Ion bombardment-resistant glass composition, microchannel plate skin glass, microchannel plate and preparation method

Abstract

The present invention belongs to the field of special glass materials and their preparation technology, and specifically relates to an ion bombardment-resistant glass composition, a microchannel plate skin material glass, a microchannel plate, and a preparation method. The present invention achieves this by combining the various components and adjusting their amounts, particularly by introducing oxides containing scandium and / or strontium and / or zirconium and / or molybdenum with high single-bond energy into the glass material. While satisfying the glass's other necessary properties, such as good anti-devitrification performance, good acid and alkali resistance, an appropriate softening temperature, expansion coefficient, and bulk resistance, the surface binding energy of the glass material is increased, thereby improving the ion bombardment resistance of the skin material glass material for the microchannel plate, thereby significantly extending the service life of the microchannel plate during direct detection of high-energy ions.

Description

Technical Field

[0001] The present invention belongs to the technical field of special glass materials and preparation thereof, and particularly relates to an ion bombardment resistant glass composition, a microchannel plate skin material glass, a microchannel plate and a preparation method thereof. Background Art

[0002] A microchannel plate (MCP) is a specialized glass material and device that multiplies charged particle streams distributed in two dimensions. Due to its advantages, including high temporal and spatial resolution, extremely high signal amplification, compact structure, and low noise, MCPs have become a promising and important device for high-energy ion detection. MCPs are composed of millions of hollow glass channels with micron-sized apertures. Each individual hollow glass channel wall features a secondary electron emission layer and an electron conduction layer, enabling independent secondary electron emission and weak current amplification. The input signal particles to a MCP are typically electrons, and signal amplification typically occurs through direct electron bombardment of the plate. However, when high-energy ions directly bombard a MCP, generating electron multiplication, the ions have a mass thousands or tens of thousands of times greater than electrons. Under the same electric field, the ion bombardment generates high momentum and relative impulse, leading to collision and sputtering effects. These can easily cause MCP performance degradation and failure, shortening the device's lifespan.

[0003] The basic principle of signal amplification in a microchannel plate (MCP) is that incident charged particles, under the action of an accelerating electric field, bombard the inner surface of the channel, generating secondary emitted electrons. Multiple collisions within the channel achieve electron avalanche multiplication, thereby enabling the reading and detection of weak signals. When the incident charged particles are ions, due to their large mass and high bombardment energy, they inevitably interact with the MCP material, producing impact and sputtering effects. During this continuous ion impact process, atoms on the MCP surface will, with a certain probability, continuously overcome the surface binding energy and detach from the material surface, causing surface damage and device performance degradation. Therefore, poor ion bombardment resistance has become a major bottleneck in high-energy ion detection in MCPs.

[0004] Currently, existing literature indicates that material damage caused by ion bombardment is one of the main causes of failure in multiplication devices used for low-energy and high-energy ion detection. In the design and manufacture of devices potentially exposed to ion bombardment, such as field-effect transistors, plasma displays, and cold cathodes of electron-emitting devices, there are patents that address the use of ion-resistant materials to improve device lifespan. However, for microchannel plates (MCPs) used for ion detection, there are currently no patents or published literature that address the design and optimization of the glass material composition to improve the ion bombardment resistance of the MCPs. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present invention is to overcome the defects of the microchannel plate glass material in the prior art, such as poor ion bombardment resistance, thereby providing an ion bombardment-resistant glass composition, microchannel plate skin glass, microchannel plate and preparation method.

[0006] To this end, the present invention provides the following technical solutions:

[0007] The present invention provides an ion bombardment resistant glass composition, which comprises the following components in terms of molar percentage:

[0008] SiO2 60~78%;

[0009] Bi2O3 1~6%;

[0010] PbO 5~18%;

[0011] Alkali metal oxides 5-20%;

[0012] Alkaline earth metal oxides 2-8%;

[0013] Al2O3 0.1~2.5%;

[0014] Special oxides 3-9%;

[0015] Wherein, the special oxide is at least one of Sc2O3, SrO, ZrO2, MoO3, and MoO2, and:

[0016] Sc2O3 0~9%;

[0017] SrO 0~9%;

[0018] ZrO2 0~6%;

[0019] MoO3 and / or MoO2 0~3%.

[0020] Optionally, based on the total mass of the components in the above composition, the composition further includes a clarifier in an amount of 0.1 to 0.8% of the total mass of the above components.

[0021] Optionally, the alkali metal oxide is at least one of Na2O, K2O and Cs2O;

[0022] The alkaline earth metal oxide is at least one of MgO, BaO and CaO;

[0023] The clarifier is Sb2O3 and / or As2O3.

[0024] It should be noted that there is no specific requirement for the composition of the alkali metal oxide and the alkaline earth metal oxide, as long as their usage can meet the requirements of the present invention.

[0025] The present invention provides a microchannel plate skin material glass resistant to ion bombardment, the composition of which is the same as the above-mentioned glass composition.

[0026] The present invention also provides a method for preparing ion bombardment resistant microchannel plate skin material glass, comprising the following steps:

[0027] The ingredients are proportioned and mixed evenly, and then melted, clarified, homogenized, drawn and annealed to obtain the ion bombardment resistant microchannel plate skin material glass.

[0028] Optionally, the temperature of the melting step is 1250-1550°C;

[0029] In the melting step, the mixed materials can be added to the crucible once or multiple times according to the total weight of the raw materials for melting. When adding the materials to the crucible multiple times, the interval between each addition is 10 minutes to 90 minutes;

[0030] Optionally, the melting step is performed in a weak oxidizing atmosphere, wherein the oxygen partial pressure in the weak oxidizing atmosphere is 25 kPa to 100 kPa.

[0031] The temperature of the clarification step is 1400-1600°C and the time is 2-12 hours;

[0032] The temperature of the homogenization step is 1200-1500°C and the time is 1-5 hours;

[0033] The starting temperature of the drawing step is 1000-1350°C, and the temperature is lowered to below 600-750°C to form a glass tube material;

[0034] In the annealing step, the annealing temperature is 550-750° C., the holding time is 2-12 hours, and then the temperature is cooled to room temperature along with the furnace.

[0035] The present invention provides a microchannel plate resistant to ion bombardment, comprising a substrate and electrodes arranged on the upper and lower surfaces of the substrate, wherein the substrate comprises a leather glass having independent hollow channels and an edge glass covering the outer surface of the leather glass, wherein the leather glass is the above-mentioned leather glass or the leather glass prepared by the above-mentioned preparation method.

[0036] The present invention also provides a method for preparing a microchannel plate resistant to ion bombardment, comprising the following steps:

[0037] S1. Drawn leather glass tube;

[0038] S2. Preparation of core glass rod;

[0039] S3. The core glass rod is nested into the leather glass tube and drawn into a monofilament;

[0040] S4. Combining several monofilaments and drawing them into multifilaments;

[0041] S5. The multifilaments are regularly arranged and melt-pressed into blank segments;

[0042] S6. The blank section is sliced, chamfered, ground and polished to obtain a blank plate;

[0043] S7. After the blank plate is cored by acid solution, reduced by hydrogen, and plated with metal electrodes, the ion bombardment-resistant microchannel plate is obtained.

