High gamma-ray detection efficiency and high light yield glass scintillators, methods of making and applications thereof

Abstract

The application relates to a kind of high neutron detection efficiency and high light yield glass scintillator and its preparation method and application, and belongs to the technical field of scintillator material.The scintillator includes main component and reducing agent.The components of main component and its mass percentage are as follows: SiO2 40-60%, Li2O 10-22%, Al2O3 4-10%, CeO2 4-12%, MgO 2-10%, XF n 0-25%, X is one or several of alkali metal, alkaline earth metal, boron group and rare earth, and XF n Is not equal to 0.The glass scintillator improves the scintillation performance of neutron detection glass scintillator by component regulation, the light yield is as high as 8000 ph / MeV, reaches the level of BGO commercial crystal, the energy resolution is less than 16%, the neutron gamma misjudgment rate is less than or equal to 14%, and the neutron detection efficiency is greater than or equal to 95%.The glass scintillator has good uniformity without micro-bubble in glass, and the product has high good product rate, good batch stability, and application prospect in the field of neutron detection.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of scintillator materials, and particularly relates to a glass scintillator with high neutron detection efficiency and high light yield and a preparation method and application thereof. BACKGROUND

[0002] Neutron detection technology has wide application value in many fields such as high-energy physics, atomic energy and medicine. The core of a neutron detector is a scintillator material. As a kind of luminescent material, a scintillator material can absorb high-energy rays such as gamma rays, x-rays and neutrons, and convert these energies into visible light photons. Traditional neutron detectors mostly use gas scintillators or crystal scintillators. These scintillators generally use isotopes with a large absorption cross section for neutrons as a sensitive component, such as 3 He, 6 Li, 10 B and 157 Gd, and in practical applications, 6 Li and 10 B isotopes are mainly used as neutron absorbers. Gas scintillators have certain limitations in neutron detection, such as relatively low detection efficiency, and are prone to performance degradation in high-energy neutron or strong radiation environments. Crystal scintillators have high detection efficiency, but their preparation process is complex and costly. Glass scintillators, as a new type of scintillator material, have gradually attracted people's attention. Glass scintillators have excellent properties such as non-deliquescence, acid and alkali resistance, high and low temperature resistance, and can maintain stable detection performance in harsh environments. In addition, the preparation process of glass scintillators is relatively simple and the cost is relatively low. At present, the most widely used neutron detection glass scintillator is the commercially available GS series lithium glass, such as GS20, which is a Ce 6 Li-doped lithium aluminosilicate oxide glass enriched with 3+ Li.

[0003] At present, the preparation temperature of the lithium aluminosilicate oxide-based neutron detection glass is above 1550℃, the high-temperature viscosity of the glass liquid is large, and micro-bubbles and stripes are easily generated during the preparation process. At the same time, high-temperature preparation also has problems such as difficulty in controlling the valence state of Ce 3+ ions, which leads to poor batch stability and low yield of the product. Due to the difficulty in maintaining the single stability of the valence state of Ce 3+ ions, the light yield of the glass scintillator is low, which affects the neutron and gamma discrimination ability and causes the occurrence of neutron and gamma misjudgment. In order to stabilize the valence state of Ce 3+ ions, carbon powder and other reducing agents are often added to the glass mixture, but the introduction of reducing agents can easily cause the glass to be colored at high temperatures, resulting in a serious decrease in the transmittance of the glass in the visible light band, which seriously affects the performance of the scintillator and also brings problems such as unstable glass quality, which hinders the practical application of the product.

[0004] At present, there are few patents about scintillating glass ceramics. Chinese patent CN100526244C discloses a glass scintillator, a preparation method thereof, and a thermal neutron detection method, which has high luminous efficiency and a thermal neutron detection efficiency of about 90%. However, the preparation process is complicated, a platinum crucible is needed for secondary melting, the preparation temperature is high, and the holding time is long, which greatly increases the production energy consumption. Chinese patent CN114133137A discloses a neutron detection glass scintillator, a preparation method thereof, and an application, which has the characteristics of one-time melting forming and provides a strong reducing atmosphere by using a graphite crucible. However, the prepared glass is transparent light gray, which affects the scintillation performance of the glass. SUMMARY

