A glass material for fiber optic imaging elements, its preparation method and application

Abstract

This invention belongs to the field of glass technology, and relates to a glass material for fiber optic imaging elements, its preparation method, and its application. The glass composition, by mass percentage, comprises the following components: 72-84% SiO2, 0.5-10% B2O3, 0.1-5.0% Al2O3, 1-10.5% K2O, 0.1-13% Na2O, 0.1-3% CaO, 0-1% CaF2, 0-1% Li2O, 0-1% MgO, 0-2% TiO2, 0-2% ZrO2, and 0-1% CeO2. The glass prepared by this invention is used for encapsulating or supporting imaging elements. It possesses a high softening point temperature, a coefficient of thermal expansion matching relevant optical materials, excellent flexural strength, elastic modulus, and good machinability. In high-temperature melting and pressing processes, it is placed on the outside of the imaging part, providing mechanical protection and thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of glass technology, specifically relating to a glass material for optical fiber imaging elements, its preparation method, and its application. Background Technology

[0002] Rigid fiber optic panels, as core components of high-end optoelectronic imaging systems, function to transmit images or light intensity distributions with high fidelity between two end faces. This function relies on its unique structure: it consists of tens of thousands or even millions of extremely thin glass fibers with diameters ranging from a few micrometers to tens of micrometers, precisely arranged and solidified at high temperatures to form a rigid, dense, integrated two-dimensional or three-dimensional array. Each fiber is an independent light transmission channel (pixel), and "pixelated" image transmission is achieved through a strict one-to-one spatial correspondence between input and output pixels. This unique function has led to its widespread application in components such as image intensifiers, CCD / CMOS couplers, low-light night vision devices, telescopes, rangefinder markers, quantum detection, high-energy physics experiments, spectrometers, and endoscopes.

[0003] High-temperature fusion bonding is the most critical and precise process in the fabrication of rigid optical fiber panels. The greatest challenge lies in maintaining the initial perfect alignment (microscopic ordered structure) of the fibers under high-temperature fluidity. This is because even slight temperature inconsistencies or pressure deviations during high-temperature fusion bonding can cause micron-level displacement, bending, or twisting of the fibers. This completely disrupts the geometric correspondence between the input and output images, leading to irreversible image distortion and blurring. Simultaneously, glass at high temperatures behaves as a viscoelastic material, undergoing slow rheological changes under gravity and pressure. This results in inconsistent shrinkage rates between the center and edges of the panel, causing overall warping, uneven thickness, and other defects. Furthermore, at high temperatures, the glass material readily undergoes physicochemical reactions with the mold walls that support or constrain it, leading to adhesion. During cooling and separation, this adhesion can tear the panel surface, causing irreparable mechanical damage and introducing additional internal stress. Summary of the Invention

[0004] The purpose of this invention is to provide a glass material for fiber optic image transmission elements, its preparation method and application, thereby overcoming the shortcomings of the prior art. It is used to support, isolate or encapsulate core optical elements. In the high-temperature melting and pressing process, it is placed on the outside of the image transmission part, playing a key role in mechanical protection and thermal stability, thereby ensuring the shape integrity and functional stability of optical devices during the manufacturing process.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a glass composition, wherein the components, by mass percentage, are as follows: 72-84% SiO2, 0.5-10% B2O3, 0.1-5.0% Al2O3, 0.5-10.5% K2O, 0.1-13% Na2O, 0.1-4% CaO, 0-1% CaF2, 0-1% Li2O, 0-1% MgO, 0-2% TiO2, 0-2% ZrO2, and 0-1% CeO2; wherein 0 < K2O + Na2O + Li2O ≤ 15.5%, 0 < CaO + MgO ≤ 3.2%, and 0 < TiO2 + ZrO2 ≤ 3.5%.

[0007] This invention utilizes components that are stably present in a glass network. These components constitute the final chemical composition of the glass network, and the precise mass percentage of each oxide in the glass is clearly defined, unaffected by the type and purity of the raw materials. The role and content of each component are explained below: SiO2 is a network-forming oxide, forming the framework and main body of glass. The interconnected [SiO4] tetrahedra constitute a continuous three-dimensional network structure, which is the fundamental reason why glass materials possess high softening points, high chemical stability, and high mechanical strength. The higher the SiO2 content, the stronger the network structure and the more prominent these properties become; however, the melting temperature also increases dramatically. Therefore, the SiO2 content is typically 72-84% by mass.