[0044] Optionally, the step S7 specifically includes: first coring the blank plate with acid solution to obtain an independent hollow channel structure with millions of micron-sized pores, then reducing it with high-temperature hydrogen, in situ growing a conductive layer resistant to ion bombardment and a secondary electron emission layer resistant to ion bombardment on the inner wall surface of the hollow channel, and then evaporating metal electrodes on the upper and lower surfaces of the reduced plate to obtain an ion bombardment-resistant microchannel plate.

[0045] Optionally, in step S1, the drawing and forming starting temperature of the leather glass tube is 1000-1350° C., and the temperature is lowered to below 600-750° C. to be formed into a glass tube material;

[0046] In step S7, the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30° C. to 90° C.;

[0047] In step S7, the temperature of the high-temperature hydrogen reduction is 350° C. to 550° C., the time of the high-temperature hydrogen reduction is 20 min to 600 min, and the flow rate of the hydrogen is 0.005 L / min to 10 L / min;

[0048] In step S7, the metal electrode is a Ti, Cr, Au, Ag, or Ni / Cr surface electrode; and the surface resistance of the metal electrode is not higher than 300Ω.

[0049] The ion bombardment-resistant glass composition provided by the present invention starts from the regulation of glass material composition and proposes the use of special oxides to directly introduce glass materials. In the glass material for microchannel plates with SiO2 as the basic skeleton of the glass structure and Bi2O3 and / or PbO as reactive oxides that can form a conductive metal phase, oxides containing scandium and / or strontium and / or zirconium and / or molybdenum with high single bond energy are introduced to achieve glass material composition regulation. While meeting the glass's required anti-devitrification performance, good acid and alkali resistance, appropriate softening temperature, expansion coefficient, bulk resistance and other necessary properties, the surface binding energy of the glass material is improved, and the sputtering threshold of the glass material is increased, thereby greatly improving the ion bombardment resistance of the glass material. Furthermore, the glass material is prepared into an ion bombardment-resistant microchannel plate, thereby greatly improving the ion bombardment-resistant service life of the microchannel plate.

[0050] Among them, SiO2 is a glass-forming oxide, the basic skeleton of the glass structure, and the main component of the skin glass. When the content exceeds 78 mol%, the glass contains a large amount of [SiO2] planar structure, which is not conducive to the chemical stability of the glass, and also reduces the viscosity of the glass, increases the thermal expansion coefficient, and worsens the compatibility with the core glass of the microchannel plate that is resistant to ion bombardment.

[0051] Bi2O3 is a network oxide of glass and a fluxing agent for glass. Adding an appropriate amount of Bi2O3 to glass can improve the material properties of glass molding, improve the thermal processing performance of glass, reduce the viscosity of glass during high-temperature melting, and form a conductive metal phase in the conductive layer after high-temperature hydrogen reduction. However, if its content exceeds 6 mol%, phase separation is likely to occur, and the resistance performance of the glass after reduction is unstable; if it is less than 1 mol%, the resistance of the microchannel plate produced is unstable.

[0052] PbO is a network oxide of glass and a good glass flux. Adding an appropriate amount of PbO to glass can improve the material properties of glass molding, improve the hot-blood processing performance of glass, reduce the viscosity of glass melt, and form a conductive metal phase in the conductive layer after high-temperature hydrogen reduction. However, if its content exceeds 18 mol%, the glass's resistance to ion bombardment will deteriorate, and the resistance stability of the glass after reduction will deteriorate; if it is less than 5 mol%, the resistance of the manufactured microchannel plate will be too high and unstable.

[0053] Na2O, K2O and Cs2O are network oxides of glass. Alkali metal ions can easily move and diffuse in the glass, which can reduce the viscosity of the glass during high-temperature melting, making the glass easy to melt. They are good fluxing agents. At the same time, they will increase the thermal expansion coefficient, reduce the chemical stability and mechanical strength of the glass, and reduce the glass's resistance to ion bombardment. The amount of introduction should not be too much. According to the content of Na2O, K2O and Cs2O in the core glass of the ion bombardment-resistant microchannel plate, one or more of them can be introduced to reduce the core-skin diffusion degree during fiber drawing and high-temperature hot pressing. If the total content of Na2O, K2O and Cs2O is less than 5%, the glass-forming properties are poor. However, if the total content is greater than 20 mol%, the expansion is too high, the glass stability is poor, and the glass's resistance to ion bombardment is poor.

[0054] MgO, BaO, and CaO are the network oxides of glass. They are alkaline earth metal oxides that help improve the glass's anti-devitrification ability, adjust the glass's material properties, and improve the glass's thermal processing performance. However, adding too much will lead to unstable glass performance and phase separation. If the total content of MgO, BaO, and CaO is less than 2 mol%, the glass's thermal processing performance is poor; but if the total content exceeds 8 mol%, the glass is prone to phase separation.

[0055] Al2O3 is a glass structure-regulating oxide. Its content affects the thermal expansion coefficient and chemical and thermal stability of the glass. However, if its content exceeds 2.5 mol%, it will increase the glass's refractive index and dispersion, reduce the glass's electrical conductivity, and be detrimental to the glass's resistance to ion bombardment. If its content is less than 0.1 mol%, the glass's thermal stability will be poor.

[0056] Sc2O3 is a glass intermediate oxide and an oxide that regulates the ion bombardment resistance of glass. It can improve the hardness, ion bombardment resistance and softening temperature of glass and reduce the thermal expansion coefficient of glass. However, when its content exceeds 9 mol%, crystallization will occur, the glass stability will deteriorate, and the glass transition temperature and softening temperature will be too high, which is not conducive to the subsequent preparation of ion bombardment-resistant glass microchannel plates.

[0057] SrO is an oxide that regulates the ion bombardment resistance of glass. It can improve the hardness and ion bombardment resistance of glass and reduce the high-temperature viscosity of glass. However, when its content exceeds 9 mol%, crystallization will occur, the stability of the glass will deteriorate, and the thermal expansion coefficient of the glass will be too large, which is not conducive to the subsequent preparation of ion bombardment-resistant glass microchannel plates.

[0058] ZrO2 is a glass intermediate oxide that can improve the viscosity, hardness, and chemical stability of glass and reduce the thermal expansion coefficient of glass. However, when its content exceeds 6 mol%, the glass forming range is narrow and the softening temperature is too high, which is not conducive to the hot forming and processing of ion bombardment resistant glass. It is also prone to crystallization and phase separation, and the glass performance is unstable.

[0059] MoO3 and MoO2 are oxides that regulate the ion bombardment resistance of glass. They can improve the hardness and ion bombardment resistance of glass. However, when their content exceeds 3 mol%, crystallization and phase separation will occur, and the stability of the glass will deteriorate.

[0060] When the total content of Sc2O3, SrO, ZrO2, MoO3, and MoO2 is less than 3 mol%, the glass's resistance to ion bombardment is insufficient; but when it exceeds 9 mol%, crystallization and phase separation will occur, and the glass stability will deteriorate.

[0061] Preferably, the aforementioned ion bombardment resistant microchannel plate skin material glass, wherein the transition temperature of the ion bombardment resistant microchannel plate skin material glass is T g ≥545℃, softening temperature is T f ≥627℃.

[0062] Preferably, the aforementioned ion bombardment-resistant microchannel plate skin material glass, wherein the thermal expansion coefficient of the ion bombardment-resistant microchannel plate skin material glass at 20°C to 300°C is (61-95)×10 -7 / ℃.

