A glass material with high corrosion resistance and stability, and a preparation method and application thereof

Abstract

The application belongs to the technical field of glass and specifically relates to a glass material with high corrosion resistance and stability, the cation composition of which is as follows in terms of mole percentage: 61-70% of Si 4+ , 3-12.5% of B 3+ , 1-5.5% of Al 3+ , 5-13% of K + , 5-13% of Na + , 0.2-3% of Ca 2+ , 0.1-2% of Li + , 0.1-1% of Mg 2+ , and 0.1-1% of Ti 4+ . The application is designed in a multi-component and multi-functional synergistic manner, so that the prepared glass meets the harsh requirements on thermal, optical, chemical and processing properties, is suitable for high-end optical devices such as micro-channel plates, and has a wide application prospect in the fields of photoelectric detection and imaging, mass spectrometers, high-energy physics, streak cameras, high-end medical imaging and the like.

Description

Technical Field

[0001] This invention belongs to the field of glass technology, and relates to structural glass materials, specifically to a glass material with high corrosion resistance and stability, its preparation method, and its application. Background Technology

[0002] Microchannel plates (MCPs) are two-dimensional array electron multiplier devices containing numerous micrometer-scale channel structures. They are widely used in high-performance detection devices such as image intensifiers, photomultiplier tubes, mass spectrometry systems, high-energy physics detectors, streak cameras, and advanced medical imaging equipment. The performance of MCPs directly determines the overall detection capabilities of high-performance detection devices, such as detection sensitivity, resolution, and signal-to-noise ratio. The traditional fabrication process for MCPs typically involves an "arrangement-fiber drawing-hot-melt pressing-slicing-acid etching" process. Hot-melt pressing is one of the most critical steps, aiming to integrate composite glass fiber bundles into a dense, monolithic preform. This composite fiber bundle consists of acid-etchable functional glass and non-acid-etchable support glass. During hot-melt pressing, precise temperature and pressure control allows the interfacial bonding between fibers to form a preform with mechanical strength and channel structure stability. Subsequently, slices of a specified thickness are obtained, and then selective acid etching removes the acid-etchable glass portion, thereby forming a regularly arranged hollow microchannel array within the preform.

[0003] The aforementioned hot-melt pressing process places stringent requirements on the material properties of the support glass: First, it must withstand the subsequent harsh acid etching process. If the corrosion rate of the support glass in high-temperature, high-concentration strong acids (such as hydrochloric acid, nitric acid, and hydrofluoric acid) is too high, its structure will be destroyed, leading to thinning, roughening, or even collapse of the microchannel walls, resulting in a significant decrease in key performance characteristics of the MCP, such as gain and resolution. Second, its thermal properties (especially the coefficient of thermal expansion and softening point) must be highly compatible with those of the acid-etchable glass. Significant differences will introduce internal stress or cause interface deformation during the hot-melt pressing process, directly affecting the structural integrity of the MCP.

[0004] However, currently widely used support glasses, such as acid-resistant glasses like high-alumina silicates, struggle to achieve both excellent corrosion resistance and perfect thermal compatibility. This is because their chemical stability under high-temperature, high-concentration acid etching environments remains insufficient, and their corrosion resistance needs improvement. Furthermore, the matching degree between key thermal parameters such as the coefficient of thermal expansion and softening point and mainstream acid-etchable glasses is still not ideal. This has become a key factor restricting further improvements in the performance of microchannel plates. Summary of the Invention

[0005] The purpose of this invention is to provide a glass material with high corrosion resistance and stability, its preparation method and application, thereby overcoming the shortcomings of the prior art. This novel glass material has excellent corrosion resistance, superior thermal properties and good process compatibility, which is crucial for the preparation of high-performance, highly consistent microchannel plates.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] In a first aspect, the present invention provides a glass composition having, by molar percentage, a cationic composition of the following: 61%-70% Si 4+ 3%-12.5% ​​of B 3+ 1%-5.5% Al 3+ 5%-13% K + , 5%-13% Na + 0.2%-3% Ca 2+ 0.1%-2% Li + 0.1%-1% Mg 2+ 0.1%-1% Ti 4+ .

[0008] The glass material composition of this invention, based on high-silicon boron, ensures a core framework with a high softening temperature and high chemical stability, further enhanced and stabilized by the introduction of aluminum. Simultaneously, the mixed alkali effect of lithium, sodium, and potassium is cleverly utilized to optimize the coefficient of thermal expansion and chemical stability, while divalent ions such as calcium and magnesium significantly improve water resistance and adjust processing performance. Finally, the introduction of titanium pushes corrosion resistance (especially acid and water resistance) to its extreme. This multi-component, multi-functional synergistic design enables it to simultaneously meet stringent requirements for thermal, optical, chemical, and processing performance, making it ideal for high-end optical devices such as microchannel plates, and showing broad application prospects in fields such as photoelectric detection and imaging, mass spectrometry, high-energy physics, streak cameras, and advanced medical imaging.