[0005] In view of the problems in the prior art, the present application provides a glass scintillator with high neutron detection efficiency and high light yield, a preparation method thereof, and an application. The first technical problem solved by the present application is to provide a glass scintillator with high neutron detection efficiency and high light yield, which is a new type of Ce 3+ doped fluorosilicate neutron detection glass. Compared with commercial neutron detection glass based on lithium aluminum silicate oxide, such as GS20, the Ce 3+ doped fluorosilicate neutron detection glass has higher Li + ion doping concentration, which helps to improve the neutron detection efficiency. Moreover, due to the introduction of fluoride, the ultraviolet absorption cutoff edge of the glass is blue-shifted, the transmittance of the glass at short wavelengths is increased, the self-absorption of the scintillator material is reduced, and the light yield of the glass is greatly improved. The special network structure of the Ce 3+ doped fluorosilicate neutron detection glass can effectively increase the solubility of Ce 3+ ions, avoid Ce 3+ ion clusters, and help to improve the Ce 3+ luminescence intensity and the light yield of the glass.

[0006] The second technical problem solved by the present application is to provide a preparation method of the above-mentioned glass scintillator with high neutron detection efficiency and high light yield. In the preparation method, a reducing atmosphere is introduced into the atmosphere furnace to provide a stable strong reducing atmosphere for the glass body. Without using a platinum crucible, a glass scintillator with good uniformity and without micro-bubbles can be prepared at a lower preparation temperature, realizing one-time forming. The glass scintillator with good uniformity and without bubbles saves a large amount of production cost and effectively ensures the stability of the product. In addition, another aspect of the present application is to provide a low-temperature melting neutron detection glass. Compared with traditional lithium aluminum silicate oxide glass, the Ce 3+ doped fluorosilicate neutron detection glass has a lower melting temperature and a lower glass liquid viscosity, which helps to obtain a glass product with good performance, high yield, and good batch stability.

[0007] The third technical problem to be solved by the present application is to provide an application of the high-neutron-detection-efficiency and high-light-yield glass scintillator 3+ The ion doping concentration, the high light yield (up to 8000 ph / MeV) for 662 keV gamma light, the excellent energy resolution (<16%), the light yield (up to 11000 ph / n) for thermal neutrons, and the excellent neutron-gamma discrimination capability (neutron-gamma misjudgment rate ≤14% and neutron detection efficiency ≥95%) all exceed those of the commercial GS20 neutron detection glass, and the high-neutron-detection-efficiency and high-light-yield glass scintillator can be used as a high-light-yield glass scintillator for neutron detection.

[0008] To solve the above technical problems, the present application adopts the following technical scheme:

[0009] The high-neutron-detection-efficiency and high-light-yield glass scintillator comprises a main component and a reducing agent. n 0-25%, wherein X is one or more of an alkali metal element, an alkaline earth metal element, a boron group element, and a rare earth element; the alkali metal is Li and / or Na; the alkaline earth metal element is Mg and / or Zn; the boron group element is Al and / or Ga; the rare earth element is one or more of Y, La, and Gd; n is determined according to the corresponding metal valence of X, and XF n is not equal to 0; the balance is the reducing agent.

[0010] The reducing agent is one or more of Sb2O3, AlN, SiC, and Si3N4, and the mass percentage of the reducing agent in the high-neutron-detection-efficiency and high-light-yield glass scintillator is 0.2-1%.

[0011] The preparation method of the high-neutron-detection-efficiency and high-light-yield glass scintillator comprises the following steps:

[0012] (1) according to the selected main component and reducing agent of the high-neutron-detection-efficiency and high-light-yield glass scintillator and the corresponding ratio, the corresponding raw materials are selected and uniformly mixed to obtain a glass mixture, which is ready for use;

[0013] (2) the glass mixture is placed in a corundum crucible or a quartz crucible and placed in a high-temperature reducing atmosphere furnace, and the glass mixture is exposed to a reducing atmosphere for high-temperature melting;

[0014] (3) pouring the high-temperature melted glass melt into an annealing mold to perform annealing treatment, slowly reducing to room temperature to obtain the required high-neutron-detecting-efficiency and high-light-yield glass scintillator.

