CN115611514A - Ce 3+ Gallium-boron-gadolinium-doped scintillation glass and preparation method and application thereof - Google Patents
Ce 3+ Gallium-boron-gadolinium-doped scintillation glass and preparation method and application thereof Download PDFInfo
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- C03C—CHEMICAL 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
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Abstract
The invention discloses Ce 3+ The scintillation glass doped with gallium, boron and gadolinium and the preparation method and the application thereof comprise a main component, a reducing agent and externally doped Ce 3+ (ii) a The main component comprises B 2 O 3 、Gd 2 O 3 、GdF 3 And X, B 2 O 3 、Gd 2 O 3 、GdF 3 X is respectively B 2 O 3 (15‑45mol％)，Gd 2 O 3 (10‑45mol％)，GdF 3 (10-50 mol%), X (5-30 mol%); x is Ga 2 O 3 、SiO 2 、Al 2 O 3 、AlF 3 、BaO、BaF 2 One or more ofSeveral glass main components, the sum of which is 100mol%; the mol percentage of the reducing agent is 0.5-2mol%; doped with Ce 3+ The mol percentage is 0.5-4mol%. The invention greatly improves the density and the light yield of the scintillation glass and reduces the preparation cost of the high-density scintillation glass.
Description
Technical Field
The invention belongs to the field of scintillation luminescent materials, and relates to Ce 3+ Gallium-boron-gadolinium-doped scintillation glass and preparation method and application thereof, in particular to high-density Ce 3+ Gallium-boron-gadolinium doped scintillation glass and a preparation method and application thereof.
Background
The scintillating material is a material which generates fluorescence under the action of radioactive rays or atomic particles, and is widely applied to the fields of high-energy physics, nuclear physics, industrial nondestructive inspection, medical imaging, safety detection and the like.
The high-density scintillation glass can convert absorbed high-energy particles and rays into ultraviolet light or visible light, and then detect the high-energy particles and the rays. Compared with the traditional scintillation crystal, the high-density scintillation glass has high density and high light yield, is lower in cost, simpler in preparation process, short in preparation period, suitable for large-size production and fiber transformation, and is expected to replace the scintillation crystal with high cost in high-energy physical experimental equipment.
The high-density scintillation glass researched at present mainly comprises silicate glass, germanium bismuthate glass, germanate glass, phosphate glass and other glass, and most of the glass components with higher density comprise TeO 2 ，Bi 2 O 3 ，PbO，GeO 2 ，Lu 2 O 3 An oxide of heavy metal, with patent publication No. CN 107759079B, is prepared by adding Lu into glass 2 O 3 The raw material improves the glass density to 6g/cm 3 And the radiation resistance of the glass is enhanced; patent publication No. CN 114409252A, by incorporating high levels of GeO in a glass matrix 2 And Lu 2 O 3 The density of the glass can reach 6.046g/cm 3 (ii) a Patent publication No. CN 110451795B, by adding high content of TeO to glass matrix 2 、Lu 2 O 3 And WO 3 Can maximize the density of the glassThe height reaches 6.5g/cm 3 . But GeO 2 And Lu 2 O 3 The high price of raw materials can greatly increase the manufacturing cost of the scintillation glass, lu 2 O 3 A radiation background is also introduced to reduce the energy resolution of the scintillation glass; teO 2 、Bi 2 O 3 、WO 3 The raw materials with valence-variable characteristics are easy to cause glass coloring in the glass melting process and are not beneficial to Ce 3+ The light emission of (1); pbO is not only not friendly to human body and environment, but also easily causes glass coloring. The density of the existing scintillation glass with relatively high light yield is generally less than 5.0g/cm 3 Has reported high density of>6.0g/cm 3 ) Scintillation glass is commonly subject to low light yield. Therefore, the development of a scintillating glass with high density and high brightness (light yield) remains a hot spot and difficulty in the current scintillating glass field. Has been reported to increase Gd 2 O 3 The content is to increase the glass density, but is limited by the lower solubility of rare earth oxides in the glass and the higher glass melting temperature, and the glass density is increased only to a limited extent.