[0063] Preferably, the aforementioned ion bombardment-resistant microchannel plate skin material glass has no devitrification at a temperature between 530° C. and 950° C., and has good anti-devitrification performance.

[0064] Optionally, the ion bombardment resistant microchannel plate skin material glass composition is characterized by comprising the following raw materials, calculated in molar percentage:

[0065]

[0066] in:

[0067]

[0068]

[0069] Wherein, the lead oxide is red lead or yellow lead; the barium salt is barium nitrate or barium carbonate; the potassium salt is potassium carbonate or potassium nitrate; the scandium salt is scandium nitrate or scandium carbonate; the strontium salt is strontium carbonate or strontium nitrate; the zirconium compound is zirconium oxide, zirconium carbonate or zirconium nitrate; the molybdenum compound is molybdic acid, molybdenum trioxide or molybdenum dioxide; and the clarifier is Sb2O3 and / or As2O3.

[0070] The technical solution of the present invention has the following advantages:

[0071] 1. The ion bombardment-resistant glass composition provided by the present invention starts from the regulation of the glass material composition, proposes to use special oxides to directly introduce into the glass material to achieve the regulation of the glass material composition, improve the sputtering threshold of the glass material, greatly improve the ion bombardment resistance and ion bombardment resistance service life of the glass material, and promote the further application of the glass material in the fields of time-of-flight mass spectrometers, precision timing instruments, high-energy ion detection, etc. Specifically, the present invention introduces scandium and / or strontium and / or zirconium and / or molybdenum oxides with high single bond energy into the glass material through the coordination between the various components and the adjustment of the dosage. While meeting the other necessary properties required by the glass, such as good anti-crystallization performance, good acid and alkali resistance, appropriate softening temperature, expansion coefficient, and bulk resistance, the surface binding energy of the glass material is improved, thereby improving the ion bombardment resistance of the skin glass material used for the microchannel plate, thereby significantly improving the service life of the microchannel plate when directly detecting high-energy ions.

[0072] 2. The ion bombardment-resistant microchannel plate provided by the present invention starts from the regulation of the composition of the microchannel plate glass material, and proposes to use special oxides to directly introduce into the glass material to realize the microchannel plate with regulated glass material composition, thereby improving the sputtering threshold of the microchannel plate glass material, greatly improving the ion bombardment resistance and ion bombardment resistance service life of the microchannel plate, and promoting the further application of the microchannel plate in the fields of time-of-flight mass spectrometers, precision timing instruments, high-energy ion detection, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0074] Figure 1 A comparison chart of the ion etching rates of the microchannel plate glass provided in the embodiments of the present invention and the comparative examples;

[0075] Figure 2Comparison curves of the accumulated charge pickup (working life) of the microchannel plates provided in the embodiments of the present invention and the comparative examples under 5 keV argon ion bombardment and 2.5 keV cesium ion bombardment;

[0076] Figure 3 This is a schematic diagram of the structure of the ion bombardment resistant microchannel plate blank of the present invention;

[0077] Figure 4 This is a schematic diagram of the structure of the ion bombardment resistant microchannel slab of the present invention;

[0078] Figure 5 This is a schematic structural diagram of the ion bombardment resistant microchannel plate of the present invention.

[0079] Description of the meaning of each symbol in the accompanying drawings:

[0080] Ion etching rates of different glasses when bombarded by 1-5keV argon ions; Ion etching rates of different glasses when bombarded by 2-2.5keV cesium ions; Quartz glass (glass of Comparative Example 3); C1-glass of Comparative Example 1, C2-glass of Comparative Example 2; C3-glass of Example 1; C4-glass of Example 7; C5-glass of Example 11, C6-glass of Example 16; C7-glass of Example 21; Cumulative ion-bombardment-resistant microchannel plate of Example 1 of the present invention when bombarded by 3-5keV argon ions Pickup charge curve; cumulative picked-up charge curve of comparative example 1 under 4-5keV argon ion bombardment; cumulative picked-up charge curve of the ion bombardment resistant microchannel plate of Example 1 of the present invention under 5-2.5keV cesium ion bombardment; cumulative picked-up charge curve of the microchannel plate of comparative example 1 under 6-2.5keV cesium ion bombardment; 7-leather glass; 8-core glass; 9-edge glass; 10-microchannel plate substrate; 11-inner wall of the microchannel plate channel; 12-electrode; 13-in situ generated ion bombardment resistant emission layer and conductive layer. DETAILED DESCRIPTION

[0081] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0082] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0083] Example 1 (1-5)

[0084] This embodiment provides an ion bombardment resistant microchannel plate, comprising a substrate and electrodes disposed on the upper and lower surfaces of the substrate. The substrate comprises a frit glass having independent hollow channels and an edge glass covering the outer surface of the frit glass. The preparation steps are as follows:

[0085] (1) Preparation of leather glass tube: The composition of the glass material is shown in Table 1, and the preparation method is as follows:

[0086] 1) Mixing quartz sand, red lead, bismuth oxide, barium carbonate, sodium carbonate, cesium carbonate, potassium nitrate, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, and scandium salt as raw materials, and adding a clarifier Sb2O3;

[0087] More specifically, in Example 1, sodium carbonate:cesium carbonate:potassium nitrate = 1:2:1, barium carbonate:basic magnesium carbonate:calcium carbonate = 120:100:1, the scandium salts in Examples 1 to 5 are scandium nitrate and / or scandium carbonate, in Example 1, the scandium salt is scandium nitrate; in Example 2, the scandium salt is scandium carbonate; in Example 3, the scandium salt is scandium nitrate:scandium carbonate = 1:1; in Example 4, the scandium salt is scandium nitrate:scandium carbonate = 3:1; in Example 5, the scandium salt is scandium nitrate:scandium carbonate = 1:2;

[0088] 2) adding the batch material containing the clarifier and mixing it uniformly into a crucible and melting it at 1250°C to 1490°C;

[0089] 3) After melting, heat to 1550±50℃ and clarify for 2.5 hours;

[0090] 4) Cool down to 1440±40℃~1480℃ and keep warm for 2 hours for homogenization;

[0091] 5) Drawing the glass tube from the molten glass at 1150±150°C until the temperature drops below 650°C to form the glass tube;

[0092] 6) Anneal the formed glass tube material at 600±50℃ for 12 hours, then cool it to room temperature and take it out of the furnace.

[0093] (2) The glass tube is embedded with the ion bombardment resistant microchannel plate core glass rod, and the glass fiber monofilament and glass fiber multifilament are drawn, and the multifilament is regularly arranged and melted into a blank section. Then, the blank plate is obtained by slicing, chamfering, grinding and polishing. Its structure is as follows Figure 3 As shown, it includes: skin glass 7, core glass 8 and cladding glass 9.

[0094] (3) The blank plate is corroded by acid solution to form a microchannel plate blank plate, wherein the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30°C to 90°C; more specifically, the preferred acid solution in the embodiment is nitric acid: hydrochloric acid = 1:1, the total acid solution concentration is 15 mol%, the acid solution corrosion time is 150 min, and the acid solution corrosion temperature is 70°C ± 5°C; the obtained microchannel plate blank plate structure is as follows Figure 4 As shown, it includes: skin glass 7 and edging glass 9.

