Ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass and its preparation method and application

Abstract

The present application relates to an ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass. The glass is prepared from the following raw materials through thorough mixing, high-temperature melting, mold casting, and precision annealing, including the following: 10-35 mol% B2O3, 10-35 mol% SiO2, 0-70 mol% Gd2O3, and 0-20 mol% CeO2; the sum of these components is 100 mol%. The present application also relates to a preparation method and application of the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass. The scintillating glass of the present application can achieve an ultra-high concentration of 5-15 mol% doping of CeO2, the luminescent center, in the Gd2O3-rich borosilicate scintillating glass. While ensuring high density, it can also achieve a high light yield of 1300 ph / MeV and a scintillation decay time of approximately 100 ns. On the other hand, due to the inherent transparency of glass, simple preparation process, easy adjustment of components, and the ability to achieve low cost and large volume, it has important application value in nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, industrial online detection, and national security monitoring.

Description

Technical Field

[0001] The present application belongs to the field of luminescent materials, and relates to scintillating glass materials, preparation methods and applications thereof, and in particular to an ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass, and preparation methods and applications thereof. Background Art

[0002] Scintillator detectors are one of the most important radiation detectors and are often used in high-energy physics experiments, nuclear radiation detection, nuclear medicine, and industrial flaw detection. Scintillating materials can convert high-energy particles or radiation into visible light and are considered optically functional materials. Scintillating crystals are currently the most widely studied and applied scintillators, such as Bi4Ge3O 12 (BGO), CeF3, PbWO4 (PWO), etc. However, scintillating crystals have disadvantages such as complex preparation process, long growth cycle, high cost, and difficulty in producing large-sized single crystals. In particular, traditional crystal growth technology cannot ensure ultra-high concentration and uniform distribution of dopant ions, and thus cannot achieve the optimization of the optical properties of the material, which greatly limits its application.

[0003] With the rapid development of high-energy physics, the performance requirements for scintillating materials are becoming increasingly stringent, driving high-quality research on scintillating materials. To achieve precise measurements of particles such as Higgs, W, and bosons, the Chinese particle physics community has proposed the construction of a circular electron-positron collider (CEPC). The CEPC requires coverage of a wide solid angle, excellent particle discrimination capabilities, precise measurement of particle energy-momentum, high-precision collision vertex resolution, jet resolution, and flavor signatures. For the CEPC's hadron calorimeter system, an efficient supply of bulk scintillating materials is a key guarantee. Scintillating glass is a priority for hadron calorimeters due to its advantages such as easily tunable chemical composition, good optical uniformity, easy large-scale fabrication, and simple preparation methods. However, hadron calorimeters require scintillating glass to simultaneously possess high density, a visible optical yield, a fast decay time, and strong radiation resistance. Meanwhile, the Compact Muon Solenoid (CMS) at the Large Hadron Collider (LHC) at CERN is also considering replacing scintillator crystals with scintillator glass. The Large Hadron ion Collider (EIC) in the United States is also actively developing scintillator glass calorimeters. Therefore, scintillator glass is likely to become the most important scintillator in the next generation of high-energy physics experiments and is currently a major research hotspot for scintillating materials.

[0004] High density is one of the important performance indicators of scintillating materials in high-energy physics experiments. High-density scintillators have a shorter radiation length and better blocking ability for high-energy particles, which can improve the energy resolution of detectors and facilitate the compact design of large scientific equipment. However, scintillating glass has a contradiction between density and light yield, such as "high density but low light yield" or "low density but high light yield", which is difficult to reconcile. The current glass density is 3.5-8.5g / cm 3 For example, the invention patent with the publication number CN1087066A, entitled “High-density, radiation-resistant, fast-scintillation inorganic glass”, discloses that the density of the glass with PbO and Bi2O3 as the main components exceeds 8.0 g / cm 3 scintillating glass, but the glass component contains a large amount of PbO, which seriously pollutes the environment, thus limiting its practical application. For example, the invention patent with the publication number CN101913767A and the name “Rare earth doped fluorine oxytellurate scintillating glass and its preparation method” discloses a high-density scintillating glass with TeO2, PbF2, BaF2 and Gd2O3 as the main components and rare earth as the luminescence center. The scintillating glass still contains highly toxic PbF2 and other fluorides, which seriously pollute the environment, thus limiting the promotion and application of this type of scintillating glass. For example, the invention patent with the publication number CN 114409252A and the name “A boron-free high-density gadolinium lutetium germanate glass and its preparation” discloses a high-density gadolinium lutetium germanate glass with a density of more than 6.0 g / cm 3 Germanate scintillating glass, but the components GeO2, Lu2O3 and Ga2O3 in the glass are expensive and have high melting temperatures, which are not conducive to the promotion and application of this type of scintillating glass. For example, the patent publication number is CN 115611514 A, which is named "A Ce 3+ The invention patent of "GaB-doped Gadolinium Scintillating Glass and Its Preparation Method and Application" discloses a glass with a density higher than 6.0g / cm 3 However, the Ga2O3 component in the glass is expensive, and its CeO2 doping concentration is lower than 4 mol%, which is not conducive to reducing the scintillation decay time.