[0015] In the step (1), in the high-neutron-detecting-efficiency and high-light-yield glass scintillator, the raw material of lithium oxide is selected from one or more of natural abundance lithium, natural lithium carbonate or enriched 6 Li (mass percentage content ≥ 95%) oxide.

[0016] In the step (1), in the high-neutron-detecting-efficiency and high-light-yield glass scintillator, the reducing agent is one or more of Si3N4, Sb2O3, AlN, SiC.

[0017] In the step (2), the reducing atmosphere of the high-temperature reducing atmosphere furnace is a nitrogen-hydrogen mixed gas, and as a preferred, the hydrogen:nitrogen ratio is (5%-10%):(90%-95%) by volume percentage, and more preferably 5%:95%.

[0018] Preferably, in the step (2), the high-temperature melting temperature is 1100-1400℃, the melting time is 60-180min, and the melting atmosphere is a reducing atmosphere.

[0019] In the step (2) of high-temperature melting, the glass melt after high-temperature melting also includes the step of stirring the glass melt before pouring into the annealing mold.

[0020] In the step (3), the annealing mold is preferably an annealing mold made of stainless steel.

[0021] Preferably, in the step (3), the preheating temperature of the annealing mold is 400-600℃.

[0022] Preferably, in the step (3), the annealing temperature is 400-600℃, and the annealing time is 3-6 hours.

[0023] Preferably, in the step (3), after annealing, it also includes: cooling, including reducing to 200℃ at a cooling rate of 5-10℃ / min, and then cooling to room temperature with the furnace.

[0024] The application also provides the application of the high-neutron-detecting-efficiency and high-light-yield glass scintillator or the high-neutron-detecting-efficiency and high-light-yield glass scintillator prepared by the above preparation method in the field of neutron detection.

[0025] The high neutron detection efficiency and high light yield glass scintillator has a light yield of 4200-8000 ph / MeV under 662 keV gamma light, an energy resolution of < 16%, and more preferably 12-13%; a light yield of 6500-11000 ph / n for thermal neutrons, a neutron gamma misjudgment rate of <= 14%, and more preferably < 10%, a thermal neutron resolution of 9.5-16%, and a neutron detection efficiency of >= 95%.

[0026] Compared with the prior art, the high neutron detection efficiency and high light yield glass scintillator has the following beneficial effects:

[0027] The high neutron detection efficiency and high light yield glass scintillator has a lithium mass percentage of up to 13.4%, and has a high light yield of 8000 ph / MeV while ensuring high lithium doping, reaches the level of BGO commercial crystals, has excellent energy resolution (11%-13%), a high thermal neutron peak channel address, and a neutron gamma misjudgment rate of less than 10%, which is better than that of commercial GS20 lithium glass. 3+ The introduction of fluorides can effectively reduce the preparation temperature of the glass, and the preparation temperature of the glass is 1100-1400 DEG C, which is lower than the manufacturing temperature (1600 DEG C) of the commercial GS20 glass, thereby reducing the manufacturing difficulty of the glass.

[0028] In the selection process of fluorides, lithium fluoride is introduced to increase more lithium elements in the glass scintillator, and the density of lithium fluoride is low, thereby further increasing the thermal neutron response of the glass scintillator.

[0029] The present application selects an atmosphere furnace for melting, and introduces a trace reducing agent in the components to effectively provide a reducing atmosphere in the melting process of the glass, so that the Ce 3+ Valence state of the glass scintillator with high-doped Ce elements can be stabilized, and the glass scintillator can be formed by one-time melting.

[0030] The glass scintillator prepared by the present application is convenient for large-size preparation, can be prepared into a large optical device, and is used in the field of neutron imaging.

