Microchannel plate glass and method of making same

Abstract

This invention discloses a microchannel plate glass and its preparation method, relating to the field of special glass materials technology. The microchannel plate glass includes a skin glass and a core glass. The skin glass includes P2O5, V2O5, BaO, La2O3, Li2O+Na2O+K2O, ZrO, Al2O3 and Al(OH)3, PbO, and Fe2O3. The core glass includes P2O5, ZnO, Al2O3 and Al(OH)3, SiO2, CaO+MgO, and BaO. This invention overcomes the shortcomings of traditional lead-containing silicate glass as a substrate material for MCP microporous arrays. Furthermore, the microchannel plate made of semiconductor glass does not require hydrogenation heat treatment and does not exhibit this "cation feedback" phenomenon. Compared to microchannel plates made of ordinary glass, the bulk conductivity microchannel plate can maintain stable performance over a long period. By screening specific material components and optimizing the ratio of each component, the skin glass and core glass can simultaneously possess a stable network framework and a high softening temperature, while achieving a precise match between their coefficients of thermal expansion and high-temperature viscosity coefficients.

Description

Technical Field

[0001] This invention relates to the field of special glass materials technology, specifically to a microchannel plate glass and its preparation method. Background Technology

[0002] Microchannel plates are a type of excellent two-dimensional electron multiplier material made of glass fiber. They have characteristics such as high gain, high spatial resolution, and high temporal resolution, and are the core material for extremely weak photoelectric detection devices such as intensifiers, photomultiplier tubes, and photon counters.

[0003] The current mainstream manufacturing process for microchannel plates relies on multi-fiber glass drawing technology. This process involves preparing two complementary glass materials: a skin glass tube that is insoluble in acids and a core glass rod that is soluble in acids. Under high temperature conditions, the skin glass tube and the core glass rod are drawn together into single glass fibers. Subsequently, a large number of these single fibers are regularly arranged and bundled to form a multifilament structure. Several multifilaments are further combined and bundled together, and then wrapped with edge glass. This is then integrated through a high-temperature fusion process and cut into thin sheets. The final crucial step is acid etching, which selectively dissolves and removes the core glass, thereby forming the desired microporous array structure within the matrix. This series of process steps imposes strict matching requirements on the physicochemical properties of the core and skin glass: they must be highly synergistic in terms of thermal properties, mechanical properties, and chemical compatibility to ensure good interfacial bonding and a defect-free process during drawing and fusion. Crucially, when faced with the same acid etching solution, the core and the outer layer must exhibit distinctly different corrosion behaviors: the core glass must be easily dissolved by the acid, while the outer glass must demonstrate superior acid resistance to ensure the precise formation of the microchannel structure.

[0004] Currently, lead silicate glass is a widely used material in the manufacture of microchannel plates. However, this type of material has some inherent limitations. Its low softening temperature can lead to thermal distortion or micro-stress during multifilament drawing and high-temperature pressing. These micro-stresses can be amplified instantaneously during subsequent acid etching of the core glass. Furthermore, after hydrogen reduction treatment, residual hydrogen and water on the channel surface can escape during vacuum operation, creating interference signals as cations move towards the cathode within the channel. This manifests primarily as high background noise and susceptibility to aging and deformation. These defects directly limit the operating voltage to a relatively low level, thus restricting electronic gain. Therefore, traditional microchannel plate glass fabrication methods need improvement. Summary of the Invention

[0005] The purpose of this invention is to provide a microchannel plate glass and its preparation method, which overcomes the problems of high background noise, easy aging and deformation of existing microporous substrates, and solves the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a microchannel plate glass, wherein the microchannel plate glass comprises a skin glass and a core glass; The glass material comprises: P2O5, V2O5, BaO, La2O3, Li2O + Na2O + K2O, ZrO, Al2O3 and Al(OH)3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 1.0-4.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 25.0-75.0 wt%, ZnO is 13.0-30.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO+MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%.

[0007] Optionally, the glass material comprises, by weight percentage: 50wt% P2O5, 15wt% V2O5, 1wt% BaO, 1wt% La2O3, 2wt% Li2O + Na2O + K2O, 1wt% ZrO, 2wt% Al2O3 and Al(OH)3, 14.6wt% PbO, 13.4wt% Fe2O3; The core glass comprises, by weight percentage: 58wt% P2O5, 20wt% ZnO, 6wt% Al2O3 and Al(OH)3, 10wt% SiO2, 5wt% CaO + MgO and 1wt% BaO.

[0008] Optionally, the glass material comprises, by weight percentage: 49wt% P2O5, 12wt% V2O5, 2.5wt% BaO, 1wt% La2O3, 1wt% Li2O + Na2O + K2O, 0.5wt% ZrO, 4wt% Al2O3 and Al(OH)3, 19wt% PbO, 11wt% Fe2O3; The core glass comprises, by weight percentage: 65wt% P2O5, 30wt% ZnO, 1wt% BaO, 2wt% Al2O3 and Al(OH)3, 1wt% SiO2, 1wt% CaO + MgO.