[0095] (4) Subsequently, the microchannel plate blank is subjected to high-temperature hydrogen reduction and metal electrode plating to obtain a microchannel plate resistant to ion bombardment. The high-temperature hydrogen reduction temperature is 350°C to 550°C, the high-temperature hydrogen reduction time is 20min to 600min, and the hydrogen flow rate is 0.005L / min to 10L / min, and then the conductive layer and the emission layer resistant to ion bombardment are generated in situ; more specifically, the embodiment preferably has a high-temperature hydrogen reduction temperature of 550°C, a reduction time of 240min, and a hydrogen flow rate of 0.5L / min; the metal electrode is preferably a Ni-Cr surface electrode using electron beam evaporation; the surface resistance of the metal electrode is not higher than 300Ω. The obtained microchannel plate has a pore size of 4 to 20 μm, a thickness of 0.20 to 0.80 mm, an outer diameter of Φ=10 mm to 60 mm, and a solid edging resistant to ion bombardment. More specifically, the obtained microchannel plate has a pore size of 8 μm, a thickness of 0.32±0.02 mm, and an outer diameter of Φ=25 mm. The structure of the obtained microchannel plate is as follows: Figure 5 As shown, it comprises: an ion bombardment resistant microchannel plate substrate 10, a microchannel plate channel inner wall 11, and an electrode 12. The microchannel plate channel inner wall structure comprises: an ion bombardment resistant conductive layer and an emission layer 13 generated in situ.

[0096] Example II (6-10)

[0097] This embodiment provides an ion bombardment resistant microchannel plate, comprising a substrate and electrodes disposed on the upper and lower surfaces of the substrate. The substrate comprises a frit glass having independent hollow channels and an edge glass covering the outer surface of the frit glass. The preparation steps are as follows:

[0098] (1) Preparation of leather glass tube: The composition of the glass material is shown in Table 1, and the preparation method is as follows:

[0099] 1) Mix quartz sand, yellow lead, bismuth oxide, barium nitrate, sodium carbonate, cesium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, and strontium salt as raw materials, and add a clarifier As2O3;

[0100] More specifically, in Example II, sodium carbonate:cesium carbonate:potassium carbonate=11:53:13, barium nitrate:basic magnesium carbonate:calcium carbonate=50:3:2, the strontium salts in Examples 6 to 10 are strontium nitrate and / or strontium carbonate, in Example 6, the strontium salt is strontium nitrate; in Example 7, the strontium salt is strontium carbonate; in Example 8, the strontium salt is strontium nitrate:strontium carbonate=1:2; in Example 9, the strontium salt is strontium nitrate:strontium carbonate=3:1; in Example 10, the strontium salt is strontium nitrate:strontium carbonate=3:2;

[0101] 2) adding the mixed batch containing the clarifier into a crucible and melting it at 1250-1550°C;

[0102] 3) After melting, heat to 1575±25℃ and clarify for about 12 hours;

[0103] 4) After clarification, cool to 1525±25℃ and keep for 1 hour for homogenization;

[0104] 5) Drawing the glass tube from the glass liquid at 1200±100℃ until the temperature drops to below 700℃ and the glass tube is formed;

[0105] 6) Anneal the formed glass tube material at 650±50℃ for 2 hours, then cool it to room temperature and take it out of the furnace.

[0106] (2) The glass tube is embedded with the ion bombardment resistant microchannel plate core glass rod, which is drawn into single-filament and multi-filament, and the multi-filament is regularly arranged and melted into a blank section. Then, the blank plate is obtained by slicing, chamfering, grinding and polishing. Its structure is as follows Figure 3 As shown, it includes: skin glass 7, core glass 8 and cladding glass 9.

[0107] (3) The blank plate is corroded by acid solution to form a microchannel plate blank plate, wherein the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30°C to 90°C; more specifically, the preferred acid solution in the embodiment is nitric acid, the acid solution concentration is 5 mol%, the acid solution corrosion time is 100 min, and the acid solution corrosion temperature is 65°C ± 5°C; the obtained microchannel plate blank plate structure is as follows Figure 4 As shown, it includes: skin glass 7 and edging glass 9.

[0108] (4) Subsequently, the microchannel plate blank is subjected to high-temperature hydrogen reduction and metal electrode plating to obtain a microchannel plate resistant to ion bombardment. The high-temperature hydrogen reduction temperature is 350°C to 550°C, the high-temperature hydrogen reduction time is 20min to 600min, and the hydrogen flow rate is 0.005L / min to 10L / min, and then the conductive layer and the emission layer resistant to ion bombardment are generated in situ; more specifically, the embodiment preferably has a high-temperature hydrogen reduction temperature of 520°C, a reduction time of 300min, and a hydrogen flow rate of 0.3L / min; the metal electrode is preferably an electron beam evaporated Au surface electrode; the surface resistance of the metal electrode is not higher than 300Ω. The obtained microchannel plate has a pore size of 4 to 20 μm, a thickness of 0.20 to 0.80 mm, an outer diameter of Φ=10 mm to 60 mm, and a solid edging ion-bombardment-resistant microchannel plate. More specifically, the obtained microchannel plate has a pore size of 10 μm, a thickness of 0.40 ± 0.02 mm, and an outer diameter of Φ=25 mm. The structure of the obtained microchannel plate is as follows: Figure 5 As shown, it comprises: an ion bombardment resistant microchannel plate substrate 10, a microchannel plate channel inner wall 11, and an electrode 12. The microchannel plate channel inner wall structure comprises: an ion bombardment resistant conductive layer and an emission layer 13 generated in situ.

[0109] Example III (11-15)

[0110] This embodiment provides an ion bombardment resistant microchannel plate, comprising a substrate and electrodes disposed on the upper and lower surfaces of the substrate. The substrate comprises a frit glass having independent hollow channels and an edge glass covering the outer surface of the frit glass. The preparation steps are as follows:

[0111] (1) Preparation of leather glass tube: The composition of the glass material is shown in Table 1, and the preparation method is as follows:

[0112] 1) Quartz sand, red lead: yellow lead = 1:1, bismuth oxide, barium nitrate: barium carbonate = 1:2, sodium carbonate, cesium carbonate, potassium carbonate: potassium nitrate = 2:3, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, and a zirconium compound are mixed as raw materials, and clarifiers Sb2O3 and As2O3 are added, with the ratio of Sb2O3 to As2O3 being 2:1;

[0113] More specifically, in Example III, sodium carbonate:cesium carbonate:(potassium carbonate + potassium nitrate) = 7:5:1, (barium nitrate + barium carbonate):basic magnesium carbonate:calcium carbonate = 1:10:3, the zirconium compound in Examples 11 to 15 is zirconium oxide and / or zirconium nitrate and / or zirconium carbonate, in Example 11, the zirconium compound is zirconium oxide; in Example 12, the zirconium compound is zirconium oxide:zirconium nitrate = 1:1; in Example 13, the zirconium compound is zirconium oxide:zirconium carbonate = 1:1; in Example 14, the zirconium compound is zirconium oxide:zirconium nitrate:zirconium carbonate = 1:1:1; in Example 15, the zirconium compound is zirconium oxide:zirconium nitrate:zirconium carbonate = 2:1:3;

[0114] 2) adding the mixed batch containing the clarifier into a crucible and melting it at 1250-1550°C;

[0115] 3) After melting, heat to 1575±25℃ and clarify for 10 hours;

[0116] 4) After clarification, cool to 1475±25℃ and keep for about 4.5 hours for homogenization;

[0117] 5) Drawing the glass tube from the molten glass at 1225±125°C until the temperature drops below 730°C to form the glass tube;

[0118] 6) Anneal the formed glass tube material at 675±75℃ for about 11 hours, then cool it to room temperature and take it out of the furnace.

