Glass for liquid scintillation capillary array, method of making and use thereof

Abstract

The application relates to a glass for liquid scintillation capillary array and a preparation method and application thereof. The glass components in terms of mole percentage include: 80-85% of SiO2; 0.5-4% of Al2O3; 4.5-8% of B2O3; the sum of K2O and Na2O is 2-8%; the sum of PbO and CdO is 1-2%; 1.5-4% of ZrO2; the sum of KFH2 and K2SiF6 is 1-4%; 0.2-0.5% of BaF2; and 0.5-1% of CeO2. The technical problem solved is how to provide a glass with low refractive index, high softening point, good anti-crystallization performance, good pressure resistance and radiation resistance, so that the glass can be used for preparing a liquid scintillation capillary array.

Description

Technical Field

[0001] This invention belongs to the field of fast neutron imaging detection technology, and in particular relates to a glass for liquid scintillator arrays, its preparation method and application. Background Technology

[0002] In the field of nuclear detection, image diagnostic technology based on the fast neutron imaging principle is widely used in order to obtain information such as the radiation intensity distribution and dynamic surface density distribution in the source region and to study the physical process characteristics under extreme conditions. The selection of scintillation fiber array material in fast neutron imaging detectors is the key to achieving high-resolution fast neutron imaging.

[0003] Liquid scintillation microporous capillary array detectors have been a focus of research due to their potential to achieve micrometer-level resolution for fusion neutrons. A high numerical aperture is crucial for achieving high detection efficiency in liquid scintillation capillary arrays, and it depends on the refractive index of the capillary glass material and the liquid scintillation. Depending on the application requirements, the numerical aperture of the liquid scintillation capillary array needs to be greater than 0.50. The numerical aperture is calculated using the following formula:

[0004]

[0005] Where NA is the numerical aperture size, n core Let n be the refractive index of the liquid scintillator. cladding The refractive index of the capillary glass is given. When using EJ-309 liquid scintillator (refractive index 1.57), which is currently used internationally, as the filler, the refractive index of the capillary glass should be less than 1.48.

[0006] However, existing glass materials, such as quartz glass with a refractive index of 1.46, cannot accommodate an external absorption layer due to their high softening point, thus failing to solve the problem of optical crosstalk between capillaries. Phosphate glass, with a low refractive index that can be reduced to below 1.4, has poor fiber-forming properties and is prone to crystallization at high temperatures, making it unsuitable for capillary drawing. Therefore, there is an urgent need in this field for glass materials that meet the refractive index requirements of liquid scintillator capillary arrays and possess anti-crystallization properties at high temperatures. Furthermore, the capillary glass material used in liquid scintillator capillary arrays should also have a suitable softening point to avoid deformation during hot-melt pressing due to an excessively low softening point, which would reduce the sphericity of the micropore array. Furthermore, to ensure high detection efficiency of the liquid scintillator micropore capillary array, glass tubes with an opening area ratio of ≥70% must be used. Such a large opening ratio requires the use of thin-walled glass tubes, which necessitates that the glass material have high compressive strength to prevent breakage due to wall thinning during fiber drawing. At the same time, the glass material should also have neutron irradiation resistance to ensure its service life during fast neutron imaging detection.

[0007] How to fabricate glass that meets the requirements of liquid scintillator microporous capillary array detectors and possesses the aforementioned properties, so that it can be better applied to liquid scintillator capillary array detectors, is a research hotspot in the field of fast neutron imaging detectors. Summary of the Invention

[0008] The main objective of this invention is to provide a glass for liquid scintillator arrays, its preparation method, and its applications. The technical problem this invention aims to solve is how to provide a glass for liquid scintillator arrays that possesses a low refractive index, excellent anti-crystallization properties, a suitable softening point, good pressure resistance, and strong radiation resistance, making it suitable as a framework material for liquid scintillator arrays for fabricating liquid scintillator micro-aperture detectors and further applicable to fast neutron imaging detection.

[0009] The objective of this invention and the technical problem it solves are achieved by the following technical solution. According to this invention, a glass for preparing liquid scintillation capillary arrays comprises, by mole percentage:

[0010] 80–85% SiO2; 0.5–4% Al2O3; 4.5–8% B2O3; 2–8% K2O and Na2O combined; 1–2% PbO and CdO combined; 1.5–4% ZrO2; 1–4% KFH2 and K2SiF6 combined; 0.2–0.5% BaF2; 0.5–1% CeO2.

[0011] Preferably, in the aforementioned glass, the sum of the contents of K2O and Na2O is 2-5%.

[0012] Preferably, in the aforementioned glass, the ZrO2 content is 2-4%.

[0013] Preferably, in the aforementioned glass, the sum of the contents of KFH2 and K2SiF6 is 1.5% to 4%.

[0014] Preferably, the aforementioned glass satisfies the following conditions:

[0015] a. With the molar percentage of SiO2 as X1 and the total molar percentage of KHF2 and K2SiF6 as X2, the ratio of X1 to X2 is 20 to 75:1;

[0016] b. The total molar percentage of SiO2, K2O and Na2O is X3, and the total molar percentage of B2O3 and Al2O3 is X4; the ratio of X3 to X4 is 9 to 14 to 1.

