Light-absorbing glass for making liquid scintillation capillary arrays, and methods of making and using the same

Abstract

The application relates to light-absorbing glass for preparing liquid scintillation capillary arrays and a preparation method and application thereof, which comprises the following components in terms of mass percentage of oxides: SiO2: 70-78%; Al2O3: 3-6%; B2O3: 5-12%; Mn2O3: 0.5-1.5%; Fe2O3: 0.2-0.7%; CuO: 0.1-0.3%; CoO: 0.1-0.3%; ZnO: 1-3%; CeO2: 0.2-1%; the total content of K2O and Na2O is 5-8%; and the total content of KHF2 and K2SiF6 is 0.8-1.5%. The light-absorbing glass for preparing liquid scintillation capillary arrays has high absorption performance to light in the wavelength range of 375-700 nm, excellent anti-crystallization performance and neutron irradiation resistance, and a softening temperature matched with low-refractive-index tube material glass of the liquid scintillation capillary array, and is suitable for preparing the liquid scintillation capillary array.

Description

Technical Field

[0001] This application relates to the field of scintillator materials technology, and in particular to light-absorbing glass for preparing liquid scintillator capillary arrays, its preparation method, and its application. Background Technology

[0002] Liquid scintillator capillary arrays are the core material of fast neutron imaging detectors. They convert fast neutron signals into visible light signals by filling the capillary with liquid scintillator, and then achieve light transmission by forming a total internal reflection interface based on the refractive index difference between the capillary wall and the liquid scintillator. This ultimately achieves high-resolution imaging of fast neutrons and plays an irreplaceable role in major national scientific projects and key fields such as inertial confinement fusion diagnostics, nuclear power plant safety monitoring, and nuclear medicine detection.

[0003] The spatial resolution of fast neutron imaging directly depends on the performance of the liquid scintillator capillary array, and optical crosstalk between capillaries is the core bottleneck restricting the improvement of imaging resolution. The fluorescence generated by fast neutron-excited liquid scintillator exhibits a 4π omnidirectional distribution. Only light rays with incident angles within the critical angle range of total internal reflection can effectively propagate along the capillary. A large amount of fluorescence exceeding the critical angle overflows from the sides of the capillary and enters adjacent capillaries, forming severe optical crosstalk. This leads to distortion of the detection signal and significantly reduces spatial resolution. Especially in applications requiring ultra-high spatial resolution on the order of 10 μm, the capillary aperture is extremely small, making optical crosstalk even more pronounced. It is estimated that crosstalk can account for over 80% of the total optical resolution, becoming a major technical obstacle to achieving high-resolution imaging.

[0004] To suppress optical crosstalk, existing technologies have proposed adding a light-absorbing glass layer to the capillary wall. This layer absorbs the overflowing crosstalk light, ensuring the accuracy of the single-channel signal. However, the fabrication of this light-absorbing glass layer still faces several key technical challenges: First, the light-absorbing glass has poor chemical and thermal compatibility with the low-refractive-index glass of the capillary inner wall, making it prone to component diffusion during repeated thermal processing, leading to changes in the refractive index of the inner wall glass and disrupting the total internal reflection condition. Second, its light absorption performance is insufficient, making it difficult to efficiently absorb crosstalk light in the 375-700nm wavelength band emitted by liquid scintillator. Third, the glass has poor forming properties, easily crystallizing and cracking during processes such as wire drawing and fusion, affecting the structural integrity of the capillary array. Fourth, the introduction of light-absorbing glass can easily reduce the array duty cycle, thus affecting the detection efficiency.

[0005] Therefore, it is of great significance to develop a light-absorbing glass that can meet the requirements of liquid scintillator capillary arrays. Summary of the Invention

[0006] The main objective of this application is to provide a light-absorbing glass for fabricating liquid scintillator arrays, a method for fabricating the glass, and its application. The technical problem to be solved is to make it have high absorption performance for light in the wavelength range of 375~700nm, and excellent anti-crystallization performance and neutron irradiation resistance. At the same time, it has a softening temperature that matches the low refractive index tubular glass of liquid scintillator arrays, making it suitable for fabricating liquid scintillator arrays and thus more suitable for practical use.

[0007] The objective of this application and the technical problem it solves are achieved by the following technical solution. According to this application, a light-absorbing glass for preparing liquid scintillation capillary arrays comprises, by weight percentage of oxides: SiO2: 70~78%; Al2O3: 3~6%; B2O3: 5~12%; Mn2O3: 0.5~1.5%; Fe2O3: 0.2~0.7%; CuO: 0.1~0.3%; CoO: 0.1~0.3%; ZnO: 1~3%; CeO2: 0.2~1%; The combined content of K2O and Na2O is 5-8%; The combined content of KHF2 and K2SiF6 is 0.8-1.5%.

