A high-temperature resistant structural glass material, its preparation method and application

Abstract

This invention belongs to the field of glass technology and relates to a high-temperature resistant structural glass material, its preparation method, and its applications. The glass is composed of the following components by mass percentage: 60%-70% silicon dioxide, 5.5%-11% boric acid, 0.1%-5% aluminum hydroxide, 0%-3% potassium nitrate, 5.5%-13% potassium carbonate, 0%-12% sodium carbonate, 0.1%-4% calcium carbonate, 0%-2% calcium fluoride, 0%-1% lithium carbonate, 0%-2% basic magnesium carbonate, 0.1%-1% titanium dioxide, 0%-2% zirconium dioxide, and 0%-1% cerium dioxide; the total mass percentage of potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate does not exceed 22%. This structural glass possesses a high softening temperature, a suitable coefficient of thermal expansion, high-temperature resistance, thermal shock resistance, and processing performance, making it suitable as a structural material for optoelectronic devices.

Description

Technical Field

[0001] This invention belongs to the field of glass technology, specifically relating to a high-temperature resistant structural glass material, its preparation method, and its application. Background Technology

[0002] Rigid fiber optic imaging elements are devices that use rigid optical fibers as a substrate and, through careful fiber arrangement design and back-end processing, enable high-fidelity image transmission from one end to the other. They are widely used in optical imaging and optical transmission applications, such as image intensifiers, CCD / CMOS sensor coupling, astronomical telescopes, laser ranging, low-light night vision, and quantum detection. The fabrication process of rigid fiber optic imaging elements mainly includes two key steps: the first step is to combine optical glass preforms and glass tubes and draw them into single optical fibers with a diameter of tens of micrometers; the second step is to arrange, bundle, and assemble hundreds of thousands or even millions of such fibers into a whole in a certain way, and then heat and press them in a high-temperature furnace.

[0003] High-temperature heating and pressing is a key process in transforming loose fiber bundles into robust, dense, rigid fiber optic imaging elements. Specifically, this process typically involves placing neatly arranged fiber pre-bundles in a specialized high-temperature mold and heating them to a critical temperature between the softening points of the core and the sheath glass under a precisely controlled protective atmosphere. Within this temperature range, the sheath glass softens first, becoming a viscous fluid, while the core glass maintains high shape stability. Subsequently, uniform isostatic pressing or mechanical pressure is applied, causing the softened sheath glass to flow and deform, achieving mutual fusion and bonding between adjacent fibers. After cooling and solidification, a completely dense, rigid glass entity containing millions of independent optical channels is finally formed.

[0004] However, during the high-temperature heating and pressing process, the fibers may shift, bend, or twist at high temperatures, disrupting the strict correspondence between input and output pixels and causing image distortion. Simultaneously, glass exhibits viscoelastic flow characteristics at high temperatures, making it prone to rheological changes under gravity or adhesion to the mold interface. This results in uneven surface texture, inconsistent thickness distribution, or edge collapse in the finished panel, severely impacting its optical performance and geometric integrity. Summary of the Invention

[0005] The purpose of this invention is to provide a high-temperature resistant structural glass material, its preparation method, and its application, thereby overcoming the shortcomings of the prior art. The high-temperature resistant structural glass material is provided on the outside of the image transmission part to prevent the glass fibers from shifting, bending, or twisting during the high-temperature melting and pressing process, and to prevent the image transmission part from rheologically changing or sticking to the mold due to gravity at high temperatures.

[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 raw material comprising, by mass percentage, the following components: 60%-70% silicon dioxide, 5.5%-11% boric acid, 0.1%-5% aluminum hydroxide, 0%-3% potassium nitrate, 5.5%-13% potassium carbonate, 0%-12% sodium carbonate, 0.1%-4% calcium carbonate, 0%-2% calcium fluoride, 0%-1% lithium carbonate, 0%-2% basic magnesium carbonate, 0.1%-1% titanium dioxide, 0%-2% zirconium dioxide, and 0%-1% cerium dioxide; wherein the total mass percentage of potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate does not exceed 22%.

[0008] In some other embodiments, by mass percentage, silicon dioxide is specifically used at 60%-64%, 63%-65%, 63%-66%, 63%-70%, 63%-64%, or 63%-65%, etc.; boric acid is specifically used at 5.5%-8.5%, 8%-8.5%, 8%-10%, 8.1%-8.5%, or 8.0%-11%, etc.; aluminum hydroxide is specifically used at 0.1%-2.5%, 2%-2.5%, 2.1%-2.3%, 2%-3%, 2%-4%, or 2%-5%, etc. Potassium nitrate is specifically used at concentrations of 0%-1.5%, 1%-1.5%, 1.3%-1.5%, 1%-2%, or 1%-3%, etc.; potassium carbonate is specifically used at concentrations of 5.5%-10%, 8.5%-10%, 9%-10%, 9%-9.5%, 9%-10%, 9.5%-11%, 9.0%-12%, or 9.5%-13%, etc.; sodium carbonate is specifically used at concentrations of 0%-9%, 8%-9%, 8.5%-9%, 8.5%-10%, 8.5%-11%, or 8.5%-12%, etc.; calcium carbonate is specifically used at concentrations of... Use concentrations of 0.1%-3%, 2%-4%, 2%-3%, 2.5%-3%, or 2.5%-2.7%, etc.; for calcium fluoride, use concentrations of 0%-0.5%, 0.2%-0.5%, 0.2%-0.5%, or 0.2%-1%, 0.2%-2%, etc.; for lithium carbonate, use concentrations of 0%-0.5%, 0.2%-0.5%, 0.4%-0.5%, 0.4%-0.6%, 0.4%-0.8%, or 0.4%-1%, etc.; for basic magnesium carbonate, use concentrations of 0%-0.8%, 0.5%-1%, 0%, etc. The specific concentrations of potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate are as follows: 0.5%-0.8%, 0.7%-0.9%, 0.6%-1.5%, or 0.7%-2%, etc.; titanium dioxide is specifically used at concentrations of 0.1%-0.5%, 0.3%-0.5%, 0.3%-0.6%, 0.3%-0.8%, or 0.3%-1%, etc.; zirconium dioxide is specifically used at concentrations of 0%-1%, 0.5%-1%, 1%-1.5%, 1%-1.2%, or 0.8%-1.2%, etc.; cerium dioxide is specifically used at concentrations of 0.50%-1%, 0.4%-0.6%, or 0.3-0.5%, etc. The total mass percentage of potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate shall not exceed 15%, 20%, or 22%, respectively.