[0009] Optionally, the glass material comprises, by weight percentage: 46wt% P2O5, 14wt% V2O5, 2.5wt% BaO, 1wt% La2O3, 1wt% Li2O + Na2O + K2O, 0.5wt% ZrO, 2wt% Al2O3 and Al(OH)3, 22wt% PbO, 11wt% Fe2O3; The core glass comprises, by weight percentage: 72wt% P2O5, 20wt% ZnO, 1wt% BaO, 2wt% Al2O3 and Al(OH)3, 3wt% SiO2, 2wt% CaO + MgO.

[0010] Optionally, in the glass material: BaO is introduced in the form of BaCO3 and Ba(NO3)2, with a molar ratio of BaCO3∶Ba(NO3)2<2∶1; MgO is introduced in the form of (MgCO3)4・Mg(OH)2・5H2O; CaO is introduced in the form of CaCO3; and the molar ratio of Al2O3 and Al(OH)3 in the glass is 1∶1. In the core glass: BaO is introduced in the form of BaCO3 and Ba(NO3)2, with a molar ratio of BaCO3:Ba(NO3) < 1:3; MgO is introduced in the form of (MgCO3)4・Mg(OH)2・5H2O; CaO is introduced in the form of CaCO3, with a molar ratio of MgO:CaO < 2:3; and the molar ratio of Al2O3 to Al(OH)3 in the core glass is 1:2.

[0011] Optionally, the glass material comprises: P2O5, V2O5, BaO, La2O3, CeO2, Li2O + Na2O + K2O, ZrO, Al2O3 and Al(OH)3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 0-3.0 wt%, CeO2 is 1.0-3.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 25.0-75.0 wt%, ZnO is 13.0-30.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO + MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%. The softening temperature of the outer glass is Tf≥550℃, and the softening temperature of the core glass is Tf≥510℃.

[0012] Optionally, the glass material comprises: P2O5, V2O5, BaO, La2O3, Li2O+Na2O+K2O, ZrO, Al2O3 and Al(OH)3, PbO, Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 1.0-4.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Bi2O3, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 23.0-73.0 wt%, ZnO is 10.0-28.0 wt%, Bi2O3 is 2.0-5.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO + MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%. The softening temperature (Tf) of the glass is ≥550℃, and the coefficient of thermal expansion at 20-300℃ is 70-85×10⁻⁶. -7 / ℃; the softening temperature of the core glass Tf≥510℃, and the coefficient of thermal expansion at 20-300℃ is 69-85×10. -7 / ℃.

[0013] Optionally, the glass material comprises: P2O5, V2O5, BaO, La2O3, Li2O+Na2O+K2O, ZrO, Al2O3 and Al(OH)3, Y2O3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 1.0-4.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 0-8.0 wt%, Y2O3 is 0.5-2.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Y2O3, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 25.0-75.0 wt%, ZnO is 10.0-27.0 wt%, Y2O3 is 1.0-3.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO+MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%.

[0014] The present invention also improves the following preparation method: a method for preparing microchannel plate glass, comprising preparing a skin glass and preparing a core glass; The preparation of the glass substrate includes the following process: S1: Weigh the corresponding raw materials according to the proportion, mix them evenly, and when the furnace temperature rises to 1150-1250℃, add the mixture to the Pt crucible located in the furnace in multiple batches. S2: Heat to 1300-1380℃, continuously stir, clarify, and homogenize the glass melt for the set time; S3: After cooling to 1200-1275℃, pour into the mold. After pouring, perform gradient cooling annealing. The gradient cooling annealing method is as follows: heat up to 450℃ at 2.5-5℃ / min and hold for 10 hours; cool down to 350℃ at 5-8℃ / hour; cool down to 200℃ at 2-3℃ / hour; cool down to room temperature at 1-2℃ / hour. S4: The glass sample to be tested is obtained after optical cold processing; The preparation of the core glass includes the following process: S1: Weigh each component according to the formula, mix them evenly, and when the furnace temperature rises to 1100-1180℃, add the mixture to the Pt crucible located in the furnace in multiple batches. S2: Heat to 1300-1380℃, continuously stir, clarify, and homogenize the glass melt for the set time; S3: After cooling to 1200-1260℃, pour into the mold. After pouring, perform precision annealing, with a heating rate of 1.0-2.5℃ / min, heat to 450℃ and hold for 5 hours, then cool to room temperature at 1.0-2.0℃ / h. S4: The glass sample to be tested is obtained after optical cold processing.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: I. The bulk conductive microchannel plate substrate material provided by this invention is vanadium phosphate glass, which overcomes the defects of traditional lead-containing silicate glass as MCP micropore array substrate material. Furthermore, the microchannel plate made of semiconductor glass does not require hydrogen heat treatment and does not have this "cation feedback" phenomenon. Compared with microchannel plates made of ordinary glass, the performance of the bulk conductive microchannel plate can remain stable for a long time.