[0017] c. The total molar percentage of SiO2 and Al2O3 is X5, and the total molar percentage of PbO and CdO is X6, with X5:X6 being 40 to 90:1.

[0018] Preferably, the aforementioned glass satisfies one or more of the following conditions: a. the X1:X2 ratio is 20 to 60:1; b. the X3:X4 ratio is 10 to 14:1; c. the X5:X6 ratio is 50 to 90:1.

[0019] Preferably, in the aforementioned glass, the refractive index n is... d Its value is 1.465–1.480; no crystallization occurs at 750–1100℃; softening temperature T f The temperature is 650–700℃; the compressive strength of the glass is ≥1500 MPa; when the glass is 10 mm thick, it uses… 252 As a fast neutron radiation source, Cf, after being irradiated with a total dose of 100 Gy of fast neutrons, shows a decrease in transmittance at 560 nm of ≤1.3%.

[0020] The objective of this invention and the technical problem it solves are further achieved by the following technical solution. A method for preparing glass for fabricating liquid scintillator arrays according to this invention includes the following steps:

[0021] S1: The raw materials are uniformly mixed to prepare a batch; by molar percentage, the batch comprises 80-85% SiO2; 0.5-4% Al2O3; 4.5-8% B2O3; the sum of K2O and Na2O is 2-8%; the sum of PbO and CdO is 1-2%; 1.5-4% ZrO2; the sum of KFH2 and K2SiF6 is 1-4%; 0.2-0.5% BaF2; 0.5-1% CeO2;

[0022] S2: The batch material prepared in S1 is melted, clarified, and homogenized to obtain molten glass;

[0023] S3: After cooling the glass melt obtained in S2 to 1200-1300℃, it is shaped and precision annealed in sequence.

[0024] Preferably, in the aforementioned preparation method, the melting temperature of S2 is 1500–1600°C, and the melting time is 10–15 h.

[0025] Preferably, the aforementioned preparation method further includes the following step: before melting the batch material, the melting device used to melt the batch material is preheated to a temperature of 1300-1400°C.

[0026] Preferably, in the aforementioned preparation method, the precision annealing includes: heating to 550-650°C at a rate of 1.5-2.5°C / min and holding at that temperature for 5-8 hours, then cooling to room temperature at a rate of 1.0-2.0°C / h.

[0027] The objective of this invention and the solution to its technical problem are also achieved by the following technical solution. According to this invention, a liquid scintillator micro-aperture array detector is provided, wherein the glass capillaries of its micro-aperture array region are made of the glass described in the aforementioned technical solution; a liquid scintillator is filled within each micro-capillary of the capillary array.

[0028] By employing the above technical solution, the glass for liquid scintillator arrays, its preparation method, and its application proposed in this invention have at least the following advantages:

[0029] 1. The glass for liquid scintillator arrays provided by this invention has a refractive index n. d The range of T is 1.465–1.480, ensuring that the prepared liquid scintillation capillary array has a high fiber optical numerical aperture and further ensuring that the liquid scintillation capillary array has a high detection efficiency; the softening temperature T f The temperature range is 650–700℃; this ensures that the liquid scintillation capillary array is formed solely by the compression of the cladding glass during the hot-melt pressing process, resulting in minimal deformation of the liquid scintillation capillary array, guaranteeing its sphericity and further ensuring its detection efficiency. Simultaneously, it avoids excessively high softening points, preventing the inability to add light-absorbing materials. At 750–1100℃, without crystallization or phase separation, it exhibits excellent anti-crystallization properties and glass stability, with a compressive strength ≥1500MPa, meeting the special fabrication process requirements of liquid scintillation capillary arrays. It also possesses excellent radiation resistance. Therefore, the glass material provided by this invention can be used to prepare liquid scintillation capillary arrays and further applied in fast neutron imaging detectors, showing broad application prospects in the field of neutron detection.

[0030] 2. The glass preparation method for liquid scintillator arrays provided by the present invention, by limiting the glass composition and adjusting the process steps and process parameters, enables the glass material to meet the preset glass performance requirements.

[0031] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings. Attached Figure Description

[0032] Figure 1 The transmittance (at 560 nm) of the glass material prepared in Example 1 of the present invention before and after being irradiated with a total dose of 100 Gy fast neutrons is shown. Detailed Implementation

[0033] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following detailed description, in conjunction with the accompanying drawings and preferred embodiments, describes a glass for liquid scintillator arrays, its preparation method, and its application, as well as its specific implementation methods, structure, features, and effects.

[0034] The component (composition) ranges of the glass material of the present invention are described below. In the present invention, unless otherwise specified, the content and total content of each component are expressed as molar percentages, that is, the molar percentage of the content and total content of each component relative to the total amount of glass material converted into oxides or fluorides. Here, "converted into oxides or fluorides" means that when the oxides, fluorides, complex salts, and hydroxides used as raw materials for the glass material of the present invention decompose and transform into oxides or fluorides upon melting, the total amount of such oxides or fluorides is taken as 100%.