[0031] The high neutron detection efficiency and high light yield glass scintillator selects a Ce-doped lithium aluminum fluorosilicon system, and the special network structure of fluorosilicon glass can effectively increase the solubility of Ce 3+ Ions, and the glass scintillator can be melted at a lower temperature (compared with GS20). BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1Transmittance curve of high neutron detection efficiency and high light yield glass scintillator prepared for example 3;

[0033] Figure 2 Emission spectrum of high neutron detection efficiency and high light yield glass scintillator prepared for example 3 under X-ray excitation;

[0034] Figure 3 Gamma ray pulse integral spectrum of high neutron detection efficiency and high light yield glass scintillator prepared for example 4 at 662 keV @ Cs source and BGO crystal, GS20 glass;

[0035] Figure 4 Neutron response energy spectrum of high neutron detection efficiency and high light yield glass scintillator prepared for example 4 under Am-Be neutron source;

[0036] Figure 5 Neutron response energy spectrum of high neutron detection efficiency and high light yield glass scintillator prepared for example 5 under Am-Be neutron source;

[0037] Figure 6 Neutron gamma ratio of high neutron detection efficiency and high light yield glass scintillator prepared for example 6. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. The described embodiments are only some examples of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0039] Example 1

[0040] The high neutron detection efficiency and high light yield glass scintillator comprises the following components and their mass percentages: 40SiO2-18Li2O-8Al2O3-8.5CeO2-10MgO-5YF3-5LiF-5LaF3-0.5Sb2O3

[0041] 1. 30g of raw materials according to the above high neutron detection efficiency and high light yield glass scintillator composition are weighed and mixed uniformly by grinding to obtain a glass batch;

[0042] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible with a mass purity of more than 99%, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature is 1350℃, and the melting time is 80min;

[0043] 3. The glass scintillator with high neutron detection efficiency and high light yield is obtained by stirring the glass melt in the crucible with a quartz rod for 0-5 seconds, pouring into a 500℃ preheated stainless steel annealing mold to cool and form, then transferring to a 500℃ annealing furnace to anneal at constant temperature to eliminate internal stress, keeping for 3 hours, then cooling to room temperature with the furnace, and obtaining the glass scintillator with high neutron detection efficiency and high light yield.

[0044] Example 2

[0045] The glass scintillator with high neutron detection efficiency and high light yield comprises the following components and mass percentages: 40SiO2-18Li2O-8Al2O3-8.5CeO2-10MgO-5YF3-5LiF-5AlF3-0.5Sb2O3

[0046] 1. The raw materials of 30g are weighed according to the above components of the glass scintillator with high neutron detection efficiency and high light yield, and are fully ground and mixed uniformly to obtain the glass batch;

[0047] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature is 1350℃, and the melting time is 80min;

[0048] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds, poured into a 500℃ preheated stainless steel annealing mold to cool and form, then transferred to a 500℃ annealing furnace to anneal at constant temperature to eliminate internal stress, keeping for 3 hours, then cooling to room temperature with the furnace, and obtaining the glass scintillator with high neutron detection efficiency and high light yield.

[0049] Example 3

[0050] The glass scintillator with high neutron detection efficiency and high light yield comprises the following components and mass percentages: 40SiO2-18Li2O-8Al2O3-8.5CeO2-5MgO-5LaF3-5YF3-5LiF-5AlF3-0.5Sb2O3

[0051] 1. The raw materials of 30g are weighed according to the above components of the glass scintillator with high neutron detection efficiency and high light yield, and are fully ground and mixed uniformly to obtain the glass batch;

[0052] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature is 1350℃, and the melting time is 80min;

[0053] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500℃ preheated stainless steel annealing mold to cool and form, and then transferred to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress, and after 3 hours of heat preservation, the furnace is cooled to room temperature, to obtain a high neutron detection efficiency and high light yield glass scintillator.

[0054] The high neutron detection efficiency and high light yield glass scintillator is subjected to transmittance testing, and the transmittance curve is shown in Figure 1 It can be seen that the transmittance of Example 3 at 400 nm is about 90%, and the excellent transmittance can reduce the self-absorption of the sample and ensure excellent scintillation performance of the sample. The emission spectrum of the prepared high neutron detection efficiency and high light yield glass scintillator under X-ray excitation is shown in Figure 2 It can be seen that the XEL emission peak of Example 3 is 390 nm, and compared with the commercial scintillation crystal BGO, the peak intensity is about 6 times that of BGO.