[0016] II. This invention, by screening specific material components and optimizing the proportions of each component, enables the production of glass coatings. It possesses a stable network framework and a high softening temperature along with the core glass, while also achieving a precise match between their coefficients of thermal expansion and high-temperature viscosity.

[0017] Third, the anti-crystallization temperature of the skin glass and core glass provided by this invention reaches 850℃.

[0018] Fourth, by introducing cerium oxide, this invention can significantly enhance the radiation damage resistance of the glass substrate and maintain the long-term stability of the bulk conductive channel. This allows the microchannel plate to significantly improve the consistency and stability of electronic gain in extreme environments such as deep space exploration and nuclear physics experiments, effectively solving the problems of increased noise and performance degradation caused by radiation aging of traditional microchannel plates, and extending the service life of the equipment.

[0019] V. By introducing bismuth trioxide, this invention can reduce scattering loss during electron transport, enabling electrons to travel in a straight line along the channel and improving electron transport efficiency. At the same time, it can also ensure the uniformity of the secondary electron emission coefficient of the inner wall of the channel, avoiding the problems of blurred imaging and reduced detection signal resolution caused by the roughness of the inner wall of traditional microchannel plates. It is especially suitable for scenarios with imaging requirements such as medical fluorescence microscopes and low-light night vision systems.

[0020] VI. This invention introduces yttrium oxide into both the skin glass and the core glass, enhancing the cross-linking degree of the glass network and significantly improving the mechanical strength and impact resistance of both the skin and core glass. During assembly, transportation, and use, the glass is less prone to microcracks, especially in high-vibration environments, avoiding the channel structure damage problems caused by vibration in traditional microchannel plates. Simultaneously, yttrium oxide optimizes the interfacial bonding between the skin and core materials, reducing stress concentration at the interface and preventing interfacial delamination caused by long-term thermal cycling stress, further improving the structural stability and service life of the microchannel plate and reducing equipment maintenance costs.

[0021] VII. This invention utilizes a gradient cooling annealing process to precisely control the release of thermal stress within the glass, ensuring that the temperature gradient between the glass surface and interior remains within a reasonable range. This significantly reduces residual stress and greatly improves the dimensional stability of the glass. Consequently, during subsequent cutting and drawing processes, the glass is less prone to deformation and cracking, resulting in a higher yield rate. Attached Figure Description

[0022] Figure 1 The preparation principle of this invention Figure 1 ; Figure 2 For the present invention Figure 1 First proportion diagram; Figure 3 For the present invention Figure 1 The second proportion diagram; Figure 4 For the present invention Figure 1 The third proportion diagram; Figure 5 The preparation principle of this invention Figure 2 ; Figure 6 The preparation principle of this invention Figure 3 ; Figure 7 The preparation principle of this invention Figure 4 ; Figure 8 This is a flowchart illustrating the preparation process of the glass material of this invention. Figure 9 This is a flowchart illustrating the preparation process of the core glass of this invention. Detailed Implementation

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1, please refer to Figure 1 This invention provides a microchannel plate glass, comprising a skin glass and a core glass. By screening specific components and optimizing the proportions of each component, both types of glass can possess a stable network framework and excellent mechanical properties, while achieving a precise match between their coefficients of thermal expansion and viscosity. The skin glass comprises: 45.0-55.0 wt% P2O5, 12.0-20.0 wt% V2O5, 1.0-5.0 wt% BaO, 1.0-4.0 wt% La2O3, 1.0-4.0 wt% Li2O + Na2O + K2O, 0-1.0 wt% ZrO, 2.0-10.0 wt% Al2O3 and Al(OH)3, 12.0-25.0 wt% PbO, 10.0-15.0 wt% Fe2O3; The core glass comprises 25.0-75.0 wt% P2O5, 13.0-30.0 wt% ZnO, 2.0-10.0 wt% Al2O3 and Al(OH)3, 1.0-10.0 wt% SiO2, 0-5.0 wt% CaO + MgO, and 0-1.0 wt% BaO.

[0025] In the glass cladding: BaO is introduced in the form of BaCO3 and Ba(NO3)2, with a molar ratio of BaCO3:Ba(NO3)2 < 2:1; MgO is introduced in the form of (MgCO3)4・Mg(OH)2・5H2O; CaO is introduced in the form of CaCO3; and the molar ratio of Al2O3 and Al(OH)3 in the glass cladding is 1:1. In the core glass: BaO is introduced in the form of BaCO3 and Ba(NO3)2, with a molar ratio of BaCO3:Ba(NO3) < 1:3; MgO is introduced in the form of (MgCO3)4・Mg(OH)2・5H2O; CaO is introduced in the form of CaCO3, with a molar ratio of MgO:CaO < 2:3; and the molar ratio of Al2O3 to Al(OH)3 in the core glass is 1:2.

