ba2LaF7:Tb3 +The main peak of an X-ray fluorescence spectrum of the microcrystalline glass scintillator material is 545nm, and is close to the most sensitive waveband 545-555 nm of human eyes, so that the fluorescence of the scintillator material has high human eye recognition;
(3) ba2LaF7 Tb in the invention3+The microcrystalline glass scintillator material can be used for fluorescent screens of X-ray imaging, radiation irradiation monitoring, safety inspection, X-ray astronomy, petroleum detection and other fields.
Drawings
FIG. 1 is a differential thermal spectrum of a microcrystalline glass scintillator of example 1;
FIG. 2 shows different Tb's of example 13+Microcrystalline glass scintillator and precursor Ba with doping concentration2LaF7:Tb3+XRD pattern of quantum dot glass;
FIG. 3 shows different Tb's of example 13+Photoluminescence spectrum and Tb of doped concentration microcrystalline glass scintillator3+Excitation spectrum of a microcrystalline glass scintillator with doping concentration of 2.5 mol%;
FIG. 4 shows Ba in example 12LaF7:Tb3+Different peak intensities of photoluminescence with Tb3+A profile of doping concentration;
FIG. 5 shows Tb as example 13+Transmission spectrum of microcrystalline glass scintillator with doping concentration of 2.5 mol%;
FIG. 6 shows Tb as example 13+An emission spectrum of a microcrystalline glass scintillator with a doping concentration of 2.5 mol% under X-ray excitation;
FIG. 7 shows Tb as an example 13+An X-ray fluorescence imaging object picture (insect) with a microcrystalline glass scintillator with the doping concentration of 2.5mol percent as a fluorescent screen.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a high-transparency microcrystal glass scintillator with Ba as chemical formula2LaF7:Tb3+
A preparation method of a high-transparency microcrystalline glass scintillator comprises the following specific steps:
(1) mixing high-purity Na2CO3、SiO2、Al2O3、BaF2、LaF3And TbF3Grinding to obtain mixed powder; wherein Na2CO3、SiO2And Al2O3Being a glass matrix, BaF2、LaF3And TbF3The microcrystalline material is obtained, and the mole fraction of the raw materials in the mixed powder is shown in table 1;
(2) melting the mixed powder in the step (1) at 1450 ℃ in an air atmosphere for 45min, pouring the molten mixed powder onto a preheating lining plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain Ba2LaF7:Tb3+A high transparent microcrystalline glass scintillator; wherein the temperature of the high-temperature stress relief treatment is 450 ℃, the stress relief time is 8h, the temperature of the high-temperature heat treatment is 640 ℃, and the heat treatment time is 2 h;
TABLE 1 molar fraction of raw materials in the powder mixture
Sample (I) Na2CO3 SiO2 Al2O3 BaF2 LaF3 TbF3
1 12% 45% 15% 21% 6.0% 1.0%
2 12% 45% 15% 21% 5.5% 1.5%
3 12% 45% 15% 21% 5.0% 2.0%
4 12% 45% 15% 21% 4.5% 2.5%
5 12% 45% 15% 21% 4.0% 3.0%
Tb3+Ba with a molar doping concentration of 2.5%2LaF7:Tb3+The differential thermal spectrum of the highly transparent microcrystalline glass scintillator (sample 4) is shown in FIG. 1, and Tb is shown in FIG. 13+Ba with a molar doping concentration of 2.5%2LaF7:Tb3+Transition temperature T of high-transparency microcrystalline glass scintillatorgAt 574 ℃ and a crystallization absorption peak Tc1630 ℃ indicates that the stress removal temperature cannot be higher than 574 ℃, and about 630 ℃ is selected as the annealing temperature, which is more suitable;
different Tb3+Microcrystalline glass scintillator and precursor Ba with doping concentration2LaF7:Tb3+The XRD pattern of the quantum dot glass is shown in FIG. 2, and Ba is shown in FIG. 22LaF7Self-crystallization phenomenon exists, and a relatively obvious diffraction peak exists in precursor glass; after annealing, the diffraction peak is obviously enhanced, which shows that the crystallinity of the annealed material is obviously enhanced; and standard card Ba2LaF7After JCPDS NO.48-0099 comparison, all the above samples are cubic phase Ba2LaF7A crystal; in addition, when the XRD pattern is observed, diffraction peaks are compared with a standard card, and the peak positions are slightly shifted to the left, which shows that Tb3+Is doped into Ba2LaF7Crystalline, slight lattice shrinkage occurs;