[0035] The glass used in this invention for liquid scintillator micropore arrays comprises, by molar percentage, the following components:

[0036] 80–85% SiO2; 0.5–4% Al2O3; 4.5–8% B2O3; the sum of K2O and Na2O content is 2–8%; the sum of PbO and CdO content is 1–2%; 1.5–4% ZrO2; the sum of KFH2 and K2SiF6 content is 1–4%; 0.2–0.5% BaF2; 0.5–1% CeO2.

[0037] SiO2, a glass-forming oxide, is an important component of the basic framework structure of glass. This invention strictly limits the SiO2 content in the glass to 80-85%, which not only helps provide structural stability and chemical durability but also helps maintain the glass's radiation resistance. Excessive SiO2 content raises the glass's melting point, making the melting process difficult and hindering its compatibility with light-absorbing filaments for fiber drawing. Conversely, insufficient SiO2 content reduces the stability of the glass's framework network structure, thereby decreasing its structural stability and chemical durability, and potentially making it more susceptible to chemical corrosion and environmental factors.

[0038] Al₂O₃ is a glass structure-regulating oxide, and its content in glass affects the softening temperature and melting temperature required for glass production. Therefore, this invention limits its content in glass to 0.5%–4%. If its content exceeds 4%, the glass melting temperature will increase significantly, making glass melting difficult. A higher Al₂O₃ content also leads to enhanced glass network bonding, further increasing the softening temperature and making it difficult to add an external absorption layer, thus making capillary crosstalk problems unavoidable. Conversely, if its content is below 0.5%, the chemical and thermal stability of the glass will decrease, and the softening temperature will be difficult to achieve the design requirements.

[0039] B₂O₃ is a glass-forming oxide and a major component of the glass framework. It also acts as a flux to reduce the viscosity of molten glass. Its structural components include boron-oxygen trigonal [BO₃] and boron-oxygen tetrahedron [BO₄]. Under high-temperature melting conditions, B₂O₃ generally struggles to form boron-oxygen tetrahedra, but under certain conditions at low temperatures, it can form boron-oxygen tetrahedra. 3+ There is a tendency for B2O3 to capture free oxygen and form tetrahedra, which not only helps to improve the compactness of the glass structure but also helps to increase the low-temperature viscosity of the glass. However, because B2O3 has the property of reducing glass viscosity at high temperatures and increasing glass viscosity at low temperatures, and is also the main component that reduces the refractive index of glass, the range of B2O3 content in glass is relatively small. This invention limits its content in glass to 4.5-8%. A B2O3 content below 4.5% results in poor fluxing effect and also reduces the chemical stability of the glass; a B2O3 content above 8% significantly deteriorates the glass's resistance to crystallization. Preferably, the B2O3 content in glass is 4.5-7.5%, under which conditions the glass prepared has better resistance to crystallization.

[0040] Na₂O and K₂O are network oxides in glass. Alkali metal ions readily move and diffuse within the glass, reducing the viscosity during high-temperature melting and facilitating melting, thus acting as excellent fluxes. However, excessive Na₂O and K₂O can lower the glass's refractive index, making it impossible to meet the numerical aperture requirements of liquid scintillation capillaries. Therefore, this invention limits the sum of their contents to 2-8%, and this can be appropriately adjusted based on the thermal properties of the glass material used for the matching absorber wire, introducing one or more of them. Preferably, the sum of Na₂O and K₂O contents is limited to 2-5%, within which the resulting glass refractive index better meets the preset requirements.

[0041] Lead and cadmium are both heavy metal elements with high atomic numbers and high mass decay coefficients, hence PbO and CdO are widely used in radiation shielding. In the glass composition of this invention, adding PbO and CdO can improve the glass's radiation resistance; however, excessive PbO and CdO may reduce the glass's thermal stability and also pose environmental and health risks. The glass material of this invention contains at least one of PbO and CdO, and the sum of the PbO and CdO content in the glass is strictly limited to 1-2%. This content of PbO and CdO helps to balance the stability and radiation resistance of the glass material.

[0042] The ZrO2 content is 1.5–4%. In the glass material of this invention, ZrO2 can increase the glass transition temperature and softening temperature, and enhance the glass's chemical stability and mechanical strength. This invention limits its content to 1.5–4% to improve the softening temperature and compressive strength of the glass material. However, adding too much ZrO2 will increase the glass's phase separation tendency; adding too little may not achieve the design objectives of this invention. Preferably, the ZrO2 content is 2–4%; strictly limiting its minimum amount ensures that the softening temperature and compressive strength of the glass material meet the preset requirements.

[0043] KFH2 and K2SiF6 are both potassium fluoride complex salts used to reduce the refractive index of the glass of this invention. They also reduce the high-temperature melting viscosity of the glass, thus acting as a flux. This invention limits the total content of KFH2 and K2SiF6 to 1-4% to avoid excessive addition which might increase the glass's phase separation tendency. Preferably, this invention limits the total content of KFH2 and K2SiF6 to 1.5-4%, which allows for better control of the glass's phase separation problem while ensuring the glass refractive index meets the preset requirements.

[0044] BaF2 is a fluoride of barium. Adding a small amount can significantly reduce the refractive index of glass. However, since a single fluoride can easily damage the glass structure and cause phase separation, the allowable range of BaF2 content in the glass is relatively small. Preferably, the glass material of the present invention allows a maximum of 0.5% BaF2 to be added.