[0009] Specifically, Si 4+ SiO4 is the core component of glass and the main component forming the glass's skeletal network structure. It exists in the glass structure as [SiO4] tetrahedra. The Si-O bond is strong, exhibiting resistance to water and acid corrosion. Its robust three-dimensional network structure ensures the glass's high chemical stability and high softening temperature. Therefore, in this invention, the cations in the glass material composition, by molar percentage, include 61%-70% SiO4. 4+ .

[0010] B 3+ It is a network-forming ion that can enter the network in the form of [BO3]trigonometric or [BO4]tetrahedral ions. 3+The addition of [a specific ingredient] can effectively suppress the thermal vibration of the network and is a key component for adjusting the coefficient of thermal expansion (CTE). Within an appropriate range, it can strengthen the network and improve acid resistance (especially hydrolysis resistance). Meanwhile, [the following text appears to be unrelated and possibly a separate sentence fragment:] B 3+ It can also reduce the high-temperature viscosity of glass and improve its melting performance. Therefore, in this invention, the cations in the glass material composition, by molar percentage, include: 3%-12.5% ​​B. 3+ .

[0011] Al 3+ These are network intermediate ions, typically replacing [SiO4] in the form of [AlO4] tetrahedra, but requiring alkali metal ions to balance their charge. [AlO4] tetrahedra can connect and reinforce broken silicon-oxygen networks, significantly improving chemical durability (moisture and acid resistance), and making the glass structure more complex, less prone to crystallization, and improving processing safety. Therefore, in this invention, the cations in the glass material composition, by molar percentage, include: 1%-5.5% Al 3+ .

[0012] Li + Na + and K + It is a network-modifying ion, an alkali metal ion, which readily moves and diffuses within the glass, disrupting the glass's network structure, lowering its melting point and viscosity, thus making the glass easier to melt and form at lower temperatures, improving melting efficiency, and acting as a good flux. Additionally, the simultaneous use of Na... + and K + Two alkali metal ions, due to the "mixed alkali effect," can effectively reduce the coefficient of thermal expansion of glass and significantly improve its chemical stability (especially water resistance), which is superior to using only a single alkali metal ion. Therefore, in this invention, the cations in the glass material composition, by molar percentage, include: 0.1%-2% Li. + , 5%-13% Na + and 5%-13% K + .

[0013] Ca 2+ and Mg 2+ It is a network modifier, consisting of divalent alkaline earth metal ions. Compared to alkali metal ions, they are less susceptible to leaching and can prevent water or acid from corroding the glass network, which is key to improving corrosion resistance. Ca 2+ It can increase the viscosity of glass in the low-temperature range, improve its "material properties," making it more suitable for hot processing (such as molding and wire drawing) and less prone to deformation. Mg 2+ This is used to suppress the crystallization tendency of certain glasses. Therefore, in this invention, the cations in the glass material composition, by molar percentage, include: 0.2%-3% Ca. 2+ and 0.1%-1% Mg 2+.

[0014] Ti 4+ It is a network intermediate and can exist as a [TiO4] tetrahedron or a [TiO6] octahedron. Ti 4+ The addition of [a specific ingredient] greatly enhances the glass network's resistance to acids, alkalis, and especially water, making it the secret weapon for achieving "high corrosion resistance and stability." Therefore, in this invention, the cations in the glass material composition, by molar percentage, include: 0.1%-1% Ti. 4+ .

[0015] In some other embodiments, the glass composition, by molar percentage, comprises the following cationic composition: 61%-68% Si 4+ 3%-12.5% ​​of B 3+ 1%-5.5% Al 3+ 7%-13% K + , 7%-13% Na + 0.5%-3% Ca 2 + 0.8%-1.5% Li + 0.5%-1% Mg 2+ 0.1%-0.8% Ti 4+ .

[0016] Specifically, Si 4+ The content may be further selected from the following content ranges or be any value within the following content ranges: 62%-70%, 64.5%-70%, 65.5%-70%, 68%-70%, 61%-68%, 62%-68%, 64.5%-68%, 65.5%-68%, 61%-65.5%, 62%-65.5%, 64.5%-65.5%, 61%-64.5%, 62%-64.5%, 61%-62%.

[0017] B 3+ The content may be further selected from the following content ranges or be any value within the following content ranges: 8%-12.5%, 8.2%-12.5%, 9%-12.5%, 12%-12.5%, 3%-12%, 8%-12%, 8.2%-12%, 9%-12%, 3%-9%, 8%-9%, 8.2%-9%, 3%-8.2%, 8%-8.2%, 3%-8%.