[0008] The purpose of this application and the technical problems to be solved can also be further achieved by the following technical measures.

[0009] Preferably, the aforementioned light-absorbing glass for preparing liquid scintillation capillary arrays comprises, by mass percentage of oxides: SiO2: 74~76%; Al2O3: 4~5%; B2O3: 6~8%; Mn2O3: 0.5~1%; Fe2O3: 0.3~0.5%; CuO: 0.2~0.3%; CoO: 0.2~0.3%; ZnO: 2~3%; CeO2: 0.5~0.8%; The combined content of K2O and Na2O is 6-7%; The combined content of KHF2 and K2SiF6 is 1~1.2%.

[0010] Preferably, the aforementioned light-absorbing glass for preparing liquid scintillation capillary arrays comprises, by mass percentage of oxides, SiO2 / (KHF2+K2SiF6) = 60~90; and / or, (SiO2+Al2O3) / (Mn2O3+Fe2O3+CuO+CoO)=45~75.

[0011] Preferably, the aforementioned light-absorbing glass for preparing liquid scintillation capillary arrays comprises, by mass percentage of oxides, SiO2 / (KHF2+K2SiF6) = 65~75; and / or, (SiO2+Al2O3) / (Mn2O3+Fe2O3+CuO+CoO)=60~70.

[0012] Preferably, when the thickness of the aforementioned light-absorbing glass used to prepare the liquid scintillation capillary array is 0.5 mm, its transmittance does not exceed 2% in the wavelength range of 375~700 nm.

[0013] Preferably, when the thickness of the aforementioned light-absorbing glass used to prepare the liquid scintillation capillary array is 0.5 mm, it is used... 252 Cf, as a fast neutron radiation source, was tested for transmittance after being irradiated with a total dose of 100 Gy of fast neutrons, and the measured value was <2%.

[0014] Preferably, the softening temperature T of the aforementioned light-absorbing glass used to prepare the liquid scintillation capillary array is... f Between 600 and 650℃.

[0015] The objective of this application and the technical problem it solves are further achieved by the following technical solution. A method for preparing light-absorbing glass for fabricating liquid scintillation capillary arrays, according to this application, is characterized by the following steps: The raw materials are thoroughly mixed and heated to 1450~1500℃ for melting. During the melting process, the mixture is stirred, clarified, and oxygen is continuously introduced to obtain glass melt. The aforementioned glass melt is cooled to 1150~1200℃, then poured into a mold, and cooled to room temperature to obtain a molded glass body; The aforementioned shaped glass body was annealed at a heating rate of 1.0~2.0℃ / min, heated to 500~550℃ and held for 6~8h, and then cooled to room temperature at 0.5~2℃ / min to obtain light-absorbing glass for preparing liquid scintillation capillary arrays. The aforementioned raw materials, in terms of oxide mass percentage, include: SiO2: 70~78%; Al2O3: 3~6%; B2O3: 5~12%; Mn2O3: 0.5~1.5%; Fe2O3: 0.2~0.7%; CuO: 0.1~0.3%; CoO: 0.1~0.3%; ZnO: 1~3%; CeO2: 0.2~1%; The combined content of K2O and Na2O is 5-8%; The combined content of KHF2 and K2SiF6 is 0.8-1.5%.

[0016] The objective of this application and the technical problem it solves are also achieved by the following technical solution. A liquid scintillation capillary array according to this application comprises any of the aforementioned light-absorbing glasses used to fabricate the liquid scintillation capillary array.

[0017] The purpose of this application and the technical problem it solves are also achieved by the following technical solutions. This application proposes the application of any of the aforementioned light-absorbing glasses used in the fabrication of liquid scintillator arrays in the field of fast neutron imaging detectors.

[0018] By employing the above technical solutions, the optically absorbing glass used in this application for preparing liquid scintillation capillary arrays, its preparation method, and its application have at least the following advantages: 1. The light-absorbing glass used in this application for preparing liquid scintillation capillary arrays, with a test sample of 0.5 mm, has a transmittance of 375~700 nm, and its peak value does not exceed 2%, achieving strong absorption of crosstalk light and reducing signal interference between capillaries.

[0019] 2. The softening temperature T of the light-absorbing glass used in this application for preparing liquid scintillation capillary arrays f With a temperature between 620 and 650 degrees Celsius, tens of degrees lower than that of low-refractive-index glass, it is key to adapting the composite wall structure and thermal processing technology of liquid scintillation capillary arrays. The low softening point allows it to soften first, enabling capillary bundle fusion and buffering stress, while also suppressing the diffusion of coloring ions. It can also bridge the temperature gradient between the edging glass and the low-refractive-index glass, ensuring array forming accuracy and optical performance while reducing processing difficulty.