[0119] (2) The glass tube is embedded with the ion bombardment resistant microchannel plate core glass rod, which is drawn into single-filament and multi-filament, and the multi-filament is regularly arranged and melted into a blank section. Then, the blank plate is obtained by slicing, chamfering, grinding and polishing. Its structure is as follows Figure 3 As shown, it includes: skin glass 7, core glass 8 and cladding glass 9.

[0120] (3) The blank plate is corroded by acid solution to form a microchannel plate blank plate, wherein the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30°C to 90°C; more specifically, the preferred acid solution in the embodiment is nitric acid, the total acid solution concentration is 30 mol%, the acid solution corrosion time is 20 min, and the acid solution corrosion temperature is 35°C ± 5°C; the obtained microchannel plate blank plate structure is as follows Figure 4 As shown, it includes: skin glass 7 and edging glass 9.

[0121] (4) Subsequently, the microchannel plate blank is subjected to high-temperature hydrogen reduction and metal electrode plating to obtain a microchannel plate resistant to ion bombardment. The high-temperature hydrogen reduction temperature is 350°C to 550°C, the high-temperature hydrogen reduction time is 20min to 600min, and the hydrogen flow rate is 0.005L / min to 10L / min, and then the conductive layer and the emission layer resistant to ion bombardment are generated in situ; more specifically, the embodiment preferably has a high-temperature hydrogen reduction temperature of 350°C, a reduction time of 600min, and a hydrogen flow rate of 10L / min; the metal electrode is preferably a Ti surface electrode using electron beam evaporation; and the surface resistance of the metal electrode is not higher than 300Ω. The obtained microchannel plate has a pore size of 4 to 20 μm, a thickness of 0.20 to 0.80 mm, and an outer diameter of Φ = 10 mm to 60 mm, and is a solid-edged microchannel plate resistant to ion bombardment. More specifically, the obtained microchannel plate has a pore size of 4 μm, a thickness of 0.20 ± 0.02 mm, and an outer diameter of Φ = 10 mm, and is a solid-edged microchannel plate resistant to ion bombardment. The structure of the obtained microchannel plate is as follows: Figure 5 As shown, it comprises: an ion bombardment resistant microchannel plate substrate 10, a microchannel plate channel inner wall 11, and an electrode 12. The microchannel plate channel inner wall structure comprises: an ion bombardment resistant conductive layer and an emission layer 13 generated in situ.

[0122] Example IV (16-20)

[0123] This embodiment provides an ion bombardment resistant microchannel plate, comprising a substrate and electrodes disposed on the upper and lower surfaces of the substrate. The substrate comprises a frit glass having independent hollow channels and an edge glass covering the outer surface of the frit glass. The preparation steps are as follows:

[0124] (1) Preparation of leather glass tube: The composition of the glass material is shown in Table 1, and the preparation method is as follows:

[0125] 1) Quartz sand, red lead, bismuth oxide, barium nitrate:barium carbonate=1:1, sodium carbonate, cesium carbonate, potassium nitrate, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, and a molybdenum compound are mixed as raw materials, and clarifiers Sb2O3 and As2O3 are added, with the ratio of Sb2O3 to As2O3 being 1:2;

[0126] More specifically, in Example IV, sodium carbonate:cesium carbonate:potassium nitrate = 2:9:3, (barium nitrate + barium carbonate):basic magnesium carbonate:calcium carbonate = 3:3:2, the molybdenum compound in Examples 16 to 20 is molybdic acid and / or molybdenum trioxide and / or molybdenum dioxide, in Example 16, the molybdenum compound is molybdic acid; in Example 17, the molybdenum compound is molybdenum acid:molybdenum dioxide = 1:2; in Example 18, the molybdenum compound is molybdenum trioxide:molybdenum dioxide = 2:1; in Example 19, the molybdenum compound is molybdenum acid:molybdenum dioxide:molybdenum trioxide = 1:1:1; in Example 20, the molybdenum compound is molybdenum dioxide;

[0127] 2) adding the mixed batch containing the clarifier into a crucible and melting it at 1250-1500°C;

[0128] 3) After melting, heat to 1525±25℃ and let it settle for about 3 hours;

[0129] 4) After clarification, cool to 1250±50℃ and keep for 5 hours for homogenization;

[0130] 5) Drawing the glass tube from the molten glass at 1150±150°C until the temperature drops below 700°C to form the glass tube;

[0131] 6) Anneal the formed glass tube material at 650±50℃ for about 10 hours, then cool it to room temperature and take it out of the furnace.

[0132] (2) The glass tube is embedded with the ion bombardment resistant microchannel plate core glass rod, which is drawn into single-filament and multi-filament, and the multi-filament is regularly arranged and melted into a blank section. Then, the blank plate is obtained by slicing, chamfering, grinding and polishing. Its structure is as follows Figure 3 As shown, it includes: skin glass 7, core glass 8 and cladding glass 9.

[0133] (3) The blank plate is corroded by acid solution to form a microchannel plate blank plate, wherein the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30°C to 90°C; more specifically, the preferred acid solution in the embodiment is hydrochloric acid, the total acid solution concentration is 0.2 mol%, the acid solution corrosion time is 550 min, and the acid solution corrosion temperature is 85°C ± 5°C; the obtained microchannel plate blank plate structure is as follows Figure 4 As shown, it includes: skin glass 7 and edging glass 9.

[0134] (4) Subsequently, the microchannel plate blank is subjected to high-temperature hydrogen reduction and metal electrode plating to obtain a microchannel plate resistant to ion bombardment. The high-temperature hydrogen reduction temperature is 350°C to 550°C, the high-temperature hydrogen reduction time is 20min to 600min, and the hydrogen flow rate is 0.005L / min to 10L / min, and then the conductive layer and the emission layer resistant to ion bombardment are generated in situ; more specifically, the embodiment preferably has a high-temperature hydrogen reduction temperature of 450°C, a reduction time of 420min, and a hydrogen flow rate of 0.005L / min; the metal electrode is preferably a Cr surface electrode deposited by electron beam evaporation; and the surface resistance of the metal electrode is not higher than 300Ω. The obtained microchannel plate has a pore size of 4 to 20 μm, a thickness of 0.20 to 0.80 mm, an outer diameter of Φ=10 mm to 60 mm, and a solid edging resistant to ion bombardment. More specifically, the obtained microchannel plate has a pore size of 20 μm, a thickness of 0.80 ± 0.02 mm, and an outer diameter of Φ=60 mm. The structure of the obtained microchannel plate is as follows: Figure 5 As shown, it comprises: an ion bombardment resistant microchannel plate substrate 10, a microchannel plate channel inner wall 11, and an electrode 12. The microchannel plate channel inner wall structure comprises: an ion bombardment resistant conductive layer and an emission layer 13 generated in situ.