[0026] Furthermore, in vanadium phosphate glass, P2O5 is the main oxide, forming an irregular continuous network of phosphorus-oxygen tetrahedral PO4 structural elements that constitute the glass framework. Its structural state within the glass plays a decisive role in the properties of vanadium phosphate glass. P2O5 exists in the glass network structure as layered P2O5 and chain-like PO3. - and isolated PO4 3- Equal structure; V₂O₅ exists in glass as vanadium-oxygen polyhedra, such as VO₄. 3- VO5 5-As a structural unit, this invention can significantly reduce the glass melting point and improve melt flowability by adjusting its dosage. Furthermore, vanadium phosphate glass with high P2O5 content has a tendency to phase separation. For multi-component vanadium phosphate glass, the ratio of P2O5% to V2O5% should be less than 5-6:1. Adding a certain amount of barium oxide (BaO) can optimize the material properties of glass when it is taken out of the furnace at high temperature, thereby increasing its transformation temperature and softening temperature, enhancing the viscosity of glass in high-temperature environments, and improving its resistance to acid corrosion. Adding an appropriate amount of lanthanum oxide (La2O3) can improve the material properties when it is taken out of the furnace, enhance its chemical and thermal stability, and suppress its tendency to crystallize. Adding an appropriate amount of iron oxide (Fe2O3) can also act as a network modifier, affecting chemical and thermal stability to a certain extent. Furthermore, Fe+2 / Fe+3 can exhibit an electronic transition effect in vanadium phosphate glass, introducing conductivity that can improve electronic properties. Adding appropriate amounts of specific proportions of alkali metal oxides, such as Li2O, Na2O, and K2O, can, on the one hand, destroy the three-dimensional main network structure composed of network forgings, transforming it into an intermediate state between chain-like and framework-like structures. This can effectively maintain the strength of the glass main framework and moderately increase its coefficient of expansion. On the other hand, these oxides can also reduce the viscosity of the glass, thus facilitating the glass melting process. PbO, Al2O3, and ZrO can increase the transition temperature and softening temperature of glass, enhance its chemical stability, acid resistance, and the strength of the channel array support.

[0027] Furthermore, in the core glass: P2O5, as the main oxide of phosphate glass, plays a crucial role in the glass network. The phosphorus-oxygen tetrahedron (PO4) exists in the structure, forming the glass network framework. The chain-like or layered structure of the phosphorus-oxygen tetrahedrons gives the glass a certain degree of chemical stability, while also affecting the glass's coefficient of thermal expansion and high-temperature viscosity. In core glass, its structural characteristics are beneficial for controlling the glass's melting properties, but it needs to work in conjunction with other oxides to match the viscosity and coefficient of thermal expansion of the skin glass; therefore, its content must be controlled within a reasonable range. ZnO acts as both a network intermediate and a modifier, forming zinc-oxygen tetrahedral or triangular structures within the glass network. Appropriate addition can increase the glass transition temperature and softening temperature, while simultaneously reducing its high-temperature viscosity, improving melting and formability, facilitating matching with the drawing properties of sheet glass, suppressing glass crystallization tendency, and enhancing the glass's mechanical strength.

[0028] This invention introduces Ba by adding an appropriate amount of BaO. 2+It can increase the glass transition temperature and softening temperature, increase the high-temperature viscosity coefficient, and have the same drawing performance as the skin. Adding a specific amount of SiO2 can improve the strength of the network skeleton through the silicon-oxygen tetrahedral SiO4 structure, increase the high-temperature viscosity coefficient, and make the furnace material properties of the core glass and the viscosity of the skin glass precisely match. This is the key to ensuring the interfacial bonding and drawing performance of the skin and core glass. Adding appropriate amounts of CaO and MgO can reduce the viscosity of glass at high temperatures, promoting high-temperature melting and clarification; MgO can reduce the tendency and rate of glass crystallization, increase the high-temperature viscosity of glass, and improve the chemical stability and mechanical strength of glass. The synergistic effect of the two can adjust the melting performance and structural stability of the core glass, achieving performance matching with the skin glass.

[0029] By adding small amounts of Al2O3 and Al(OH)3, aluminum-oxygen tetrahedra can be formed with the oxygen with double bonds in phosphate glass to strengthen the structure of phosphate glass and significantly increase the glass transition temperature and softening temperature.