[0009] In the composition of the glass raw material of this invention, the initial raw material is directly added, weighed, and batched without the need for oxide conversion. The anions (CO3) in this raw material... 2- NO3 - OH - F - By altering the melting atmosphere (oxidation / reduction), volatile components are introduced, affecting homogenization, bubbles, and OH groups in the glass. -Content; alters melt properties (such as viscosity and melting point), thereby affecting glass processing parameters and energy consumption.

[0010] In a specific implementation, the glass raw material is melted in a high-temperature furnace. Potassium nitrate (KNO3) in the raw material decomposes upon heating to produce oxygen (4KNO3 → 2K2O + 2N2 + 5O2), providing an oxidizing atmosphere. This helps prevent the reduction of metallic impurities (such as iron) in the glass, reduces color center formation, and improves the glass's transparency. Simultaneously, carbonates (such as potassium carbonate, sodium carbonate, and calcium carbonate) decompose to release CO2 gas (e.g., K2CO3 → K2O + CO2). These gases form bubbles in the melt and promote melt stirring, thereby accelerating the homogenization process, reducing reliance on mechanical stirring, and lowering the complexity of the melting process. The introduction of volatile components (such as the decomposition of calcium fluoride to produce fluoride vapor) helps remove OH groups from the melt. - Groups, reducing the OH groups in glass - Content, reduce OH - The resulting infrared absorption loss is crucial for optical applications. The decomposition of hydroxides (such as aluminum hydroxide) in the raw materials produces water vapor (2Al(OH)3 → Al2O3 + 3H2O). This water vapor, along with other gases (such as CO2), promotes melt homogenization and carries away impurities. Improvements in the homogenization process reduce bubbles and streak defects. Therefore, this raw material composition can significantly reduce overall energy consumption by lowering the melting temperature, shortening melting and homogenization times, and reducing defect handling.

[0011] Specifically, silicon dioxide is the glass network forger, the framework of glass, forming a continuous, disordered [SiO4] tetrahedral network structure. The silicon dioxide content in glass determines its most basic structural strength, chemical stability, and thermal stability. The higher the silicon dioxide content, the higher the softening point, annealing point, and strain point of the glass, meaning the glass is less prone to deformation at high temperatures. Therefore, the silicon dioxide content in the raw material composition ranges from 60-70%.

[0012] Boric acid, also a glass forging agent, can integrate into the silicon-oxygen network in the form of [BO3]trigonal or [BO4]tetrahedral structures, forming a robust and stable borosilicate network with silicon dioxide. This allows the glass material to maintain a high viscosity at high temperatures, thus exhibiting good heat resistance. More importantly, it significantly improves the thermal properties of glass, substantially reducing its coefficient of thermal expansion. This results in minimal deformation and internal thermal stress during heating or cooling, making the glass less prone to cracking. Therefore, the boric acid content in the raw material composition ranges from 5.0% to 9.0%.

[0013] Aluminum hydroxide is a glass network intermediate, Al 3+ Ions can replace part of Si 4+The aluminum hydroxide enters the network to form [AlO4] tetrahedra, enhancing the network structure and improving high-temperature stability. It can suppress glass phase separation (preventing the formation of an inhomogeneous structure during glass cooling), significantly improving the chemical durability, mechanical strength, and toughness of the glass. Therefore, the aluminum hydroxide content in the raw material composition ranges from 0.1% to 5%.

[0014] Titanium dioxide and zirconium dioxide are both powerful intermediate network modifiers that can significantly improve the chemical stability and mechanical strength of glass. Furthermore, they can further reduce the coefficient of thermal expansion and substantially improve the fracture toughness of the material. This means that the glass not only expands and contracts less, but is also more resistant to crack propagation; even if micro-thermal stress cracks occur, they are less likely to propagate and lead to overall rupture. Therefore, the content of titanium dioxide in the raw material composition ranges from 0.1% to 0.5%, and the content of zirconium dioxide ranges from 0.5% to 2.0%.

[0015] Potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate are primarily used as fluxes, providing alkali metal oxides. Alkali metal ions readily move and diffuse within the glass, disrupting the glass's silica-oxygen network structure, lowering its melting point and viscosity, thus making the glass easier to melt and form at lower temperatures, making them excellent fluxes. Additionally, potassium nitrate acts as an oxidizing and clarifying agent, providing oxygen during batch heating to help oxidize organic impurities and promote the function of clarifying agents such as cerium dioxide, while also stabilizing boron in a [BO4] tetracoordinate state. Therefore, the raw material composition typically includes 1.0-3.0% potassium nitrate, 5.0-11.0% potassium carbonate, 5.0-12.0% sodium carbonate, and 0.1-1.0% lithium carbonate. Furthermore, the total weight percentage of potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate should not exceed 22%. Excessive amounts of these alkali metal compounds (above 22%) can lead to excessive weakening of the glass network structure, significantly reducing the glass's softening point, thermal stability, and mechanical strength. In this invention, the glass material needs to possess high-temperature resistance to provide structural support during the high-temperature melting and pressing process of rigid optical fiber imaging elements (typically heated to a temperature between the softening points of the core and sheath glass). If the glass softens too easily, it cannot effectively prevent fiber displacement, bending, or rheological problems. Furthermore, excessive alkali metal oxides make the glass more susceptible to moisture or chemical corrosion, affecting its long-term service life.