[0055] Example 4

[0056] The components and mass percentages of the high neutron detection efficiency and high light yield glass scintillator are as follows:

[0057] 40SiO2-13Li2O-8Al2O3-10.5CeO2-5MgO-8YF3-10LiF-5LaF3-0.5Sb2O3

[0058] 1. 30g of raw materials according to the components of the high neutron detection efficiency and high light yield glass scintillator above are weighed and thoroughly ground and mixed to obtain a glass batch;

[0059] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and a uniform glass melt is prepared under a reducing atmosphere with a nitrogen-hydrogen volume ratio of 95:5, the melting temperature is 1350℃, and the melting time is 80min;

[0060] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500℃ preheated stainless steel annealing mold to cool and form, and then transferred to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress, and after 3 hours of heat preservation, the furnace is cooled to room temperature, to obtain a high neutron detection efficiency and high light yield glass scintillator.

[0061] The high neutron detection efficiency and high light yield glass scintillator is tested under gamma rays, and the gamma ray pulse integral spectrum is shown in Figure 3 The gamma ray pulse integral spectrum of BGO crystal and GS20 glass is also detected. Figure 3It can be seen that by Gaussian fitting of the full energy peak of 662 keV, the channel number is obtained, and the GS20 sample, the glass sample of Example 4 and the BGO crystal standard sample are compared. The light yield of the BGO crystal standard sample is calculated to be 8843 ph / MeV, the light yield of the glass sample of Example 4 is 5436 ph / MeV, and the light yield of the GS20 sample is 2171 ph / MeV. According to the product information of the GS20 sample, the light yield of the GS20 sample is 4000 ph / MeV. The reason for the low light yield of the test sample of the GS20 sample is that the sample thickness is only 1 mm, but the Compton cutoff edge of the sample can be clearly observed.

[0062] Under the Am-Be neutron source, the neutron response spectrum of the high neutron detection efficiency and high light yield glass scintillator prepared in this embodiment is shown in Figure 8. Figure 4 It can be seen that this embodiment has a clear thermal neutron peak, and the thermal neutron resolution is calculated to be 11.98%.

[0063] Example 5

[0064] The high neutron detection efficiency and high light yield glass scintillator contains the following components and their mass percentages:

[0065] 1. 30 g of raw materials of the high neutron detection efficiency and high light yield glass scintillator is weighed according to the above components and is fully ground and mixed uniformly to obtain a glass batch;

[0066] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen-hydrogen volume ratio of 95:5. The melting temperature is 1350℃, and the melting time is 80 min;

[0067] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500℃ preheated stainless steel annealing mold to cool and form, and then transferred to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After 3 hours of heat preservation, it is cooled to room temperature with the furnace, and the high neutron detection efficiency and high light yield glass scintillator is obtained.

[0068] Under the Am-Be neutron source, the neutron response spectrum of the high neutron detection efficiency and high light yield glass scintillator prepared in this embodiment is shown in Figure 8. Figure 5 It can be seen that this embodiment has a clear thermal neutron peak, and the thermal neutron resolution is calculated to be 10.90%.

[0069] Example 6

[0070] The high neutron detection efficiency and high light yield glass scintillator contains the following components and their mass percentages:

[0071] 45SiO2-5MgO-8Al2O3-18Li2O-10LiF-5AlF3-7.5CeO2-0.5Sb2O3

[0072] 1. According to the components of the high-neutron-detection-efficiency and high-light-yield glass scintillator, 30 g of raw materials are weighed and fully ground and mixed uniformly to obtain a glass batch;

[0073] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen-hydrogen volume ratio of 95:5, the melting temperature is 1380°C, and the melting time is 80 min;

[0074] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500°C preheated stainless steel annealing mold to cool and form, and then transferred to a 500°C annealing furnace for constant temperature annealing to eliminate internal stress, and after 3 hours of heat preservation, the furnace is cooled to room temperature, thereby obtaining the high-neutron-detection-efficiency and high-light-yield glass scintillator.

[0075] The neutron gamma ratio graph of the high-neutron-detection-efficiency and high-light-yield glass scintillator prepared in this embodiment is shown in Figure 6 , by Gaussian fitting of the thermal neutron peak, the gamma ray background is derived using a quadratic polynomial, the gamma ray ratio in the range of 3 times the standard deviation is obtained, and the gamma ray percentage in this embodiment is calculated to be 9.5%.