[0030] Example 2, please refer to Figure 1 and Figure 2 Furthermore, the microchannel plate glass is prepared according to the following proportions: the glass material consists of 50wt% P2O5, 15wt% V2O5, 1wt% BaO, 1wt% La2O3, 2wt% Li2O + Na2O + K2O, 1wt% ZrO, 2wt% Al2O3 and Al(OH)3, 14.6wt% PbO, and 13.4wt% Fe2O3 by weight percentage. The core glass comprises, by weight percentage, 58 wt% P2O5, 20 wt% ZnO, 6 wt% Al2O3 and Al(OH)3, 10 wt% SiO2, 5 wt% CaO + MgO and 1 wt% BaO. After preparation according to the above proportions, the softening temperature of the glass is 568℃, and the coefficient of thermal expansion between 20-300℃ is 75x10⁻⁶. -7 The viscosity coefficient at 700-850℃ is 4.2-3.5 (log function value). The acid and alkali resistance of the core material was tested according to GB / T 7962.14-2010 Test Method for Acid Stability of Colorless Optical Glass. It belongs to Class 1. No crystallization occurs at 300-1200℃.

[0031] The core glass has a softening temperature of 520℃ and a coefficient of thermal expansion of 70x10⁻⁶ at 20-300℃. -7The viscosity coefficient at 700-850℃ is 3.9-3.3 (log function value). The acid and alkali resistance of the core material was tested according to GB / T 7962.14-2010 Test Method for Acid Stability of Colorless Optical Glass. It belongs to Class 5. No crystallization occurs at 300-1200℃. The high-temperature viscosity coefficient (log function value) and linear expansion coefficient of the obtained skin glass and core glass are very close. Both skin glass and core glass have high softening temperature and good acid solubility.

[0032] Example 3, please refer to Figure 1 and Figure 4 The microchannel plate glass was prepared according to the following proportions: the glass material consisted of 46wt% P2O5, 14wt% V2O5, 2.5wt% BaO, 1wt% La2O3, 1wt% Li2O + Na2O + K2O, 0.5wt% ZrO, 2wt% Al2O3 and Al(OH)3, 22wt% PbO, and 11wt% Fe2O3 by weight percentage. The core glass comprises, by weight percentage, 72 wt% P2O5, 20 wt% ZnO, 1 wt% BaO, 2 wt% Al2O3 and Al(OH)3, 3 wt% SiO2, and 2 wt% CaO + MgO.

[0033] After preparation using the above method, the softening temperature of the glass is 557℃, and the coefficient of thermal expansion between 20-300℃ is 70x10⁻⁶. -7 The viscosity coefficient at 700-850℃ is 4.1-3.6 (log function value). The core material's acid and alkali resistance was tested according to GB / T 7962.14-2010, "Test Method for Acid Stability of Colorless Optical Glass," and it belongs to Class 1, showing no crystallization at 300-1200℃. After preparation using the above method, the core material glass softening temperature is 517℃, and the coefficient of thermal expansion at 20-300℃ is 69 x 10⁻⁶. -7 The viscosity coefficient at 700-850℃ is 3.7-3.3 (log function value). The acid and alkali resistance of the core material was tested according to GB / T 7962.14-2010 Test Method for Acid Stability of Colorless Optical Glass. It belongs to Class 5. No crystallization occurs at 300-1200℃.

[0034] Example 4, please refer to Figure 1 and Figure 3 The microchannel plate glass was prepared according to the following ratio: The glass material, by weight percentage, contains 49wt% P2O5, 12wt% V2O5, 2.5wt% BaO, 1wt% La2O3, 1wt% Li2O + Na2O + K2O, 0.5wt% ZrO, 4wt% Al2O3 and Al(OH)3, 19wt% PbO, and 11wt% Fe2O3. The core glass comprises, by weight percentage, 65 wt% P2O5, 30 wt% ZnO, 1 wt% BaO, 2 wt% Al2O3 and Al(OH)3, 1 wt% SiO2, and 1 wt% CaO + MgO.

[0035] After preparation using the above method, the softening temperature of the glass is 564℃, and the coefficient of thermal expansion between 20-300℃ is 71x10⁻⁶. -7 The viscosity coefficient at 700-850℃ is 4.1-3.5 (log function value). According to GB / T 7962.14-2010, the acid and alkali resistance of the core material was tested and it belongs to Class 1, with no crystallization at 300-1200℃. After oxidation and preparation using the above method, the softening temperature of the core material glass is 531℃, and the coefficient of thermal expansion at 20-300℃ is 70 x 10⁻⁶. -7 The viscosity coefficient at 700-850℃ is 3.8-3.4 (log function value). The acid and alkali resistance of the core material was tested according to GB / T 7962.14-2010 Test Method for Acid Stability of Colorless Optical Glass. It belongs to Class 5. No crystallization occurs at 300-1200℃.