[0045] In the glass material of this invention, CeO2 plays two roles: firstly, it acts as a stabilizer, as Ce exists in the glass structure. 3+ With Ce 4+ The electricity price balance of mutual conversion, where Ce 3+ It has a tendency to capture holes and be oxidized, forming Ce. 3+(+) Ce 4 + It has a tendency to capture free electrons and be reduced to form Ce4. 4+(-)This prevents free electrons generated by irradiation from entering defects in the glass structure, thereby inhibiting the formation of color centers and avoiding glass coloration. On the other hand, CeO2 also serves as a glass melting and clarifying agent. Therefore, CeO2 is indispensable in this glass system. In this invention, its content is limited to 0.5% to 1%. Excessive CeO2 can cause changes in glass color, thereby affecting its transparency, and may also increase the glass's tendency to crystallize.

[0046] The glass prepared using the above method has low refractive index, high softening point, and resistance to crystallization. It also has strong pressure resistance and good radiation resistance. It can be used as a framework material for liquid scintillator arrays to prepare liquid scintillator microcapillary array detectors and further applied to fast neutron imaging detection.

[0047] Preferably, the aforementioned technical solution satisfies the following conditions:

[0048] In some embodiments, the molar percentage of SiO2 in the glass composition is X1, and the total molar percentage of KHF2 and K2SiF6 is X2, with X1:X2 being 20 to 75:1. This ensures that the glass has high resistance to crystallization and effectively suppresses the tendency of phase separation. More preferably, the X1:X2 ratio is 20 to 60:1, which further enhances the glass's resistance to crystallization and further suppresses the tendency of phase separation.

[0049] In some embodiments, the total molar percentage of SiO2, K2O and Na2O in the glass composition is X3, and the total molar percentage of B2O3 and Al2O3 is X4; X3:X4 is 9 to 14:1; more preferably, X4:X3:X4 is 10 to 14:1. Strictly limiting the ratio of the aforementioned components is beneficial to improving the anti-crystallization performance of the glass and maintaining the softening temperature of the glass within a specific range.

[0050] In some embodiments, the total molar percentage of SiO2 and Al2O3 in the glass composition is X5, preferably, the total molar percentage of PbO and CdO is X6, and X5:X6 is 40 to 90:1; more preferably, X5:X6 is 50 to 90:1. Strictly limiting the ratio of the aforementioned components helps to better balance the glass transmittance, chemical stability, thermal stability, optical transmittance, and radiation resistance.

[0051] The glass material provided by this invention has a refractive index n d The range is 1.465–1.480, ensuring that the fabricated liquid scintillation capillary array possesses a high fiber optic numerical aperture and further ensuring high detection efficiency. Glass softening temperature T fThe temperature range of 650–700℃ ensures that the liquid scintillation capillary array is formed solely by the compression of the encapsulated glass during the hot-melt pressing process. Compared to traditional liquid scintillation capillary array preparation methods, this simplifies the process steps, minimizes the deformation of the liquid scintillation capillary array, ensures its sphericity, and further guarantees the detection efficiency of the liquid scintillation capillary array; at the same time, it avoids the problem of excessively high softening points that would preclude the addition of light-absorbing materials. The glass provided by this invention exhibits excellent anti-crystallization properties at 750–1100℃; it possesses excellent anti-crystallization properties and glass stability, meeting the special manufacturing process requirements of liquid scintillation capillary arrays, ensuring that the glass retains its inherent properties unchanged even after multiple high-temperature drawing and high-temperature melting pressing processes; furthermore, the compressive strength of the glass material is ≥1500MPa, ensuring the stability of the glass material during the drawing process; when the glass material is 10mm thick, it can be used… 252 As a fast neutron radiation source, Cf exhibits excellent radiation resistance, with a transmittance at 560 nm decreasing by ≤1.3% after irradiation with a total dose of 100 Gy of fast neutrons. Therefore, the glass material provided by this invention can serve as a framework material for liquid scintillator capillary arrays, used to fabricate liquid scintillator micro-aperture array detectors, and further applied to fast neutron imaging detection.

[0052] The present invention also provides a method for preparing a liquid scintillator capillary array glass, which includes the following steps:

[0053] Preparation of S1 batch material: Weigh the raw materials and mix them evenly. According to the molar percentage, the batch material includes 80-85% SiO2; 0.5-4% Al2O3; 4.5-8% B2O3; the sum of K2O and Na2O content is 2-8%; the sum of PbO and CdO content is 1-2%; 1.5-4% ZrO2; the sum of KFH2 and K2SiF6 content is 1-4%; 0.2-0.5% BaF2; and 0.5-1% CeO2.

[0054] S2 Melting, Clarification, and Homogenization: In this invention, the furnace is first heated to 1300-1400°C before the batch material is added. This is because certain chemical reactions in the batch material can only occur when the furnace is preheated to the above temperature. If the furnace is not preheated or the preheating temperature is insufficient, the batch material will be loose and have poor heat conduction, making it difficult to melt it fully and form a homogenized glass melt. Furthermore, if the furnace preheating temperature is too low, most of the heat will be used to raise the temperature of the raw materials themselves to the reaction temperature, rather than being used directly for melting the batch material, thus reducing the efficiency of the entire melting process.