[0008] B2O3 also acts as a glass forging agent, incorporating into the silicon-oxygen network in the form of [BO3]trigonal or [BO4]tetrahedral structures. Together with silicon dioxide, it forms a robust and stable borosilicate network and modulates the coefficient of thermal expansion, thereby improving chemical stability. Therefore, the content of B2O3 is 0.5% to 10% by mass.

[0009] Al2O3 is a network intermediate, existing in the form of [AlO4] tetrahedra, and can replace Si. + By entering the network, it repairs the network bonds broken by alkali metal ions, thereby significantly improving chemical stability, mechanical strength (flexural strength), and hardness. Simultaneously, it can increase the elastic modulus and reduce the tendency for crystallization, improving the thermal stability of the glass and preventing crystal precipitation during processing. Therefore, the Al2O3 content, by mass percentage, is 0.1–5.0%.

[0010] K₂O, Na₂O, and Li₂O are network modifiers, primarily used as fluxes. Their function is to break the silicon-oxygen network (Si-O-Si), introducing non-bridging oxygen, thereby significantly reducing the melting temperature and viscosity of the glass, and improving its coefficient of thermal expansion and processability. Therefore, by mass percentage, the content of K₂O is 1–10.5%, Na₂O is 0.1–13%, and Li₂O is 0–1%, with 0 < K₂O + Na₂O + Li₂O ≤ 15.5%.

[0011] CaO and MgO are alkaline earth metal oxides, acting as network modifiers primarily as stabilizers. They provide additional oxygen ions, adjust the glass network structure, and improve the glass's chemical durability and mechanical strength. Simultaneously, they improve melting behavior and enhance the elastic modulus and resistance to crystallization. However, their content cannot be too high, otherwise it will significantly increase the glass's tendency to crystallize and reduce its thermal stability. Therefore, by mass percentage, the CaO content is 0.1–3%, and the MgO content is 0–1%, with 0 < CaO + MgO ≤ 3.2%.

[0012] CaF2 can provide F - The addition of CaF2 ions opens up the silicon-oxygen network, significantly reducing the melting temperature and melt viscosity of glass and greatly improving processability. However, excessive addition can lead to opacity (precipitation of fluoride crystals) and severely reduce chemical stability. Therefore, the content of CaF2 is 0-1% by mass.

[0013] TiO2 and ZrO2 are network intermediates that can improve the chemical durability and mechanical properties of glass materials, especially alkali resistance. ZrO2, in particular, can very effectively improve the elastic modulus, hardness, and fracture toughness (flexural strength) of glass because it has a high electric field strength, which strongly tightens the glass network. Therefore, by mass percentage, the content of TiO2 is 0-2%, the content of ZrO2 is 0-2%, and 0 < TiO2 + ZrO2 ≤ 3.5%. This maximizes mechanical strength without significantly affecting melting performance.

[0014] CeO2 is a special additive used as a clarifying agent. During the glass melting process, CeO2 decomposes to release oxygen, which helps to remove bubbles from the melt. Therefore, the content of CeO2 is 0-1% by mass.

[0015] Based on the above analysis, it can be seen that the glass material of this invention uses a high SiO2 content as a framework to ensure fundamental high performance (high softening point, high strength). An appropriate amount of alkali metal oxides is introduced to overcome the refractory problem caused by high SiO2 content, and the coefficient of thermal expansion is precisely controlled. B2O3, Al2O3, ZrO2, TiO2, etc., are used as "reinforcing phases" to significantly improve mechanical properties and chemical stability. Strong fluxing agents such as CaF2 are used with extreme caution to minimize their negative impact on core high-performance indicators while ensuring meltability and processability.

[0016] Through the ingenious proportions and synergistic effects of these components, this glass material simultaneously possesses a high softening temperature, a coefficient of thermal expansion matching that of relevant optical materials, excellent flexural strength, elastic modulus, and good machinability. These properties enable it to maintain structural integrity in harsh thermal environments, making it suitable for the manufacturing needs of various high-precision optoelectronic devices. It can serve as a support, isolation, or encapsulation component for key structural parts, improving the overall device's reliability, lifespan, and imaging quality under high-temperature conditions.