[0036] Example 5, please refer to Figure 5 The glass material comprises 45.0-55.0 wt% P2O5, 12.0-20.0 wt% V2O5, 1.0-5.0 wt% BaO, 0-3.0 wt% La2O3, 1.0-3.0 wt% CeO2, 1.0-4.0 wt% Li2O + Na2O + K2O, 0-1.0 wt% ZrO, 2.0-10.0 wt% Al2O3 and Al(OH)3, 12.0-25.0 wt% PbO, and 10.0-15.0 wt% Fe2O3. The core glass comprises 25.0-75.0 wt% P2O5, 13.0-30.0 wt% ZnO, 2.0-10.0 wt% Al2O3 and Al(OH)3, 1.0-10.0 wt% SiO2, 0-5.0 wt% CaO + MgO, and 0-1.0 wt% BaO; After the introduction of CeO2, its Ce 4+ / Ce 3+Reversible redox pairs can form stable electron trapping centers in the glass network, which can efficiently trap free electrons and holes generated by cosmic rays and nuclear radiation, preventing radiation particles from directly damaging the glass network structure and greatly enhancing the radiation damage resistance of the glass.

[0037] Meanwhile, Ce 3+ The presence of Fe can suppress Fe at high temperatures 3+ / Fe 2+ The migration behavior of conductive ions maintains the long-term stability of the bulk conductive channel, which significantly improves the consistency and stability of electronic gain in extreme environments such as deep space exploration and nuclear physics experiments. This effectively solves the problems of increased noise and performance degradation caused by radiation aging of traditional microchannel plates, and extends the service life of equipment.

[0038] The softening temperature (Tf) of the glass in the outer casing is ≥550℃, and the coefficient of thermal expansion at 20-300℃ is 70-85×10⁻⁶. -7 / ℃; the softening temperature of the core glass Tf≥510℃, and the coefficient of thermal expansion at 20-300℃ is 69-85×10. -7 / ℃.

[0039] Example 6, please refer to Figure 6 The glass material comprises 45.0-55.0 wt% P2O5, 12.0-20.0 wt% V2O5, 1.0-5.0 wt% BaO, 1.0-4.0 wt% La2O3, 1.0-4.0 wt% Li2O + Na2O + K2O, 0-1.0 wt% ZrO, 2.0-10.0 wt% Al2O3 and Al(OH)3, 12.0-25.0 wt% PbO, and 10.0-15.0 wt% Fe2O3. The core glass comprises 23.0-73.0 wt% P2O5, 10.0-28.0 wt% ZnO, 2.0-5.0 wt% Bi2O3, 2.0-10.0 wt% Al2O3 and Al(OH)3, 1.0-10.0 wt% SiO2, 0-5.0 wt% CaO + MgO, and 0-1.0 wt% BaO.

[0040] The lone pair electrons of Bi2O3 can optimize the network structure of phosphate glass, making the chain-like PO structure and ZnO tetrahedral structure more uniformly interwoven and eliminating local structural differences. During acid etching, the dissolution rate of each region of the core glass tends to be uniform, the microscopic defects on the inner wall of the micropores are significantly reduced, and the smoothness is greatly improved. This not only reduces the scattering loss during electron transport, enabling electrons to transport in a straight line along the channel and improving electron transport efficiency, but also ensures the uniformity of the secondary electron emission coefficient of the inner wall of the channel. This avoids the problems of blurred imaging and reduced detection signal resolution caused by the roughness of the inner wall of traditional microchannel plates, making it particularly suitable for scenarios with high imaging requirements, such as medical fluorescence microscopes and low-light night vision systems.

[0041] The softening temperature (Tf) of the glass is ≥550℃, and the coefficient of thermal expansion at 20-300℃ is 70-85×10⁻⁶. -7 / ℃; the softening temperature of the core glass Tf≥510℃, and the coefficient of thermal expansion at 20-300℃ is 69-85×10. -7 / ℃.

[0042] Example 7, please refer to Figure 7 The glass material comprises 45.0-55.0 wt% P2O5, 12.0-20.0 wt% V2O5, 1.0-5.0 wt% BaO, 1.0-4.0 wt% La2O3, 1.0-4.0 wt% Li2O + Na2O + K2O, 0-1.0 wt% ZrO, 0-8.0 wt% Al2O3 and Al(OH)3, 0.5-2.0 wt% Y2O3, 12.0-25.0 wt% PbO, and 10.0-15.0 wt% Fe2O3. The core glass comprises 25.0-75.0 wt% P2O5, 10.0-27.0 wt% ZnO, 1.0-3.0 wt% Y2O3, 2.0-10.0 wt% Al2O3 and Al(OH)3, 1.0-10.0 wt% SiO2, 0-5.0 wt% CaO + MgO, and 0-1.0 wt% BaO.

[0043] Y₂O₃'s Y 3+ Ionic radius and Al 3+ Y₂O₃ can effectively integrate into the glass network structure, forming higher-energy YO bonds, enhancing the cross-linking degree of the glass network, and significantly improving the mechanical strength and impact resistance of both the skin and core glass. During assembly, transportation, and use, the glass is less prone to microcracks, especially in high-vibration environments, avoiding the channel structure damage problems caused by vibration in traditional microchannel plates. Simultaneously, Y₂O₃ can optimize the interfacial bonding force between the skin and core materials, reducing stress concentration at the interface and preventing interfacial delamination caused by long-term thermal cycling stress, further improving the structural stability and service life of the microchannel plate and reducing equipment maintenance costs.