[0055] Once the furnace reaches the preset temperature, the batch material prepared in S1 is gradually added to the crucible within the furnace in multiple batches. The temperature is then raised to 1500–1600°C for high-temperature melting, which takes 10–15 hours. During the melting process, continuous stirring and clarification are maintained. This invention strictly limits the melting temperature and time to ensure that the glass molten metal melts completely in the shortest possible time, improving efficiency and conserving resources. The crucible and stirring rod must be corrosion-resistant to prevent corrosion by the molten glass from affecting the glass's properties. In some embodiments, a pure platinum (Pt) crucible is used.

[0056] S3 Forming and Annealing: The molten glass obtained in S2 is cooled to 1200–1300°C and then mechanically formed. After mechanical forming, precision annealing is performed. During precision annealing, the temperature is raised from room temperature to 550–650°C at a heating rate of 1.5–2.5°C / min and held for 5–8 hours, then lowered to room temperature at a rate of 1.0–2.0°C / h. In some embodiments, the room temperature is 25 ± 1°C. This invention strictly limits the precision annealing process conditions, which is beneficial for better eliminating stress in the glass and improving its mechanical strength.

[0057] The present invention also provides a liquid scintillator micro-aperture array detector, wherein the glass capillaries of the micro-aperture array region are made of glass prepared by the aforementioned technical solution; and a liquid scintillator is filled in each micro-capillary of the capillary array.

[0058] This invention also provides a method for fabricating a liquid scintillation capillary array, which includes the following steps:

[0059] The glass material prepared by the aforementioned scheme is made into a glass capillary. Then, an absorbent wire is wrapped around the capillary glass tube. The capillary is drawn by drawing single and multifilaments. The multifilaments are regularly arranged on the cladding glass with matching shape. Then, it is hot-melted and pressed into a blank plate segment. After mechanical processing, cleaning, liquid scintillator filling, and adhesive sealing, a liquid scintillator micropore array is obtained.

[0060] The present invention will be further described below with reference to specific embodiments, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0061] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art to which this invention pertains.

[0062] The testing methods for various performance indicators in the embodiments and comparative examples of this invention are as follows:

[0063] glass refractive index n d Test: Tested according to GB / T 7962.1-2010 Test Method for Colorless Optical Glass;

[0064] Softening temperature T of glass f Test: Tested according to GB / T 7962.16-2010 Test Method for Colorless Optical Glass;

[0065] Compressive strength test of glass: Tested according to GB / T 43874-2024 Test Method for Compressive Properties of Glass Materials and Products;

[0066] Anti-crystallization test of glass: Observe and test crystallization and phase separation at 750-1100℃;

[0067] Neutron irradiation resistance test of glass: When the glass material is 10mm thick, the test is performed using... 252 Using Cf as a fast neutron radiation source, the changes in the transmittance of the test glass material were observed after irradiation with a total dose of 100 Gy.

[0068] Example 1

[0069] This embodiment provides a glass for liquid scintillator arrays, its preparation method, and its application, comprising the following steps:

[0070] S1: The raw materials are mixed evenly to prepare a batch; by molar percentage, the batch comprises 82% SiO2; 2.2% Al2O3; 5% B2O3; the sum of K2O and Na2O is 5%; the sum of PbO and CdO is 1.5%; 2% ZrO2; the sum of KFH2 and K2SiF6 is 1.5%; 0.3% BaF2; and 0.5% CeO2; the specific components are shown in Table 1.

[0071] S2: After preheating the furnace to 1350℃, gradually add the batch material prepared in S1 into the platinum crucible located in the furnace, raise the temperature to 1550℃ for high-temperature melting, and the melting time is 12h; continuously stir, clarify and homogenize during the melting process.

[0072] S3: After cooling the glass melt obtained in S2 to 1250℃, mechanically shape it; after mechanical shaping, perform precision annealing, which includes heating to 580℃ at a heating rate of 2.0℃ / min and holding for 6 hours, and then cooling to room temperature at a rate of 1.5℃ / h.

[0073] The refractive index n of the glass material prepared above was determined. d Test; softening temperature T f Tests included: compressive strength test; anti-crystallization test; neutron irradiation resistance test; test methods as described above.

[0074] Preparation of liquid scintillator capillary array: Capillary glass tubes are prepared using the glass material prepared in this embodiment. Then, absorbent wires are wrapped around the capillary glass tubes. After drawing monofilaments and multifilaments, the multifilaments are regularly arranged on the cladding glass with matching shape. The cladding glass is then hot-melted and pressed into a blank plate segment. After machining, cleaning, liquid scintillator filling, and adhesive encapsulation, a liquid scintillator micropore array is obtained.

[0075] Example 2

[0076] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0077] Example 3

[0078] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0079] Example 4

[0080] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0081] Example 5

[0082] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0083] Example 6

[0084] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0085] Example 7

[0086] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0087] Example 8

[0088] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0089] Example 9

[0090] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0091] Example 10

[0092] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0093] Example 11

[0094] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0095] Example 12

[0096] The difference between this embodiment and embodiment 1 is that the process parameters in this embodiment are shown in Table 2, while the remaining steps are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0097] Example 13

[0098] The difference between this embodiment and embodiment 1 is that the process parameters in this embodiment are shown in Table 2, while the remaining steps are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0099] Example 14

[0100] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0101] Comparative Example 1

[0102] The difference between this comparative example and Example 1 is that the composition of each component in the raw materials of this comparative example is shown in Table 3, and the sum of the contents of PbO and CdO in the compound, expressed as a molar percentage, is 0.5%, which is significantly lower than the sum of the contents of PbO and CdO in Example 1. The remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are the same as in Example 1.

