A Tb 3+ Doped high density all-oxide germanate scintillator glasses and methods of making same

Abstract

The application discloses a high-density Tb 3+ The application discloses a doped full-oxide germanate scintillation glass and a preparation method thereof. The scintillation glass comprises a matrix glass and a luminescent center. The matrix glass is composed of oxides, and specific components are GeO2-Al2O3-BaO-La2O3-Lu2O3-Gd2O3; and the luminescent center is a Tb 3+ The application does not involve Pb, Cd and other high-pollution heavy metals, is environment-friendly, does not contain B2O3, P2O5 and other substances with high phonon energy, and is beneficial to improving the luminescent efficiency of Tb 3+ The full-oxide scintillation glass is prepared by a melting quenching method, and has the characteristics of environment-friendliness and high density.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of scintillator materials, in particular, the present application relates to a Tb 3+ Doped high-density all-oxide germanate scintillation glass and preparation method thereof. BACKGROUND

[0002] Scintillator is a kind of light functional material that can absorb high-energy particles or rays and emit visible light, which has a wide range of applications in high-energy physics, space exploration, medical imaging, security inspection and other fields. With the improvement of technology, there are new demands for the performance of scintillator materials. Some traditional scintillators (such as NaI: Tl, CsI: Tl, BGO, etc.) cannot meet the needs of some special application scenarios due to high preparation cost, complex process, size limitation and other shortcomings. Therefore, in recent years, the academic circles at home and abroad have reported many new types of scintillator materials. Among them, the research and development of scintillation glass is one of the hotspots. This is mainly because the preparation cost of glass is low, which is very obvious for the preparation of large-scale scintillators such as volume energy meter with cubic meter level. In addition, scintillation glass has the advantages of continuous adjustable composition, good optical uniformity, no size limitation and simple process, which is expected to replace commercial scintillation crystals in some application scenarios.

[0003] The patent with publication number CN102775063A and the title of "Lead-containing oxyfluoride scintillation glass and its preparation method" discloses a kind of lead is introduced into matrix glass, with Tb 3+ As the luminescent center of scintillation glass. This proves the feasibility of scintillation glass with Tb 3+ As the luminescent center, but the lead contained in it ensures that its density is higher than 6.0 g / cm 3 However, it also means that the practical application of this scintillation glass will be strictly limited. For example, the patent with publication number CN104743885A and the title of "Rare earth doped oxyfluoride germanate glass and its preparation method" discloses an oxyfluoride germanate scintillation glass. The germanate glass itself has the advantages of good mechanical properties, high physicochemical stability and low phonon energy. In order to further reduce the phonon energy of the matrix glass, fluorine is introduced, which reduces the mechanical properties and physicochemical stability of the matrix glass, thereby limiting its application. In addition, high density can improve the radiation resistance of glass, avoid defects caused by high-energy radiation, increase the absorption of high-energy particles / rays by glass, improve the light yield of scintillation glass, and improve the signal-to-noise ratio of radiation detection. Tb 3+ In the glass, the doping concentration is high, the luminescence intensity is high, and good scintillation performance can be obtained. SUMMARY

[0004] In order to solve the above technical problems existing in the prior art, the present application aims to provide a rare earth doped full oxide germanate scintillation glass with high density, high physical and chemical stability and strong scintillation light output, which has a simple preparation process.

[0005] A Tb 3+ The high-density full oxide germanate scintillation glass comprises the following components in terms of molar percentage: GeO2: 40-60 mol%, Al2O3: 0-20 mol%, BaO: 0-20 mol%, La2O3: 5-20 mol%, Lu2O3: 10-25 mol%, Gd2O3: 5-20 mol%, and the sum of the above components is 100 mol%; and the high-density full oxide germanate scintillation glass is externally doped with Tb2O3: 0.5-10 mol%.

[0006] Further, the high-density full oxide germanate scintillation glass comprises the following components in terms of molar percentage: GeO2: 45-55 mol%, Al2O3: 3-10 mol%, BaO: 3-15 mol%, La2O3: 5-15 mol%, Lu2O3: 10-20 mol%, Gd2O3: 5-15 mol%, and the sum of the above components is 100 mol%; and the high-density full oxide germanate scintillation glass is externally doped with Tb2O3: 0.5-10 mol%.