Disclosure of Invention
Aiming at the prior art, the technical problem to be solved by the invention is to provide high-density Ce 3+ Ga-B-Gd-doped scintillating glass, and preparation method and application thereof, by jointly using Gd 2 O 3 And GdF 3 The density of the scintillation glass is greatly improved, the preparation cost of the high-density scintillation glass is reduced, and the requirements of high-energy rays, high-energy particle detection, high-energy physical experiments and nuclear science experiments can be better met.
To solve the above technical problems, a Ce of the present invention 3+ The gallium-boron-gadolinium doped scintillation glass comprises a main component, a reducing agent and externally-doped Ce 3+ ；
The main component comprises B 2 O 3 、Gd 2 O 3 、GdF 3 And X, B 2 O 3 、Gd 2 O 3 、GdF 3 X is respectively B 2 O 3 (15-45mol％)，Gd 2 O 3 (10-45mol％)，GdF 3 (10-50mol％)，X(5-30mol%); x is Ga 2 O 3 、SiO 2 、Al 2 O 3 、AlF 3 、BaO、BaF 2 One or more of the glass main body components, wherein the sum of the glass main body components is 100mol%;
the mol percentage of the reducing agent is 0.5-2mol%;
the externally doped Ce 3+ The mole percentage of (B) is 0.5-4mol%.
Preferably, the reducing agent is Si 3 N 4 One or more of AlN and SiC.
Preferably, the doped Ce 3+ Introduced by CeF3 and/or CeO 2.
The invention also includes any of the above Ce 3+ The preparation method of the gallium, boron and gadolinium doped scintillation glass comprises the following steps:
a) Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing;
b) Pouring the uniformly mixed glass raw materials into a covered corundum crucible or a SiC crucible to be melted into a uniform glass melt;
c) And pouring the glass melt into a preheated mold, cooling and molding, and transferring to an annealing furnace for constant-temperature annealing treatment to eliminate internal stress to obtain the scintillation glass.
Preferably, in the step B), when a corundum crucible is adopted, the melting temperature is 1250-1550 ℃, the melting time is 20-50min, and the melting atmosphere is air atmosphere; when the SiC crucible is adopted, the melting temperature is 1250-1350 ℃, the melting time is 20-40min, and the melting atmosphere is air atmosphere.
Preferably, in step C), the preheating temperature of the mold is 400 to 600 ℃.
Preferably, in the step C), the annealing temperature is 400-600 ℃, and the annealing time is 3-8 hours.
Preferably, step C) further comprises, after the annealing: cooling, including cooling to 200 deg.C at a rate of 5-10 deg.C/min, and cooling to room temperature.
The invention also comprises a Ce 3+ Application of gallium-boron-gadolinium doped scintillation glass and Ce as described in any one of the above 3+ Doped with gallium, boron, gadoliniumScintillation glass or Ce prepared by adopting preparation method of any one of the above 3+ The gallium, boron and gadolinium doped scintillating glass is used for medical imaging, radiation detection, industrial nondestructive testing or an intense quantum energy device.
Compared with the prior art, the invention has the beneficial effects that:
the present invention does not use heavy metal element compounds such as W, pb, lu, te, ge, la, tl and the like, and only uses Gd in combination 2 O 3 And GdF 3 Greatly improve the glass density to be more than 6g/cm 3 The total content of rare earth element-containing compounds in the glass component can reach 65mol%, the mass fraction can reach 80%, the high light yield can be achieved under the excitation of X rays, the light-emitting integral intensity can reach 40% -100% of that of BGO scintillation crystal, and the total content of rare earth element-containing compounds in the glass component can reach 65mol%, the total content of rare earth element-containing compounds in the glass component can reach 80%, the total light yield can reach 40% -100% of that of BGO scintillation crystal under the excitation of X rays, and the total light yield can reach 40% -100% of that of BGO scintillation crystal under the excitation of X rays 137 The light yield under Cs gamma-ray excitation can be greater than 850ph/Mev.