[0020] 3. The light-absorbing glass material used in this application for preparing liquid scintillation capillary arrays does not exhibit crystallization or phase separation at 650~1000℃, and has good anti-crystallization performance and glass stability. It can meet the manufacturing process requirements of liquid scintillation capillary arrays and ensure that the glass maintains its own properties unchanged after multiple high-temperature drawing and high-temperature melting and pressing.

[0021] 4. The light-absorbing glass material used in this application for preparing liquid scintillation capillary arrays, when 0.5 mm thick, uses... 252 Using Cf as a fast neutron radiation source, after being irradiated with a total dose of 100 Gy of fast neutrons, the transmittance of the glass was tested, and the measured value was <2%, demonstrating excellent radiation resistance. This glass material 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.

[0022] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, the preferred embodiments of this application are described in detail below. Detailed Implementation

[0023] To further illustrate the technical means and effects adopted by this application to achieve its intended purpose, the following, in conjunction with preferred embodiments, provides a detailed description of the specific implementation methods, structures, features, and effects of the light-absorbing glass for preparing liquid scintillation capillary arrays, its preparation method, and its application. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable manner.

[0024] In this application, unless otherwise specified, the content of each component and the total content are all expressed as a mass percentage, that is, the mass percentage of the content of each component and the total content relative to the total mass of the 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 this application decompose and transform into oxides or fluorides upon melting, the total amount of such oxides or fluorides is taken as 100%.

[0025] This application provides a light-absorbing glass for fabricating liquid scintillation capillary arrays, the composition of which, by mass percentage of oxides, includes: SiO2: 70~78%; Al2O3: 3~6%; B2O3: 5~12%; Mn2O3: 0.5~1.5%; Fe2O3: 0.2~0.7%; CuO: 0.1~0.3%; CoO: 0.1~0.3%; ZnO: 1~3%; CeO2: 0.2~1%; The combined content of K2O and Na2O is 5-8%; The combined content of KHF2 and K2SiF6 is 0.8-1.5%.

[0026] Specifically, SiO2 is the core framework component of the glass network, directly determining the mechanical strength, chemical stability, and structural integrity of the glass. This application limits the SiO2 content to 70-78%, more preferably 74-76%. If the SiO2 content is below 70%, the glass network framework is loose, mechanical strength decreases, it is prone to breakage during capillary drawing, and chemical stability is insufficient. If the SiO2 content is above 78%, it significantly increases the glass melting temperature and melt viscosity, making it difficult for coloring ions such as Mn2O3 and Fe2O3 to disperse uniformly, resulting in uneven absorption. It also increases the difficulty of glass material forming and makes it unsuitable for related processes.

[0027] Al2O3 is a glass structure regulating oxide, whose main functions are to optimize network stability, suppress crystallization, and match the softening temperature and thermal expansion coefficient of low-refractive-index glass. This application limits the Al2O3 content to 3-6%, more preferably 4-5%. If the Al2O3 content is below 3%, it cannot effectively fill defects in the glass network, and coloring ions easily aggregate to form crystal nuclei, leading to crystallization during annealing and fusion. Simultaneously, the glass's mechanical strength is insufficient, making it difficult to withstand the processing stress of the capillary array. If the Al2O3 content is above 6%, it significantly increases the difficulty of glass melting, requiring higher melting temperatures, and easily triggers the "aluminum anomalous effect." When the ratio with alkali metal oxides is unbalanced, an unstable aluminum-oxygen octahedral structure is formed, which reduces the glass's resistance to crystallization and may also lead to excessive melt viscosity, affecting molding accuracy.

[0028] B2O3 functions as both a glass forging agent and a flux, adjusting the glass structure by forming boron-oxygen trigonometric bodies [BO3] and boron-oxygen tetrahedra [BO4], while simultaneously reducing high-temperature melting viscosity. This application limits the B2O3 content to 5-12%, more preferably 6-8%. If the B2O3 content is below 5%, the fluxing effect is insufficient, the glass melting temperature is too high, and the loss of coloring ions due to volatilization increases, leading to a decrease in absorption intensity in the target wavelength band. Simultaneously, its structural compatibility with low-refractive-index glasses deteriorates, making interface delamination more likely during hot processing. If the B2O3 content is above 12%, it lowers the glass softening point, overlapping with the edge-sealing glass temperature, causing capillary deformation during melting and pressing. Furthermore, excessive boron-oxygen structures weaken the glass's resistance to crystallization, requiring additional network forging to maintain balance, increasing the difficulty of process control.