[0076] Example 7

[0077] The components and mass percentages of the high-neutron-detection-efficiency and high-light-yield glass scintillator are: 46SiO2-5MgO-8Al2O3-18Li2O-10LiF-5AlF3-6.5CeO2-0.5Sb2O3

[0078] 1. According to the components of the high-neutron-detection-efficiency and high-light-yield glass scintillator, 30 g of raw materials are weighed and fully ground and mixed uniformly to obtain a glass batch;

[0079] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen-hydrogen volume ratio of 95:5, the melting temperature is 1350°C, and the melting time is 80 min;

[0080] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500°C preheated mold to cool and form, and then transferred to a 500°C annealing furnace for constant temperature annealing to eliminate internal stress, and after 3 hours of heat preservation, the furnace is cooled to room temperature, thereby obtaining the high-neutron-detection-efficiency and high-light-yield glass scintillator.

[0081] Example 8

[0082] The high-neutron-detecting-efficiency and high-light-yield glass scintillator contains the following components and their mass percentages:

[0083] 50SiO2-5MgO-5Al2O3-20Li2O-10LiF-5AlF3-4.5CeO2-0.5Sb2O3

[0084] 1. The raw materials are weighed according to the components of the high-neutron-detecting-efficiency and high-light-yield glass scintillator above, and are thoroughly ground and mixed to obtain a glass batch;

[0085] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen-hydrogen volume ratio of 95:5, the melting temperature is 1400°C, and the melting time is 80 min;

[0086] 3. The glass melt in the crucible is stirred with a quartz rod and then poured into a preheated mold at 500°C to cool and form, and then is transferred to an annealing furnace at 500°C to anneal and eliminate internal stress, and after 3 hours of heat preservation, is cooled to room temperature with the furnace, to obtain the high-neutron-detecting-efficiency and high-light-yield glass scintillator.

[0087] Example 9

[0088] The raw material composition and preparation method of the high-neutron-detecting-efficiency and high-light-yield glass scintillator described in this example are the same as those of Example 1, and the only difference is that the lithium oxide raw material is selected to be a lithium carbonate compound enriched with 6 Li(95%).

[0089] The scintillating glass contains the following components and their corresponding mass percentages: 40SiO2-5MgO-8Al2O3-13 6 Li2O-8YF3-10LiF-5LaF3-10.5CeO2-0.5Sb2O3

[0090] 1. The raw materials are weighed according to the components of the high-neutron-detecting-efficiency and high-light-yield glass scintillator above, and are thoroughly ground and mixed to obtain a glass batch;

[0091] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible, and is melted into a uniform glass melt under a reducing atmosphere with a nitrogen-hydrogen volume ratio of 95:5, the melting temperature is 1400°C, and the melting time is 80 min;

[0092] 3. The glass melt in the crucible is stirred with a quartz rod and then poured into a preheated mold at 500°C to cool and form, and then is transferred to an annealing furnace at 500°C to anneal and eliminate internal stress, and after 3 hours of heat preservation, is cooled to room temperature with the furnace, to obtain the high-neutron-detecting-efficiency and high-light-yield glass scintillator.

[0093] Comparative Example 1

[0094] The raw material composition and preparation method of the high neutron detection efficiency and high light yield glass scintillator described in this example are the same as those of Example 2, and the only difference is that the crucible is selected to be a silicon nitride crucible.

[0095] The components contained in the scintillating glass and their mass percentages are: 40SiO2-10MgO-8Al2O3-18Li2O-5AlF3-5LiF-5YF3-8.5CeO2-0.5Sb2O3

[0096] 1. 30g of raw materials were weighed according to the above glass component and thoroughly ground and mixed uniformly;

[0097] 2. The uniformly mixed glass batch was poured into a high-purity silicon nitride crucible and melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature was 1350℃, and the melting time was 80min;

[0098] 3. The glass melt in the crucible was stirred with a quartz rod for 0-5 seconds and then poured into a 500℃ preheated mold to cool and form, then transferred to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress, after 3 hours of heat preservation, cooled to room temperature with the furnace, and the scintillating glass was obtained.

[0099] Comparative Example 2

[0100] The raw material composition and preparation method of the high neutron detection efficiency and high light yield glass scintillator described in this example are the same as those of Example 5, and the only difference is that the reducing agent is selected to be C.