[0018] Al 3+The content may be further selected from the following content ranges or be any value within the following content ranges: 1.8%-5.5%, 2%-5.5%, 4%-5.5%, 5%-5.5%, 1%-5%, 1.8%-5%, 2%-5%, 4%-5%, 5%-5.5%, 1%-4%, 1.8%-4%, 2%-4%, 1%-2%, 1.8%-2%, 1%-1.8%.

[0019] The Li+ content may be further selected from the following content ranges or any value within the following content ranges: 0.8%-2%, 1.5%-2%, 0.1%-1.5%, 0.8%-1.5%, 0.1%-0.8%; the Na+ content may be further selected from the following content ranges or any value within the following content ranges: 8%-13%, 9%-13%, 11.2%-13%, 12.5%-13%, 5%-12.5%, 8%-12.5%, 9%-12.5%, 11.2%-12.5%, 5%-11.2%, 8%-11.2%, 9%-11.2%, 5%-9%, 8%-9%, 5%-8%; K + The content may be further selected from the following content ranges or be any value within the following content ranges: 7.4%-13%, 8%-13%, 9.8%-13%, 11.6%-13%, 5%-11.6%, 7.4%-11.6%, 8%-11.6%, 9.8%-11.6%, 5%-9.8%, 7.4%-9.8%, 8%-9.8%, 5%-8%, 7.4%-8%, 5%-7.4%.

[0020] Ca 2+ The content can be further selected from the following content ranges or any value within the following content ranges: 0.5%-3%, 1.4%-3%, 1.9%-3%, 2%-3%, 0.2%-2%, 0.5%-2%, 1.4%-2%, 1.9%-2%, 0.2%-1.9%, 0.5%-1.9%, 1.4%-1.9%, 0.2%-1.4%, 0.5%-1.4%, 0.2%-0.5%, Mg 2+ The content may be further selected from the following content range or be any value within the following content range: 0.5%-1%, 0.1%-0.5%.

[0021] Ti 4+ The content may be further selected from the following content ranges or be any value within the following content ranges: 0.3%-1%, 0.5%-1%, 0.8%-1%, 0.1%-0.8%, 0.3%-0.8%, 0.5%-0.8%, 0.1%-0.5%, 0.3%-0.5%, 0.1%-0.3%.

[0022] In a second aspect, the present invention provides a glass material blank with high corrosion resistance and stability, made from the glass composition described in the first aspect.

[0023] Thirdly, the present invention provides a glass material with high corrosion resistance stability, made from the glass composition described in the first aspect or the glass material blank with high corrosion resistance stability described in the second aspect.

[0024] Specifically, high corrosion-resistant glass materials are manufactured by processing glass blanks through at least one of the following methods: physical morphology, surface quality, and appearance. Physical morphology processing can involve cutting the glass blank into the desired shape and size, or drilling holes of the required diameter and position. Surface quality processing can involve polishing (e.g., mechanical polishing) to improve the smoothness and transparency of the glass blank surface, or grinding the glass edges to remove sharp edges and improve safety. Appearance processing can involve engraving (e.g., mechanical engraving) to create various patterns or markings on the surface of the glass blank.

[0025] In some other embodiments, the glass material with high corrosion resistance has a coefficient of thermal expansion of 84 × 10⁻⁶ at 20-300°C. -7 / ℃-92×10 -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, glass softening point temperature T s ≥740℃, moisture resistance is RC1 grade, acid resistance is RA1 grade.

[0026] During the research process, this invention discovered that the correlation mechanism between glass composition and performance is complex. Multiple key properties (such as acid resistance, softening point temperature, coefficient of thermal expansion, and stability) are often inversely related and mutually restrictive, making it impossible to simultaneously achieve all objectives through direct compositional fine-tuning. Specifically: The acid resistance of glass is highly dependent on the network formation (such as Si). 4+ B 3+ Al 3+ ) and network modifiers (such as K) + Na + Li + Ca 2+ Mg 2+ A reasonable balance must be struck between the two. The challenge lies in maintaining sufficient network modifiers to ensure the material's meltability and process adaptability, while ensuring that the network-forming body dominates to maintain the integrity of the glass structure in a strongly acidic environment. This invention achieves this by precisely controlling the ratio of the two and introducing Ti. 4+As an intermediate, it further strengthens the network, thereby achieving excellent corrosion resistance while taking into account process feasibility.

[0027] The control of softening point temperature is also subject to the mutual constraints of the effects of network forging bodies and network modifiers. Network forging bodies help to increase the softening point, while network modifiers have the opposite effect. Therefore, it is necessary to carefully match the ratio of the two in the composition design to ensure that the softening point of the corrosion-resistant glass is higher than that of the core glass, thereby maintaining structural support during the high-temperature melting and pressing stage.