[0029] Mn₂O₃ is a source of Mn 3+ The core raw material, Mn 3+Through dd transitions, absorption bands exist at 450 nm, 490 nm, and 650 nm, making it a key component for suppressing crosstalk. This application limits the Mn2O3 content to 0.5% to 1.5%, more preferably, to 0.5% to 1.0%. If the Mn2O3 content is below 0.5%, Mn... 3+ Insufficient concentration results in a low absorption peak in the corresponding wavelength band, failing to effectively attenuate crosstalk light and causing signal interference; if the Mn2O3 content is higher than 1.5%, excessive Mn... 3+ It easily aggregates to form local high-concentration areas, becoming crystallization nuclei and inducing glass crystallization; at the same time, it can lead to interaction with other coloring ions, causing the absorption peak to shift and disrupting the integrity of the absorption coverage across the entire 375~700nm wavelength range.

[0030] Fe2O3 provides Fe 3+ Its characteristic absorption peaks are at 380nm, 420nm, and 435nm, which can enhance the absorption of the main peak of liquid scintillation and supplement the absorption in the 375~400nm band, and are similar to Mn. 3+ This creates a synergistic effect. The Fe2O3 content is limited to 0.2-0.7%, more preferably 0.3-0.5%. If the Fe2O3 content is below 0.2%, insufficient absorption in the short-wavelength ultraviolet to visible light band results in an absorption blind zone and incomplete suppression of crosstalk light; if the Fe2O3 content is above 0.7%, some Fe2O3 will be lost during high-temperature melting. 3+ Easily reduced to weakly absorbed Fe 2+ This reduces the overall absorption efficiency; at the same time, excessive iron ions can lead to uneven glass coloring and may compete with CeO2 for valence state, affecting radiation resistance.

[0031] CuO provides Cu 2+ By supplementing the absorption in the 500-700nm band through dd transitions, the long-wavelength blind zone of visible light is eliminated, achieving full-band coverage in synergy with CoO. This application limits the CuO content to 0.1-0.3%, more preferably 0.2-0.3%. If the CuO content is below 0.1%, the long-wavelength absorption intensity is insufficient, the absorption continuity in the 375-700nm band is poor, and crosstalk light cannot be completely suppressed; if the CuO content is above 0.3%, Cu… 2+ Copper ions tend to aggregate and form local color centers, which can form a low-melting-point eutectic phase with CoO, increasing the risk of glass crystallization. At the same time, excessive copper ions can reduce the chemical stability of glass and affect its long-term reliability.

[0032] CoO provides Co 2+ Its characteristic absorption peaks are located at 530nm, 590nm, and 645nm, which can accurately cover the mid-to-long wavelength range of visible light, and are similar to Mn. 3+ Fe 3+ Cu 2+This creates complementary absorption. The CoO content is limited to 0.1-0.3%, more preferably 0.2-0.3%. If the CoO content is below 0.1%, insufficient absorption in the mid-to-long wavelength range will fail to fill the absorption gaps of other ions, leading to crosstalk light leakage. If the CoO content is above 0.3%, excessive CoO will increase the glass melt viscosity, increase the risk of defects such as bubbles and crystallization, deteriorate forming and processing performance, cause compositional fluctuations, and disrupt absorption uniformity.

[0033] K₂O and Na₂O are network-external oxides and core fluxes. They reduce high-temperature viscosity by disrupting the silicon-oxygen network and simultaneously regulate the glass's coefficient of thermal expansion. This application limits the total content of K₂O and Na₂O to 5-8%, more preferably 6-7%. If the total content of K₂O and Na₂O is less than 5%, the fluxing effect is insufficient, resulting in high glass melt viscosity, uneven dispersion of coloring ions, and an imbalance in the ratio with Al₂O₃, failing to form a stable aluminum-oxygen tetrahedral structure and reducing the glass's resistance to crystallization. If the total content of K₂O and Na₂O is greater than 8%, it reduces the glass's chemical stability and mechanical strength. Excessive alkali metal ions are prone to migration, which can lead to internal component segregation within the glass. Under long-term use or irradiation, localized areas may become enriched with alkali metal ions, causing structural defects such as microcracks and crystallization.

[0034] In this application, KHF2 and K2SiF6 are both potassium fluoride complex salts, whose core function focuses on improving fluxing effect and compatibility with low-refractive-index glass. This application limits the total content of KHF2 and K2SiF6 to 0.8-1.5%, more preferably, to 1.0-1.2%. If the total content of KHF2 and K2SiF6 is less than 0.8%, the compositional similarity with low-refractive-index glass is insufficient, resulting in decreased interfacial compatibility, structural defects, difficulties in wire drawing, and insufficient fluxing effect, leading to higher glass melt viscosity and incomplete melting of raw materials. If the total content of KHF2 and K2SiF6 is greater than 1.5%, excessive fluoride ions will damage the integrity of the glass network, leading to a significant increase in glass phase separation and crystallization tendency, reducing the structural stability and chemical durability of the glass. Simultaneously, it may cause excessive fluoride volatilization, resulting in compositional fluctuations and affecting compatibility with low-refractive-index glass.