[0101] The components contained in the scintillating glass and their corresponding mass percentages are: 44SiO2-5MgO-8Al2O3-18Li2O-10LiF-5AlF3-9.5CeO2-0.5C

[0102] 1. 30g of raw materials were weighed according to the above glass component and thoroughly ground and mixed uniformly;

[0103] 2. The uniformly mixed glass batch was poured into a high-purity silicon nitride crucible and melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature was 1350℃, and the melting time was 80min;

[0104] 3. The glass melt in the crucible was stirred with a quartz rod for 0-5 seconds and then poured into a 500℃ preheated mold to cool and form, then transferred to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress, after 3 hours of heat preservation, cooled to room temperature with the furnace, and the scintillating glass was obtained.

[0105] Comparative Example 3

[0106] The raw material composition and preparation method of the high neutron detection efficiency and high light yield glass scintillator of the present comparative example are the same as those of Example 1, and the only difference is that the crucible is capped.

[0107] The components contained in the scintillating glass and their corresponding mass percentages are: 40SiO2-10MgO-8Al2O3-18Li2O-5YF3-5LiF-5LaF 3- 8.5CeO2-0.5Sb2O3

[0108] 1. The raw materials 30g are weighed according to the above glass composition and are thoroughly ground and mixed uniformly.

[0109] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible and a crucible cover is added, and the glass is melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature is 1350°C, and the melting time is 80 min.

[0110] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500°C preheated mold to cool and form, and then transferred to a 500°C annealing furnace for constant temperature annealing to eliminate internal stress, and after 3 hours of heat preservation, the furnace is cooled to room temperature, obtaining the scintillating glass. After the corundum crucible is capped, bubbles will appear inside the glass, causing the light yield and other indicators to decrease.

[0111] Comparative Example 4

[0112] The components of the glass scintillator and their mass percentages are:

[0113] 50SiO2-20Li2O-10Al2O3-10CeO2-10MgO

[0114] 1. The raw materials 30g are weighed according to the above high neutron detection efficiency and high light yield glass scintillator composition and are thoroughly ground and mixed uniformly to obtain a glass batch.

[0115] 2. The uniformly mixed glass batch is poured into a high-purity corundum crucible and melted into a uniform glass melt under a reducing atmosphere with a nitrogen and hydrogen volume ratio of 95:5, the melting temperature is 1400°C, and the melting time is 80 min.

[0116] 3. The glass melt in the crucible is stirred with a quartz rod for 0-5 seconds and then poured into a 500°C preheated stainless steel annealing mold to cool and form, and then transferred to a 500°C annealing furnace for constant temperature annealing to eliminate internal stress, and after 3 hours of heat preservation, the furnace is cooled to room temperature, obtaining the glass scintillator. In this comparative example, the fluoride in the example is deleted, and the scintillating glass is tested, and its scintillation performance is not as good as that of the high neutron detection efficiency and high light yield glass scintillator of the present application.

[0117] Performance test results of the high light yield glass scintillator for neutron detection in Table 1

[0118]

[0119]

[0120] As can be seen from the data in the above table, the high neutron detection efficiency and high light yield glass scintillator provided by the present application has a high light yield of 4200-8000 ph / MeV, and an energy resolution of less than 16%, wherein the energy resolution of Example 4 and Example 5 is as low as 13%, the thermal neutron resolution is excellent, the thermal neutron light yield is ≥6500-11000 ph / n, and the neutron gamma discrimination effect is good.

[0121] In Comparative Example 1, silicon nitride crucible was selected, and the silicon nitride in the silicon nitride crucible was used as a reducing agent to provide an additional reducing atmosphere for the glass during the melting process. However, due to the poor compactness of the silicon nitride crucible and the presence of many internal impurities, the powder raw material will be converted into a glass liquid at high temperature and react with the silicon nitride crucible, and the impurities in the crucible enter the glass liquid, and the sample does not form a glass. In Comparative Example 2, the reducing agent was changed to C, and the sample appeared to be colored, which caused the self-absorption phenomenon of the sample to be obvious, resulting in a decrease in the scintillation performance of the sample. In Comparative Example 4, the fluoride in the component was removed, and it can be found that the scintillation performance of the glass decreased significantly. This example proves that Ce 3+ Doped fluorosilicate phase compared to Ce 3+ Doped silicate glass has advantages in light yield, energy resolution, neutron yield, thermal neutron resolution, and neutron gamma discrimination capability.