[0028] Matching the coefficient of thermal expansion (α) is another key challenge. Alkali metal ion content (K...) + Na + Li + The total amount (10.1%–28%) would normally lead to a higher coefficient of thermal expansion, but this invention introduces a high proportion of Si. 4+ B 3+ Al 3+ The formation of the network effectively suppresses the rise of the α value, ensuring a high degree of matching between the microchannel plate and the core glass throughout the entire processing temperature range, thereby guaranteeing the structural stability and reliability of the microchannel plate at the thermodynamic level.

[0029] Fourthly, the present invention provides a method for preparing the high corrosion resistance glass material described in the third aspect, comprising the following steps: After mixing raw materials containing cations, the mixture is heated and melted, mechanically stirred to assist in bubbling and clarification, cooled, shaped, and annealed to obtain a glass material with high corrosion resistance and stability. The heating and melting temperature is 1500-1600℃, the forming temperature is 1250-1350℃, and the annealing temperature is 520-600℃. Specifically, the heating and melting temperature is 1500, 1510, 1530, 1560, 1588, or 1600℃; the forming temperature is 1250, 1255, 1260, 1288, 1300, 1305, or 1350℃; and the annealing temperature is 520, 540, 555, 578, 588, or 600℃. Forming can be done mechanically or by manual casting. Within this temperature range, higher temperatures can shorten the preparation process compared to lower temperatures. If it is necessary to minimize time costs, those skilled in the art can select a relatively higher temperature within the temperature range disclosed in this invention.

[0030] In some other embodiments, the cationic raw material is one or more of the following: carbonates, nitrates, phosphates, sulfates, hydroxides, oxides, fluorides, and chlorides.

[0031] Fifthly, the present invention provides the application of the high corrosion resistance and stability glass material described in the third aspect in the preparation of microchannel plates.

[0032] In a sixth aspect, the present invention provides a microchannel plate, wherein the support glass material is the high corrosion-resistant and stable glass material described in the third aspect.

[0033] The high corrosion-resistant glass material prepared by this invention, as a support glass material in microchannel plates, can withstand long-term corrosion by high-concentration acid solutions (including hydrochloric acid, nitric acid, sulfuric acid or their mixtures) under elevated temperature conditions during the microchannel plate preparation process. Its acid resistance reaches Grade 1 (superior), demonstrating excellent chemical stability.

[0034] The coefficient of thermal expansion of this highly corrosion-resistant glass is similar to that of commonly used lead-silicate or borosilicate core glass (typically (85–95) × 10⁻⁶) over the entire processing temperature range. -7 The high degree of matching (740℃) effectively avoids structural stress and interface problems caused by thermal mismatch during hot processing. The softening point of this corrosion-resistant glass is higher than that of the core glass (740℃), ensuring that it maintains shape stability as a supporting frame during high-temperature melting and pressing, preventing structural collapse or deformation, and thus ensuring the formation of a regular and tightly arranged channel structure for the microchannels.

[0035] To meet the reliability requirements of microchannel plate fabrication and application, this glass material also has excellent anti-crystallization stability, avoiding performance degradation caused by crystallization during heat treatment; at the same time, it has sufficient mechanical strength to withstand mechanical stress during wire drawing, cutting and subsequent processing, ensuring that it is not easily damaged during the process, and improving yield and product reliability.

[0036] Research has found that only the glass material composed according to this invention can simultaneously meet the stringent requirements of corrosion resistance, matching coefficients of thermal expansion, and matching softening points. This ensures tight interfacial bonding, no internal stress or deformation during the melting and pressing process, guaranteeing the high performance and high consistency of the microchannel plate. If other compositions (such as conventional high-alumina silicate glass) are used, the acid resistance or thermal compatibility may be insufficient, leading to a deterioration in the performance of the MCP.

[0037] In a seventh aspect, the present invention provides the application of the microchannel plate described in the sixth aspect 9 in image intensifiers, photomultiplier tubes, mass spectrometry analysis systems, high-energy physics detectors, streak cameras and high-end medical imaging equipment.

[0038] The beneficial effects of this invention are: (1) The glass composition provided by this invention has a synergistic effect among the types and amounts of cations, enabling the glass to simultaneously meet the three stringent requirements of high corrosion resistance, matching coefficients of thermal expansion, and matching softening points. Specifically, the high Si content... 4+ (61%-70%) laid the foundation for high corrosion resistance and high softening point; B 3+The introduction of (3%-12.5%) improved meltability and helped regulate thermal expansion behavior; Al 3+ (1%-5.5%) enhances network stability. Furthermore, utilizing K... + with Na + The "mixed alkali effect" (5%-13% each) further optimizes chemical stability and precisely controls the coefficient of thermal expansion; while a small amount of Li + Ca 2+ Mg 2+ Ti 4+ Other components are used to fine-tune the softening point, coefficient of thermal expansion, and acid resistance. Compared with traditional high-alumina silicate glass, this material fundamentally solves the problems of interfacial stress, structural defects, and performance degradation caused by thermal mismatch, providing a key material guarantee for the fabrication of high-performance, highly consistent microchannel plates.