[0035] ZnO is an auxiliary flux and structural stabilizer that can lower the melting temperature, improve the corrosion resistance of glass, and inhibit crystallization. This application limits the ZnO content to 1-3%, more preferably 2-3%. If the ZnO content is less than 1%, the fluxing effect is not significant and the melting temperature cannot be effectively lowered; if the ZnO content is greater than 3%, it easily forms a low-melting-point eutectic phase with CuO and CoO, lowering the glass softening point and causing capillary deformation during melting and pressing; simultaneously, excessive Zn²⁺ will disrupt the charge balance of the glass network, increase the tendency for phase separation, and affect the uniformity of light absorption.

[0036] CeO2 combines the functions of radiation-resistant modification and valence state stabilizer. 3+ / Ce 4+ The valence balance of CeO2 acts as an electron / hole trap, blocking the destruction pathway of coloring centers induced by neutron irradiation. Its irradiation protection effect inhibits the decolorization of coloring centers, and CeO2 of less than 1% exhibits no additional coloring / decolorization behavior, while simultaneously stabilizing Mn. 3+ Fe 3+ The high valence state of the CeO2 is specified in this application as 0.2-1.0%, more preferably 0.5-0.8%. If the CeO2 content is below 0.2%, it cannot effectively block the destruction of coloring centers caused by neutron irradiation, resulting in a lighter color and decreased absorption performance of the glass after fast neutron irradiation; furthermore, it is difficult to stabilize high valence coloring ions, leading to the partial loss of Mn. 3+ Fe 3+ Reduction reduces crosstalk light absorption efficiency; if the CeO2 content is higher than 1.0%, then excess Ce... 4+ It will increase the tendency of glass crystallization and may interact with other coloring ions, causing absorption peak shift and disrupting the full-band absorption coverage.

[0037] In some embodiments, the ratio of SiO2 / (KHF2+K2SiF6) is limited to 60~90, preferably 65~75. The principle is that SiO2 is the core of the glass network skeleton, and fluoride plays the role of fluxing and reducing viscosity. This ratio can avoid excessive fluoride damaging the silicon-oxygen network and causing the structure to become loose, while preventing insufficient fluoride from causing the melting temperature to be too high and the number of bubble defects to increase. The preferred range can balance the network density and the melt flowability.

[0038] In some embodiments, the ratio (SiO2+Al2O3) / (Mn2O3+Fe2O3+CuO+CoO) is limited to 45~75, preferably 60~70. This ratio can control the concentration of transition metal ions and suppress the tendency of crystallization. The preferred range can ensure the stability of the black tone of the glass and improve its radiation resistance.

[0039] This application discloses a method for preparing light-absorbing glass for fabricating liquid scintillator capillary arrays, the steps of which include: Prepare any of the aforementioned raw materials for fabricating the light-absorbing glass of the liquid scintillator capillary array, and mix them according to the corresponding mass percentages. Preferably, SiO2 is introduced from quartz sand, Mn, Co, Fe, and Cu are introduced in the form of oxides, K2O and Na2O are introduced in the form of carbonates. When introducing carbonates, high-temperature drying is required to avoid introducing moisture that could cause bubbles to form in the glass. Al2O3 and B2O3 are introduced in the form of hydroxides, and the remaining raw materials are added directly on their own.

[0040] After the raw materials are thoroughly mixed, and the furnace temperature is raised to 1250~1300℃, the raw materials are gradually added to the platinum crucible located in the furnace in multiple batches. Then the temperature is raised to 1450~1500℃, and the mixture is continuously stirred and clarified. During the stirring and clarification process, oxygen is continuously introduced to maintain the oxidizing atmosphere during glass melting, ensuring that Mn and Fe exist in high oxidation states, guaranteeing the absorption effect, and obtaining glass melt.

[0041] The glass melt is cooled to 1150~1200℃, then poured into a mold, and cooled to room temperature to obtain the molded glass body.

[0042] The shaped glass body is subjected to precision annealing. The heating rate during annealing is 1.0~2.0℃ / min. The temperature is raised to 500~550℃ and held for 6~8h. Then it is cooled to room temperature at 0.5~2℃ / min to obtain light-absorbing glass for preparing liquid scintillation capillary arrays.

[0043] This application proposes a liquid scintillation capillary array comprising any of the aforementioned light-absorbing glasses used to fabricate the liquid scintillation capillary array.

[0044] This application proposes a method for fabricating a liquid scintillator array, the steps of which include: After drawing any of the aforementioned light-absorbing glass used to prepare liquid scintillator capillary arrays into fibers, they are wrapped around a glass tube with a low refractive index and a high softening point. The fibers are drawn into monofilaments and multifilaments, and the multifilaments are regularly arranged in a matching cladding glass. The fibers are then hot-melted and pressed into blank segments. After machining, cleaning, liquid scintillator filling, and adhesive encapsulation, a liquid scintillator micropore array, i.e., a liquid scintillator capillary array, is obtained.