[0135] Example V (21-25)

[0136] This embodiment provides an ion bombardment resistant microchannel plate, comprising a substrate and electrodes disposed on the upper and lower surfaces of the substrate. The substrate comprises a frit glass having independent hollow channels and an edge glass covering the outer surface of the frit glass. The preparation steps are as follows:

[0137] (1) Preparation of leather glass tube: The composition of the glass material is shown in Table 1, and the preparation method is as follows:

[0138] 1) Mixing quartz sand, yellow lead, bismuth oxide, barium nitrate:barium carbonate = 2:1, sodium carbonate, cesium carbonate, potassium nitrate, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, scandium salt, strontium salt, zirconium oxide, and molybdenum oxide as raw materials, and adding clarifiers Sb2O3 and As2O3, with the ratio of Sb2O3 to As2O3 being 1:2;

[0139] More specifically, in Example V, sodium carbonate:cesium carbonate:potassium nitrate = 1:100:3, (barium nitrate + barium carbonate):basic magnesium carbonate:calcium carbonate = 1:1:1, the scandium salt in Examples 21 to 25 is scandium nitrate and / or scandium carbonate, the strontium salt is strontium nitrate and / or strontium carbonate, the zirconium oxide is zirconium oxide and / or zirconium carbonate and / or zirconium nitrate, and the molybdenum oxide is molybdic acid and / or molybdenum trioxide and / or molybdenum dioxide. In Example 21, the scandium salt is scandium nitrate, the strontium salt is strontium carbonate, the zirconium oxide is zirconium oxide, and the molybdenum oxide is molybdic acid; in Example 22, the scandium salt is scandium nitrate:scandium carbonate=1:1, the strontium salt is strontium nitrate, the zirconium oxide is zirconium oxide:zirconium carbonate=1:2, and the molybdenum oxide is molybdenum trioxide:molybdenum dioxide=1:1; in Example 23, the scandium salt is scandium nitrate, the strontium salt is strontium nitrate:strontium carbonate=1:1, and the zirconium oxide is zirconium oxide:zirconium carbonate: Zirconium nitrate = 2:1:1, the molybdenum oxide is molybdic acid: molybdenum trioxide: molybdenum dioxide = 1:1:1; in Example 24, the scandium salt is scandium nitrate, the strontium salt is strontium nitrate, the zirconium oxide is zirconium oxide, and the molybdenum oxide is molybdenum trioxide: molybdenum dioxide = 2:1; in Example 25, the scandium salt is scandium nitrate: scandium carbonate = 1:2, the strontium salt is strontium nitrate: strontium carbonate = 1:1, the zirconium oxide is zirconium oxide: zirconium nitrate = 1:1, and the molybdenum oxide is molybdic acid;

[0140] 2) adding the batch material containing the clarifier into a crucible and melting it at 1300°C to 1550°C;

[0141] 3) After melting, heat to 1575±25°C for clarification for about 9 hours;

[0142] 4) After clarification, cool to 1450±50℃ and keep for 3 hours for homogenization;

[0143] 5) Drawing the glass tube from the molten glass at 1225±125°C until the temperature drops below 730°C to form the glass tube;

[0144] 6) Anneal the formed glass tube material at 655±55℃ for 6 hours, then cool it to room temperature and take it out of the furnace.

[0145] (2) The glass tube is embedded with the ion bombardment resistant microchannel plate core glass rod, which is drawn into single-filament and multi-filament, and the multi-filament is regularly arranged and melted into a blank section. Then, the blank plate is obtained by slicing, chamfering, grinding and polishing. Its structure is as follows Figure 3 As shown, it includes: skin glass 7, core glass 8 and cladding glass 9.

[0146] (3) The blank plate is corroded by acid solution to form a microchannel plate blank plate, wherein the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30°C to 90°C; more specifically, the preferred acid solution in the embodiment is nitric acid: hydrochloric acid = 1:1, the total acid solution concentration is 13 mol%, the acid solution corrosion time is 100 min, and the acid solution corrosion temperature is 55°C ± 5°C; the obtained microchannel plate blank plate structure is as follows Figure 4 As shown, it includes: skin glass 7 and edging glass 9.

[0147] (4) Subsequently, the microchannel plate blank is subjected to high-temperature hydrogen reduction and metal electrode plating to obtain a microchannel plate resistant to ion bombardment. The high-temperature hydrogen reduction temperature is 350°C to 550°C, the high-temperature hydrogen reduction time is 20min to 600min, and the hydrogen flow rate is 0.005L / min to 10L / min, and then the conductive layer and the emission layer resistant to ion bombardment are generated in situ; more specifically, the embodiment preferably has a high-temperature hydrogen reduction temperature of 510°C, a reduction time of 320min, and a hydrogen flow rate of 1.1L / min; the metal electrode is preferably an Ag surface electrode deposited by electron beam evaporation; and the surface resistance of the metal electrode is not higher than 300Ω. The obtained microchannel plate has a pore size of 4 to 20 μm, a thickness of 0.20 to 0.80 mm, an outer diameter of Φ=10 mm to 60 mm, and a solid edging resistant to ion bombardment. More specifically, the obtained microchannel plate has a pore size of 8 μm, a thickness of 0.38±0.02 mm, and an outer diameter of Φ=25 mm. The structure of the obtained microchannel plate is as follows: Figure 5 As shown, it comprises: an ion bombardment resistant microchannel plate substrate 10, a microchannel plate channel inner wall 11, and an electrode 12. The microchannel plate channel inner wall structure comprises: an ion bombardment resistant conductive layer and an emission layer 13 generated in situ.

[0148] Comparative Example 1 and Comparative Example 2

[0149] This comparative example proposes a microchannel plate, comprising a substrate and electrodes provided on the upper and lower surfaces of the substrate. The substrate comprises a leather glass having independent hollow channels and an edge glass covering the outer surface of the leather glass. The preparation steps are as follows:

[0150] (1) Preparation of leather glass tube: The composition of the glass material is shown in Table 1, and the preparation method is as follows:

[0151] 1) Quartz sand, red lead, bismuth oxide, barium nitrate, sodium carbonate, cesium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, and aluminum hydroxide are mixed as raw materials, and a clarifier Sb2O3 is added; wherein, in Comparative Example 1, the ratio of sodium carbonate:cesium carbonate:potassium carbonate is 1:2:1, and the ratio of barium carbonate:basic magnesium carbonate:calcium carbonate is 120:70:1; in Comparative Example 2, the ratio of sodium carbonate:cesium carbonate:potassium carbonate is 1:100:3, and the ratio of barium carbonate:basic magnesium carbonate:calcium carbonate is 1:1:1;

[0152] 2) adding the mixed batch containing the clarifier into a crucible and melting it at 1100°C to 1450°C;

[0153] 3) After melting, maintain the temperature at 1500°C for clarification for about 3 hours;

[0154] 4) Cool down to 1200℃ and keep it for about 1 hour to homogenize;

[0155] 5) Drawing the molten glass at 1150±50°C into a glass tube material until the temperature drops below 630°C to form a glass tube material;

[0156] 6) The formed glass tube material is annealed at 600°C for 8 hours and then cooled to room temperature before being taken out of the furnace.

[0157] (2) The glass tube is embedded with the ion bombardment resistant microchannel plate core glass rod, which is drawn into single-filament and multi-filament, and the multi-filament is regularly arranged and melted into a blank section. Then, the blank plate is obtained by slicing, chamfering, grinding and polishing. Its structure is as follows Figure 3 As shown, it includes: skin glass 7, core glass 8 and cladding glass 9.