[0039] (2) The high corrosion-resistant glass material obtained by this invention has excellent thermal properties, good chemical stability, moisture resistance, corrosion resistance, and good process compatibility. Specifically, its coefficient of thermal expansion at 20-300℃ is (84-92)×10⁻⁶. -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, glass softening point temperature T s With a temperature of ≥740℃, it has good chemical stability, moisture resistance, and acid corrosion resistance. The moisture resistance of the glass material is rated as RC1, and the acid resistance is rated as RA1.

[0040] (3) The high corrosion-resistant glass material of this invention, used as the support glass material for the microchannel plate, can simultaneously meet the stringent requirements of corrosion resistance, matching coefficient of thermal expansion, and matching softening point. This ensures tight interfacial bonding and the absence of internal stress or deformation during the melting and pressing process, guaranteeing the high performance and high consistency of the microchannel plate. The resulting microchannel plate has broad application prospects in fields such as photoelectric detection and imaging, mass spectrometry, high-energy physics, streak cameras, and high-end medical imaging. Detailed Implementation

[0041] Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be construed as limiting the scope of the invention. Specific conditions not specified in the embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Components whose manufacturers are not specified are all commercially available conventional products.

[0042] The testing methods for glass properties in the embodiments and comparative examples of this invention: (1) The coefficient of thermal expansion (α) and glass transition temperature (T) of the glass sample were tested using a Netzsch DIL 402 thermal expansion coefficient measuring instrument. g ) and relaxation temperature (T)f The glass sample was ground and polished into a cylindrical glass strip with a diameter of 6mm × 50mm, and both ends were made parallel. The instrument heating rate was set to 5℃ / min, and the data acquisition period was 20ms. The data were plotted as a temperature versus linear expansion curve, and the glass transition temperature (Tg) was obtained using the tangent method. g ) and relaxation temperature (T) f The coefficient of thermal expansion (α) of glass refers to the elongation per unit length of glass when the temperature increases by 1°C within a certain temperature range. The glass transition temperature (T) g The sag temperature (Ts) refers to the temperature at which the extended lines of the low-temperature and high-temperature regions of a glass sample intersect when the sample is heated from room temperature to the sag temperature. f The temperature at which the structure of the tested glass sample begins to relax and collapse during the heating process is the starting temperature at which the glass begins to deform when heated. (GB / T 7962.16-2010) (2) The softening point temperature (T) of the glass samples was tested using an Orton Model PPV-1000 / 1200 plate viscometer. s Sample preparation: The glass sample was ground into a cylindrical strip of Φ6×6mm, with both ends parallel. The sample was placed between top and bottom discs made of a heat-resistant metal alloy, 44mm in diameter and 6mm thick. The top metal disc was attached to the bottom of the probe rod. Two very thin platinum films (40mm in diameter and 0.001 inch thick) were placed between the sample and the top and bottom discs for easy sampling and placement. The softening point temperature of the glass (T0) is... s Its viscosity is 10. 7.65 Temperature corresponding to dPa·s. (ASTM C-1351M) (3) The principle of the moisture resistance stability test for glass materials is as follows: After glass is etched, a metamorphic layer such as "white spots" or "haze" is produced on its surface. The metamorphic layer significantly increases the scattering of parallel light. Therefore, the degree of degradation of the etched surface can be measured by the intensity of light scattering on the surface of the etched sample. After etching a glass sample polished on both sides in saturated water vapor at 70℃±1℃ for 7 days and nights, its light scattering is measured using an integrating sphere turbidimeter. (GB / T 7962.15-2010) (4) The acid resistance stability of glass materials indicates the glass's ability to resist corrosion by acidic solutions. Solutions with pH values ​​of 2.9, 4.6, and 6.0 are used as the test medium. After the polished glass sample surface is corroded by the test medium, the time it takes for the glass surface to show a violet-blue interference color, or for the surface to exhibit discoloration or peel off is observed under an incandescent lamp. The acid resistance stability of colorless optical glass is classified in descending order based on the length of time. (GB / T 7962.14-2010). Example 1 A glass material with high corrosion resistance and stability, whose cationic composition is shown in Table 1 by molar percentage, is prepared by mixing quartz sand, boric acid, aluminum hydroxide, potassium carbonate, sodium nitrate, calcium carbonate, lithium carbonate, magnesium oxide, and titanium oxide, and then melting it at a high temperature of 1588℃. After melting, the mixture is mechanically stirred to assist in bubbling clarification, and then cooled to 1300℃ for molding. Finally, it is annealed at 600℃ to obtain a glass blank. The blank is then cut and polished to produce glass material.