[0016] Calcium carbonate and basic magnesium carbonate, as network stabilizers, provide Ca... 2+ and Mg 2+ It can penetrate the gaps in the glass network, providing a "gathering" effect and improving the glass's hardness, chemical stability, and resistance to crystallization at high temperatures (preventing glass devitrification). Therefore, the raw material composition contains 0.1-4.0% calcium carbonate and 0.5-2.0% basic magnesium carbonate.

[0017] Calcium fluoride can reduce the surface tension of glass, thus improving the melting process. Therefore, the content of calcium fluoride in the raw material composition ranges from 0.1% to 2.0%.

[0018] Cerium dioxide, as a clarifying agent and ultraviolet absorber, during the melting process, Ce... 4+ It will decompose into Ce 3+ It releases oxygen (4CeO2→2Ce2O3+O2), helping to expel bubbles from the molten glass. By improving clarity, it reduces bubbles and defects inside the glass, thereby improving overall uniformity and mechanical strength, and indirectly contributing to thermal shock resistance. Simultaneously, it effectively absorbs ultraviolet light. Therefore, the cerium dioxide content in the raw material composition ranges from 0.5% to 1.0%.

[0019] In summary, the glass material of this invention uses silica-boric acid as the core framework, is stabilized and strengthened with aluminum hydroxide, and precisely controls the alkali metal content to balance solubility and performance. Finally, zirconium dioxide, titanium dioxide and other components are added to optimize performance, successfully obtaining excellent properties such as high softening temperature, suitable coefficient of expansion, excellent thermal stability and processing performance.

[0020] In some other embodiments, the glass raw material comprises, by weight percentage, the following components: 60%-66.4% silicon dioxide, 5.5%-8.8% boric acid, 0.1%-5% aluminum hydroxide, 1.1%-3.0% potassium nitrate, 5.5%-10.5% potassium carbonate, 5%-12% sodium carbonate, 0.1%-3.6% calcium carbonate, 0.1%-1.5% calcium fluoride, 0.2%-1% lithium carbonate, 0.5%-2% basic magnesium carbonate, 0.1%-0.4% titanium dioxide, 0.5%-2% zirconium dioxide, and 0.5%-1% cerium dioxide.

[0021] In a second aspect, the present invention provides high-temperature resistant structural glass made from the glass raw materials described in the first aspect.

[0022] In some other embodiments, the glass softening point temperature T of the high-temperature resistant structural glass s The coefficient of thermal expansion is (84-92)×10 at temperatures ≥740℃ and 20-300℃. -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, thermal shock resistance ΔT≥180℃.

[0023] During their research, the inventors discovered that glass is a typical multi-component, non-equilibrium "chaotic body". The macroscopic properties of glass (such as softening point and coefficient of thermal expansion) have a highly nonlinear and complex structure-property relationship with its chemical composition. The effects of each component on different properties often exhibit interrelated and mutually restrictive characteristics, making it difficult to independently and precisely control a specific property by adjusting a single component. This inherent complexity poses a challenge to simultaneously optimizing multiple properties of glass.

[0024] Specifically, in this invention, the coefficient of thermal expansion (α) and softening point temperature (T) of glass are... s The coefficient of thermal expansion (α) and thermal shock resistance are interrelated and mutually restrictive, and the requirements of each property on the glass composition present a relationship that requires comprehensive trade-offs. Specifically, the coefficient of thermal expansion (α) is mainly regulated by the ratio of alkali metal oxides (as network modifiers) to network-forming agents / intermediates (such as SiO2, B2O3, Al2O3, etc.). The former significantly increases α by breaking the glass network and weakening the structural rigidity; the latter effectively reduces α by enhancing network connectivity and density. Softening point temperature (T s The same proportion applies, but its trend differs from the control requirements for α: increasing the content of network-forming organisms or decreasing the content of alkali metals can enhance T. s At the same time, this often leads to a decrease in α. Thermal shock resistance is negatively correlated with α and with T. s They are positively correlated. This means that in order to achieve excellent thermal shock resistance (i.e., low α, high T), s The adjustment of components required to meet the processing requirements necessitates striking a delicate balance between maintaining appropriate α and suitable Ts. Therefore, the glass composition design of this invention essentially involves synergistic optimization among these interrelated properties to achieve the best overall performance match.

[0025] Only by using the glass material composed according to the present invention can the stringent requirements of softening point temperature, expansion coefficient, high temperature resistance, thermal shock resistance and processing performance be met simultaneously, thereby ensuring that the glass fiber is prevented from shifting, bending or twisting during high temperature melting and pressing, and preventing the image transmission part from rheological or reacting and sticking to the mold under the action of gravity at high temperature.

[0026] Thirdly, the present invention provides a method for preparing the high-temperature resistant structural glass described in the second aspect, comprising the following steps: mixing raw materials evenly, melting, stirring and clarifying at a high temperature of 1520-1600℃, then cooling to 1230-1350℃ to form, and annealing at 500-600℃ after forming to obtain the final product.