[0005] Borosilicate system is often used as scintillating glass matrix due to its strong ability to dissolve rare earth, good optical properties, stable physical and chemical properties, and abundant raw materials. Low-valent cerium ions are often used as luminescence centers because they allow 5d-4f transitions and can produce decay times of nanoseconds. Therefore, cerium ion-doped borosilicate glass is a very important scintillating material and has long been highly concerned by academia and industry. However, cerium ion luminescence is Ce 3+ Luminescence, the preparation of this type of scintillating glass requires the use of H2 / N2 mixed gas or CO gas to maintain low-valence Ce 3+Luminescence, or by introducing different strong reducing components in air atmosphere to simplify the preparation process and reduce the cost of glass preparation. 3+ Two invention patents, "A method for preparing activated scintillating glass" (patent publication number CN104058578A) and "A colorless and transparent cerium-activated borosilicate scintillating glass and its preparation method" (patent publication number CN108249757A), both disclose a series of methods for preparing colorless and transparent cerium ion-activated scintillating glass in an air atmosphere, providing an important method for the synthesis of a series of low-valent cerium ion-doped scintillating glasses in an air atmosphere.

[0006] On the other hand, researchers have been working to optimize the scintillation properties of cerium-doped borosilicate glass. For example, patent publication number CN114772922A, entitled "Scintillator Glass for Electromagnetic Calorimeters, Preparation Method, Melting Apparatus, and Application thereof," discloses a borosilicate scintillating glass doped with cerium dioxide (concentration less than 3 mol%), with a fluorescence decay time of 20-48 ns and a maximum light yield of 770 ph / MeV. For example, Chinese patent CN110734223B discloses a lutetium-based silicate scintillating glass with a glass density exceeding 6.5 g / cm 3 However, the CeO2 doping concentration is less than 2.0 mol%, which is detrimental to the radiation resistance of the scintillating glass and does not reveal any further scintillation properties. Glass, due to its inherently complex amorphous structure, has a rich variety and number of internal defects, which complicate the scintillation process and significantly degrade the glass's scintillation properties. For example, the aforementioned cerium ion-doped scintillating glass (publication number CN114772922A) has a fluorescence decay time of 20-48 ns, but a scintillation time of nearly 1000 ns.

[0007] In summary, the currently reported cerium ion-doped borosilicate scintillating glass is difficult to simultaneously possess the characteristics of high density, high light yield, and fast attenuation. Summary of the Invention

[0008] The purpose of this application is to prepare a nanostructured carbon nanotube with a density exceeding 7.0 g / cm2 by enriching (Gd, Lu)2O3 in a borosilicate system, focusing on the three performance indicators of high density, visible light yield, and fast decay that are closely related to practical application needs. 3 High-performance scintillating glass is optimized for its light yield and decay time by ultra-high concentration CeO2 doping to achieve practical application purposes. To this end, this patent discloses an ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass, its preparation method and application.

[0009] In order to solve the above technical problems, this application provides the following technical solutions.

[0010] In a first aspect, the present application provides an ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass, characterized in that the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass is prepared from the following raw material components through a process of thorough mixing, high-temperature melting, mold casting, and precision annealing:

[0011] B2O3 10-35mol%,

[0012] SiO2 10-35mol%,

[0013] Gd2O3 0-70mol%

[0014] CeO2: 0-20mol%;

[0015] The sum of the above components is 100 mol%.

[0016] In one embodiment of the first aspect, the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass is made of the following raw material components:

[0017] B2O3 15-30mol%

[0018] SiO2 15-28mol%

[0019] Gd2O3 35-65mol%

[0020] CeO2: 5-15 mol%.