[0043] Example 2 A glass material with high corrosion resistance and stability, whose cationic composition is shown in Table 1 by molar percentage, is prepared by mixing quartz sand, boric acid, aluminum hydroxide, potassium nitrate, sodium nitrate, calcium carbonate, lithium carbonate, basic magnesium carbonate, and titanium oxide, and then melting it at a high temperature of 1560℃. After melting, the mixture is mechanically stirred and bubbled to clarify it. Then, the temperature is lowered to 1305℃ to form the glass, and then annealed at 588℃ to obtain a glass blank. The blank is then cut and polished to produce the glass material.

[0044] Example 3 A glass material with high corrosion resistance and stability, whose cationic composition is shown in Table 1 by molar percentage, is prepared by mixing quartz sand, boric acid, aluminum hydroxide, potassium nitrate, sodium nitrate, calcium carbonate, calcium fluoride, lithium carbonate, magnesium oxide, and titanium oxide, and then melting it at a high temperature of 1530℃. After melting, the mixture is mechanically stirred to assist in bubbling clarification, and then cooled to 1260℃ to form a glass blank. The blank is then annealed at 540℃ to obtain a glass blank. The blank is then cut and polished to produce glass material.

[0045] Example 4 A glass material with high corrosion resistance and stability, whose cationic composition is shown in Table 1 by molar percentage, is prepared by mixing quartz sand, boric acid, aluminum hydroxide, potassium nitrate, sodium nitrate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, and titanium oxide, and then melting it at 1500℃. After melting, the mixture is mechanically stirred to assist in bubbling clarification, then cooled to 1255℃ to form a glass blank, and then annealed at 578℃ to obtain a glass blank. The blank is then cut and polished to produce glass material.

[0046] Example 5 A glass material with high corrosion resistance and stability, whose cationic composition is shown in Table 1 by molar percentage, is prepared by mixing quartz sand, boric acid, aluminum hydroxide, potassium nitrate, sodium nitrate, calcium carbonate, lithium carbonate, basic magnesium carbonate, and titanium oxide, and then melting it at a high temperature of 1510℃. After melting, the mixture is mechanically stirred and bubbled to clarify it. The mixture is then cooled to 1350℃ to form a glass blank, and then annealed at 520℃ to obtain a glass blank. The blank is then cut and polished to produce glass material.

[0047] Example 6 A glass material with high corrosion resistance and stability, whose cationic composition is shown in Table 1 by molar percentage, is prepared by mixing quartz sand, boric acid, aluminum hydroxide, potassium nitrate, sodium nitrate, calcium carbonate, calcium fluoride, lithium carbonate, magnesium oxide, and titanium oxide, and then melting it at 1600℃. After melting, the mixture is mechanically stirred to assist in bubbling clarification, then cooled to 1288℃ to form a glass blank, and then annealed at 555℃ to obtain a glass blank. The blank is then cut and polished to produce glass material.

[0048] Comparative Examples 1-8 A glass material, unlike Example 6, has the following cation composition in the glass composition as shown in Table 2, by mole percentage, and is prepared according to the method of Example 6.

[0049] The chemical composition and properties of the glass samples in Examples 1-6 of this invention are shown in Table 1.

[0050] Table 1. Chemical composition and properties of glass samples from Examples 1-6 Components (mol%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 <![CDATA[Si 4+ ]]> 68.0 65.5 61.0 70.0 62.0 64.5 <![CDATA[B 3+ ]]> 3.0 8.2 12.0 9.0 8.0 12.5 <![CDATA[Al 3+ ]]> 4.0 1.8 5.0 1.0 2.0 5.5 <![CDATA[K + ]]> 13.0 9.8 5.0 8.0 11.6 7.4 <![CDATA[Na + ]]> 8.0 11.2 12.5 9.0 13.0 5.0 <![CDATA[Ca 2+ ]]> 1.4 1.9 0.5 0.2 2.0 3.0 <![CDATA[Li + ]]> 2.0 0.8 2.0 0.8 0.1 1.5 <![CDATA[Mg 2+ ]]> 0.1 0.5 1.0 1.0 0.5 0.5 <![CDATA[Ti 4+ ]]> 0.5 0.3 1.0 1.0 0.8 0.1 total 100.0 100.0 100.0 100.0 100.0 100.0 <![CDATA[Thermal expansion coefficient (×10 -7 / °C) at 20 - 300°C]]> 88.3 90.1 87.5 85.6 91.9 84.2 <![CDATA[Glass transition temperature T g (°C)]]> 566.4 558.7 560.8 567.2 553.2 561.9 <![CDATA[Slack temperature T f (°C)]]> 643.3 638.9 645.6 635.1 630.5 643.1 <![CDATA[Softening point temperature T s (°C)]]> 751.2 744.5 760.1 741.7 748.2 759.6 Moisture resistance and stability RC Level 1 Level 1 Level 1 Level 1 Level 1 Level 1 Acid resistance stability RA Level 1 Level 1 Level 1 Level 1 Level 1 Level 1 Table 1 shows that the glass materials of the various embodiments provided by the present invention have excellent thermal properties and good process compatibility (among which Example 6 has the best overall performance), and the coefficient of thermal expansion at 20-300℃ is (84-92)×10. -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, glass softening point temperature T s It has a temperature of ≥740℃ and features good chemical stability, moisture resistance, and corrosion resistance. The glass material has a moisture resistance rating of RC1 and an acid resistance rating of RA1.