[0027] Specifically, the high-temperature melting temperature is 1520, 1550, 1580, or 1600°C, the forming temperature is 1230, 1240, or 1350°C, and the annealing temperature is 500, 520, 525, 545, 565, 585, or 600°C. Glass materials prepared within this temperature range exhibit stable properties. It is understood that 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.

[0028] In some other embodiments, the molding method is mechanical molding or manual casting.

[0029] Fourthly, the present invention provides the application of the high-temperature resistant structural glass described in the second aspect in rigid optical fiber panels, image intensifiers, CCD / CMOS couplings, telescopes, rangefinders, low-light night vision, and quantum detection.

[0030] Fifthly, the present invention provides a rigid optical fiber panel, comprising an image transmission portion and a structural portion, wherein the structural portion is disposed on the outside of the image transmission portion; the structural portion adopts the high-temperature resistant structural glass described in the second aspect.

[0031] The structural components are positioned on the outside of the image transmission components to prevent the glass fibers from shifting, bending, or twisting during the high-temperature melting and pressing process, and to prevent the image transmission components from rheologically changing or reacting and sticking to the mold under the influence of gravity at high temperatures.

[0032] In a sixth aspect, the present invention provides a method for preparing a rigid optical fiber panel, wherein, during a high-temperature and high-pressure melting process, the high-temperature resistant structural glass described in the second aspect is placed in the gap between the image transmission part and the external mold.

[0033] In a seventh aspect, the present invention provides an optoelectronic device comprising the rigid optical fiber panel described in the fifth aspect.

[0034] The following beneficial effects can be achieved through one or more of the above-mentioned technical means: (1) The high-temperature resistant structural glass made according to the raw material composition of the present invention has a high softening point temperature and a suitable coefficient of thermal expansion, and its glass softening point temperature T s The coefficient of thermal expansion is (84-92)×10 at temperatures ≥740℃ and 20-300℃. -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f With a temperature of ≥630℃, it has excellent high temperature resistance, thermal shock resistance (ΔT≥180℃) and processing performance, and can be used as a structural material for optoelectronic devices.

[0035] (2) The structural glass material obtained by the present invention is disposed on the outside of the image transmission part, which can be used in the high temperature melting and pressing process of rigid optical fiber image transmission element to prevent the glass fiber from being displaced, bent or twisted, and to prevent the image transmission part from rheological or reacting and sticking with the mold under the action of gravity at high temperature.

[0036] (3) The high-temperature resistant structural glass material provided by the present invention has a high softening point temperature and a suitable coefficient of expansion, excellent high temperature resistance, thermal shock resistance and processing performance, and can be used as a structural material for optoelectronic devices. It has broad application prospects in medical and scientific imaging, helmet display, light weapon aiming scope, image intensifier, quantum detection and other fields. Attached Figure Description

[0037] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0038] Figure 1 The coefficient of thermal expansion (α) of the glass materials of Examples 1-6 and Comparative Examples 1-12 of the present invention at 20-300℃. Figure 2 The glass softening point temperature (Ts) of the glass materials in Examples 1-6 and Comparative Examples 1-12 of the present invention. Figure 3 The thermal shock (ΔT) resistance of the glass materials in Examples 1-6 and Comparative Examples 1-12 of this invention is shown. Detailed Implementation

[0039] 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.

[0040] Rigid fiber optic imaging elements for optical systems consist of a high-refractive-index core glass and a low-refractive-index sheath glass. During the high-temperature heating and pressing process, the fiber bundle may shift, bend, or twist, which can completely disrupt the one-to-one correspondence between the input and output pixels, leading to severe image distortion. Simultaneously, glass is a viscous fluid at high temperatures and may undergo rheological changes under gravity or react and adhere to the mold, resulting in an uneven final panel surface, inconsistent thickness, or edge collapse.

[0041] This invention incorporates structural glass between the image-transmitting fiber bundle and the external mold. This structural glass directly contacts the image-transmitting fibers, which soften at high temperatures, thus preventing direct contact between the fibers and the mold and completely eliminating the reaction and adhesion between the fibers and the mold. Simultaneously, at high temperatures, the structural glass itself softens and tightly supports the internal image-transmitting fiber bundle from all sides, significantly limiting the fiber's rheological changes under gravity (such as edge collapse) and internal displacement and bending. After melting and cooling, the structural glass permanently fuses with the internal image-transmitting fiber bundle, becoming an inseparable component of the finished rigid optical fiber image-transmitting element.

[0042] As can be seen, the structural glass of this invention integrates mold, support, protection, and stress buffer functions into a single rigid fiber optic image transmission element. Although it is not a directly involved part in image transmission, it is an essential structure for achieving high-precision, high-yield image transmission element manufacturing. The softening point and high-temperature viscosity of this structural glass are compatible with those of the skin glass to ensure that it can deform and fuse synchronously with the image transmission fiber bundle at the melting and pressing temperature, providing effective support without excessive flow. Simultaneously, its coefficient of thermal expansion must be highly matched with that of the core glass and the skin glass. If the difference is too large, enormous internal stress will be generated at the interface during the cooling process after melting and pressing, leading to element warping or even cracking.

[0043] The testing methods for glass properties in the embodiments and comparative examples of this invention: The coefficient of thermal expansion (α) and glass transition temperature (T) of the glass samples were measured using a Netzsch DIL 402 thermal expansion coefficient measuring instrument. g ) and relaxation temperature (T f The test method can be found in GB / T 7962.16-2010, and the specific test method is as follows: 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 glass sample under test begins to relax and collapse during the heating process is the starting temperature at which the glass begins to deform when heated.