different Tb3+Photoluminescence spectrum and Tb of doped concentration microcrystalline glass scintillator3+The excitation spectrum of the microcrystalline glass scintillator having a doping concentration of 2.5 mol% is shown in FIG. 3, and it can be seen from FIG. 3 that Tb is associated with Tb3+The increase of the doping concentration gradually increases the light emission under the excitation of 369nm until the light emission intensity reaches the strongest when the doping concentration is 2.5 mol%, and then gradually decreases;
Ba2LaF7:Tb3+different peak intensities of photoluminescence with Tb3+The variation curve of the doping concentration is shown in fig. 4, and it can be seen from fig. 4 that the growth trend of the main peak 545nm of the photoluminescence spectrum is most obvious, so that the sample shows a bright green color at the optimal concentration for easy identification;
Tb3+the transmission spectrum of the microcrystalline glass scintillator with the doping concentration of 2.5 mol% is shown in fig. 5, and as can be seen from fig. 5, the transmittance in the visible light range (380 nm-760 nm) exceeds 89%, and the microcrystalline glass scintillator has high transparency;
Tb3+an emission spectrum of the microcrystalline glass scintillator with the doping concentration of 2.5 mol% under X-ray is shown in FIG. 6, as can be seen from FIG. 6, a main peak of the emission spectrum is at 545nm, and compared with other luminescence peaks, the intensity at 545nm is dominant, and the 545nm light is close to 545-555 nm of a color (yellow green) wave band which is most sensitive to human eyes, so that the fluorescence of the scintillator material has high human eye recognition;
with Tb3+An X-ray fluorescence imaging object picture (insect) with the microcrystalline glass scintillator with the doping concentration of 2.5 mol% as a fluorescent screen is shown in figure 7, and clear outlines, skeletons and other structures in the insect can be seen from the figure 7, which shows that the microcrystalline glass scintillator is in the field of X-ray fluorescence imaging.
Example 2: a high-transparency microcrystal glass scintillator with Ba as chemical formula2LaF7:Tb3+
A preparation method of a high-transparency microcrystalline glass scintillator comprises the following specific steps:
(1) mixing high-purity Na2CO3、SiO2、Al2O3、BaF2、LaF3And TbF3Grinding to obtain mixed powder; wherein Na2CO3、SiO2And Al2O3Being a glass matrix, BaF2、LaF3And TbF3The microcrystalline material is obtained, and the mole fraction of the raw materials in the mixed powder is shown in Table 2;
(2) melting the mixed powder in the step (1) in an air atmosphere at 1400 ℃ for 60min, pouring the melted mixed powder onto a preheating lining plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain Ba2LaF7:Tb3+A high transparent microcrystalline glass scintillator; wherein the high-temperature stress relief treatment temperature is 400 ℃, the stress relief time is 10h, the high-temperature heat treatment temperature is 700 ℃, and the heat treatment time is 2 h;
TABLE 2 molar fractions of the starting materials in the powder mixture
Sample (I) Na2CO3 SiO2 Al2O3 BaF2 LaF3 TbF3
1 10% 50% 15% 18% 6.0% 1.0%
2 10% 50% 15% 18% 5.5% 1.5%
3 10% 50% 15% 18% 5.0% 2.0%
4 10% 50% 15% 18% 4.5% 2.5%
5 10% 50% 15% 18% 4.0% 3.0%
Tb3+The transmission spectrum of the microcrystalline glass scintillator with the doping concentration of 2.5 mol% shows that the transmittance in the visible light range (380 nm-760 nm) exceeds 90%, and the microcrystalline glass scintillator has high transparency.