[0021] The sum of the above components is 100 mol%.

[0022] In one embodiment of the first aspect, at least a portion of the Gd2O3 is replaced by Al2O3 or Lu2O3.

[0023] In one embodiment of the first aspect, an appropriate amount of SiO2 component is replaced by one or more of reducing Si3N4, SiC, SiO or elemental Si; or an appropriate amount of B2O3 component is replaced by one or more of reducing BN, B4C or elemental B.

[0024] In one embodiment of the first aspect, the composition of the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass is as follows: 20B2O3-20SiO2-30Gd2O3-15Gd2F6; 24B2O3-21SiO2-40Lu2O3-15Gd2F6; 19Gd2O3-15Gd2F6-1Al2O3-22B2O3-17.75SiO2-0.25Si3N4-1CeO2; 23B2O3-20SiO2-15Gd2F6-(40-x)Gd2O3-xLu2O3, wherein x=0, 10, 20, 30, or 40; 24B2O3-23SiO2-(37Gd-x)2O3-2x Al(OH)3-15Gd2F6, wherein x=0, 5, 10, or 15; or 23B2O3-23SiO2-(39-x)Gd2O3-xCeO2-15Gd2F6, wherein x=1, 3, 5, 7, 9, 12, or 16.

[0025] In a second aspect, the present application provides a method for preparing the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass as described in the first aspect, characterized in that the preparation method comprises the following steps:

[0026] S1: Accurately weigh the raw materials according to the composition of the scintillating glass, and mix all the raw materials uniformly to obtain a uniformly mixed glass material;

[0027] S2: Melting the mixed glass material into a glass melt at a melting temperature of 1000-1400°C and keeping the temperature for 10-120 minutes after melting;

[0028] S3: After the glass melt is uniform, it is cooled to the melting temperature of 100-200°C and clarified for 15-60 minutes to obtain a clarified glass melt;

[0029] S4: pouring the clarified glass melt into a mold preheated to 350-550° C., casting and forming, and then naturally cooling to form glass;

[0030] S5: performing a constant temperature precision annealing treatment on the glass to obtain the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass. The annealing conditions are: annealing temperature of 450-700°C, and annealing time of 3-30 hours.

[0031] In one embodiment of the second aspect, the B2O3 component is introduced by boron oxide or boric acid; the SiO2 raw material is directly introduced by the SiO2 raw material; and the Gd2O3 and CeO2 rare earth compounds are introduced in the form of corresponding oxides, fluorides, carbonates or nitrates; Al2O3 or Lu2O3 replacing Gd2O3 can also be introduced in the form of corresponding oxides, fluorides, hydroxides, carbonates or nitrates; the purity of all raw materials is required to be analytically pure or above.

[0032] In one embodiment of the second aspect, the B2O3 component is 10 B2O3 is introduced, while Gd2O3 component is introduced through 155 Gd2O3 and / or 157 Gd2O3 is introduced.

[0033] In one embodiment of the second aspect, the working atmosphere during the preparation process is an air atmosphere.

[0034] In the third aspect, the present application provides an application of the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass as described in the first aspect, characterized in that the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass is used to directly make a scintillating screen or a scintillating array, or to be drawn into an optical fiber to make an optical fiber panel.

[0035] In a fourth aspect, the present application provides an application of the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass as described in the first aspect, characterized in that the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass is used for nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, industrial online detection and national security monitoring.

[0036] Compared with existing technologies, the present invention demonstrates a significant advantage: the density of the ultra-high-concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass described herein is closely related to melting temperature, holding time, and crucible type. The density and luminescence properties of the ultra-high-concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass can also be regulated by partially replacing the Gd2O3 in the glass with Lu2O3 or Al2O3. The primary advantage of the present invention's scintillating glass is that it achieves an ultra-high concentration of 5-15 mol% doping of CeO2, the luminescent center, in the Gd2O3-rich borosilicate scintillating glass. While ensuring high density, it also achieves a high light yield of 1300 ph / MeV and a scintillation decay time of approximately 100 ns. Furthermore, due to the inherent transparency of the glass, its simple preparation process, and easily adjustable composition, it can be manufactured at low cost and in large volumes, making it valuable for applications in nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, industrial online testing, and national security monitoring. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a density comparison diagram of the scintillating glasses obtained in Examples 1-3;

[0038] Figure 2 This is a density comparison diagram of the scintillating glasses obtained in Examples 4-8;