[0044] The softening point temperature (Ts) of the glass sample was tested using a Model PPV-1000 / 1200 flat viscometer produced by Orton Corporation. The testing method can refer to ASTM C-1351M. The specific testing method is as follows: Sample preparation: The glass sample was polished into a cylindrical glass bar with a diameter of Φ6×6 mm, and both end faces were parallel. The sample was placed between the top and bottom disks, which were made of heat-resistant metal alloy, with a diameter of 44 mm and a thickness of 6 mm. The top metal disk was connected to the bottom of the probe rod. Two very thin platinum films (with a diameter of 40 mm and a thickness of 0.001 inches) were placed between the sample and the top and bottom disks to facilitate sampling and sample placement. The softening point temperature (T s ) is the temperature corresponding to a viscosity of 107.65 dPa·s.

[0045] The thermal shock resistance performance test of the glass sample can refer to GB / T 6579-2007. The specific testing method is as follows: First, place the sample at room temperature for more than 30 minutes, and then place a single sample or the samples in a basket in an oven preheated to the upper limit temperature and keep it warm for enough time to ensure that the glass product reaches temperature equilibrium, generally 30 minutes is sufficient. (Note: The time required to reach temperature equilibrium depends on the maximum wall thickness of the glass. Experience has shown that it takes at least 6 minutes to reach temperature equilibrium for each millimeter of wall thickness.) Place a cold water bath near the oven and reach and maintain the specified lower limit temperature (within 0°C - 27°C).

[0046] For large samples or samples in a basket, use tongs or wear gloves to take the sample out of the oven at one time and immerse it in the cold water bath. The immersion time of the sample is at least 8 s but not more than 2 min. The head of the tongs or the fingers of the gloves should be kept dry, and the hot sample cannot be touched with wet tongs or gloves. The transfer time of the sample, that is, the time from opening the oven to complete immersion, should be completed within 5 s ± 1 s for a single sample or samples in a basket. The transfer time causes a temperature difference between the test oven and the cold water bath, which does not exceed ±3°C of the specified value. Immediately detect the sample after taking it out of the cold water bath. Samples without cracks, fractures, and damage can be determined to pass the thermal shock test with a temperature difference of T1 - T2 = ΔT. Increase the temperature difference T1 - T2 and repeat the test until all samples are broken. When ΔT < 100°C, increase the temperature difference by 5°C each time; when ΔT > 100°C, increase the temperature difference by 10°C each time.

[0047] The composition, preparation method, and performance of the high-temperature-resistant structural glass material are described below in combination with specific embodiments: Example 1 A high-temperature resistant structural glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Table 1. The preparation method is as follows: silicon dioxide, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide and cerium dioxide are mixed in proportion, melted at 1550℃, mechanically stirred after melting, assisted by bubbling and clarification, then cooled to 1320℃ for molding, and then annealed at 570℃ to obtain glass blank. The blank is then cut and polished to process into glass material.

[0048] Example 2 A high-temperature resistant structural glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Table 1. The preparation method is as follows: silicon dioxide, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide and cerium dioxide are mixed in proportion, melted at 1580℃, mechanically stirred after melting, assisted by bubbling and clarification, then cooled to 1300℃ for molding, and then annealed at 580℃ to obtain glass blank. The blank is then cut and polished to process into glass material.

[0049] Example 3 A high-temperature resistant structural glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Table 1. The preparation method is as follows: silicon dioxide, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide and cerium dioxide are mixed in proportion, melted at 1530℃, mechanically stirred after melting, assisted by bubbling and clarification, then cooled to 1230℃ for molding, and then annealed at 525℃ to obtain glass blank. The blank is then cut and polished to process into glass material.

[0050] Example 4 A high-temperature resistant structural glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Table 1. The preparation method is as follows: silicon dioxide, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide and cerium dioxide are mixed in proportion, melted at 1600℃, mechanically stirred after melting, assisted by bubbling and clarification, then cooled to 1345℃ for molding, and then annealed at 600℃ to obtain glass blank. The blank is then cut and polished to process into glass material.

[0051] Example 5 A high-temperature resistant structural glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Table 1. The preparation method is as follows: silicon dioxide, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide and cerium dioxide are mixed in proportion, melted at 1555℃, mechanically stirred after melting, assisted by bubbling and clarification, then cooled to 1230℃ for molding, and then annealed at 550℃ to obtain glass blank. The blank is then cut and polished to process into glass material.

[0052] Example 6 A high-temperature resistant structural glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Table 1. The preparation method is as follows: silicon dioxide, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide and cerium dioxide are mixed in proportion, melted at 1560℃, mechanically stirred after melting, assisted by bubbling and clarification, then cooled to 1335℃ for molding, and then annealed at 585℃ to obtain glass blank. The blank is then cut and polished to process into glass material.

[0053] Comparative Examples 1-12 A glass material and its preparation method are disclosed. The raw material composition by mass percentage is shown in Tables 2 and 3. The preparation method is the same as that in Example 1.