[0007] A Tb 3+ The preparation method of the high-density full oxide germanate scintillation glass comprises the following steps:

[0008] 1) batching: the raw materials are accurately weighed according to the above glass components and are fully mixed, wherein BaO can be introduced by barium oxide or / and barium carbonate, Tb2O3 is introduced by Tb4O7, and the remaining components are directly introduced as raw materials;

[0009] 2) melting: the mixed raw materials are placed in a crucible and are melted in a high-temperature resistance furnace at a temperature of 1500-1600 DEG C for 30-60 minutes;

[0010] 3) pouring: the molten glass liquid is taken out of the resistance furnace and is poured into a preheated mold at 400-500 DEG C;

[0011] 4) annealing: the solidified glass product is placed in a muffle furnace at 400-600 DEG C for 3-6 hours to eliminate stress, and then is cooled to room temperature with the furnace and is taken out;

[0012] 5) sizing: the glass after annealing is cut, polished and polished to complete the preparation of the sample.

[0013] The high-density germanate scintillation glass taking oxide as raw material has high mechanical strength, low phonon energy, and meanwhile maintains high transmittance and physical and chemical stability; the Tb 3+ The high-density all-oxide germanate scintillation glass taking oxide as raw material has high mechanical strength, low phonon energy, and meanwhile maintains high transmittance and physical and chemical stability; the Tb BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 The X-ray excitation luminescence spectrum of the glass with different rare earth ion doping concentrations in Examples 5-7. DETAILED DESCRIPTION

[0015] The application will be further described below in combination with the drawings.

[0016] The Tb 3+ The glass components of the five specific embodiments of the high-density all-oxide germanate scintillation glass are shown in Table 1:

[0017]

[0018] Table 1: Glass components of the five specific embodiments (mole percent, doping with Tb2O3)

[0019] Example 1

[0020] According to the composition: 52GeO2-10Al2O3-3BaO-10La2O3-15Lu2O3-10Gd2O3-0.5Tb2O3(mol%), the required raw materials are weighed, the total mass of the raw materials is 15g, and the raw materials are put into an agate mortar for mixing and grinding. The mixed glass raw materials are poured into a crucible and placed in a high-temperature resistance furnace at 1550℃ for 30 minutes. Then the glass melt is quickly poured into a preheated 400℃ mold, and after the glass is formed, it is placed in a 500℃ muffle furnace for annealing for 3 hours, and then the furnace is cooled to room temperature. The obtained glass is cut, polished and polished to complete the preparation of the scintillation glass sample.

[0021] Example 2

[0022] According to the composition: 52GeO2-8Al2O3-3BaO-17La2O3-15Lu2O3-5Gd2O3-0.5Tb2O3(mol%) respectively take the required raw materials, the total mass of the raw materials is 15g, put into the agate mortar and mix well. The mixed glass raw materials are poured into a crucible, placed in a high temperature resistance furnace at 1500℃ for 45 minutes, then the glass melt is quickly poured into a preheated 450℃ mold, after the glass is formed, it is placed in a 600℃ muffle furnace for annealing for 5 hours, then the furnace is cooled to room temperature, the obtained glass is cut, polished and polished, etc. Process, complete the preparation of scintillation glass sample.

[0023] Example 3

[0024] According to the composition: 52GeO2-9Al2O3-3BaO-15La2O3-15Lu2O3-6Gd2O3-0.5Tb2O3(mol%) respectively take the required raw materials, the total mass of the raw materials is 15g, put into the agate mortar and mix well. The mixed glass raw materials are poured into a crucible, placed in a high temperature resistance furnace at 1600℃ for 60 minutes, then the glass melt is quickly poured into a preheated 400℃ mold, after the glass is formed, it is placed in a 400℃ muffle furnace for annealing for 5 hours, then the furnace is cooled to room temperature, the obtained glass is cut, polished and polished, etc. Process, complete the preparation of scintillation glass sample.

[0025] Example 4

[0026] According to the composition: 54GeO2-8Al2O3-3BaO-13La2O3-15Lu2O3-7Gd2O3-0.5Tb2O3(mol%) respectively take the required raw materials, the total mass of the raw materials is 15g, put into the agate mortar and mix well. The mixed glass raw materials are poured into a crucible, placed in a high temperature resistance furnace at 1570℃ for 50 minutes, then the glass melt is quickly poured into a preheated 400℃ mold, after the glass is formed, it is placed in a 450℃ muffle furnace for annealing for 6 hours, then the furnace is cooled to room temperature, the obtained glass is cut, polished and polished, etc. Process, complete the preparation of scintillation glass sample.

[0027] Example 5

[0028] The required raw materials are weighed according to the composition: 55GeO2-3Al2O3-7BaO-13La2O3-15Lu2O3-7Gd2O3-0.5Tb2O3(mol%), the total mass of the raw materials is 15g, and the raw materials are put into an agate mortar for fully mixing and grinding. The mixed glass raw materials are poured into a crucible, placed in a high-temperature resistance furnace at 1520°C for 35 minutes, and then the glass melt is quickly poured into a preheated mold at 500°C. After the glass is formed, it is placed in a muffle furnace at 550°C for annealing for 3.5 hours, and then the furnace is cooled to room temperature. The obtained glass is cut, polished and polished to complete the preparation of the scintillation glass sample.