[0039] Figure 3 This is a density comparison diagram of the scintillating glasses obtained in Examples 9-10;

[0040] Figure 4 This is a density comparison chart of the scintillating glasses obtained in Examples 11-14;

[0041] Figure 5 1 is a comparison chart of the luminous intensity of the scintillating glasses obtained in Examples 11-14;

[0042] Figure 6 : This is the transmission spectrum of the scintillating glass obtained in Examples 15-21;

[0043] Figure 7 This is the gamma-ray energy spectrum of the scintillating glass obtained in Examples 15-21;

[0044] Figure 8 This is the gamma-ray excited scintillation decay graph of the scintillating glass obtained in Examples 15-21;

[0045] Figure 9 This is the gamma-ray energy spectrum of the scintillating glass obtained in Example 22;

[0046] Figure 10 This is the gamma-ray excitation scintillation attenuation diagram of the scintillation glass obtained in Example 22. DETAILED DESCRIPTION

[0047] Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages in this application are based on weight, and the test and characterization methods used are current as of the filing date of this application. Where applicable, the contents of any patents, patent applications, or publications referred to in this application are incorporated herein by reference in their entirety, and their equivalent patent families are also incorporated by reference, especially with respect to definitions of synthetic techniques, product and processing designs, polymers, comonomers, initiators, or catalysts disclosed in these documents in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.

[0048] Numerical ranges in this application are approximate values, so unless otherwise stated, they may include numerical values ​​outside the range. Numerical ranges include all numerical values ​​from the lower limit to the upper limit increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if the recorded component, physical or other properties (such as molecular weight, melt index, etc.) are 100 to 1000, it is meant that all individual numerical values ​​are clearly enumerated, such as 100, 101, 102, etc., and all subranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For a range comprising a numerical value less than 1 or comprising a fraction greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately considered to be 0.0001, 0.001, 0.01 or 0.1. For a range comprising a single digit less than 10 (such as 1 to 5), 1 unit is typically considered to be 0.1. These are merely specific examples of what is intended, and all possible combinations of values ​​between the lowest and highest values ​​recited are considered to be expressly stated in this application. It should also be noted that the terms "first," "second," etc. herein do not limit the order of precedence, but are only used to distinguish substances of different structures.

[0049] When used with respect to chemical compounds, unless expressly stated otherwise, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). In addition, nouns using "a," "an," or "the" also include their plural forms unless expressly stated otherwise.

[0050] The terms "comprising", "including", "having" and their derivatives do not exclude the presence of any other components, steps or processes and are irrelevant to whether these other components, steps or processes are disclosed in this application. To eliminate any doubt, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, excipients or compounds unless expressly stated otherwise. In contrast, the term "essentially consisting of" excludes any other components, steps or processes from the scope of any description of the term below, except those necessary for operational performance. The term "consisting of" does not include any components, steps or processes that are not specifically described or listed. Unless expressly stated otherwise, the term "or" refers to the listed members alone or in any combination thereof.

[0051] In one embodiment, the present invention provides an ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass, which is prepared by the following raw material components through thorough mixing, high-temperature melting, mold casting, and precision annealing:

[0052] B2O3 10-35mol%,

[0053] SiO2 10-35mol%,

[0054] Gd2O3 0-70mol%

[0055] CeO2: 0-20 mol%.

[0056] CeO2 is introduced as a rare earth luminescence center, and its doping amount can reach up to 20 mol%. The sum of the above components is 100 mol%.

[0057] In one embodiment, the formula of ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass is preferably:

[0058] B2O3 15-30mol%

[0059] SiO2 15-28mol%

[0060] Gd2O3 35-65mol%

[0061] CeO2: 5-15 mol%.

[0062] The sum of the above components is 100 mol%.

[0063] In a specific embodiment, part of Gd2O3 can be replaced by Al2O3 or Lu2O3. This replacement is beneficial to further optimize the luminescence performance of the scintillating glass to realize its specific application in different scenarios.

[0064] In one embodiment, the present application provides a method for preparing ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass, specifically comprising the following steps:

[0065] 1) Accurately weigh the raw materials according to the composition of the scintillating glass and mix them evenly. The B2O3 raw material is introduced from boron oxide (B2O3) or boric acid (H3BO3); the SiO2 raw material is introduced directly from the SiO2 raw material; the Gd2O3 and CeO2 rare earth compounds can be introduced in the form of corresponding oxides, fluorides, carbonates, or nitrates; Al2O3 and Lu2O3 that replace Gd2O3 can also be introduced in the form of corresponding oxides, fluorides, hydroxides, carbonates, or nitrates; the purity of all raw materials must be analytical grade or higher.