[0054] Table 1. Composition and properties of glass raw materials in Examples 1-6 wt% Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 silicon dioxide 63.8 60.0 66.0 70.0 65.5 66.4 Boric acid 8.3 6.4 8.8 6.2 11.0 5.5 Aluminum hydroxide 2.2 3.0 0.1 5.0 4.8 1.5 potassium nitrate 1.4 2.5 0.8 1.1 0.0 3.0 Potassium carbonate 9.5 7.0 13.0 10.5 8.0 5.5 Sodium carbonate 8.7 12.0 0.0 5.1 5.1 10.0 Calcium carbonate 2.6 3.0 4.0 0.1 1.5 3.6 Calcium fluoride 0.3 2.0 1.5 0.5 2.0 0.0 lithium carbonate 0.5 0.5 0.8 0.2 0.0 1.0 Basic magnesium carbonate 0.8 1.5 2.0 0.0 0.5 1.5 Titanium dioxide 0.4 0.1 1.0 0.3 0.4 1.0 Zirconium dioxide 1.0 2.0 1.0 0.5 1.0 0.0 Cerium dioxide 0.5 0.0 1.0 0.5 0.2 1.0 total 100.0 100.0 100.0 100.0 100.0 100.0 <![CDATA[Thermal expansion coefficient (×10 -7 / °C) at 20 - 300 °C]]> 88.6 91.8 86.8 84.6 85.5 90.5 <![CDATA[Glass transition temperature T g (°C)]]> 565.1 558.2 568.3 553.2 550.0 570.2 <![CDATA[Slack temperature T f (°C)]]> 651.3 648.1 632.0 637.9 642.1 658.0 Softening point temperature Ts (°C) 742.2 746.0 751.0 743.1 760.0 754.8 Thermal shock resistance ΔT 180.0 180.0 180.0 190.0 190.0 190.0 As shown in Table 1, the glass materials of each embodiment have high softening point temperatures and suitable coefficients of thermal expansion, and their glass softening point temperatures T0 are as follows: s The coefficient of thermal expansion is (84-92)×10 at temperatures ≥740℃ and 20-300℃. -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f It has a temperature of ≥630℃ and excellent high temperature resistance, thermal shock resistance (ΔT≥180℃) and processing performance.

[0055] Table 2 shows the composition and properties of the glass raw materials for Examples 1-6. wt% Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 silicon dioxide 72.1 63.8 63.8 63.8 63.8 64.1 Boric acid 0 10.5 8.3 8.3 10.6 8.3 Aluminum hydroxide 2.2 0 2.2 2.2 2.2 2.2 potassium nitrate 1.4 1.4 0 10.9 1.4 1.4 Potassium carbonate 9.5 9.5 10.9 0 9.5 9.5 Sodium carbonate 8.7 8.7 8.7 8.7 9 8.7 Calcium carbonate 2.6 2.6 2.6 2.6 0 2.6 Calcium fluoride 0.3 0.3 0.3 0.3 0.3 0 lithium carbonate 0.5 0.5 0.5 0.5 0.5 0.5 Basic magnesium carbonate 0.8 0.8 0.8 0.8 0.8 0.8 Titanium dioxide 0.4 0.4 0.4 0.4 0.4 0.4 Zirconium dioxide 1 1 1 1 1 1 Cerium dioxide 0.5 0.5 0.5 0.5 0.5 0.5 total 100.0 100.0 100.0 100.0 100.0 100.0 <![CDATA[Thermal expansion coefficient (×10 -7 / °C) at 20 - 300°C]]> 80.5 95.0 88.0 88.5 72.5 86.4 <![CDATA[Glass transition temperature T g (°C)]]> 560.1 534.6 559 556.3 568.2 568.1 <![CDATA[Slack temperature T f (°C)]]> 662.3 645.8 651.8 649.8 655.3 648.5 <![CDATA[Softening point temperature T s (°C)]]> 758.8 725.6 739 739.6 761.6 748.5 Thermal shock resistance ΔT 190 130 180 160 150 170 Table 3 shows the composition and properties of the glass raw materials used in Examples 7-12. wt% Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 silicon dioxide 63.8 63.8 63.8 63.8 63.8 60.7 Boric acid 8.3 8.3 8.3 8.3 8.3 8.3 Aluminum hydroxide 2.2 2.2 2.2 2.2 2.2 2.2 potassium nitrate 1.4 1.4 1.4 1.4 1.4 3 Potassium carbonate 10 9.5 9.5 9.5 9.5 9.5 Sodium carbonate 8.7 8.7 8.7 8.7 8.7 8.7 Calcium carbonate 2.6 2.6 2.6 2.6 2.6 2.6 Calcium fluoride 0.3 0.3 0.3 0.3 0.3 0.3 lithium carbonate 0 0.5 0.5 0.5 0.5 2 Basic magnesium carbonate 0.8 0 0.8 0.8 0.8 0.8 Titanium dioxide 0.4 0.4 0 0.4 0.4 0.4 Zirconium dioxide 1 1.8 1.4 0 1.5 1 Cerium dioxide 0.5 0.5 0.5 1.5 0 0.5 total 100.0 100.0 100.0 100.0 100.0 100.0 <![CDATA[Thermal expansion coefficient (×10 -7 / °C) at 20 - 300°C]]> 89.5 69.8 90.5 94.3 71.5 99.7 <![CDATA[Glass transition temperature T g (°C)]]> 549.5 571.2 568.8 555.6 570.2 532.1 <![CDATA[Slack temperature T f (°C)]]> 635.9 658.9 655.3 641.2 660.1 608.5 <![CDATA[Softening point temperature T s (°C)]]> 740.1 753.1 744.1 728.2 751.1 719.9 Thermal shock resistance ΔT 150 190 160 170 190 120 As shown in Table 2, compared with Example 1, Comparative Example 1 increased the silica content in the glass raw material to 72.1% and reduced the boric acid content to 0%, producing a glass with a high softening point and low thermal expansion. Although its theoretical thermal shock resistance is superior, this composition severely disrupts the balance of glass components, leading to deterioration in its melting and processing performance. It is no longer suitable for the high-temperature melting and pressing process of rigid optical fiber imaging elements targeted by the original invention, because this process requires the glass to have suitable fluidity and adhesion within a specific temperature range (between the softening points of the core and sheath glass). The glass of Comparative Example 1 may require excessively high melting and pressing temperatures, causing the core glass to soften, damaging the optical fiber structure, or making effective fusion impossible. This, in turn, proves that the composition of Example 1 of the present invention achieves a delicate balance between various performance characteristics and process requirements.