[0017] Specifically, the glass composition, by mass percentage, comprises the following components: SiO2 at any content selected from 72-80%, 75-80%, 78-80%, 78-82%, 80-81%, or 80-84%; B2O3 at any content selected from 0.5-5%, 3-5%, 4-5%, 4-6%, 4-8%, or 4-10%; and Al2O3 at any content selected from 0.1-4.5%, 4-5%, 4-4.5%, or 3-4.5%. K₂O at any concentration of 0.5-1%, 0.5-2%, 1-2%, 1-5%, or 1-10.5%; Na₂O at any concentration of 0.1-5%, 4-5%, 4-6%, 3-6%, 4-8%, or 4-13%; CaO at any concentration of 0.1-3%, 2-3%, or 1-3%; and CaF₂ at any concentration of 0.1-0.5%, 0.4-0.5%, 0.4-0.6%, 0.4-0.8%, or 0.4-1%. 2. Li₂O with any content of 0~0.5%, 0.4~0.5%, 0.4~0.6%, 0.5~0.8% or 0.5%; MgO with any content of 0.1~0.2%, 0.1~0.3%, 0.2~0.4%, 0.2~0.5%, 0.2~0.6%, 0.2~0.8% or 0.2~1%; MgO with any content of 0.1~0.2%, 0.1~0.3%, 0.2~0.4%, 0.2~0.5%, 0.2~ TiO2 with any content of 0.6%, 0.2-0.8%, 0.2-1% or 0.2-2%, ZrO2 with any content of 0-1%, 0.5-1.1%, 0.8-1.2%, 1-1.2%, 1-1.5% or 1-2%, and CeO2 with any content of 0.1-0.2%, 0.1-0.3%, 0.2-0.4%, 0.2-0.5%, 0.2-0.6%, 0.2-0.8% or 0.2-1%.

[0018] The total mass percentage of K₂O, Na₂O, and Li₂O is any one of the following: 3%≤K₂O+Na₂O+Li₂O≤7%, 3%≤K₂O+Na₂O+Li₂O≤15.5%, 6%≤K₂O+Na₂O+Li₂O≤14%, and 6%≤K₂O+Na₂O+Li₂O≤10%; the total mass percentage of CaO and MgO is 0.5%≤CaO+MgO≤3.2%, 0.6%≤CaO+MgO≤3.2%, 1.2%≤CaO+MgO≤3.2%, and 2.6%≤CaO+MgO≤3.2%. The total mass percentage of TiO2 and ZrO2 is any one of the following: 0.5%≤TiO2+ZrO2≤1.5%, 1.0%≤TiO2+ZrO2≤1.5%, 1.0%≤TiO2+ZrO2≤1.2%, 1.0%≤TiO2+ZrO2≤2%, 1.0%≤TiO2+ZrO2≤2.5%, or 1.0%≤TiO2+ZrO2≤3.5%.

[0019] In some other embodiments, the glass composition comprises, by mass percentage, the following components: 73.5-84% SiO2, 1.5-10% B2O3, 0.1-4.5% Al2O3, 1.0-4% K2O, 4.5-13% Na2O, 0.6-3% CaO, 0-0.5% CaF2, 0-0.5% Li2O, 0-0.6% MgO, 0-1.5% TiO2, 0-1.8% ZrO2, and 0-0.8% CeO2.

[0020] In some other embodiments, the glass composition comprises, by mass percentage, the following components: 73.5-80% SiO2, 1.5-5% B2O3, 0.1-4.5% Al2O3, 1.0-4% K2O, 4.5-13% Na2O, 0.6-3% CaO, 0-0.5% CaF2, 0-0.5% Li2O, 0-0.6% MgO, 0.2-1.5% TiO2, 0.5-1.8% ZrO2, and 0.2-0.8% CeO2, wherein 3.2% ≤ K2O + Na2O + Li2O ≤ 15.5%, 1.2% ≤ CaO + MgO ≤ 3.2%, and 1.0% ≤ TiO2 + ZrO2 ≤ 1.5%.

[0021] In a second aspect, the present invention provides a high-strength, stable structural glass material blank comprising the glass composition described in the first aspect.

[0022] Thirdly, the present invention provides a high-strength, stable structural glass, which is manufactured from the glass material blank described in the second aspect.

[0023] In some other embodiments, the glass softening point temperature T of the high-strength stable structural glass s The coefficient of thermal expansion is 84×10 at temperatures ≥740℃ and 20~300℃. -7 / ℃~92×10 -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f With a softening temperature ≥630℃, flexural strength ≥120MPa, and elastic modulus ≥80GPa, high-strength stable structural glass exhibits a high softening temperature, a coefficient of thermal expansion matching that of relevant optical materials, and excellent flexural strength, elastic modulus, and processing performance. This ensures the shape integrity and functional stability of optical devices during manufacturing.