[0066] 2) The mixed glass material is then poured into a platinum crucible, an alumina crucible, a graphite crucible, or a quartz crucible to melt into a glass melt at a melting temperature of 1000-1400°C. After melting, the glass melt is kept warm for 10-120 minutes. The type of crucible, melting temperature, and holding time are determined according to the specific conditions such as the glass composition and its introduction form.

[0067] 3) After the glass melt is uniform, cool it down to the melting temperature of 100-200℃ and clarify it for 15-60 minutes;

[0068] 4) pouring the above-mentioned glass melt into a stainless steel mold or graphite mold preheated to 350-550°C for casting and forming, and then naturally cooling to form glass;

[0069] 5) placing the glass in a muffle furnace for constant temperature precision annealing treatment, the annealing conditions being: annealing temperature of 450-700° C., annealing time of 3-30 hours;

[0070] 6) The scintillating glass is processed into the scintillating glass sample of the present invention after cutting, surface grinding and polishing.

[0071] In a specific embodiment, the working atmosphere is mainly carried out in an air atmosphere; this is achieved by replacing an appropriate amount of SiO2 raw material in the glass component with one or more of reducing Si3N4, SiC, SiO or elemental Si; or by replacing an appropriate amount of B2O3 raw material in the glass component with one or more of reducing BN, B4C or elemental B. It should be pointed out that in the process of glass batching, by replacing an appropriate amount of SiO2 raw material in the glass with one or more of reducing Si3N4, SiC, SiO or elemental Si, or by replacing an appropriate amount of B2O3 raw material in the glass with one or more of reducing BN, B4C or elemental B, it is ensured that the glass preparation conditions can be completed in an atmospheric atmosphere, which greatly simplifies the glass preparation process and reduces the glass preparation cost.

[0072] In one embodiment, the density of ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass can be 5.0-7.1 g / cm3 depending on the glass composition and melting process. 3 The maximum light output is about 1300ph / MeV.

[0073] In one specific embodiment, in the ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass of the present application, when the CeO2 content of the luminescent center exceeds 7 mol%, the scintillation time can be reduced to approximately 100 nanoseconds; when the CeO2 content of the luminescent center exceeds 15 mol%, the scintillation time can be reduced to approximately 60 nanoseconds. Furthermore, the ultra-high concentration of cerium ions provides the scintillating glass with excellent radiation resistance, enabling practical applications of the scintillating glass.

[0074] In a specific embodiment, in the ultra-high concentration cerium ion activated Gd2O3 rich borosilicate scintillating glass of the present application, when the B2O3 component is 10 B2O3 is introduced, while Gd2O3 component is introduced through 155 Gd2O3 and (or) 157When Gd2O3 is introduced, the capture cross section of neutrons and scintillation glass can be greatly improved, so the improved scintillation glass can be used for neutron detection.

[0075] In another embodiment, the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass of the present application can be directly made into a scintillating screen or a scintillating array; it can also be further drawn into an optical fiber to make an optical fiber panel to improve its imaging resolution.

[0076] In another embodiment, the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass of the present application can be applied to nuclear radiation detection, high energy physics experiments, X-ray medical imaging, neutron detection, industrial online detection and national security monitoring.

[0077] Example

[0078] The following examples will be used to clearly and completely describe the technical solutions of the present application. Unless otherwise specified, all reagents and raw materials used can be purchased from commercial sources. The experimental methods in the following examples, where specific conditions are not specified, were performed according to conventional methods and conditions, or selected according to the product specifications.

[0079] Examples 1-3

[0080] The Gd2O3-rich borosilicate scintillating glass matrix formula is 20B2O3-20SiO2-30Gd2O3-15Gd2F6.

[0081] Analytical-grade silicon dioxide (SiO2), boric acid (H3BO3), 99.99% pure gadolinium oxide (Gd2O3), and gadolinium fluoride (GdF3) are weighed in a stoichiometric ratio and mixed uniformly to form a mixture. Partial substitution of GdF3 for Gd2O3 helps lower the melting temperature of the glass.

[0082] The mixture was transferred into a covered corundum crucible and melted in air at temperatures of 1150°C, 1200°C, and 1250°C for 30 minutes. The melt was then poured onto a steel plate preheated to 400°C for casting.