Example 3: a high-transparency microcrystal glass scintillator with Ba as chemical formula2LaF7:Tb3+
A preparation method of a high-transparency microcrystalline glass scintillator comprises the following specific steps:
(1) mixing high-purity Na2CO3、SiO2、Al2O3、BaF2、LaF3And TbF3Grinding to obtain mixed powder; wherein Na2CO3、SiO2And Al2O3Being a glass matrix, BaF2、LaF3And TbF3The microcrystalline material is obtained, and the mole fraction of the raw materials in the mixed powder is shown in Table 3;
(2) melting the mixed powder in the step (1) in an air atmosphere at 1500 ℃ for 35min, pouring the melted mixed powder onto a preheating lining plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain Ba2LaF7:Tb3+High transparencyA bright microcrystalline glass scintillator; wherein the high-temperature stress relief treatment temperature is 420 ℃, the stress relief time is 8h, the high-temperature heat treatment temperature is 500 ℃, and the heat treatment time is 5 h;
TABLE 3 molar fractions of the starting materials in the powder mixture
Sample (I) Na2CO3 SiO2 Al2O3 BaF2 LaF3 TbF3
1 15% 43% 12% 23% 6.0% 1.0%
2 15% 43% 12% 23% 5.5% 1.5%
3 15% 43% 12% 23% 5.0% 2.0%
4 15% 43% 12% 23% 4.5% 2.5%
5 15% 43% 12% 23% 4.0% 3.0%
Tb3+The transmission spectrum of the microcrystalline glass scintillator with the doping concentration of 2.5 mol% shows that the transmittance in the visible light range (380 nm-760 nm) exceeds 91%, and the microcrystalline glass scintillator has high transparency.

Claims (7)

1. A high-transparency microcrystalline glass scintillator is characterized in that the chemical formula of the microcrystalline scintillator is Ba2LaF7:Tb3+The transmittance of the high-transparency glass-ceramic scintillator in a visible light band, namely a 380-760 nm band, is not lower than 89%.
2. A preparation method of a high-transparency microcrystalline glass scintillator is characterized by comprising the following specific steps:
(1) mixing high-purity Na2CO3、SiO2、Al2O3、BaF2、LaF3And TbF3Grinding to obtain mixed powder;
(2) melting the mixed powder in the step (1) in an air atmosphere at 1400-1500 ℃ for 30-60 min, pouring the melted mixed powder onto a preheating lining plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain Ba2LaF7:Tb3+High transparent microcrystalline glass scintillator.
3. The method for preparing a high-transparency glass-ceramic scintillator according to claim 2, characterized in that: step (1) Na2CO3、SiO2And Al2O3Being a glass matrix, BaF2、LaF3And TbF3Is a microcrystalline material.
4. The method for producing a highly transparent microcrystalline glass scintillator according to claim 2 or 3, wherein: in terms of mole fraction, Na in the mixed powder in the step (1)2CO310~15%、SiO240~50%、Al2O310~20%、BaF218~23%、LaF34 to 7% and TbF31~3%。
5. The method for preparing a high-transparency glass-ceramic scintillator according to claim 2, characterized in that: the temperature of the high-temperature stress relief treatment in the step (3) is 400-450 ℃, and the stress relief time is 5-10 h.
6. The method for producing a highly transparent microcrystalline glass scintillator according to claim 2 or 5, wherein: the temperature of the high-temperature heat treatment in the step (3) is 500-700 ℃, and the heat treatment time is 2-5 h.
7. The high-transparency microcrystalline glass scintillator of claim 1 used for producing a phosphor screen for X-ray imaging.
CN202010729404.XA 2020-07-27 2020-07-27 High-transparency microcrystalline glass scintillator and preparation method and application thereof Pending CN111825332A (en)

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Application publication date: 20201027