[0024] Fourthly, the present invention provides a method for preparing the high-strength stable structural glass described in the third aspect, comprising the following steps: mixing the glass composition uniformly, melting, stirring and clarifying it at a high temperature of 1520~1600℃, then cooling it to 1230~1350℃ to form it, and annealing it at 500~660℃ after forming to obtain a glass blank; the glass blank is then precision processed by cutting, grinding and polishing to obtain the high-strength stable structural glass.

[0025] Specifically, the high-temperature melting temperature is 1526, 1525, 1536, 1550, 1565, 1580, or 1600°C; the forming temperature is 1230, 1258, 1280, 1288, 1300, 1310, or 1350°C; and the annealing temperature is 500, 541, 555, 588, 599, 635, 652, or 660°C. Forming can be achieved by mechanical forming or 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.

[0026] Fifthly, the present invention provides the application of the high-strength stable structural glass described in the third aspect in optical fiber imaging elements.

[0027] Sixthly, the present invention provides an optical fiber imaging element, including an imaging portion and a structural portion, wherein the structural portion is disposed outside the imaging portion, and the structural portion adopts the high-strength stable structural glass described in the third aspect. The structural portion, disposed outside the imaging portion, can serve as a key structural component to support, isolate, or encapsulate core optical elements, thereby improving the overall device's reliability, lifespan, and imaging quality under high-temperature conditions.

[0028] In a seventh aspect, the present invention provides the application of the fiber optic imaging element described in the sixth aspect in medical and scientific imaging equipment, helmet-mounted displays, sights, image intensifiers, and quantum detectors. Specifically, the medical and scientific imaging equipment is an endoscope or an X-ray imaging system.

[0029] The beneficial effects of this invention are: (1) The glass material of the present invention uses a high SiO2 content as a skeleton to ensure fundamental high performance (high softening point, high strength), introduces an appropriate amount of alkali metal oxides to overcome the refractory problem caused by high SiO2, and precisely controls the coefficient of thermal expansion. B2O3, Al2O3, ZrO2, TiO2 and other "reinforcing phases" are used to greatly improve mechanical properties and chemical stability. Strong fluxing agents such as CaF2 are used with extreme caution to minimize their negative impact on core high performance indicators while ensuring meltability and processability.

[0030] (2) The present invention provides a glass composition and a glass material with a high-strength and stable structure prepared from the glass composition. This material, as a key structural component of optical elements, has a high softening point temperature and a coefficient of thermal expansion that matches that of related optical materials. Specifically, 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 It has a temperature of ≥630℃ and excellent bending strength, elastic modulus and processing performance, with bending strength ≥120MPa and elastic modulus ≥80GPa.

[0031] (3) The structural glass material of this invention has shown broad application potential in many high-tech fields, including but not limited to medical and scientific imaging equipment (such as endoscopes and X-ray imaging systems), helmet displays, light weapon sights, image intensifiers, quantum detectors, etc. It can be used as a key structural component to support, isolate or encapsulate core optical elements, thereby improving the reliability, service life and imaging quality of the overall device under high temperature conditions. Detailed Implementation

[0032] 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.

[0033] During their research, the inventors discovered the following technical challenges in the high-temperature fusion bonding process of rigid optical fiber panels: ① The challenge of precise thermal expansion matching: For fiber optic panels, thermal stress leads to significant performance degradation. Thermal mismatch generates residual stress at the interface, which not only alters optical transmission characteristics but may also cause material breakage during processing or use. ② The obstacle of softening point temperature coordination: During high-temperature melting and pressing, the viscosity characteristics of the core, sheath, and structural glass must be precisely matched. Existing glass systems often struggle to achieve this complex viscosity coordination, leading to fiber displacement or deformation at high temperatures. ③ The balance between anti-crystallization performance and processability: To improve the chemical stability and mechanical properties of glass, it is often necessary to increase the content of network forgings and intermediates, but this exacerbates the tendency of glass to crystallize. Existing technologies struggle to maintain high anti-crystallization performance while meeting good processability requirements. ④ The contradiction between mechanical properties and thermal stability: High SiO2 content provides excellent mechanical properties but leads to a sharp increase in melting temperature; while adding flux can improve processability, it may impair chemical stability and mechanical strength. Existing technologies struggle to overcome this performance trade-off and cannot provide a comprehensive solution that simultaneously meets multiple requirements.