[0103] Comparative Example 2

[0104] The difference between this comparative example and Example 1 is that the composition of each component in the raw materials of this comparative example is shown in Table 3, and its components do not contain BaF2; the remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are the same as in Example 1.

[0105] Comparative Example 3

[0106] The difference between this comparative example and Example 1 is that the composition of each component in the raw materials of this comparative example is shown in Table 3. The molar percentage of SiO2 in the glass component is 75%, which is significantly lower than the SiO2 content in the example; and Al2O3 is not added to its glass component; the remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are the same as in Example 1.

[0107] Comparative Example 4

[0108] The difference between this comparative example and Example 1 is that the composition of each component in the raw materials of this comparative example is shown in Table 3. In terms of molar percentage, the sum of the contents of KFH2 and K2SiF6 is 5%, which is significantly higher than the sum of the contents of KFH2 and K2SiF6 in Example 1. The remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are also the same as in Example 1.

[0109] Comparative Example 5

[0110] The difference between this comparative example and Example 1 is that the composition of each component in the raw materials of this comparative example is shown in Table 3. The sum of the K2O and Na2O contents, expressed as a molar percentage, is 1%, which is significantly lower than the sum of the K2O and Na2O contents in Example 1. The remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are also the same as in Example 1.

[0111] Comparative Example 6

[0112] The difference between this comparative example and Example 1 is that its preparation process is shown in Table 4. During the glass preparation process, the melting temperature is 1700℃, which is significantly higher than the melting temperature of Example 1. The remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are also the same as in Example 1.

[0113] Comparative Example 7

[0114] The difference between this comparative example and Example 1 is that the preparation process is as shown in Table 4. During the glass precision annealing process, the temperature is increased to 700℃ at a heating rate of 3.0℃ / min. The remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are also the same as in Example 1.

[0115] Comparative Example 8

[0116] The difference between this comparative example and Example 1 is that the preparation process is as shown in Table 4. Before adding the batch material to the furnace, the furnace was not preheated; the batch material was directly added to the furnace and then heated. The remaining steps and parameters are the same as in Example 1, and the detection indicators and methods are also the same as in Example 1.

[0117] In the table below, Table 1 shows the glass composition of each embodiment; Table 2 shows the process conditions of each embodiment; Table 3 shows the glass composition of each comparative example; Table 4 shows the process conditions of each comparative example; and Table 5 shows the test results of the embodiments and comparative examples.

[0118] In Tables 1 and 3, all components are expressed as molar percentages, in %. Specifically, K1 in Tables 1 and 3 represents the molar percentage of SiO2 and (KHF2+K2SiF6); K2 represents the molar percentage of (SiO2+K2O+Na2O) and (B2O3+Al2O3); and K3 represents the molar percentage of (SiO2+Al2O3) and (PbO+CdO).

[0119] Table 5 is supplemented with the following explanation:

[0120] A represents the refractive index of the glass;

[0121] B represents the softening temperature T of the glass. f The unit is ℃;

[0122] C represents the compressive strength of the glass; unit: MPa

[0123] D indicates the glass's resistance to crystallization;

[0124] E represents the transmittance of the glass before irradiation, expressed in %; its transmittance at 560 nm is measured using a UV spectrophotometer.

[0125] F indicates that the glass has been irradiated with 100 Gy of neutrons; its transmittance at 560 nm was measured by an ultraviolet spectrophotometer, and the unit is %;

[0126] G represents the difference between E and F, which is the difference in transmittance of glass after being irradiated with 100 Gy of neutrons, expressed in %;

[0127] H indicates the thickness of the glass sample used in the neutron irradiation test, in mm. The test method involves optically processing a glass sample with a thickness of 10 mm that is polished on both sides.

[0128] Table 1. Raw material component distribution ratios for each embodiment.

[0129]

[0130] Table 2. Preparation process conditions for each embodiment

[0131]

[0132] Table 3. Distribution ratio of raw material groups in each comparative example

[0133]

[0134]

[0135] Table 4. Preparation process conditions for each comparative example

[0136]