[0083] The prepared glass was placed in a muffle furnace heated to 530°C for annealing, kept at this temperature for 200 minutes, and then cooled to room temperature along with the furnace.

[0084] The annealed scintillating glass is cut and its surface is polished to obtain the colorless, transparent, Gd2O3-rich borosilicate scintillating glass matrix.

[0085] The test results show that the melting temperature has a significant effect on the density of scintillating glass, and a lower melting temperature is conducive to increasing the density of scintillating glass.

[0086] Table 1. Effect of different melting temperatures on the density of Gd2O3-rich borosilicate scintillating glass

[0087]

[0088]

[0089] Examples 4-8

[0090] The formula of the Gd2O3-rich borosilicate scintillating glass matrix is ​​23B2O3-20SiO2-15Gd2F6-(40-x)Gd2O3-xLu2O3 (x=0, 10, 20, 30, 40), where the increase in the x value indicates a higher content of Lu2O3 replacing Gd2O3.

[0091] Analytical-grade silica (SiO2), boric acid (H3BO3), and 99.99% pure gadolinium oxide (Gd2O3), lutetium oxide (Lu2O3), and gadolinium fluoride (GdF3) are weighed in stoichiometric proportions and mixed uniformly to form a mixture. Partial substitution of GdF3 for Gd2O3 helps lower the melting temperature of the glass.

[0092] The mixture was transferred into a covered corundum crucible and melted in air at a melting temperature of 1190°C for 30 minutes. The melt was poured onto a steel plate preheated to 460°C for casting.

[0093] The prepared glass was placed in a muffle furnace heated to 570°C for annealing, kept at this temperature for 200 minutes, and then cooled to room temperature along with the furnace.

[0094] The annealed scintillating glass is cut and its surface is polished to obtain the colorless, transparent, Gd2O3-rich borosilicate scintillating glass matrix.

[0095] The test results show that as the x value increases, that is, when the amount of Lu2O3 replacing Gd2O3 is higher, the density of the scintillating glass increases significantly, from 6.0386 g / cm3 before replacement (x=0). 3 , increased to 6.8337 g / cm after complete substitution (x = 40) 3 On the other hand, as more Lu2O3 replaces Gd2O3, the fluorescence intensity of the scintillating glass increases from 5.70337×10 7 (arbitrary intensity), increased to half of the part (x = 20) 6.59545 × 10 7 (arbitrary intensity), the fluorescence intensity increased by 15.64%.

[0096] Table 2. Effect of different concentrations of Lu2O3 replacing Gd2O3 on the density and luminescence intensity of Gd2O3-rich borosilicate scintillating glass

[0097]

[0098]

[0099] Examples 9-10

[0100] The Gd2O3-rich borosilicate scintillating glass matrix formula is 24B2O3-21SiO2-40Lu2O3-15Gd2F6.

[0101] Analytical-grade silicon dioxide (SiO2), boric acid (H3BO3), 99.99% pure lutetium oxide (Lu2O3), and gadolinium fluoride (GdF3) are weighed in stoichiometric proportions and mixed uniformly to form a mixture. Partial substitution of GdF3 for Gd2O3 helps lower the melting temperature of the glass.

[0102] The mixture was transferred into a covered corundum crucible and a Pt gold crucible, respectively, and melted in air at a melting temperature of 1175°C for 45 minutes. The molten liquid was poured onto a steel plate preheated to 380°C for casting.

[0103] The prepared glass was placed in a muffle furnace heated to 430°C for annealing, kept at this temperature for 200 minutes, and then cooled to room temperature along with the furnace.

[0104] The annealed scintillating glass is cut and its surface is polished to obtain the colorless, transparent, Gd2O3-rich borosilicate scintillating glass matrix.

[0105] The test results show that the density characteristics of Gd2O3-rich borosilicate scintillating glass are related to the type of crucible. When a corundum crucible is selected, its density is 6.5438g / cm 3 If platinum crucible is selected for melting, its density is 7.1376g / cm under the same conditions. 3 , an increase of more than 10%.

[0106] Table 3. Effect of using a non-conducting crucible on the density of Gd2O3-rich borosilicate scintillating glass

[0107]

[0108] Examples 11-14

[0109] The formula of the Gd2O3-rich borosilicate scintillating glass activated with a fixed concentration of 1 mol% CeO2 is 24B2O3-23SiO2-(37Gd-x)2O3-2x Al(OH)3-15Gd2F6 (x=0, 5, 10, 15).