[0051] The chemical composition and properties of the glass samples of Comparative Examples 1-8 of this invention are shown in Table 2.

[0052] Table 2 Chemical composition and properties of glass samples from Comparative Examples 1-8 Components (mol%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 <![CDATA[Si 4+ ]]> 77 64.5 64.5 64.5 67.5 64.5 64.5 64.5 <![CDATA[B 3+ ]]> 0 12.5 12.5 12.5 12.5 12.5 12.5 12.5 <![CDATA[Al 3+ ]]> 5.5 5.5 0 5.5 5.5 5.5 5.5 5.5 <![CDATA[K + ]]> 7.4 12.4 12.9 0 7.4 7.4 7.4 7.4 <![CDATA[Na + ]]> 5 0 5 12.4 5 5 5 6.5 <![CDATA[Ca 2+ ]]> 3 3 3 3 0 3 3 3 <![CDATA[Li + ]]> 1.5 1.5 1.5 1.5 1.5 2 1.5 0 <![CDATA[Mg 2+ ]]> 0.5 0.5 0.5 0.5 0.5 0 0.6 0.5 <![CDATA[Ti 4+ ]]> 0.1 0.1 0.1 0.1 0.1 0.1 0 0.1 total 100 100 100 100 100 100 100 100 <![CDATA[Thermal expansion coefficient (×10 -7 / °C) at 20 - 300 °C]]> 75.5 95.1 100.3 102.3 80.8 88.8 87.6 92.8 <![CDATA[Glass transition temperature T g (°C)]]> 565.8 538.5 521.3 522.6 566.8 538.2 543.2 541.2 <![CDATA[Slack temperature T f (°C)]]> 654.8 628.9 615.8 621.3 645.5 629.7 633.1 629.5 <![CDATA[Softening point temperature T s (°C)]]> 769.5 700.5 715.6 699.8 765.2 710.0 739.9 738.6 Moisture resistance and stability RC Level 1 Level 2 Level 3 Level 3 Level 2 Level 2 Level 2 Level 3 Acid resistance stability RA Level 2 Level 3 Level 3 Level 3 Level 2 Level 2 Level 2 Level 3 As shown in Table 2, compared with Example 6, Comparative Example 1 uses Si 4+The content increased to 77%, B 3+ When the content is reduced to 0%, the study found that the coefficient of thermal expansion of the glass is significantly reduced, indicating that the glass network is more stable and compact, which increases the burden on the glass melting process.

[0053] Compared with Example 6, Comparative Example 2 uses K + The content increased to 12.4%, Na + When the content was reduced to 0%, the study found that T g T f and T s Decreased chemical durability (RC and RA) and increased coefficient of thermal expansion indicate that the decrease in Na... + K + Complete substitution eliminates the mixed alkali effect, failing to effectively suppress the thermal expansion coefficient of glass, and K + The ionic radius is greater than that of Na. + As a network modifier, K + This will further weaken the glass network structure and reduce T g T f T s , RC and RA.

[0054] Compared with Example 6, Comparative Example 3 uses K + The content increased to 12.9%, Al 3+ When the content was reduced to 0%, the study found that T g T f and T s Decreased chemical durability (RC and RA) and increased coefficient of thermal expansion indicate that the removal of Al... 3+ And added K + This weakens the glass network structure.

[0055] Compared with Example 6, Comparative Example 4 uses Na + The content increased to 12.9%, K + When the content was reduced to 0%, the study found that T g T f and T s The decrease in K+ and the deterioration in RC and RA indicate that the complete removal of K+ and the increase in Na+ have transformed the glass from a mixed alkali system to a single alkali system, resulting in a weakened glass network structure and a general deterioration in performance. This change is common in glass engineering, highlighting the importance of the mixed alkali effect in regulating glass properties.