[0056] Compared to Example 1, Comparative Example 2 increased the boric acid content in the glass raw material composition to 10.5% and reduced the aluminum hydroxide content to 0%. By increasing boric acid and completely removing aluminum hydroxide, Comparative Example 2 disrupted the synergistic reinforcing network structure formed between boron and aluminum in Example 1. This change led to a comprehensive decrease in the thermal stability of the glass, manifested as an increase in the coefficient of thermal expansion and a decrease in the characteristic temperature, ultimately impairing its key performance (thermal shock resistance) as a structural glass material. This, in turn, proves the scientific validity and rationality of the component ratios in Example 1, successfully achieving an optimal balance among various properties.

[0057] Compared to Example 1, Comparative Example 3 increased the potassium carbonate content in the glass raw material composition to 10.9% and reduced the potassium nitrate content to 0%. This resulted in improved macroscopic thermodynamic properties (T0). g T f T s While not expected to have a significant impact on the melting processability (α, ΔT), this change negatively affects the glass's melting processability and final intrinsic quality (such as uniformity, bubble rate, and color). Potassium nitrate (KNO3) decomposes upon heating, releasing oxygen (O2), providing an oxidizing atmosphere in the early stages of melting. This helps maintain multivalent ions (such as Ti in the formulation). 4+ and Ce 4+ ( ) is in a high valence state, avoid its reduction (e.g., becoming Ti) 3+ Ce 3+ This prevents unnecessary coloring of the glass due to reduced ions, which confirms the point emphasized in the patent: anions in the raw materials are crucial to the quality of the processing and the final product by changing the melting atmosphere and melt properties.

[0058] Compared to Example 1, Comparative Example 4 increased the potassium nitrate content in the glass raw material composition to 10.9% and decreased the potassium carbonate content to 0%. Although this did not significantly change the final chemical composition of the glass, it resulted in a significant difference due to the presence of anions (CO3-). 2- and NO3 - The behavior of potassium nitrate during the melting process is drastically different, severely deteriorating the glass melting processability. Besides producing K₂O, potassium nitrate also releases nitrogen and oxygen. Compared to potassium carbonate decomposition, which only releases CO₂, the introduction of a large amount of nitrate leads to more intense and complex gas release behavior, making it difficult to remove bubbles in the molten glass and increasing the bubble content in the finished product. The release of CO₂ has a certain stirring effect on the melt, which helps with homogenization. Completely removing potassium carbonate may weaken this effect. This, in turn, confirms the importance of anion selection for process and performance emphasized in the original patent, and the need to seek a balance between components rather than simple substitution. In Comparative Example 5, compared to Example 1, the boric acid content in the glass raw material composition was increased to 10.6%, the sodium carbonate content to 9%, and the calcium carbonate content to 0%. These two major changes in boric acid and calcium carbonate both point to a reduction in the coefficient of thermal expansion and an increase in characteristic temperature. However, this also leads to an increase in the elastic modulus, meaning the glass is more brittle under thermal stress, which is detrimental to thermal shock resistance and breaks the performance balance achieved in Example 1 through the specific ratio of boron and calcium.

[0059] Compared with Example 1, Comparative Example 6 increased the silica content in the glass raw material to 64.1% and reduced the calcium fluoride content to 0%, which will result in a deterioration in the melting and processing performance of the glass material (requiring higher melting and processing temperatures and increased energy consumption).

[0060] Compared to Example 1, Comparative Example 7 increased the potassium carbonate content in the glass raw material composition to 10%. Reducing the lithium carbonate content to 0% results in a slight increase in the coefficient of thermal expansion of the glass, a decrease in the glass transition temperature, relaxation temperature, and softening point temperature, and a deterioration in thermal shock resistance. This indicates that due to the differences in the influence of different alkali metal ions on the glass network structure, even with similar total alkali content, the balance and selection among different alkali metal oxides play a crucial role in the final performance.

[0061] Compared to Example 1, Comparative Example 8 increased the zirconium dioxide content in the glass raw material composition to 1.8% and reduced the basic magnesium carbonate content to 0%. This resulted in a significant reduction in the coefficient of thermal expansion of the glass, and achieved T0 without excessively sacrificing other processing properties. g T f T s In addition to the increased thermal shock resistance, it also increases the burden on glass melting.

[0062] Compared to Example 1, Comparative Example 9 increased the zirconium dioxide content in the glass raw material composition to 1.4% and reduced the titanium dioxide content to 0%, resulting in changes in the glass's coefficient of thermal expansion and To. g T f T s Both increased, while thermal shock resistance decreased, indicating that removing titanium dioxide disrupted the optimal balance achieved in Example 1 through the synergistic effect of titanium and zirconium.

[0063] Compared to Example 1, Comparative Example 10 increased the cerium dioxide content in the glass raw material to 1.5% and decreased the zirconium dioxide content to 0%, resulting in an increase in the coefficient of thermal expansion of the glass, T. g T f T s While thermal shock resistance is reduced, the introduction of excessive cerium dioxide can alter the redox balance within the glass, leading to glass coloring. This demonstrates that glass design seeks a delicate balance between different performance requirements. Adjusting one component to optimize a certain performance often has a chain reaction on other properties.