[0137] Table 5 Test results of each embodiment and comparative example

[0138] Group A B C D E F G H Example 1 1.472 692 1520 excellent 91.8 90.7 1.1 10 Example 2 1.472 682 1620 excellent 91.5 90.3 1.2 10 Example 3 1.465 674 1670 excellent 92.1 91.3 0.8 10 Example 4 1.468 683 1590 excellent 92.1 90.9 1.2 10 Example 5 1.473 699 1760 excellent 91.9 90.7 1.2 10 Example 6 1.474 653 1575 excellent 92.3 91.3 1.0 10 Example 7 1.476 651 1610 excellent 93.1 92.1 1.0 10 Example 8 1.479 679 1630 excellent 92.8 91.6 1.2 10 Example 9 1.468 677 1680 excellent 91.6 90.7 0.9 10 Example 10 1.479 691 1590 good 91.4 90.1 1.3 10 Example 11 1.475 669 1710 good 92.3 91.0 1.3 10 Example 12 1.477 683 1730 excellent 91.9 91.3 0.6 10 Example 13 1.466 692 1590 excellent 91.4 90.9 0.5 10 Example 14 1.470 684 1640 excellent 92.3 91.6 0.7 10 Comparative Example 1 1.476 671 1550 excellent 92.2 75.3 16.9 10 Comparative Example 2 1.492 661 1480 excellent 91.5 90.2 1.3 10 Comparative Example 3 1.473 629 1670 good 91.2 90.6 0.6 10 Comparative Example 4 - - - Difference - - - - Comparative Example 5 1.465 738 1610 excellent 92.2 91.3 0.9 10 Comparative Example 6 1.508 702 1570 excellent 92.8 91.8 1.0 10 Comparative Example 7 - - - - - - - - Comparative Example 8 - - - - - - - -

[0139] In conjunction with the embodiments, the data in Tables 1, 2, and 5, and the appendix Figure 1 As can be seen, the glass n prepared by this invention for liquid scintillation capillary arrays d The softening temperature T is 1.465–1.480. f Between 650 and 700℃; exhibiting no crystallization or phase separation at 750 and 1100℃, demonstrating good anti-crystallization properties and glass stability; compressive strength ≥1500 MPa; for use in liquid scintillation capillary arrays, when the glass is 10 mm thick, it uses... 252 As a fast neutron radiation source, Cf exhibits excellent radiation resistance, with a transmittance decrease of ≤1.3% at 560 nm after irradiation with a total dose of 100 Gy. Therefore, the glass prepared in this embodiment possesses multiple superior properties and can be used to fabricate liquid scintillator arrays, and further applied in fast neutron imaging detectors, showing broad application prospects in the field of neutron detection.

[0140] Further analysis of the various embodiments reveals that when the sum of the contents of Na2O and K2O is limited to 2-5%, the refractive index of the prepared glass is lower. When the sum of the contents of KFH2 and K2SiF6 is 2-4%, and the contents of KHF2 and K2SiF6 are in the range of 20-60:1, the ratio of the total contents of SiO2, K2O, and Na2O to the total contents of B2O3 and Al2O3 is in the range of 10-14:1, and the ratio of the total contents of SiO2 and Al2O3 to the total contents of PbO and CdO is in the range of 40-90:1, the prepared glass has a lower refractive index, better anti-crystallization performance, and excellent glass transmittance and radiation resistance.

[0141] Furthermore, in Comparative Example 1, the combined content of PbO and CdO was less than 1%, only 0.5%, resulting in poor radiation resistance. After 100 Gy neutron irradiation, the transmittance decreased by 16.9%, making it difficult to meet the application requirements.

[0142] Furthermore, in Comparative Example 2, the absence of BaF2 resulted in a glass refractive index exceeding 1.48%, which was insufficient to meet the application requirements.

[0143] Furthermore, in Comparative Example 3, the molar percentages of SiO2 and Al2O3 were significantly lower than those in the Example. The test results show that the softening point was significantly reduced, resulting in severe deformation during the hot-melt pressing process of capillary array fabrication, which led to a decrease in detection efficiency. At the same time, due to the reduced proportion of skeleton structure components, the anti-crystallization performance deteriorated, resulting in varying degrees of crystallization during hot-melt pressing processes such as wire drawing.

[0144] Furthermore, in Comparative Example 4, the sum of KFH2 and K2SiF6 contents was significantly higher than the maximum value of the sum of KFH2 and K2SiF6 contents strictly limited by the present invention, resulting in a significant increase in the tendency of glass to crystallize, making it difficult to prepare the corresponding glass tube. The reason is that excessive fluoride doping leads to glass emulsification. This is because the solubility of fluoride in glass melt is limited, and excessive fluoride will precipitate in the form of tiny crystalline particles, thereby reducing the glass forming performance and increasing the tendency of crystallization.

[0145] Furthermore, in Comparative Example 5, the sum of K₂O and Na₂O content was 1%, significantly lower than the minimum limit imposed by this invention. This increased the difficulty of glass melting and significantly raised the softening temperature, further hindering the compatibility of the glass tube with light-absorbing materials and impeding subsequent wire drawing processes. The reason is that potassium and sodium are typical alkali metals, existing in glass as ions. When potassium and sodium ions are doped into glass, they enter the silica-oxygen network structure. These alkali metal ions have large radii and low charge numbers, acting as "network disruptors" in the glass structure, making the silica-oxygen network structure more porous. When heated, this porous structure allows ions to move more easily, making the glass soften more readily. Conversely, when the potassium and sodium doping content is reduced, the silica-oxygen network structure of the glass becomes relatively complete and compact, making ion movement and rearrangement more difficult. Therefore, a higher temperature is required for the glass to soften, i.e., the softening temperature of the glass increases. The increased softening temperature of the glass further amplifies the viscosity difference between it and the light-absorbing filament, leading to difficulties in matching the glass with the light-absorbing filament and subsequent drawing processes.