[0056] Compared with Example 6, Comparative Example 5 uses Si 4+ The content increased to 67.5%, Ca 2+ When the content was reduced to 0%, the study found that the coefficient of thermal expansion decreased, while Ts, Tg, and Tf all increased. This indicates that Si4+ It is the main network agglomerant, and increasing its content will make the glass network structure more compact; while Ca 2+ As a network modifier, its removal reduces the damage to the network.

[0057] Compared with Example 6, Comparative Example 6 uses Li + The content increased to 2%, Mg 2+ When the content was reduced to 0%, the study found that T g T f and T s The decrease in Li and the worsening of RC and RA indicate that the Li + Increased content and Mg 2+ With reduced content, the stability of the overall glass network structure is weakened.

[0058] Compared with Example 6, Comparative Example 7 uses Mg 2+ The content increased to 2%, Ti 4+ When the content is reduced to 0%, studies have found that the thermal properties (T) of glass decrease. s T g T f The coefficient of thermal expansion decreased slightly, while the chemical durability (moisture resistance and acid resistance) decreased significantly. This indicates that Ti... 4+ Removal of Mg reduces network density, hydrolysis resistance, and acid resistance. 2+ The addition of [a specific ingredient] may slightly improve durability, but the effect is not as good as that of Ti. 4+ Significant.

[0059] Compared with Example 6, Comparative Example 8 uses Na + The content increased to 6.5%, Li + When the content was reduced to 0%, the study found that the moisture resistance and acid resistance of the glass decreased significantly, indicating that Li... + It can improve the chemical durability of glass because its strong bond with oxygen atoms can weaken the corrosive effect. When Li... + Be Na + When substituted, Na + It is easier for it to leach out, which leads to a decrease in the glass's moisture resistance and acid resistance.

[0060] In summary, only the glass material composed according to this invention can simultaneously meet the stringent requirements of corrosion resistance, matching coefficient of thermal expansion, and matching softening point. This ensures tight interfacial bonding, no internal stress or deformation during the melting and pressing process, guaranteeing the high performance and high consistency of the microchannel plate. If other compositions (such as conventional high-alumina silicate glass) are used, the acid resistance or thermal compatibility may be insufficient, leading to deterioration of MCP performance.

[0061] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A glass composition, characterized in that, The cation composition, in molar percentage terms, is as follows: 61%-70% Si 4+ 3%-12.5% ​​of B 3+ 1%-5.5% Al 3+ 5%-13% K + ,5%-13% Na + 0.2%-3% Ca 2+ 0.1%-2% Li + 0.1%-1% Mg 2+ 0.1%-1% Ti 4+ .

2. The glass composition according to claim 1, characterized in that, The cation composition, in molar percentage terms, is as follows: 61%-68% Si 4+ 3%-12.5% ​​of B 3+ 1%-5.5% Al 3+ 7%-13% K + , 7%-13% Na + 0.5%-3% Ca 2+ 0.8%-1.5% Li + 0.5%-1% Mg 2+ 0.1%-0.8% Ti 4+ .

3. A glass material blank with high corrosion resistance and stability, characterized in that, Made from the glass composition of claim 1 or 2.

4. A glass material with high corrosion resistance and stability, characterized in that, Made from the glass composition of claim 1 or 2 or the glass material blank with high corrosion resistance stability as described in claim 3.

5. The glass material with high corrosion resistance according to claim 4, characterized in that, The high corrosion-resistant glass material has a coefficient of thermal expansion of 84 × 10⁻⁶ at 20-300℃. -7 / ℃-92×10 -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, glass softening point temperature T s ≥740℃, moisture resistance is RC1 grade, acid resistance is RA1 grade.

6. A method for preparing a glass material with high corrosion resistance as described in claim 4 or 5, characterized in that, Includes the following steps: After mixing raw materials containing cations, the mixture is heated and melted, mechanically stirred to assist in bubbling and clarification, cooled, shaped, and annealed to obtain a glass material with high corrosion resistance and stability. The heating and melting temperature is 1500-1600℃, the forming temperature is 1250-1350℃, and the annealing temperature is 520-600℃.

7. The method for preparing a glass material with high corrosion resistance according to claim 6, characterized in that, The cationic raw material is one or more of the following: carbonates, nitrates, phosphates, sulfates, hydroxides, oxides, fluorides, and chlorides.

8. The application of the high corrosion resistance glass material as described in claim 4 or 5 in the preparation of microchannel plates.

9. A microchannel plate, characterized in that, The supporting glass material is the high corrosion-resistant glass material described in claim 4 or 5.

10. The application of the microchannel plate of claim 9 in image intensifiers, photomultiplier tubes, mass spectrometry analysis systems, high-energy physics detectors, streak cameras, and high-end medical imaging equipment.