[0064] Compared to Example 1, Comparative Example 11 increased the zirconium dioxide content in the glass raw material composition to 1.5% and decreased the cerium dioxide content to 0%, resulting in a decrease in the coefficient of thermal expansion of the glass, T. g T f T s While cerium dioxide improves thermal shock resistance, it is a refractory material that increases the high-temperature viscosity of glass, leading to higher melting temperatures or longer melting times, thus increasing energy consumption. Removing cerium dioxide will cause it to lose its function as a clarifying agent (absorbing and eliminating bubbles), which will negatively affect the transparency of the glass.

[0065] Compared to Example 1, Comparative Example 12 increased the potassium nitrate content to 3%, the lithium carbonate content to 2%, and reduced the silica content to 60.7% in the glass raw material composition, resulting in a total mass percentage of 23.1% (over 22%) for potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate. The formulation of Comparative Example 12 leans towards "high fluidity and easy melting," but at the cost of sacrificing the high-temperature performance, thermal stability, and thermal shock resistance of the glass material, leading to a significant increase in the coefficient of thermal expansion of the glass. g T f T s The thermal shock performance is significantly reduced, which indicates that the composition of the embodiments of the present invention has found an optimal balance point suitable for the high-temperature melting and pressing process of rigid optical fiber imaging elements in this contradiction.

[0066] Based on the above analysis, it can be seen that only the glass material composed of the present invention can simultaneously meet the stringent requirements of softening point temperature, expansion coefficient, high temperature resistance, thermal shock resistance and processing performance, thereby ensuring that the glass fiber may be displaced, bent or twisted during the high temperature melting and pressing process, and preventing the image transmission part from rheological or reacting and sticking to the mold under the action of gravity at high temperature.

[0067] Furthermore, the high-temperature resistant structural glass produced by this invention is placed in the gap between the image transmission part and the external mold, and the rigid fiber optic panel is prepared using the existing method for preparing rigid fiber optic panels. Research has found that the softening point and viscosity at high temperatures of the high-temperature resistant structural glass produced by this invention are compatible with the shell glass (softening point is generally 740±5℃, melting temperature is generally 1500~1600℃), ensuring that it can deform and fuse synchronously with the image transmission fiber bundle at the melting and pressing temperature, providing effective support without excessive flow. Simultaneously, its coefficient of thermal expansion must be compatible with that of the core glass and the shell glass (the coefficient of thermal expansion of the core glass is generally (92±5)×10⁻⁶). -7 The coefficient of thermal expansion of glass is generally (87±5)×10 at / ℃. -7 / ℃ High matching. The resulting rigid fiber optic panel has a smooth surface, uniform thickness distribution, or no edge collapse issues. Panels made without structural glass or using comparative proportions have uneven surfaces, uneven thickness distribution, or edge collapse issues, which seriously affect their optical performance and geometric integrity.

[0068] 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 raw material, characterized in that, It is composed of the following components by mass percentage: 60%-70% silicon dioxide, 5.5%-11% boric acid, 0.1%-5% aluminum hydroxide, 0%-3% potassium nitrate, 5.5%-13% potassium carbonate, 0%-12% sodium carbonate, 0.1%-4% calcium carbonate, 0%-2% calcium fluoride, 0%-1% lithium carbonate, 0%-2% basic magnesium carbonate, 0.1%-1% titanium dioxide, 0%-2% zirconium dioxide, and 0%-1% cerium dioxide; wherein the total mass percentage of potassium nitrate, potassium carbonate, sodium carbonate, and lithium carbonate does not exceed 22%.

2. The glass raw material according to claim 1, characterized in that, It consists of the following components by mass percentage: 60%-66.4% silicon dioxide, 5.5%-8.8% boric acid, 0.1%-5% aluminum hydroxide, 1.1%-3.0% potassium nitrate, 5.5%-10.5% potassium carbonate, 5%-12% sodium carbonate, 0.1%-3.6% calcium carbonate, 0.1%-1.5% calcium fluoride, 0.2%-1% lithium carbonate, 0.5%-2% basic magnesium carbonate, 0.1%-0.4% titanium dioxide, 0.5%-2% zirconium dioxide, and 0.5%-1% cerium dioxide.

3. A high-temperature resistant structural glass made from the glass raw material described in claim 1 or 2.

4. The high-temperature resistant structural glass according to claim 3, characterized in that, The glass softening point temperature T of the high-temperature resistant structural glass s The coefficient of thermal expansion is (84-92)×10 at temperatures ≥740℃ and 20-300℃. -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, thermal shock resistance ΔT≥180℃.

5. A method for preparing the high-temperature resistant structural glass according to claim 3 or 4, characterized in that, The process includes the following steps: mixing the raw materials evenly, melting them at a high temperature of 1520-1600℃, stirring and clarifying them, then cooling them down to 1230-1350℃ to form them, and finally annealing them at 500-600℃ to obtain the final product.

6. The method for preparing high-temperature resistant structural glass according to claim 5, characterized in that, The forming method is mechanical forming or manual casting.

7. The application of the high-temperature resistant structural glass as described in claim 3 or 4 in rigid fiber optic panels, image intensifiers, CCD / CMOS couplings, telescopes, rangefinders, low-light night vision, and quantum detection.

8. A rigid optical fiber panel, characterized in that, It includes an image transmission section and a structural section, wherein the structural section is disposed on the outside of the image transmission section; the structural section is made of the high-temperature resistant structural glass as described in claim 3 or 4.

9. A method for fabricating a rigid optical fiber panel, characterized in that, During the high-temperature and high-pressure melting process, the high-temperature resistant structural glass described in claim 3 or 4 is placed in the gap between the image transmission part and the external mold.

10. An optoelectronic device, characterized in that, It includes the rigid optical fiber panel as described in claim 8.

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