In particular GdF 3 The Gd serving as the heavy metal fluoride not only has high density, but also can be used as a fluxing agent to reduce the melting temperature and viscosity of the glass, improve the openness of a glass network structure and the solubility of rare earth oxide in the glass, and is combined with Gd with lower price 2 O 3 And GdF 3 And the preparation cost of the high-density scintillation glass is also reduced. By adding high amounts of B 2 O 3 The preparation temperature of the scintillation glass is effectively reduced, so that the preparation cost and the preparation difficulty of the scintillation glass are reduced. Ga 2 O 3 The mechanical property of the boron-gadolinium glass is improved, the glass forming property of the high-content rare earth compound glass and the stability of the glass are effectively improved, and the density of the scintillation glass is further effectively improved. The scintillation glass does not contain PbO, and is more friendly to human body and environment; does not contain GeO 2 And Lu 2 O 3 The raw materials with high price are equal, the preparation cost is lower, and the radiation back bottom can not be introduced; does not contain TeO 2 、Bi 2 O 3 、WO 3 And the raw materials with variable valence characteristics can not cause glass coloring in the glass melting process. The use of the silicon carbide crucible improves the corrosion of molten glass liquid to the corundum crucible, more directly and effectively improves the density of glass, and does not need additional reductionThe introduction of the agent can obtain transparent colorless scintillation glass. Si 3 N 4 The introduction of reducing agent can effectively provide reducing atmosphere in the melting process of glass, and can ensure Ce 3+ Will not be oxidized and no extra instrument is needed to provide a reducing gas atmosphere. The invention is convenient for large-size preparation, can be prepared into large-size optical devices, and can be drawn into optical fibers. Ce prepared by the invention 3+ The high-density gallium, boron and gadolinium doped scintillation glass has good physical and chemical stability.
Drawings
FIG. 1 is a comparison of the X-ray excitation emission spectra of the scintillation glass of example 1 and a BGO crystal.
FIG. 2 is a comparison of the X-ray excitation emission spectra of the scintillation glass of example 2 and a BGO crystal.
FIG. 3 is a comparison of the X-ray excitation emission spectra of the scintillation glass of example 3 and a BGO crystal.
FIG. 4 is a comparison of the X-ray excitation emission spectra of the scintillation glass of example 4 and a BGO crystal.
FIG. 5 is a comparison of the X-ray excitation emission spectra of the scintillation glass of example 5 and a BGO crystal.
FIG. 6 is a comparison of the X-ray excitation emission spectra of the scintillation glass of example 6 and a BGO crystal.
FIG. 7 is a photograph of the morphology of the scintillating glass of example 1.
FIG. 8 is a photograph of the morphology of the scintillating glass of example 2.
FIG. 9 is a photograph of the morphology of the scintillating glass of example 3.
FIG. 10 is a photograph of the morphology of the scintillating glass of example 4.
FIG. 11 is a photograph of the morphology of the scintillating glass of example 5.
