Tb < 3 + >-doped high-density all-oxide germanate scintillation glass and preparation method thereof

Abstract

The invention discloses high-density Tb < 3 + >-doped all-oxide germanate scintillation glass and a preparation method thereof. The scintillation glass comprises matrix glass and a light-emitting center. The components of the matrix glass are all oxides, the specific components are GeO2-Al2O3-BaO-La2O3-Lu2O3-Gd2O3, and the luminescent center is Tb < 3 + > doped with the matrix glass. The required raw materials do not involve Pb, Cd and other high-pollution heavy metals, and are environment-friendly; and substances with high phonon energy, such as B2O3 and P2O5, are not contained, so that the luminous efficiency of Tb < 3 + > is favorably improved. The all-oxide scintillation glass provided by the invention is prepared by a melting quenching method, and has the characteristics of environmental friendliness and high density.

Description

Technical Field

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

[0002] Scintillator is a photofunctional material that can absorb high-energy particles or rays and emit visible light. It has a wide range of applications in high-energy physics, space exploration, medical imaging, security inspection and other fields. With the improvement of science and technology, there are new requirements for the performance of scintillating materials. Some traditional scintillating materials (such as NaI:Tl, CsI:Tl, BGO, etc.) cannot meet the needs of some special application scenarios due to their high preparation cost, complex process, limited size and other disadvantages. Therefore, in recent years, domestic and foreign academic circles have made many reports on new scintillating materials. Among them, the research and development of scintillating glass is one of the hot spots. This is mainly because the preparation cost of glass is low, and this advantage is very obvious for the preparation of large scintillators such as calorimeters with a volume of cubic meters. In addition, scintillating glass has the advantages of continuously adjustable components, good optical uniformity, no size restrictions and simple process, and is expected to replace commercial scintillating crystals in some application scenarios.

[0003] The invention patent with the publication number CN102775063A and the name of "Lead-containing oxyfluoride scintillating glass and its preparation method" discloses a method of introducing lead into the matrix glass to form a fluoride-containing scintillation glass with Tb 3+ As a scintillation glass of luminescence center. This proves that Tb 3+ The feasibility of scintillating glass as a luminescent center, but the lead it contains ensures that its density is higher than 6.0g / cm 3 But it also means that the practical application of this scintillating glass will be strictly limited. For example, the patent publication number is CN104743885A, and the patent name is "A rare earth doped fluorine oxygermanate glass-ceramic and its preparation method", which discloses a fluorine oxygermanate scintillating 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, fluoride is introduced, which reduces the mechanical properties and physicochemical stability of the matrix glass, which in turn limits its application. In addition, high density can improve the radiation resistance of the glass and avoid defects caused by high-energy ray irradiation. At the same time, it increases the glass's absorption of high-energy particles / rays, increases the light yield of the scintillating glass, and is beneficial to improving the signal-to-noise ratio of radiation detection. Tb 3+ The high doping concentration in the glass can provide strong luminescence and good scintillation performance. Summary of the invention

[0004] In order to solve the above technical problems existing in the prior art, the purpose of the present invention is to provide a rare earth doped full oxide high density germanate scintillating glass with simple preparation process, high density, high physical and chemical stability, and strong scintillating light output. The specific technical scheme is as follows:

[0005] A Tb 3+ Doped high-density all-oxide germanate scintillating glass, the matrix molar percentage composition of the germanate scintillating glass is: GeO2: 40-60mol%, Al2O3: 0-20mol%, BaO: 0-20mol%, La2O3: 5-20mol%, Lu2O3: 10-25mol%, Gd2O3: 5-20mol%, the sum of the above components is 100mol%; external doping Tb2O3: 0.5-10mol%.

[0006] Furthermore, the molar percentage components of the germanate scintillating glass are: GeO2: 45~55mol%, Al2O3: 3~10mol%, BaO: 3~15mol%, La2O3: 5~15mol%, Lu2O3: 10~20mol%, Gd2O3: 5~15mol%, the sum of the above components is 100mol%; external doping Tb2O3: 0.5~10mol%.