[0158] (3) The blank plate is corroded by acid solution to form a microchannel plate blank plate, wherein the acid solution is nitric acid: hydrochloric acid = 1:1, the total concentration of the acid solution is 25 mol%, the acid solution corrosion time is 300 min, and the acid solution corrosion temperature is 35°C;

[0159] (4) Subsequently, the microchannel plate blank was reduced with high-temperature hydrogen and plated with a metal electrode to obtain a solid edge-wrapped microchannel plate with a pore size of 8 μm, a thickness of 0.38 mm, and an outer diameter of Φ=25 mm, wherein the temperature of the high-temperature hydrogen reduction was 380°C, the time of the high-temperature hydrogen reduction was 400 min, and the flow rate of the hydrogen was 3 L / min; the metal electrode was a Ni-Cr surface electrode; and the surface resistance of the metal electrode was not higher than 300 Ω.

[0160] Comparative Example 3 is commercial quartz glass purchased (brand: JGS1)

[0161] Comparative Example 4

[0162] This comparative example proposes a microchannel plate, comprising a substrate and electrodes provided on the upper and lower surfaces of the substrate. The substrate comprises a leather glass having independent hollow channels and an edge glass covering the outer surface of the leather glass. The preparation steps are as follows:

[0163] (1) The composition of the glass material is shown in Table 1, and the preparation method is:

[0164] 1) Quartz sand, red lead, bismuth oxide, barium nitrate, sodium carbonate, cesium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, zirconium oxide: zirconium carbonate = 1:1 as raw materials, and adding a clarifier Sb2O3; wherein, sodium carbonate: cesium carbonate: potassium carbonate = 7:5:1, barium nitrate: basic magnesium carbonate: calcium carbonate = 1:10:2;

[0165] 2) adding the mixed batch containing the clarifier into a crucible and melting it at 1250-1550°C;

[0166] 3) After melting, heat to 1575±25℃ and clarify for 10 hours;

[0167] 4) After clarification, cool to 1475±25℃ and keep for about 4 hours for homogenization;

[0168] 5) Drawing the glass tube from the molten glass at 1225±125°C until the temperature drops below 730°C to form the glass tube;

[0169] 6) Anneal the formed glass tube material at 675±75°C for 12 hours, then cool it to room temperature and take it out of the furnace.

[0170] Comparative Example 5

[0171] This comparative example proposes a microchannel plate, comprising a substrate and electrodes provided on the upper and lower surfaces of the substrate. The substrate comprises a leather glass having independent hollow channels and an edge glass covering the outer surface of the leather glass. The preparation steps are as follows:

[0172] (1) The composition of the glass material is shown in Table 1, and the preparation method is:

[0173] 1) Mixing quartz sand, red lead: yellow lead = 1:1, bismuth oxide, barium nitrate: barium carbonate = 1:1, sodium carbonate, cesium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, aluminum hydroxide, molybdic acid: molybdenum dioxide = 1:2 as raw materials, and adding a clarifier Sb2O3:As2O3 = 1:1; wherein, sodium carbonate: cesium carbonate: potassium carbonate = 3:9:2, (barium nitrate + barium carbonate): basic magnesium carbonate: calcium carbonate = 3:4:7;

[0174] 2) adding the mixed batch containing the clarifier into a crucible and melting it at 1250-1500°C;

[0175] 3) After melting, heat to 1525±25℃ and let it settle for about 2 hours;

[0176] 4) After clarification, cool to 1250±50°C and keep for 4.5 hours for homogenization;

[0177] 5) Drawing the glass tube from the molten glass at 1150±150°C until the temperature drops below 700°C to form the glass tube;

[0178] 6) Anneal the formed glass tube material at 650±50℃ for about 10 hours, then cool it to room temperature and take it out of the furnace.

[0179] Experimental example

[0180] The glass materials and microchannel plates obtained in the embodiments of the present invention and the comparative examples were subjected to performance tests, specifically including the thermal expansion coefficient, glass transition temperature, softening temperature, and anti-devitrification performance of the glass materials, and the ion bombardment resistance of the glass materials and the microchannel plates, including the ion etching rate of the glass materials and the service life of the microchannel plates.

[0181] Specific test method:

[0182] (1) Test the thermal expansion coefficient, glass transition temperature and softening temperature of glass materials according to GB / T 16920-2015;

[0183] (2) Glass resistance to argon ion bombardment test:

[0184] 1) In a vacuum chamber with a vacuum degree better than 1E-6Pa, the annealed glass material is subjected to argon ion etching using a 5keV argon ion gun for 30 minutes;

[0185] 2) In accordance with ISO 4287 / 1:1984, the etching depth of the glass material after argon ion etching was measured using a laser confocal microscope in laser scanning imaging mode. The argon ion etching rate of the glass material was calculated according to the equation: etching rate = etching depth / etching time;

[0186] (3) Glass cesium-argon ion bombardment performance test:

[0187] 1) In a vacuum chamber with a vacuum degree better than 1E-6Pa, the annealed glass material was etched using a 2.5keV cesium ion gun for 30 minutes;

[0188] 2) According to ISO 4287 / 1:1984, the etching depth of the glass material after argon ion etching was measured using a laser confocal microscope in laser scanning imaging mode. The argon ion etching rate of the glass material was calculated according to the equation of etching rate = etching depth / etching time.

[0189] (4) Microchannel plate argon ion bombardment resistance working life test:

[0190] 1) In a vacuum chamber with a vacuum degree better than 1E-6Pa, a 5keV argon ion gun was used as the argon ion signal input source. The input surface of the microchannel plate was grounded (0V), and a -1000V bias voltage was applied to the output surface of the microchannel plate. A metal anode was used to collect the output current after amplification by the microchannel plate. The metal anode was connected in series with a microammeter and then grounded. The microammeter was used to measure and record the output current of the microchannel plate.

[0191] 2) Integrating the measured ion bombardment time-microchannel plate output current curve to obtain the cumulative pickup charge of the microchannel plate resistant to argon ion bombardment, that is, the argon ion bombardment resistant working life.

[0192] (5) Microchannel plate cesium ion bombardment resistance working life test:

[0193] 1) In a vacuum chamber with a vacuum degree better than 1E-6Pa, a 2.5keV cesium ion gun was used as the cesium ion signal input source. The input surface of the microchannel plate was grounded (0V), and a -1000V bias voltage was applied to the output surface of the microchannel plate. A metal anode was used to collect the output current after amplification by the microchannel plate. The metal anode was connected in series with a microammeter and then grounded. The microammeter was used to measure and record the output current of the microchannel plate.

[0194] 2) Integrating the measured ion bombardment time-microchannel plate output current curve to obtain the cumulative charge pickup of the microchannel plate resistant to cesium ion bombardment, that is, the cesium ion bombardment resistant working life.

[0195] Table 1 Glass material composition and thermal performance test results of the embodiments of the present invention and the comparative examples

[0196]

[0197]

[0198] Comparative Example 3 is commercially available quartz glass, which is used only as a reference glass in the ion etching rate test. Since it cannot undergo high-temperature hydrogen reduction to obtain the appropriate bulk resistance required for microchannel plate applications, it can be directly excluded as a skin glass material for microchannel plates. Therefore, its thermodynamic properties are not required and were not examined.