FIG. 12 is a photograph of the morphology of the scintillating glass of example 6.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The glass comprises the following components in percentage by mole: 15Ga 2 O 3 -25B 2 O 3 -30Gd 2 O 3 -30GdF 3 -2CeO 2 -2Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a corundum crucible which is covered, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1450 ℃, and the melting time is 40min;
3. and pouring the glass melt into a preheated mould at 550 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 550 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 2
The glass comprises the following components in percentage by mole: 15Ga 2 O 3 -25B 2 O 3 -20Gd 2 O 3 -40GdF 3 -2CeO 2 -0.5Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered SiC crucible, and melting the mixture into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 20min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and molding, then transferring the glass melt into an annealing furnace at 480 ℃ for constant-temperature annealing to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 10 ℃/min after annealing for 5 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 3
The glass comprises the following components in percentage by mole: 7.5SiO 2 -7.5Ga 2 O 3 -25B 2 O 3 -20Gd 2 O 3 -40GdF 3 -2CeF 3 -0.5Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered SiC crucible, and melting the mixture into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 20min;
3. and pouring the glass melt into a preheated mold at 400 ℃ for cooling and molding, then transferring the glass melt into an annealing furnace at 400 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 4
The glass comprises the following components in percentage by mole: 5SiO 2 -5Ga 2 O 3 -25B 2 O 3 -30Gd 2 O 3 -35GdF 3 -2CeF 3 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 5
The glass comprises the following components in percentage by mole: 10Ga 2 O 3 -10BaO-25B 2 O 3 -20Gd 2 O 3 -40GdF 3 -2CeF 3 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a corundum crucible which is covered, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 20min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 6
The glass comprises the following components in percentage by mole: 10SiO 2 2 -10BaF 2 -20B 2 O 3 -20Gd 2 O 3 -40GdF 3 -2CeO 2 -0.5Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered SiC crucible, and melting into a uniform glass melt in an air atmosphere, wherein the melting temperature is 1350 ℃, and the melting time is 20min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 600 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 7 ℃/min after annealing for 8 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 7
The glass comprises the following components in percentage by mole: 5SiO 2 -5Ga 2 O 3 -5BaF 2 -25B 2 O 3 -20Gd 2 O 3 -40GdF 3 -2CeF 3 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 20min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 8
The glass comprises the following components in percentage by mole: 5SiO 2 -5Al 2 O 3 -25B 2 O 3 -30Gd 2 O 3 -35GdF 3 -4CeO 2 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a corundum crucible which is covered, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1350 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 9
The glass comprises the following components in percentage by mole: 5SiO 2 -5AlF 3 -25B 2 O 3 -30Gd 2 O 3 -35GdF 3 -2CeF 3 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1350 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 10
The glass comprises the following components in percentage by mole: 5SiO 2 2 -5BaF 2 -25B 2 O 3 -30Gd 2 O 3 -35GdF 3 -2CeF 3 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1350 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 11
The glass comprises the following components in percentage by mole: 10SiO 2 2 -15Ga 2 O 3 -15B 2 O 3 -20Gd 2 O 3 -40GdF 3 -0.5CeF 3 -0.5Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1350 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 12
The glass comprises the following components in percentage by mole: 5Ga 2 O 3 -45B 2 O 3 -30Gd 2 O 3 -20GdF 3 -1CeF 3 -2SiC；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 13
The glass comprises the following components in percentage by mole: 10Ga 2 O 3 -30B 2 O 3 -10Gd 2 O 3 -50GdF 3 -4CeF 3 -2Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1250 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 14
The glass comprises the following components in percentage by mole: 5SiO 2 -10Ga 2 O 3 -35B 2 O 3 -45Gd 2 O 3 -10GdF 3 -2CeF 3 -1Si 3 N 4 ；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a covered corundum crucible, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1550 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and molding, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
Example 15
The glass comprises the following components in percentage by mole: 10SiO 2 2 -20Ga 2 O 3 -20B 2 O 3 -30Gd 2 O 3 -20GdF 3 -1CeF 3 -2AlN；
1. Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing to prepare a glass raw material;
2. pouring the uniformly mixed glass raw materials into a corundum crucible which is covered, and melting into a uniform glass melt in the air atmosphere, wherein the melting temperature is 1450 ℃, and the melting time is 30min;
3. and pouring the glass melt into a preheated mold at 450 ℃ for cooling and forming, then transferring the glass melt into an annealing furnace at 450 ℃ for annealing at constant temperature to eliminate internal stress, reducing the temperature to 200 ℃ at a cooling rate of 5 ℃/min after annealing for 3 hours, and then cooling the glass melt to room temperature along with the furnace to obtain the scintillation glass.