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

[0008] 1) Ingredients: accurately weigh the raw materials according to the above glass components and mix the weighed raw materials thoroughly and evenly, wherein BaO can be introduced through raw materials such as barium oxide and / or barium carbonate, Tb2O3 is introduced through Tb4O7 raw materials, and the remaining components are directly introduced as raw materials;

[0009] 2) Melting: Place the uniformly mixed raw materials in a crucible and place them in a high-temperature resistance furnace for melting at a temperature of 1500-1600°C for 30-60 minutes;

[0010] 3) Casting: Take the molten glass out of the resistance furnace and pour it into a mold preheated at 400-500°C;

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

[0012] 5) Regularization: Cut, grind, and polish the annealed glass to complete sample preparation.

[0013] The high-density germanate scintillating glass using oxide as raw material has high mechanical strength, low phonon energy, and also maintains high transmittance and physical and chemical stability; the introduction of Tb 3+ High-density all-oxide germanate scintillating glass, which serves as the luminescent center, is a potential scintillating material that can be used in the field of radiation detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 These are the X-ray excited luminescence spectra of the glasses with different rare earth ion doping concentrations in Examples 5 to 7. DETAILED DESCRIPTION

[0015] The present invention will be further described below in conjunction with the accompanying drawings.

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

[0017]

[0018] Table 1: Glass components of five specific examples (molar percentage, doped with Tb2O3)

[0019] Example 1

[0020] According to the composition: 52GeO2–10Al2O3–3BaO–10La2O3–15Lu2O3–10Gd2O3–0.5Tb2O3 (mol%), the required raw materials were weighed separately, the total mass of the raw materials was 15g, and they were put into an agate mortar and mixed and ground evenly. The mixed glass raw materials were poured into a crucible, placed in a high-temperature resistance furnace at 1550°C for 30 minutes, and then the molten glass was quickly poured into a mold preheated at 400°C. After the glass was formed, it was placed in a muffle furnace at 500°C for annealing for 3 hours, and then cooled to room temperature with the furnace. The obtained glass was cut, ground, polished and other processes 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%), the required raw materials were weighed separately, the total mass of the raw materials was 15g, and they were put into an agate mortar and mixed and ground evenly. The mixed glass raw materials were poured into a crucible, placed in a high-temperature resistance furnace at 1500°C for 45 minutes, and then the molten glass was quickly poured into a mold preheated at 450°C. After the glass was formed, it was placed in a muffle furnace at 600°C for annealing for 5 hours, and then cooled to room temperature with the furnace. The obtained glass was cut, ground, polished and other processes to complete the preparation of the scintillation glass sample.

[0023] Example 3

[0024] According to the composition: 52GeO2–9Al2O3–3BaO–15La2O3–15Lu2O3–6Gd2O3–0.5Tb2O3 (mol%), the required raw materials were weighed separately, the total mass of the raw materials was 15g, and they were put into an agate mortar and mixed and ground evenly. The mixed glass raw materials were poured into a crucible, placed in a high-temperature resistance furnace at 1600°C for 60 minutes, and then the glass melt was quickly poured into a mold preheated at 400°C. After the glass was formed, it was placed in a muffle furnace at 400°C for annealing for 5 hours, and then cooled to room temperature with the furnace. The obtained glass was cut, ground, polished and other processes to complete the preparation of the scintillation glass sample.

[0025] Example 4

[0026] According to the composition: 54GeO2–8Al2O3–3BaO–13La2O3–15Lu2O3–7Gd2O3–0.5Tb2O3 (mol%), the required raw materials were weighed separately, the total mass of the raw materials was 15g, and they were put into an agate mortar and mixed and ground evenly. The mixed glass raw materials were poured into a crucible, placed in a high-temperature resistance furnace at 1570°C for 50 minutes, and then the molten glass was quickly poured into a mold preheated at 400°C. After the glass was formed, it was placed in a muffle furnace at 450°C for annealing for 6 hours, and then cooled to room temperature with the furnace. The obtained glass was cut, ground, polished and other processes were performed to complete the preparation of the scintillation glass sample.