[0122] Obviously, the above examples are merely examples for the purpose of clearly illustrating the present application, and are not intended to limit the embodiments. Based on the above description, other different forms of changes or modifications can be made by those of ordinary skill in the art. Here, it is not necessary and impossible to exhaust all embodiments. The obvious changes or modifications derived therefrom are still within the protection scope of the present application.

Claims

1. A glass scintillator with high neutron detection efficiency and high light yield, characterized in that: This high-electron-detection-efficiency and high-yield glass scintillator consists of a main component and a reducing agent. The mass percentage of each component in the main component is as follows: SiO2 40-60%, Li2O 10-22%, Al2O3 4-10%, CeO2 4-12%, MgO 2-10%, XF n 0-25%, wherein X is one or more of alkali metal elements, alkaline earth metal elements, boron group elements, and rare earth elements; the alkali metal is Li and / or Na; n is determined according to the corresponding metal valence state selected by X, and XF n Not equal to 0; The high-efficiency and high-yield glass scintillator described above has a light yield of 4200~8000ph / MeV and an energy resolution of <16% under 662keV gamma light; for thermal neutrons, the light yield is 6500~11000ph / n, the neutron gamma false positive rate is ≤14%, the thermal neutron resolution is 9.5~16%, and the neutron detection efficiency is ≥95%.

2. The high-electron-detection-efficiency and high-light-yield glass scintillator according to claim 1, characterized in that: The alkaline earth metal element is Mg and / or Zn; the boron group element is Al and / or Ga; and the rare earth element is one or more of Y, La, and Gd.

3. The high-electron-detection-efficiency and high-light-yield glass scintillator according to claim 1, characterized in that: The reducing agent is one or more of Sb2O3, AlN, SiC, and Si3N4, and the reducing agent accounts for 0.2-1% of the mass of the glass scintillator with high neutron detection efficiency and high light yield.

4. The method for preparing the high-neutron detection efficiency and high-light-yield glass scintillator according to any one of claims 1-3, characterized in that: Includes the following steps: (1) According to the selected high neutron detection efficiency and high light yield glass scintillator, the main components and reducing agent types and corresponding ratios are selected, and the appropriate raw materials are mixed evenly to obtain glass batch material for later use; (2) Place the glass batch in a high-purity corundum crucible or quartz crucible and place it in a high-temperature reducing atmosphere furnace, and expose the glass batch to the reducing atmosphere for high-temperature melting; (3) The glass melt after high temperature is poured into an annealing mold and annealed. The glass scintillator is slowly cooled to room temperature to obtain the required high neutron detection efficiency and high light yield.

5. The method for preparing a high-neutron detection efficiency and high-light-yield glass scintillator according to claim 4, characterized in that: The raw materials for lithium oxide are naturally abundant lithium, natural lithium carbonate, or enriched lithium with an abundance of ≥95% (Li₆). 6 One or more of the oxides of Li.

6. The method for preparing a high-neutron detection efficiency and high-light-yield glass scintillator according to claim 4, characterized in that: In step (2), the reducing atmosphere of the high-temperature reducing atmosphere furnace is a nitrogen-hydrogen mixture, with a volume percentage of hydrogen:nitrogen = (5%~10%): (90%~95%).

7. The method for preparing a high-neutron detection efficiency and high-light-yield glass scintillator according to claim 4, characterized in that: In step (2), the high-temperature melting temperature is 1100-1400℃ and the melting time is 60-180min.

8. The method for preparing a high-neutron detection efficiency and high-light-yield glass scintillator according to claim 4, characterized in that: In step (3), the annealing temperature is 400-600℃ and the annealing time is 3-6 hours; And / or, After annealing, the process also includes cooling, including reducing the temperature to 200°C at a rate of 5-10°C / min, and then cooling it to room temperature in the furnace.

9. The high neutron detection efficiency and high light yield glass scintillator according to any one of claims 1-3 or the high neutron detection efficiency and high light yield glass scintillator prepared by the preparation method according to any one of claims 4-8 is used for neutron detection.

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