[0045] This application proposes the application of any of the aforementioned light-absorbing glasses used in the fabrication of liquid scintillator arrays in the field of fast neutron imaging detectors.

[0046] The present application 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 application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application are still within the scope of protection of the present application.

[0047] 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 one of ordinary skill in the art to which this application pertains.

[0048] The materials and reagents used in the following examples are all commercially available. In the following examples and comparative examples, the transmittance was tested using the test method in GB / T2680-2021, and the softening temperature T was tested using the test method in GB / T7962.16-2010. f .

[0049] In the following content, the content of each component in Tables 1 and 2 are all mass percentages based on oxides; where K1 is the mass ratio of SiO2 to (KHF2+K2SiF6); K2 is the mass ratio of (SiO2+Al2O3) to (Mn2O3+Fe2O3+CuO+CoO); transmittance represents the peak value of the transmittance curve of 0.5mm thick glass in the 375~700nm range, in percentages (%). f The softening temperature of the glass is expressed in °C; resistance to crystallization indicates the glass's resistance to crystallization at temperatures ranging from 650 to 1000 °C; "Excellent" indicates that after holding at any temperature within the range for 2 hours, no crystals precipitate on the glass sample, while "Poor" indicates that after holding at any temperature within the range for 2 hours, visible crystals precipitate on the glass sample. Glass with a transmittance of 0.5 mm after irradiation... 252 The peak value of the transmittance curve of Cf as a fast neutron radiation source after irradiation with a total dose of 100 Gy, in units of . Example 1

[0050] Example 1 provides a light-absorbing glass for preparing liquid scintillation capillary arrays and a method for preparing the same.

[0051] The raw materials were prepared according to the formula for the light-absorbing glass used to prepare the liquid scintillation capillary array. The composition of the formula for the light-absorbing glass used to prepare the liquid scintillation capillary array is shown in Table 1. SiO2 was introduced from quartz sand, Mn, Co, Fe, and Cu were introduced in the form of oxides, K2O and Na2O were introduced in the form of carbonates. High-temperature drying was required when introducing carbonates to avoid introducing moisture that would cause bubbles to form in the glass. Al2O3 and B2O3 were introduced in the form of hydroxides, and the remaining raw materials were added directly on their own.

[0052] After the raw materials are thoroughly mixed, the furnace temperature is raised to 1300℃, and the raw materials are gradually added to the platinum crucible located in the furnace in multiple batches. Then the temperature is raised to 1500℃, and the mixture is continuously stirred and clarified. During the stirring and clarification process, oxygen is continuously introduced to maintain the oxidizing atmosphere during glass melting, ensuring that Mn and Fe exist in high oxidation states to guarantee the absorption effect. The melting process is carried out for 12 hours to obtain glass melt.

[0053] The glass melt is cooled to 1200℃, then poured into a mold, and cooled to room temperature to obtain the molded glass body.

[0054] The shaped glass body was subjected to precision annealing. The heating rate during annealing was 2.0℃ / min. The temperature was raised to 550℃ and held for 8 hours. Then, it was cooled to room temperature at 2℃ / min to obtain light-absorbing glass for preparing liquid scintillation capillary arrays.

[0055] The physicochemical properties of the light-absorbing glass used to prepare the liquid scintillation capillary array were tested, and the results are shown in Table 1. Example 2

[0056] Example 2 provides a light-absorbing glass for preparing liquid scintillation capillary arrays and a method for preparing the same.

[0057] The raw materials were prepared according to the formula for the light-absorbing glass used to prepare the liquid scintillation capillary array. The composition of the formula for the light-absorbing glass used to prepare the liquid scintillation capillary array is shown in Table 1. SiO2 was introduced from quartz sand, Mn, Co, Fe, and Cu were introduced in the form of oxides, K2O and Na2O were introduced in the form of carbonates. High-temperature drying was required when introducing carbonates to avoid introducing moisture that would cause bubbles to form in the glass. Al2O3 and B2O3 were introduced in the form of hydroxides, and the remaining raw materials were added directly on their own.

[0058] After the raw materials are thoroughly mixed, the furnace temperature is raised to 1250°C. The raw materials are then gradually added to the platinum crucible located in the furnace in multiple batches. The temperature is then raised to 1450°C, and the mixture is continuously stirred and clarified. During the stirring and clarification process, oxygen is continuously introduced to maintain the oxidizing atmosphere during glass melting, ensuring that Mn and Fe exist in high oxidation states to guarantee the absorption effect. The melting process is carried out for 12 hours to obtain the glass melt.

[0059] The glass melt is cooled to 1150°C, then poured into a mold, and cooled to room temperature to obtain the molded glass body.