[0146] Furthermore, in Comparative Example 6, the melting temperature was higher than the maximum melting temperature limit of this invention, resulting in excessive volatilization of volatile components in the glass composition and a higher refractive index of the melted glass. The reason is that fluorides have low boiling points, and excessively high melting temperatures cause excessive volatilization of fluoride components. Since fluorides can significantly reduce the refractive index, this leads to an increase in the refractive index, making it difficult to meet the design and usage requirements of the glass.

[0147] Furthermore, in Comparative Example 7, the excessively rapid heating rate and excessively high holding temperature during the precision annealing process led to deformation of the glass. This is because when the annealing temperature exceeds the glass's softening temperature, the glass deforms under its own weight. Above the softening temperature, the viscosity of the glass decreases significantly, allowing the particles inside the glass to move more easily, thus preventing the glass from maintaining its original shape. Simultaneously, excessively high temperatures can also generate significant thermal stress within the glass. This is because the temperature changes unevenly in different parts of the glass, resulting in varying degrees of thermal expansion. This thermal stress can cause cracks or even breakage in the glass.

[0148] Furthermore, in Comparative Example 8, the batch material was not preheated before being added to the furnace during the preparation process. This resulted in poor glass uniformity, reduced strength, and increased susceptibility to cracking. The reason is that in the initial heating stage, the batch material near the crucible wall heats up faster than the material inside, leading to uneven heating. This can cause localized differences in the composition of the molten glass, resulting in varying melting and reaction rates at different locations and affecting the uniformity of glass quality. Secondly, this uneven heating can generate a large temperature gradient in the molten glass, inducing thermal stress. Thermal stress easily leads to cracks in the glass, reducing the product yield.

[0149] The technical features in the claims and / or specification of this invention can be combined, and the combination is not limited to the combinations obtained through reference in the claims. Technical solutions obtained by combining the technical features in the claims and / or specification are also within the scope of protection of this invention.

[0150] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A glass for use in liquid scintillator arrays, characterized in that, The glass components, expressed as a molar percentage, include: 80~85% SiO2; 0.5~4% Al2O3; 4.5~8% B2O3; the sum of K2O and Na2O content is 2~8%; the sum of PbO and CdO content is 1~2%; 1.5~4% ZrO2; the sum of KHF2 and K2SiF6 content is 1~4%; 0.2~0.5% BaF2; 0.5~1% CeO2; The glass described satisfies the following conditions: a. Let the molar percentage of SiO2 be X1, and the total molar percentage of KHF2 and K2SiF6 be X2, where X1:X2 is 20~75:1; b. The total molar percentage of SiO2, K2O and Na2O is X3, and the total molar percentage of B2O3 and Al2O3 is X4; the ratio of X3 to X4 is 9~14:

1. c. The total molar percentage of SiO2 and Al2O3 is X5, and the total molar percentage of PbO and CdO is X6, with X5:X6 being 44~87:

1.

2. The glass according to claim 1, characterized in that, The sum of the K2O and Na2O contents is 2-5%.

3. The glass according to claim 1, characterized in that, The ZrO2 content is 2-4%.

4. The glass according to claim 1, characterized in that, The sum of the contents of KHF2 and K2SiF6 is 1.5-4%.

5. The glass according to claim 1, characterized in that, One or more of the following conditions must be met: a. The ratio of X1 to X2 is 20 to 60 to 1; b. The ratio of X3 to X4 is 10 to 14 to 1; c. The ratio of X5 to X6 is 50 to 87 to 1.

6. The glass according to any one of claims 1 to 5, characterized in that, The refractive index n of the glass d Its value is 1.465~1.480; no crystallization occurs at 750~1100℃; softening temperature T f The temperature is 650~700℃; the compressive strength of the glass is ≥1500Mpa; when the thickness is 10mm, it uses... 252 As a fast neutron radiation source, Cf, after being irradiated with a total dose of 100 Gy of fast neutrons, has a transmittance at 560 nm that decreases by ≤1.3%.

7. A method for preparing glass for liquid scintillator arrays according to any one of claims 1 to 6, characterized in that, It includes the following steps: S1: Raw materials are mixed evenly to prepare the batch; S2: The batch material prepared in S1 is melted, clarified, and homogenized to obtain molten glass; S3: After cooling the glass melt obtained in S2 to 1200~1300℃, it is shaped and precision annealed in sequence.

8. The preparation method according to claim 7, characterized in that, The S2 is melted at a temperature of 1500~1600℃ for 10~15 hours.

9. The preparation method according to claim 7, characterized in that, It also includes the following steps: before the batch material is melted, the melting device used to melt the batch material is preheated to a temperature of 1300~1400℃.

10. The preparation method according to any one of claims 7 to 9, characterized in that, The precision annealing process includes: heating to 550-650℃ at a rate of 1.5-2.5℃ / min and holding at that temperature for 5-8 hours, then cooling to room temperature at a rate of 1.0-2.0℃ / h.

11. A liquid scintillating micropore array detector, characterized in that, The glass capillaries of its microporous array region are made of the glass described in any one of claims 1 to 6; a liquid scintillator is filled in each microcapillary of the capillary array.

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