[0027] Example 5

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

[0029] The density of the samples prepared above was measured using an electronic density meter based on the Archimedes drainage method. The measurement results are shown in Table 2.

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

[0031]

[0032] It can be found from Table 2 that the scintillating glass of the present invention has a higher density. 3+ To verify this conclusion, the matrix glass of Example 5 was used as the matrix and the Tb 3+ The glass components of Examples 6 and 7 are shown in Table 3.

[0033] Table 3: Glass composition of Example 6 and Example 7 (mol%)

[0034]

[0035] Example 6

[0036] According to the composition: 55GeO2–3Al2O3–7BaO–13La2O3–15Lu2O3–7Gd2O3–2.5Tb2O3 (mol%), the required raw materials were weighed separately, the total mass of the raw materials was 15g, and they were put into an agate mortar and mixed and ground evenly. The mixed glass raw materials were poured into a crucible, placed in a high-temperature resistance furnace at 1550°C for 30 minutes, and then the glass melt was quickly poured into a mold preheated at 400°C. After the glass was formed, it was placed in a muffle furnace at 500°C for annealing for 3 hours, and then cooled to room temperature with the furnace. The obtained glass was cut, ground, polished and other processes 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%), the required raw materials were weighed separately, the total mass of the raw materials was 15g, and they were put into an agate mortar and mixed and ground evenly. The mixed glass raw materials were poured into a crucible, placed in a high-temperature resistance furnace at 1550°C for 30 minutes, and then the molten glass was quickly poured into a mold preheated at 400°C. After the glass was formed, it was placed in a muffle furnace at 500°C for annealing for 3 hours, and then cooled to room temperature with the furnace. The obtained glass was cut, ground, polished and other processes to complete the preparation of the scintillation glass sample.

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

[0040] Table 4: Density of Examples 6 to 7

[0041]

[0042] According to the density test results of Examples 5 to 7, it can be found that as Tb 3+ The increase in doping concentration also significantly increases the density, which means that the Tb 3+ The high density germanate scintillating glass with a doping concentration has great potential in improving the density. In addition, the scintillating glass described in Examples 5 to 7 is excited by X-rays, and the X-ray excited luminescence spectrum obtained is as follows: Figure 1 shown.

[0043] The above-described embodiments are only used for illustration of the present application and are not intended to limit the present application in any form. Any modifications and changes made to the present invention within the spirit of the present invention and the protection scope of the claims shall fall within the protection scope of the present invention.

Claims

1. A Tb 3+ Doped high-density all-oxide germanate scintillating glass, characterized in that: The matrix molar percentage composition of the germanate scintillating glass is: GeO2: 40-60mol%, Al2O3: 0-20mol%, BaO: 0-20mol%, La2O3: 5-20mol%, Lu2O3: 10-25mol%, Gd2O3: 5-20mol%, the sum of the above components is 100mol%; external doping Tb2O3: 0.5-10mol%.

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

3. Tb according to claim 1 or 2 3+ The preparation method of doped high-density full-oxide germanate scintillating glass is characterized in that The steps include: 1) Ingredients: accurately weigh the raw materials according to the above glass components and mix the weighed raw materials thoroughly and evenly, wherein BaO can be introduced through raw materials such as barium oxide and / or barium carbonate, Tb2O3 is introduced through Tb4O7 raw materials, and the remaining components are directly introduced as raw materials; 2) Melting: Place the uniformly mixed raw materials in a crucible and place them in a high-temperature resistance furnace for melting at a temperature of 1500-1600°C for 30-60 minutes; 3) Casting: Take the molten glass out of the resistance furnace and pour it into a mold preheated at 400-500°C; 4) Annealing: The solidified glass product is placed in a muffle furnace at 400-600°C for annealing to eliminate stress for 3-6 hours, and then the temperature is lowered to room temperature and taken out; 5) Regularization: Cut, grind, and polish the annealed glass to complete sample preparation.

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