The density of all the scintillation glasses was obtained by archimedes' principle, using alcohol as immersion and using a precision balance test at night. The X-ray excited luminescence spectra (XEL) of all scintillation glasses were measured in reflection mode by a Zolix Omni- λ 300i spectrometer. The light yield of all scintillation glasses was 662Kev 137 Measured in Cs-source gamma-ray transmission mode. FIGS. 1-6 are X-ray excitation emission spectra of scintillating glasses prepared in examples 1-6 and BGO crystals, and FIGS. 7-12 are photographs of the scintillating glasses prepared in examples 1-6. Examples 1-6 compositions, densities and light yields of high density gallium boron gadolinium scintillating glasses are shown in table 1, ce prepared according to the invention 3+ The gallium-boron-gadolinium-doped scintillation glass has high density and high light yield, and simultaneously has the characteristic of low cost, so that the gallium-boron-gadolinium-doped scintillation glass is suitable for medical imaging, radiation detection, industrial nondestructive testing or a hadron energy meter.
TABLE 1
Claims (9)
1. Ce 3+ The gallium-boron-gadolinium doped scintillation glass is characterized in that: comprises a main component, a reducing agent and externally doped Ce 3+ ；
The main component comprises B 2 O 3 、Gd 2 O 3 、GdF 3 And X, B 2 O 3 、Gd 2 O 3 、GdF 3 X is respectively B 2 O 3 (15-45mol％)，Gd 2 O 3 (10-45mol％)，GdF 3 (10-50 mol%), X (5-30 mol%); x is Ga 2 O 3 、SiO 2 、Al 2 O 3 、AlF 3 、BaO、BaF 2 One or more of the glass main body components, wherein the sum of the glass main body components is 100mol%;
the mol percentage of the reducing agent is 0.5-2mol%;
the externally doped Ce 3+ The mole percentage of (B) is 0.5-4mol%.
2. Ce according to claim 1 3+ The gallium boron gadolinium doped scintillation glass is characterized in that: the reducing agent is Si 3 N 4 One or more of AlN and SiC.
3. Ce according to claim 1 3+ The gallium-boron-gadolinium doped scintillation glass is characterized in that: the externally doped Ce 3+ Introduced by CeF3 and/or CeO 2.
4. Ce according to any one of claims 1 to 3 3+ The preparation method of the gallium-boron-gadolinium doped scintillation glass is characterized by comprising the following steps: the method comprises the following steps:
a) Weighing the raw materials according to the glass composition, fully grinding and uniformly mixing;
b) Pouring the uniformly mixed glass raw materials into a covered corundum crucible or a SiC crucible to be melted into a uniform glass melt;
c) And pouring the glass melt into a preheated mold, cooling and molding, and transferring to an annealing furnace for constant-temperature annealing treatment to eliminate internal stress to obtain the scintillation glass.
5. The method of manufacturing according to claim 4, characterized in that: in the step B), when a corundum crucible is adopted, the melting temperature is 1250-1550 ℃, the melting time is 20-50min, and the melting atmosphere is air atmosphere; when the SiC crucible is adopted, the melting temperature is 1250-1350 ℃, the melting time is 20-40min, and the melting atmosphere is air atmosphere.
6. The method of claim 4, wherein: in the step C), the preheating temperature of the die is 400-600 ℃.
7. The method of claim 4, wherein: in the step C), the annealing temperature is 400-600 ℃, and the annealing time is 3-8 hours.
8. The method of claim 4, wherein: in step C), after the annealing, the method further includes: cooling, including cooling to 200 deg.C at a rate of 5-10 deg.C/min, and cooling to room temperature.
9. Ce 3+ The application of the gallium-boron-gadolinium doped scintillation glass is characterized in that: the Ce of any one of claims 1 to 3 3+ Gallium boron gadolinium doped scintillation glass or Ce prepared by the preparation method of any one of claims 4 to 8 3+ The gallium, boron and gadolinium doped scintillating glass is used for medical imaging, radiation detection, industrial nondestructive testing or an intense quantum energy device.
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