[0199] From the instruction manual Figure 1It can be seen that when Sc2O3, SrO, ZrO2, MoO3, and MoO2 oxides are not introduced into the glass, such as in Comparative Examples 1 and 2, the ion etching rate of the glass material will increase significantly, that is, the ion bombardment resistance of the glass material is obviously insufficient. After Sc2O3, SrO, ZrO2, MoO3, and MoO2 oxides are introduced into the glass, the ion etching rate of the glass material will decrease significantly, that is, the ion bombardment resistance of the glass material will be significantly improved. However, as can be seen from Table 1, after the introduction of Sc2O3, SrO, ZrO2, MoO3, and MoO2 oxides into the glass, the transition temperature and softening temperature of the glass material will increase. What's more, the anti-crystallization performance of the glass will deteriorate. As shown in Comparative Examples 4 and 5 in the table, when the ZrO2 content exceeds 6 mol% (8.6 mol%), the anti-crystallization performance of the glass is poor. When the MoO3+MoO2 content exceeds 3 mol% (4.9 mol%), the anti-crystallization performance of the glass also deteriorates significantly. Therefore, the glass materials in Comparative Examples 4 and 5 cannot be subsequently processed and sampled for thermodynamic performance testing (thermodynamic expansion, transition temperature, softening temperature). Therefore, it is necessary to comprehensively consider the bombardment resistance of the glass material, the thermodynamic properties of the glass, the glass forming properties, etc., in order to obtain ion bombardment-resistant microchannel plate leather glass with excellent ion bombardment resistance suitable for microchannel plate production.

[0200] From the instruction manual Figure 2 It can be seen that the argon ion resistance working life (cumulative picked-up charge) of the microchannel plate using the skin glass as the ion bombardment-resistant glass material in Example 1 exceeds 17C, and the cesium ion resistance working life (cumulative picked-up charge) exceeds 19C, while the argon ion resistance working life (cumulative picked-up charge) of the comparative example 1 (the conventional microchannel plate that is not resistant to ion bombardment) is less than 3C, and the cesium ion resistance working life (cumulative picked-up charge) is less than 3.5C, that is, the ion resistance working life of the microchannel plate using the skin glass as the ion bombardment-resistant glass material is greatly improved.

[0201] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An ion bombardment resistant glass composition, characterized in that: In terms of molar percentage, it includes the following components: SiO2 60~78%; Bi2O3 1~6%; PbO 5~18%; Alkali metal oxides 5-20%; 2-8% alkaline earth metal oxide; the alkaline earth metal oxide is at least one of MgO, BaO and CaO; Al2O3 0.1~2.5%; Special oxides 3~9%; Wherein, the special oxide is at least one of Sc2O3, MoO3, and MoO2, and: Sc2O3 0~9%; MoO3 and / or MoO2 0~3%.

2. The ion bombardment resistant glass composition according to claim 1, characterized in that: Based on the total mass of the components in claim 1, the invention further comprises a clarifier accounting for 0.1 to 0.8% of the total mass of the above components.

3. The ion bombardment resistant glass composition according to claim 2, characterized in that: The alkali metal oxide is at least one of Na2O, K2O and Cs2O; The clarifier is Sb2O3 and / or As2O3.

4. A microchannel plate skin material glass resistant to ion bombardment, characterized in that: Its composition is the same as the glass composition described in any one of claims 1 to 3.

5. A method for preparing the ion bombardment resistant microchannel plate skin material glass according to claim 4, characterized in that: The steps include: The ingredients are proportioned and mixed evenly, and then melted, clarified, homogenized, drawn and annealed to obtain the ion bombardment resistant microchannel plate skin material glass.

6. The method for preparing ion bombardment resistant microchannel plate skin material glass according to claim 5, characterized in that: The temperature of the melting step is 1250-1550°C.

7. The method for preparing the ion bombardment resistant microchannel plate skin material glass according to claim 5 or 6, characterized in that: The melting step is carried out in a weak oxidizing atmosphere, wherein the oxygen partial pressure in the weak oxidizing atmosphere is 25 kPa to 100 kPa.

8. The method for preparing ion bombardment resistant microchannel plate skin material glass according to claim 5, characterized in that: The temperature of the clarification step is 1400-1600° C., and the time is 2-12 hours.

9. The method for preparing ion bombardment resistant microchannel plate skin material glass according to claim 5, characterized in that: The temperature of the homogenization step is 1200-1500° C., and the time is 1-5 hours.

10. The method for preparing ion bombardment resistant microchannel plate skin material glass according to claim 5, characterized in that: The starting temperature of the drawing and forming step is 1000-1350° C., and the temperature is lowered to below 600-750° C. to form a glass tube material.

11. The method for preparing ion bombardment resistant microchannel plate skin material glass according to claim 5, characterized in that: In the annealing step, the annealing temperature is 550-750° C., the holding time is 2-12 hours, and then the temperature is cooled to room temperature along with the furnace.

12. A microchannel plate resistant to ion bombardment, characterized in that: It includes a substrate and electrodes arranged on the upper and lower surfaces of the substrate, the substrate includes a leather glass with an independent hollow channel and an edge glass covering the outer surface of the leather glass, the leather glass is the leather glass described in claim 4 or the leather glass prepared by the preparation method described in any one of claims 5-11.

13. The method for preparing a microchannel plate resistant to ion bombardment according to claim 12, characterized in that: The following steps are involved: S1. Drawn leather glass tube; S2. Prepare core glass rod; S3. Inserting the core glass rod into the skin glass tube and drawing it into a monofilament; S4. Combine several monofilaments and draw them into multifilament yarn; S5. The multifilaments are regularly arranged and melt-pressed into blank segments; S6. Slice, chamfer, grind and polish the blank to obtain a blank plate; S7. The blank plate is subjected to acid etching to remove the core, hydrogen reduction, and metal electrode plating to obtain the ion bombardment-resistant microchannel plate.

14. The method for preparing a microchannel plate resistant to ion bombardment according to claim 13, characterized in that: The step S7 specifically includes: firstly subjecting the blank plate to acid corrosion to remove the core to obtain an independent hollow channel structure with millions of micron-sized pores, then subjecting it to high-temperature hydrogen reduction, in situ growing an ion-bombardment-resistant conductive layer and an ion-bombardment-resistant secondary electron emission layer on the inner wall surface of the hollow channel, and then evaporating metal electrodes on the upper and lower surfaces of the reduced plate to obtain an ion-bombardment-resistant microchannel plate.

15. The method for preparing a microchannel plate resistant to ion bombardment according to claim 14, characterized in that: In step S1, the drawing temperature of the leather glass tube is 1000-1350°C; In step S7, the acid solution is at least one of nitric acid and hydrochloric acid, the concentration of the acid solution is 0.1 mol% to 30 mol%, the acid solution corrosion time is 10 min to 600 min, and the acid solution corrosion temperature is 30° C. to 90° C.; In step S7, the temperature of the high-temperature hydrogen reduction is 350° C. to 550° C., the time of the high-temperature hydrogen reduction is 20 min to 600 min, and the flow rate of the hydrogen is 0.005 L / min to 10 L / min; In step S7, the metal electrode is a Ti, Cr, Au, Ag, or Ni / Cr surface electrode; and the surface resistance of the metal electrode is not higher than 300Ω.

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