[0110] Analytical-grade silicon dioxide (SiO2), boric acid (H3BO3), aluminum hydroxide (Al(OH)3), 99.99% pure gadolinium oxide (Gd2O3), and gadolinium fluoride (GdF3) are weighed in stoichiometric proportions and mixed uniformly to form a mixture. Partially replacing Gd2O3 with Al(OH)3 helps reduce the viscosity of the glass.

[0111] The mixed materials were transferred into covered corundum crucibles and melted in air at 1180°C for 30 minutes. The temperature was then lowered to 1030°C for about 20 minutes before the melt was poured onto a steel plate preheated to 380°C for casting.

[0112] The prepared glass was placed in a muffle furnace heated to 450°C for annealing, kept at this temperature for 200 minutes, and then cooled to room temperature along with the furnace.

[0113] The annealed scintillating glass is cut and its surface is polished to obtain the colorless, transparent, Gd2O3-rich borosilicate scintillating glass matrix.

[0114] The results show that as the value of x increases, that is, when the amount of Al(OH)3 gradually replaces Gd2O3, the density of the scintillating glass increases from 6.0494 g / cm3 before replacement (x=0) to 1. 3 , reduced to 5.1652 g / cm after partial replacement (x = 15) 3 , but the glass density is still higher than 5.0g / cm 3 On the other hand, the integrated fluorescence intensity of the glass increased from 8097.7542 (x = 0) before replacement to 12176.7708 (x = 15) after partial replacement, and the integrated luminous intensity increased by 50%. In addition, the emission center wavelength of the glass blue-shifted from 380nm before replacement (x = 0) to 357nm after partial replacement (x = 15), which is beneficial to the light output of the scintillating glass.

[0115] Table 4. Gd2O3-rich borosilicate scintillating glass with different Al(OH)3 substitutions for Gd2O3

[0116]

[0117]

[0118] Examples 15-21

[0119] The matrix formula of the Gd2O3-rich borosilicate scintillating glass activated by different concentrations of cerium ions is 23B2O3-23SiO2-(39-x)Gd2O3-xCeO2-15Gd2F6 (x=1, 3, 5, 7, 9, 12 and 16).

[0120] Analytical-grade silicon dioxide (SiO2), boric acid (H3BO3), 99.99% pure gadolinium oxide (Gd2O3), and gadolinium fluoride (GdF3) are weighed in stoichiometric proportions and mixed uniformly to form a mixture. Partial substitution of Gd2O3 with Al(OH)3 helps reduce the viscosity of the glass.

[0121] The mixed materials were transferred into covered corundum crucibles and melted in air at 1180°C for 30 minutes. The temperature was then lowered to 1030°C for about 20 minutes before the melt was poured onto a steel plate preheated to 380°C for casting.

[0122] The prepared glass was placed in a muffle furnace heated to 450°C for annealing, kept at this temperature for 200 minutes, and then cooled to room temperature along with the furnace.

[0123] The annealed scintillating glass is cut and its surface is polished to obtain the colorless, transparent, Gd2O3-rich borosilicate scintillating glass matrix.

[0124] The results show that as the x value increases, that is, the doping concentration of the scintillating glass increases, the density of the low-concentration CeO2-doped scintillating glass (x=1) is 6.0494 g / cm 3 , which is better than high concentration CeO2 doped scintillating glass (x=7) with a density of 5.9432g / cm 3 and ultra-high concentration CeO2 doped scintillating glass (x=12) with a density of 5.9152 g / cm 3 However, the scintillation light yield significantly increased from 427 ph / MeV in low-CeO2-doped scintillating glass (x=1) to 842 ph / MeV in high-CeO2-doped scintillating glass (x=7) and 903 ph / MeV in ultra-high-CeO2-doped scintillating glass (x=12). Correspondingly, the average scintillation decay time significantly decreased from 922.77 ns in low-CeO2-doped scintillating glass (x=1) to 100.81 ns in high-CeO2-doped scintillating glass (x=7) and 76.42 ns in ultra-high-CeO2-doped scintillating glass (x=12). Furthermore, it is foreseeable that further increasing the CeO2 doping concentration will further optimize its light yield and scintillation decay time, thereby realizing its practical application value.