[0044] Please see Figure 8 and Figure 9 The present invention provides a method for preparing a microchannel plate glass, including the preparation of a skin glass and the preparation of a core glass; The preparation of glass flakes includes the following processes: S1: Weigh the corresponding raw materials according to the proportion, mix them evenly, and when the furnace temperature rises to 1150-1250℃, add the mixture to the Pt crucible located in the furnace in multiple batches. S2: Heat to 1300-1380℃, continuously stir, clarify, and homogenize the glass melt for the set time; S3: After cooling to 1200-1275℃, pour into the mold. After pouring, perform gradient cooling annealing. The gradient cooling annealing method is as follows: heat up to 450℃ at 2.5-5℃ / min and hold for 10 hours; cool down to 350℃ at 5-8℃ / hour; cool down to 200℃ at 2-3℃ / hour; cool down to room temperature at 1-2℃ / hour. S4: The glass sample to be tested is obtained after optical cold processing; The preparation of core glass includes the following processes: S1: Weigh each component according to the formula, mix them evenly, and when the furnace temperature rises to 1100-1180℃, add the mixture to the Pt crucible located in the furnace in multiple batches. S2: Heat to 1300-1380℃, continuously stir, clarify, and homogenize the glass melt for the set time; S3: After cooling to 1200-1260℃, pour into the mold. After pouring, perform annealing treatment by raising the temperature to 450℃ at 2℃ / min, holding for 5 hours, then lowering to 350℃ at 4℃ / hour, then lowering to 200℃ at 1.5℃ / hour, and finally lowering to room temperature at 1℃ / hour. S4: The glass sample to be tested is obtained after optical cold processing.

[0045] Gradient cooling annealing allows for precise control of the thermal stress release process within the glass, maintaining a reasonable temperature gradient between the surface and interior. This significantly reduces residual stress and improves the dimensional stability of the glass. Subsequent cutting and drawing processes reduce the likelihood of deformation and cracking, increasing the yield rate. Furthermore, the phased, slow cooling promotes the orderly arrangement of glass atoms, eliminating microstructural inhomogeneities and resulting in a more uniform distribution of conductive ions. This leads to highly consistent electron gain and noise levels across all areas of the microchannel plate, reducing the edge darkening phenomenon common in traditional microchannel plates and improving detection accuracy in industrial flaw detection.

[0046] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A microchannel plate glass, characterized in that: The microchannel plate glass includes a skin glass and a core glass; The glass material comprises: P2O5, V2O5, BaO, La2O3, Li2O + Na2O + K2O, ZrO, Al2O3 and Al(OH)3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 1.0-4.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 25.0-75.0 wt%, ZnO is 13.0-30.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO+MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%.

2. The microchannel plate glass according to claim 1, characterized in that: The glass material, by weight percentage, comprises: 50wt% P2O5, 15wt% V2O5, 1wt% BaO, 1wt% La2O3, 2wt% Li2O + Na2O + K2O, 1wt% ZrO, 2wt% Al2O3 and Al(OH)3, 14.6wt% PbO, 13.4wt% Fe2O3; The core glass comprises, by weight percentage: 58wt% P2O5, 20wt% ZnO, 6wt% Al2O3 and Al(OH)3, 10wt% SiO2, 5wt% CaO + MgO and 1wt% BaO.

3. The microchannel plate glass according to claim 1, characterized in that: The glass material, by weight percentage, comprises: 49wt% P2O5, 12wt% V2O5, 2.5wt% BaO, 1wt% La2O3, 1wt% Li2O + Na2O + K2O, 0.5wt% ZrO, 4wt% Al2O3 and Al(OH)3, 19wt% PbO, 11wt% Fe2O3; The core glass comprises, by weight percentage: 65wt% P2O5, 30wt% ZnO, 1wt% BaO, 2wt% Al2O3 and Al(OH)3, 1wt% SiO2, 1wt% CaO + MgO.

4. The microchannel plate glass according to claim 1, characterized in that: The glass material, by weight percentage, comprises: 46wt% P2O5, 14wt% V2O5, 2.5wt% BaO, 1wt% La2O3, 1wt% Li2O + Na2O + K2O, 0.5wt% ZrO, 2wt% Al2O3 and Al(OH)3, 22wt% PbO, 11wt% Fe2O3; The core glass comprises, by weight percentage: 72wt% P2O5, 20wt% ZnO, 1wt% BaO, 2wt% Al2O3 and Al(OH)3, 3wt% SiO2, 2wt% CaO + MgO.