[0034] To address the aforementioned technical problems, this invention provides a glass composition, a high-strength stable structural glass material prepared from this glass composition, its preparation method, and its application in the field of fiber optic imaging elements. This high-strength stable structural glass material exhibits significant advantages in high-temperature performance, specifically reflected in its high softening point temperature, thermal expansion coefficient matching that of relevant optical materials, excellent flexural strength, elastic modulus, and good machinability. These characteristics enable it to maintain structural integrity in harsh thermal environments, making it suitable for the manufacturing needs of various high-precision optoelectronic devices. It can serve as a support, isolation, or encapsulation component for key structural components, improving the overall device's reliability, lifespan, and imaging quality under high-temperature conditions.

[0035] 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 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 fThe 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) is 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.

[0036] (2) The softening point temperature (T) of the glass samples was tested using an Orton Model PPV-1000 / 1200 plate viscometer. s The test method can be found in ASTM C-1351M, and the specific test method is as follows: 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, 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) was determined. s Its viscosity is 10. 7.65 The temperature corresponding to dPa·s.

[0037] (3) The bending strength of glass refers to the maximum bending stress that the material withstands before it fails under bending load. The test method can be found in GB / T 37781-2019, and the specific test method is as follows: The flexural strength (σ) of a glass sample was determined using a LE5105 microcomputer-controlled electronic universal testing machine. The sample dimensions were 10mm × 20mm × 120mm. The two long sides of the tested glass sample were optically polished, and the edges were chamfered. (4) The elastic modulus of the glass sample is tested using the pulse excitation method. This method applies a pulse excitation signal to the sample using a suitable lightweight hammer, causing it to vibrate freely. The test method can be found in GB / T 37780-2019, and the specific test method is as follows: When the excitation frequency coincides with the natural frequencies of the specimen (including the fundamental frequencies of bending and torsional vibration), the specimen will resonate. These resonant frequencies are detected and recorded using a laser sensor. Then, based on the specimen's mass, dimensions, and the measured resonant frequencies, the elastic modulus (E) of the material is calculated using a given formula. Sample preparation: The glass sample is processed into a size of 5mm × 20mm × 100mm.

[0038] The solution of the present invention will be described below with reference to specific embodiments: Example 1 The glass material of this embodiment is composed of the following components by mass percentage, as shown in Table 1: 72% SiO2, 5.5% B2O3, 3% Al2O3, 1.5% K2O, 13% Na2O, 0.6% CaO, 1% CaF2, 1% Li2O, 1.1% TiO2, 0.5% ZrO2, and 0.8% CeO2. Using quartz sand, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, titanium dioxide, zirconium dioxide, and cerium dioxide as raw materials, the various glass raw materials are mixed in proportion. The batch is then melted at 1565℃, clarified with auxiliary stirring, mechanically formed at 1258℃, and annealed at 541℃ to obtain a glass blank. The blank is then precision-processed through cutting, grinding, and polishing to obtain the glass material.

[0039] Example 2 The glass material of this embodiment is composed of the following components by mass percentage, as shown in Table 1: 74.5% SiO2, 0.5% B2O3, 5% Al2O3, 10.5% K2O, 4.5% Na2O, 0.1% CaO, 0.5% CaF2, 0.4% Li2O, 1% MgO, 2% TiO2, and 1% CeO2. Using quartz sand, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, and cerium dioxide as raw materials, the various glass raw materials are mixed in proportion. The batch is melted at 1526℃, clarified with auxiliary stirring, mechanically formed at 1310℃, and annealed at 652℃ to obtain a glass blank. The blank is then precision-processed through cutting, grinding, and polishing to obtain the glass material.

[0040] Example 3 The glass material of this embodiment is composed of the following components by mass percentage, as shown in Table 1: 77.9% SiO2, 10% B2O3, 1% Al2O3, 2.8% K2O, 3% Na2O, 2% CaO, 0.4% CaF2, 0.5% Li2O, 0.6% MgO, and 1.8% ZrO2. Using quartz sand, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, and zirconium dioxide as raw materials, the various glass raw materials are mixed in proportion. The batch is then melted at 1580℃, clarified with auxiliary stirring, mechanically formed at 1280℃, and annealed at 555℃ to obtain a glass blank. The blank is then precision-processed through cutting, grinding, and polishing to obtain the glass material.