[0060] The shaped glass body was subjected to precision annealing. The heating rate during annealing was 1.0℃ / min. The temperature was raised to 500℃ and held for 6 hours. Then, it was cooled to room temperature at 0.5℃ / min to obtain light-absorbing glass for preparing liquid scintillation capillary arrays.

[0061] The physicochemical properties of the light-absorbing glass used to prepare the liquid scintillation capillary array were tested, and the results are shown in Table 1.

[0062] Examples 3-6 The difference between Examples 3-6 and Example 1 lies in the formulation of the light-absorbing glass used to prepare the liquid scintillation capillary array; other preparation processes are the same as in Example 1. The formulations of the light-absorbing glass used to prepare the liquid scintillation capillary array in Examples 3-6 are shown in Table 1. The physicochemical properties of the light-absorbing glass used to prepare the liquid scintillation capillary array in Examples 3-6 were tested, and the results are shown in Table 1.

[0063] Comparative Examples 1-4 The difference between Comparative Examples 1-4 and Example 1 lies in the glass formulation; all other preparation processes are the same as in Example 1. The formulations of the glasses in Comparative Examples 1-4 are shown in Table 1. The physicochemical properties of the glasses in Comparative Examples 1-4 were tested, and the results are shown in Table 2.

[0064] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that Comparative Example 5 uses a melting atmosphere without oxygen during raw material melting, while the other preparation processes are the same as in Example 1. The physicochemical properties of the glass in Comparative Example 5 were tested, and the results are shown in Table 2.

[0065] Table 1. Raw material composition and physicochemical properties of light-absorbing glasses used in Examples 1-6 for preparing liquid scintillation capillary arrays.

[0066] Table 2. Raw material composition and physicochemical properties of glass in Comparative Examples 1-5

[0067] As can be seen from the test data of Examples 1-6 above, the light-absorbing glass prepared by this invention for fabricating liquid scintillator arrays has excellent comprehensive performance and can accurately meet the core usage requirements of liquid scintillator arrays: "strong absorption of crosstalk light in the 375-700nm range, compatibility with low-refractive-index glass, and ensuring structural stability and radiation resistance." Specifically, the components of Examples 1-6 are strictly controlled within the specified range, the transmittance in the 375-700nm band is stable at 0.7%-1.8%, and the crosstalk light suppression effect is significant; the glass softening point is controlled at 620-650℃, which has a high degree of matching with the thermal process of low-refractive-index glass, and there is no interface delamination or cracking during the wire drawing process; after 100Gy fast neutron irradiation, the transmittance still meets the usage requirements, and no obvious crystal phase formation is observed in the anti-crystallization test (holding at any temperature point of 650-1000℃ for 2h), and the mechanical strength and thermal properties meet the requirements for capillary drawing and hot-melt pressing.

[0068] However, Comparative Examples 1-4 all have certain defects because the content of key components deviates from the specified range: In Comparative Example 1, the contents of Mn2O3, Fe2O3, CuO, and CoO were all below the limit range, resulting in insufficient coloring centers in the glass in the 375~700nm wavelength range, weakened light absorption capacity, and the peak value of the transmittance curve rose to more than 6.7%, exceeding the limit requirement of 2%, which could not meet the strong absorption of crosstalk light between capillaries. In Comparative Example 2, the contents of Mn2O3, Fe2O3, CuO, and CoO were all higher than the limit range. Excessive heavy metal ions damaged the integrity of the glass network and crystals precipitated during the normal cooling process. The glass appeared cloudy and lost its basic performance characteristics, including the fiber drawing process, making it easy to break during processing or use. In Comparative Example 3, the contents of SiO2 and Al2O3 were both below the limit range, the glass network skeleton was loose and the bonding strength was insufficient, and the softening point dropped to below 590℃, which is below the normal range of 620~650℃. Therefore, it could not be adapted to the drawing process of tube glass with low refractive index and high softening point. In Comparative Example 4, the content of anti-crystallization elements such as CeO2 was below the specified range. CeO2 is the core regulating component for the radiation resistance of glass, and its main component in the glass is Ce. 4+ / Ce 3+ The presence of valence pairs acts as an electron / hole trap, blocking the destruction path of coloring centers caused by neutron irradiation and stabilizing the glass under irradiation. In this comparative example, the amount of CeO2 added was insufficient, and the black coloring centers in the glass underwent decolorization / decomposition under neutron irradiation, resulting in a lighter color. This manifested as an increase in peak transmittance, a decrease in irradiation resistance, and a weakening of anti-light crosstalk capability, failing to meet the application requirements.