[0125] Table 5. Activation of Gd2O3-rich borosilicate scintillating glass by different CeO2 concentrations

[0126]

[0127]

[0128] Example 22

[0129] The formula of Gd2O3-rich borosilicate scintillating glass activated with a fixed concentration of 1 mol% CeO2 is 19Gd2O3-15Gd2F6-1Al2O3-22B2O3-17.75SiO2-0.25Si3N4-1CeO2.

[0130] Analytical-grade silicon dioxide (SiO2), silicon nitride (Si3N4), boric acid (H3BO3), aluminum oxide (Al2O3), and 99.99% pure gadolinium oxide (Gd2O3) and gadolinium fluoride (GdF3) are weighed in stoichiometric proportions and mixed uniformly to form a mixture. Partially replacing Gd2O3 with Al2O3 helps optimize the light yield of the glass.

[0131] The mixed materials were transferred into covered corundum crucibles and melted in air at 1180°C for 30 minutes. The temperature was then lowered to 1030°C for about 20 minutes before the melt was poured onto a steel plate preheated to 380°C for casting.

[0132] The prepared glass was placed in a muffle furnace heated to 450°C for annealing, kept at this temperature for 200 minutes, and then cooled to room temperature along with the furnace.

[0133] The annealed scintillating glass is cut and its surface is polished to obtain the colorless, transparent, Gd2O3-rich borosilicate scintillating glass matrix.

[0134] The results show that the light yield of the optimized scintillating glass is increased to nearly 1300ph / MeV.

[0135] Table 6. Luminescence properties of Gd2O3-rich borosilicate scintillating glasses doped with different CeO2 concentrations

[0136]

[0137] The above description of the embodiments is intended to facilitate understanding and application of the present invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention should fall within the scope of protection of the present invention.

Claims

1. An ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass, characterized in that: The ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass is prepared from the following raw material components through thorough mixing, high temperature melting, mold casting and precision annealing processes: B2O3 15-30 mol%, SiO2 15-28 mol%, Gd2O335-65 mol%, CeO2: 5-15 mol% The sum of the above raw material components is 100 mol%.

2. The ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass according to claim 1, characterized in that: Part of the Gd2O3 is replaced by Al2O3 or Lu2O3; And / or, an appropriate amount of SiO2 component is replaced by one or more of reducing Si3N4, SiC, SiO or elemental Si; And / or, an appropriate amount of B2O3 component is replaced by one or more of reducing BN, B4C or elemental B.

3. The method for preparing ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: S1: Accurately weigh the raw materials according to the composition of the scintillating glass, and mix all the raw materials to obtain a uniformly mixed glass material; S2: Melting the mixed glass material into a glass melt at a melting temperature of 1000-1400°C and keeping the temperature for 10-120 minutes after melting; S3: After the glass melt is uniform, it is cooled to 100-200°C below the melting temperature and clarified for 15-60 minutes to obtain a clarified glass melt; S4: pouring the clarified glass melt into a mold preheated to 350-550° C., casting and forming, and then naturally cooling to form glass; S5: performing a constant temperature precision annealing treatment on the glass to obtain the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass. The annealing conditions are: annealing temperature of 450-700°C, and annealing time of 3-30 hours.

4. The preparation method according to claim 3, wherein The B2O3 component is introduced by boron oxide or boric acid; SiO2 is directly introduced from SiO2 raw material; and Gd2O3 and CeO2 rare earth compounds are introduced through corresponding oxides, fluorides, carbonates or nitrates; Al2O3 or Lu2O3 replacing Gd2O3 is introduced through corresponding oxides, fluorides, hydroxides, carbonates or nitrates; the purity of all raw materials is required to be analytical grade or above.

5. The preparation method according to claim 4, wherein B2O3 components through 10 B2O3 is introduced, while Gd2O3 component is introduced through 155 Gd2O3 and / or 157 Gd2O3 is introduced.

6. The preparation method according to claim 4, wherein The working atmosphere during the preparation process is air atmosphere.

7. Use of the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass according to claim 1 or 2, characterized in that: The ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass is used to directly make a scintillating screen or a scintillating array, or is drawn into an optical fiber to make an optical fiber panel.

8. Use of the ultra-high concentration cerium ion activated Gd2O3-rich borosilicate scintillating glass according to claim 1 or 2, characterized in that: The ultra-high concentration cerium ion-activated Gd2O3-rich borosilicate scintillating glass is used for nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, industrial online detection and national security monitoring.

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