[0029] The density of the sample prepared above is measured by using an electronic densimeter based on the principle of Archimedes drainage method, and the measurement results are shown in Table 2.

[0030] Table 2: Density of Examples 1-5

[0031]

[0032] It can be found from Table 2 that the scintillation glass has a high density, and the density can be further increased by appropriately increasing the doping concentration of Tb 3+ . In order to verify this conclusion, the doping concentration of Tb 3+ is increased in Examples 6-7 using the matrix glass of Example 5 as the matrix. The glass components of Examples 6 and 7 are shown in Table 3.

[0033] Table 3: Glass components of Examples 6 and 7 (mol%)

[0034]

[0035] Example 6

[0036] The required raw materials are weighed according to the composition: 55GeO2-3Al2O3-7BaO-13La2O3-15Lu2O3-7Gd2O3-2.5Tb2O3(mol%), the total mass of the raw materials is 15g, and the raw materials are put into an agate mortar for fully mixing and grinding. The mixed glass raw materials are poured into a crucible, placed in a high-temperature resistance furnace at 1520°C for 35 minutes, and then the glass melt is quickly poured into a preheated mold at 500°C. After the glass is formed, it is placed in a muffle furnace at 550°C for annealing for 3.5 hours, and then the furnace is cooled to room temperature. The obtained glass is cut, polished and polished to complete the preparation of the scintillation glass sample.

[0037] Example 7

[0038] According to the composition: 55GeO2-3Al2O3-7BaO-13La2O3-15Lu2O3-7Gd2O3-4.5Tb2O3(mol%) respectively, the required raw materials are weighed, the total mass of the raw materials is 15g, and the raw materials are put into an agate mortar for mixing and grinding. The mixed glass raw materials are poured into a crucible and placed in a high-temperature resistance furnace at 1550°C for 30 minutes. Then the glass melt is quickly poured into a preheated 400°C mold, and after the glass is formed, it is placed in a 500°C muffle furnace for annealing for 3 hours, and then the furnace is cooled to room temperature. The obtained glass is cut, polished and polished to complete the preparation of the scintillation glass sample.

[0039] The density measurement results of examples 6 and 7 are shown in table 4.

[0040] Table 4: Density of examples 6-7

[0041]

[0042] According to the density test results of examples 5-7, it can be found that with the increase of Tb 3+ The increase of the doping concentration also has a considerable increase in the density, which means that the Tb 3+ doped germanate scintillation glass disclosed in the present application has great potential in improving the density. In addition, the X-ray excited luminescence spectrum of the scintillation glass of examples 5-7 excited by X-ray is shown in Figure 1 .

[0043] The above examples are only used for illustration, and do not limit the present application in any form. Any modification and change of the present application within the spirit and protection scope of the claims falls within the protection scope of the present application.

Claims

1. A Tb 3+ Doped high density all-oxide germanate scintillating glass characterized in that, The molar percentage components of the germanate scintillation glass are: GeO2: 45-55 mol%, Al2O3: 3-10 mol%, BaO: 3-15 mol%, La2O3: 5-15 mol%, Lu2O3: 10-20 mol%, Gd2O3: 5-15 mol%, and the sum of the above components is 100 mol%; and the external doping is Tb2O3: 0.5-10 mol%.

2. The Tb of claim 1 3+ The preparation method of the doped high-density all-oxide germanate scintillation glass is characterized by comprising the steps of The method comprises the following steps: 1) batching: accurately weighing the raw materials according to the glass components described above and fully mixing the weighed raw materials uniformly, wherein BaO can be introduced by barium oxide or / and barium carbonate and the like, Tb2O3 is introduced by Tb4O7, and the rest of the components are directly introduced as raw materials; 2) melting: placing the mixed raw materials in a crucible and putting them into a high-temperature resistance furnace for melting, with the temperature being 1500-1600 DEG C and the melting time being 30-60 minutes; 3) pouring: taking the molten glass liquid out of the resistance furnace and pouring it into a preheated 400-500 DEG C mold; 4) annealing: placing the solidified and shaped glass primary product into a 400-600 DEG C muffle furnace for annealing to eliminate stress, with the time being 3-6 hours, and then slowly cooling to room temperature in the furnace and taking it out; 5) sizing: cutting, polishing and polishing the annealed glass to complete the preparation of the sample.

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