[0041] Example 4 The glass material in this embodiment is composed of the following components by mass percentage, as shown in Table 1: 80% SiO2, 4.5% B2O3, 4.5% Al2O3, 1% K2O, 4.5% Na2O, 3% CaO, 0.4% CaF2, 0.5% Li2O, 0.2% MgO, 0.2% TiO2, 1% ZrO2, and 0.2% CeO2. Using quartz sand, boric acid, aluminum hydroxide, potassium nitrate, sodium carbonate, calcium carbonate, calcium fluoride, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide, and cerium dioxide as raw materials, the various glass raw materials are mixed in proportion. The batch is melted at 1536℃, clarified with auxiliary stirring, mechanically formed at 1288℃, and annealed at 588℃ to obtain a glass blank. The blank is then precision-processed through cutting, grinding, and polishing to obtain the glass material.

[0042] Example 5 The glass material of this embodiment is composed of the following components by mass percentage, as shown in Table 1: 84% SiO2, 5% B2O3, 0.1% Al2O3, 3.1% K2O, 0.1% Na2O, 3% CaO, 0.5% CaF2, 0.2% MgO, 1.5% TiO2, 2% ZrO2, and 0.5% CeO2. Using quartz sand, boric acid, aluminum hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, calcium fluoride, basic magnesium carbonate, titanium dioxide, zirconium dioxide, and cerium dioxide as raw materials, the various glass raw materials are mixed in proportion. The batch is melted at 1526℃, clarified with auxiliary stirring, mechanically formed at 1300℃, and annealed at 635℃ to obtain a glass blank. The blank is then precision-processed through cutting, grinding, and polishing to obtain the glass material.

[0043] Example 6 The glass material of this embodiment is composed of the following components by mass percentage, as shown in Table 1: 75% SiO2, 6% B2O3, 1.5% Al2O3, 4% K2O, 9.5% Na2O, 2% CaO, 0.5% Li2O, 0.4% MgO, 0.4% TiO2, 0.5% ZrO2, and 0.2% CeO2. Using quartz sand, boric acid, aluminum hydroxide, potassium nitrate, potassium carbonate, sodium carbonate, calcium carbonate, lithium carbonate, basic magnesium carbonate, titanium dioxide, zirconium dioxide, and cerium dioxide as raw materials, the various glass raw materials are mixed in proportion. The batch is melted at 1525℃, clarified with auxiliary stirring, mechanically formed at 1280℃, and annealed at 599℃ to obtain a glass blank. The blank is then precision-processed through cutting, grinding, and polishing to obtain the glass material.

[0044] Comparative Examples 1-6 The glass materials of Comparative Examples 1-6 are composed of the following components by mass percentage as shown in Table 2, and the glass preparation method is the same as that of Example 4.

[0045] The chemical composition and properties of the glass samples in Examples 1-6 of this invention are shown in Table 1.

[0046] Table 1. Chemical composition and properties of glass samples from Examples 1-6

[0047] Table 2 Chemical composition and properties of glass samples from Comparative Examples 1-6

[0048] As shown in Table 1, the glass materials of each embodiment have high softening point temperatures and coefficients of thermal expansion that match those of related optical materials (Among them, Example 4 has the best overall performance). Its glass softening point temperature Ts ≥ 740℃, and its coefficient of thermal expansion at 20~300℃ is (84~92) × 10⁻⁶. -7 It has a glass transition temperature Tg≥550℃, a sag temperature Tf≥630℃, and excellent flexural strength, elastic modulus and processing performance, with flexural strength ≥120MPa and elastic modulus ≥80GPa.

[0049] As shown in Table 2, compared with Example 4, Comparative Example 1 showed that SiO2 increased from 80% to 84%, B2O3 decreased from 4.5% to 0%, and Al2O3 increased from 4.5% to 5%, making the overall glass network stronger and more stable, resulting in T s T g T f The coefficient of thermal expansion decreases, and the mechanical properties (elastic modulus and flexural strength) are slightly improved. This change may give Comparative Example 1 higher thermal stability and mechanical strength, but the increased difficulty in melting and processing makes it unsuitable for use as a glass material in fiber optic imaging elements.