[0069] The components of Comparative Example 5 were identical to those of Example 1, but a melting atmosphere without oxygen was used. The peak transmittance of the glass in Comparative Example 5 at 375–700 nm was 35%. This is because the electron transition energies of high-valence transition metal ions such as iron and manganese match the energy of visible light photons, resulting in characteristic absorption. The introduction of oxygen during glass melting utilizes its strong oxidizing environment to suppress the reduction reaction of high-valence metal ions, while simultaneously allowing trace amounts of Fe in the system to dissolve. 2+ Mn 2+ Oxidation to the trivalent state, and the presence of a large number of low-valent metal ions in Comparative Example 5, resulted in a significant reduction in absorption capacity.

[0070] The technical features in this application specification can be combined, and the technical solutions obtained by combining these features are also within the scope of protection of this application. The above description is merely a preferred embodiment of this application and is not intended to limit this application in any way. Any simple modifications, equivalent changes, or alterations made to the above embodiments based on the technical essence of this application shall still fall within the scope of the technical solution of this application.

Claims

1. A light-absorbing glass for preparing liquid scintillation capillary arrays, characterized in that, Its components, expressed as a percentage by mass of oxides, include: SiO2: 70~78%; Al2O3: 3~6%; B2O3: 5~12%; Mn2O3: 0.5~1.5%; Fe2O3: 0.2~0.7%; CuO: 0.1~0.3%; CoO: 0.1~0.3%; ZnO: 1~3%; CeO2: 0.2~1%; The combined content of K2O and Na2O is 5-8%; The combined content of KHF2 and K2SiF6 is 0.8-1.5%.

2. The light-absorbing glass for preparing liquid scintillation capillary arrays according to claim 1, characterized in that, SiO2: 74~76%; Al2O3: 4~5%; B2O3: 6~8%; Mn2O3: 0.5~1%; Fe2O3: 0.3~0.5%; CuO: 0.2~0.3%; CoO: 0.2~0.3%; ZnO: 2~3%; CeO2: 0.5~0.8%; The combined content of K2O and Na2O is 6-7%; The combined content of KHF2 and K2SiF6 is 1~1.2%.

3. The light-absorbing glass for preparing liquid scintillation capillary arrays according to claim 1, characterized in that, SiO2 / (KHF2+K2SiF6) = 60~90; and / or, (SiO2+Al2O3) / (Mn2O 3+ Fe2O 3+ CuO+CoO)=45~75。 4. The light-absorbing glass for preparing liquid scintillation capillary arrays according to claim 3, characterized in that, SiO2 / (KHF2+K2SiF6) = 65~75; and / or, (SiO2+Al2O3) / (Mn2O 3+ Fe2O 3+ CuO+CoO)=60~70。 5. The light-absorbing glass for preparing liquid scintillation capillary arrays according to claim 1, characterized in that, When the thickness of the light-absorbing glass used to prepare the liquid scintillation capillary array is 0.5 mm, its transmittance does not exceed 2% in the wavelength range of 375~700 nm.

6. The light-absorbing glass for preparing liquid scintillation capillary arrays according to claim 1, characterized in that, When the thickness of the light-absorbing glass used to prepare the liquid scintillation capillary array is 0.5 mm, the following is used: 252 Cf, as a fast neutron radiation source, was tested for transmittance after being irradiated with a total dose of 100 Gy of fast neutrons, and the measured value was <2%.

7. The light-absorbing glass for preparing liquid scintillation capillary arrays according to claim 1, characterized in that, The softening temperature T of the light-absorbing glass used to fabricate the liquid scintillator capillary array f Between 600 and 650℃.

8. A method for preparing light-absorbing glass for fabricating liquid scintillation capillary arrays, characterized in that, The steps include: The raw materials are thoroughly mixed and heated to 1450~1500℃ for melting. During the melting process, the mixture is stirred, clarified, and oxygen is continuously introduced to obtain glass melt. The glass melt is cooled to 1150~1200℃, then poured into a mold, and cooled to room temperature to obtain a molded glass body. The shaped glass body is annealed at a heating rate of 1.0~2.0℃ / min, heated to 500~550℃ and held for 6~8h, and then cooled to room temperature at 0.5~2℃ / min to obtain light-absorbing glass for preparing liquid scintillation capillary arrays. The components of the raw material, based on the mass percentage of oxides, include: SiO2: 70~78%; Al2O3: 3~6%; B2O3: 5~12%; Mn2O3: 0.5~1.5%; Fe2O3: 0.2~0.7%; CuO: 0.1~0.3%; CoO: 0.1~0.3%; ZnO: 1~3%; CeO2: 0.2~1%; The combined content of K2O and Na2O is 5-8%; The combined content of KHF2 and K2SiF6 is 0.8-1.5%.

9. A liquid scintillation capillary array, characterized in that, It comprises the light-absorbing glass for preparing liquid scintillation capillary arrays as described in any one of claims 1-7.

10. The application of the light-absorbing glass for fabricating liquid scintillation capillary arrays as described in any one of claims 1-7 in the field of fast neutron imaging detectors.

Images