5. The microchannel plate glass according to any one of claims 1-4, characterized in that: In the aforementioned glass: BaO is introduced in the form of BaCO3 and Ba(NO3)2, with a molar ratio of BaCO3∶Ba(NO3)2<2∶1; MgO is introduced in the form of (MgCO3)4・Mg(OH)2・5H2O; CaO is introduced in the form of CaCO3; and the molar ratio of Al2O3 and Al(OH)3 in the glass is 1∶1. In the core glass: BaO is introduced in the form of BaCO3 and Ba(NO3)2, with a molar ratio of BaCO3:Ba(NO3) < 1:3; MgO is introduced in the form of (MgCO3)4・Mg(OH)2・5H2O; CaO is introduced in the form of CaCO3, with a molar ratio of MgO:CaO < 2:3; and the molar ratio of Al2O3 to Al(OH)3 in the core glass is 1:

2.

6. The microchannel plate glass according to claim 1, characterized in that: The glass material comprises: P2O5, V2O5, BaO, La2O3, CeO2, Li2O + Na2O + K2O, ZrO, Al2O3 and Al(OH)3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 0-3.0 wt%, CeO2 is 1.0-3.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 25.0-75.0 wt%, ZnO is 13.0-30.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO + MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%. The softening temperature of the outer glass is Tf≥550℃, and the softening temperature of the core glass is Tf≥510℃.

7. The microchannel plate glass according to claim 1, characterized in that: The glass material comprises: P2O5, V2O5, BaO, La2O3, Li2O + Na2O + K2O, ZrO, Al2O3 and Al(OH)3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 1.0-4.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Bi2O3, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 23.0-73.0 wt%, ZnO is 10.0-28.0 wt%, Bi2O3 is 2.0-5.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO + MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%. The softening temperature (Tf) of the glass is ≥550℃, and the coefficient of thermal expansion at 20-300℃ is 70-85×10⁻⁶. -7 / ℃; the softening temperature of the core glass Tf≥510℃, and the coefficient of thermal expansion at 20-300℃ is 69-85×10. -7 / ℃.

8. The microchannel plate glass according to claim 1, characterized in that: The glass material comprises: P2O5, V2O5, BaO, La2O3, Li2O + Na2O + K2O, ZrO, Al2O3 and Al(OH)3, Y2O3, PbO, and Fe2O3, by weight percentage: P2O5 is 45.0-55.0 wt%, V2O5 is 12.0-20.0 wt%, BaO is 1.0-5.0 wt%, La2O3 is 1.0-4.0 wt%, Li2O + Na2O + K2O is 1.0-4.0 wt%, ZrO is 0-1.0 wt%, Al2O3 and Al(OH)3 are 0-8.0 wt%, Y2O3 is 0.5-2.0 wt%, PbO is 12.0-25.0 wt%, and Fe2O3 is 10.0-15.0 wt%. The core glass comprises: P2O5, ZnO, Y2O3, Al2O3 and Al(OH)3, SiO2, CaO + MgO, and BaO, by weight percentage: P2O5 is 25.0-75.0 wt%, ZnO is 10.0-27.0 wt%, Y2O3 is 1.0-3.0 wt%, Al2O3 and Al(OH)3 are 2.0-10.0 wt%, SiO2 is 1.0-10.0 wt%, CaO+MgO is 0-5.0 wt%, and BaO is 0-1.0 wt%.

9. The method for preparing the microchannel plate glass according to claim 1, characterized in that: This includes the preparation of glass sheet and the preparation of glass core; The preparation of the glass substrate includes the following process: S1: Weigh the corresponding raw materials according to the proportion, mix them evenly, and when the furnace temperature rises to 1150-1250℃, add the mixture to the Pt crucible located in the furnace in multiple batches. S2: Heat to 1300-1380℃, continuously stir, clarify, and homogenize the glass melt for the set time; S3: After cooling to 1200-1275℃, pour into the mold. After pouring, perform gradient cooling annealing. The gradient cooling annealing method is as follows: heat up to 450℃ at 2.5-5℃ / min and hold for 10 hours; cool down to 350℃ at 5-8℃ / hour; cool down to 200℃ at 2-3℃ / hour; cool down to room temperature at 1-2℃ / hour. S4: The glass sample to be tested is obtained after optical cold processing; The preparation of the core glass includes the following process: S1: Weigh each component according to the formula, mix them evenly, and when the furnace temperature rises to 1100-1180℃, add the mixture to the Pt crucible located in the furnace in multiple batches. S2: Heat to 1300-1380℃, continuously stir, clarify, and homogenize the glass melt for the set time; S3: After cooling to 1200-1260℃, pour into the mold. After pouring, perform precision annealing, with a heating rate of 1.0-2.5℃ / min, heat to 450℃ and hold for 5 hours, then cool to room temperature at 1.0-2.0℃ / h. S4: The glass sample to be tested is obtained after optical cold processing.

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