[0050] Compared to Example 4, Comparative Example 2 shows that Al2O3 decreased from 4.5% to 0%, while K2O increased from 1% to 5.5% (this increase precisely compensated for the reduced mass percentage of Al2O3). This is a typical example of a failure where other key properties were sacrificed in pursuit of fusibility. This comparison strongly demonstrates that 4.5% Al2O3 and controlling the low K2O content are crucial in the formulation of this invention. Al2O3 plays an irreplaceable role in building a robust, stable, and durable glass network, while the content of alkali metal oxides must be strictly limited while ensuring fusibility. The formulation of Example 4 achieves the best balance between the high performance brought by the high SiO2 content and the processability provided by the appropriate amount of flux, and through the reinforcing effect of components such as Al2O3, its final performance meets the requirements of high-end applications.

[0051] Compared to Example 4, Comparative Example 3 showed that K2O decreased from 1% to 0% and Na2O increased from 4.5% to 5.5%, which increased the coefficient of thermal expansion of the glass. s T g T f The decrease in mechanical strength indicates that K2O and Na2O, forming a mixed alkali system, can produce a synergistic effect. The mixed alkali system in Example 1 is more conducive to achieving a high softening point, a suitable coefficient of thermal expansion, and high mechanical strength, thereby better ensuring the stability of optical devices.

[0052] Compared to Example 4, Comparative Example 4 showed an increase in K₂O from 1% to 6.4%, a decrease in Na₂O from 4.5% to 0%, a decrease in Li₂O from 0.5% to 0%, and a decrease in CaF₂ from 0.4% to 0%. This resulted in a significant increase in the coefficient of thermal expansion of the glass, a slight increase in the softening point and sag temperature, and a decrease in the glass transition temperature, flexural strength, and elastic modulus. These changes indicate that the thermal compatibility between the glass of Comparative Example 4 and the core optical material may be worse (the coefficient of thermal expansion deviates from the ideal range), and the mechanical properties are also weakened. Therefore, it may not provide the same functional stability as Example 4 in fiber optic panel applications.

[0053] Compared to Example 4, Comparative Example 5 showed that TiO2 increased from 0.2% to 0.4%, while MgO decreased from 0.2% to 0%. In glass, TiO2, as a network intermediate, often enters the network in the form of [TiO4] or [TiO6], strongly tightening the glass structure and significantly improving mechanical properties such as elastic modulus and flexural strength, while reducing the coefficient of thermal expansion. Although this change is beneficial for improving the stability and mechanical protection of glass as a support material, it may have an adverse effect on melt flowability and worsen the thermal compatibility with the core optical material.

[0054] Compared to Example 4, Comparative Example 6 increased CaF2 from 0.4% to 0.6% and CeO2 from 0.2% to 0%. Increasing the CaF2 content significantly reduced the high-temperature viscosity of the glass, resulting in slightly better flowability when used as the outer support glass for the optical fiber panel compared to Example 4. However, the mechanical properties also decreased slightly. CeO2 is mainly used as a clarifying agent in glass (decomposing at high temperatures to release oxygen and expel bubbles). Reducing the CeO2 content to 0% directly affects the clarification effect (bubble level) and light transmittance of the glass. For imaging elements, tiny bubbles in the glass will affect the overall uniformity of heat conduction and structural compactness, and may even become stress concentration points under extreme conditions.

[0055] In the existing high-temperature melting and pressing process of optical fiber image transmission elements, the elastic glass material obtained by this invention is placed on the outside of the image transmission part, playing a key role in mechanical protection and thermal stability. Specifically, it is reflected in its high softening point temperature, thermal expansion coefficient that matches the relevant optical materials, excellent bending strength, elastic modulus and good machinability.

[0056] Research has found that in the high-temperature melting and pressing process, the softening point of the glass produced by this invention is compatible with that of the skin glass (which typically has a softening point of 740±5℃), and its coefficient of thermal expansion is similar to that of the core glass and the skin glass (which typically has a coefficient of thermal expansion of (92±5)×10). -7 The coefficient of thermal expansion of glass is generally (87±5)×10 at / ℃. -7 The high degree of matching ( / ℃) enables the fibers to maintain their initial perfect arrangement under high temperature fluidity, avoiding defects such as overall warping and uneven thickness caused by inconsistent shrinkage rates.

[0057] Meanwhile, the excellent flexural strength and elastic modulus provide crucial mechanical protection, preventing fiber displacement, bending, or twisting that could be caused by uneven temperature or pressure deviations. This ensures the shape integrity and functional stability of optical devices during the manufacturing process.

[0058] Fiber optic panels fabricated using the glass material of this invention, placed on the outer side of the image transmission section, exhibit significant improvements in key performance indicators: By maintaining the initial perfect alignment of the fibers and reducing interface defects, the glass of this invention helps achieve high-fidelity image transmission. Tests show that the modulation transfer function (MTF) response of the fiber optic panel composed of the optimized glass remains significant at a spatial frequency of 10 lp / mm, meeting the stringent resolution and contrast requirements of high-end imaging applications. Due to the substantial reduction in shape deformation and structural defects during the high-temperature melting and pressing process, the batch consistency of fiber optic panels fabricated using the glass of this invention is significantly improved, which is crucial for applications requiring precise geometric correspondence, such as image intensifiers and CCD / CMOS couplings. By reducing internal stress levels, suppressing crystallization tendency, and improving mechanical strength, fiber optic panels protected by the glass of this invention exhibit excellent long-term reliability and environmental adaptability, making them particularly suitable for use in harsh environments such as quantum detection and high-energy physics experiments.

[0059] 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 composition of each component by mass percentage is as follows: 72-84% SiO2, 0.5-10% B2O3, 0.1-5.0% Al2O3, 0.5-10.5% K2O, 0.1-13% Na2O, 0.1-4% CaO, 0-1% CaF2, 0-1% Li2O, 0-1% MgO, 0-2% TiO2, 0-2% ZrO2, and 0-1% CeO2; wherein, 0 < K2O + Na2O + Li2O ≤ 15.5%, 0 < CaO + MgO ≤ 3.2%, and 0 < TiO2 + ZrO2 ≤ 3.5%.

2. The glass composition according to claim 1, characterized in that, The composition of each component by mass percentage is as follows: 74.5~84% SiO2, 0.5~10% B2O3, 0.1~4.5% Al2O3, 1.0~4% K2O, 4.5~13% Na2O, 0.6~3% CaO, 0~0.5% CaF2, 0~0.5% Li2O, 0~0.6% MgO, 0~1.5% TiO2, 0~1.8% ZrO2, and 0~0.8% CeO2; wherein, 3%≤K2O+Na2O+Li2O≤15.5%, 0.6%≤CaO+MgO≤3.2%, and 0.9%≤TiO2+ZrO2≤1.5%.

3. The glass composition according to claim 2, characterized in that, The composition of each component by mass percentage is as follows: 74.5~80% SiO2, 0.5~5% B2O3, 0.1~4.5% Al2O3, 1.0~4% K2O, 4.5~13% Na2O, 0.6~3% CaO, 0~0.5% CaF2, 0~0.5% Li2O, 0~0.6% MgO, 0.2~1.5% TiO2, 0.5~1.8% ZrO2, and 0.2~0.8% CeO2; wherein, 3.2%≤K2O+Na2O+Li2O≤15.5%, 1.2%≤CaO+MgO≤3.2%, and 1.0%≤TiO2+ZrO2≤1.5%.

4. A high-strength, stable structural glass material blank, characterized in that, The glass composition comprising any one of claims 1 to 3.

5. A high-strength, stable structural glass, characterized in that, It is manufactured from the glass material blank as described in claim 4.

6. The high-strength stable structural glass according to claim 5, characterized in that, The glass softening point temperature T of the high-strength stable structural glass s The coefficient of thermal expansion is 84×10 at temperatures ≥740℃ and 20~300℃. -7 / ℃~92×10 -7 / ℃, glass transition temperature T g ≥550℃, sag temperature T f ≥630℃, flexural strength ≥120MPa, elastic modulus ≥80GPa.

7. A method for preparing the high-strength stable structural glass according to claim 5 or 6, characterized in that, The process includes the following steps: mixing the glass composition evenly, melting it at a high temperature of 1520~1600℃, stirring and clarifying it, then cooling it down to 1230~1350℃ to form it, and annealing it at 500~660℃ to obtain a glass blank; the glass blank is then precision processed by cutting, grinding and polishing to obtain high-strength stable structural glass.

8. The application of the high-strength stable structural glass as described in claim 5 or 6 in fiber optic imaging elements.

9. A fiber optic imaging element, characterized in that, It includes an image transmission section and a structural section, wherein the structural section is disposed outside the image transmission section, and the structural section adopts the high-strength stable structural glass as described in claim 5 or 6.

10. The application of the fiber optic imaging element of claim 9 in medical and scientific imaging equipment, helmet displays, sights, image intensifiers, and quantum detectors.

Images