Heat-resistant high-strength environment-friendly anti-halation photoelectric glass as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of optical glass, and relates to heat-resistant high-strength environment-friendly anti-halation photoelectric glass as well as a preparation method and application thereof. The heat-resistant high-strength environment-friendly anti-halation photoelectric glass is prepared from the following components in parts by mass: 75 to 85 parts of SiO2, 4 to 7 parts of B2O3, 1 to 6 parts of Al2O3, 1 to 4 parts of Na2O, 1 to 7 parts of K2O, 1 to 5 parts of BaO, 0.5 to 1 part of CaO, 0 to 2 parts of Bi2O3, 0 to 2 parts of Ag2O, 0 to 2 parts of In2O3 and 0.1 to 0.2 part of CeO2. Wherein Bi2O3, Ag2O and In2O3 are not 0 at the same time. The glass provided by the invention has excellent optical permeability, strength and heat resistance, is simple and convenient to prepare, and is more suitable for actual production and application.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical glass, and relates to a heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass and its preparation method and application. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the overall understanding of the present invention, and is not necessarily regarded as an admission or an implication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] As an important input window element of second-generation and third-generation low-light level night vision devices, the anti-halation cathode glass window (AVG) has a high light transmittance in the ultraviolet, visible, and near-infrared spectral ranges in its effective light-transmitting area. Through the self-substrate generation technology, a highly efficient absorption layer can be generated from the substrate around the effective area of the cathode glass window, and this absorption layer can absorb more than 99.5% of the stray light incident into the cathode glass window. This technology not only improves the cathode sensitivity, clarity, and observation range of the low-light level night vision device, but also enables the low-light level night vision device to achieve wide-spectrum detection and observation.

[0004] In anti-halation optoelectronic glass, when it contains ions that can generate color centers or be reduced and is heated to above 400 °C at high temperature and then comes into contact with hydrogen, a black glass layer will be generated on the glass surface. Therefore, this kind of glass can be used to manufacture anti-halation input windows or optical lenses. Generally speaking, as long as the glass contains ions that can generate color centers or be reduced, the reduction coloring effect can be presented on the glass surface. This new type of special glass with the function of eliminating stray light from the substrate can be used as the optical input window of optical systems and optoelectronic detection systems, and its performance and reliability directly affect the performance and service life of the whole machine. With the continuous progress and development of optoelectronic detection and precision optics fields such as low-light level night vision, ultraviolet detection, space measurement and control, information display, industrial cameras, and high-end lenses, higher requirements are put forward for the effective area transmittance, stray light absorption rate, baking temperature resistance, impact resistance, drop resistance, and bending strength of anti-halation optoelectronic glass. However, although the currently produced anti-halation input windows have high cathode sensitivity and effective area transmittance, their mechanical properties and high-temperature resistance are difficult to further improve, and they cannot meet the requirements for high strength and heat resistance in space measurement and control, industrial cameras, etc. Summary of the Invention

[0005] In order to solve the deficiencies of the prior art, the object of the present invention is to provide a heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass and its preparation method and application. The glass provided by the present invention simultaneously has excellent optical transmission performance, strength, and heat resistance, is simple to prepare, and is more suitable for actual production and application.

[0006] In order to achieve the above object, the technical solution of the present invention is as follows:

[0007] In a first aspect, a heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass is composed of the following components in parts by mass: SiO 2 75 to 85 parts, B 2 O 3 4 to 7 parts, Al 2 O 3 1 to 6 parts, Na 2 O 1 to 4 parts, K 2 O 1 to 7 parts, BaO 1 to 5 parts, CaO 0.5 - 1 part, Bi 2 O 3 0 - 2 parts, Ag 2 O 0 - 2 parts, In 2 O 3 0 - 2 parts, CeO 2 0.1 - 0.2 parts;

[0008] Among them, Bi 2 O 3 , Ag 2 O, In 2 O 3 are not all 0 at the same time.

[0009] In the glass of the present invention, the sum of the mass parts of each component is 100 parts.

[0010] In the present invention, SiO 2 is a glass-forming oxide, which is the main body of the glass-forming framework and the component that plays a major role in the glass framework. Among them, the content of SiO 2 in the present invention is 75 to 85 parts, and the content is extremely high, which can reduce the thermal expansion coefficient of the glass and improve the thermal stability, chemical stability, softening temperature, heat resistance, hardness and mechanical strength of the glass. However, the extremely high content of SiO 2 will also increase the melting point of the glass and increase the viscosity of the glass during high-temperature melting, resulting in difficult melting.

[0011] In the present invention, B 2 O 3 is also a glass-forming oxide. It forms a structural network with silicon-oxygen tetrahedrons in borosilicate glass with borate triangles [BO 3 and borate tetrahedrons [BO 4 as structural units. The content of B 2 O 3 is 4 to 7 parts, which can reduce the expansion coefficient of the glass, improve the thermal stability and chemical stability of the glass, increase the refractive index of the glass, improve the gloss of the glass, and improve the mechanical properties of the glass. In the glass embodiment of the present invention, when B 2 O 3When the amount added is too high, the expansion coefficient of the glass will increase due to the increase in boron-oxygen triangles, resulting in boron anomaly.

[0012] In the present invention, Na 2 O and K 2 O is the outer oxide of the glass network. By introducing an appropriate amount of Na 2 O and K 2 O can make the alkali metal ions in the glass move and diffuse easily, which can reduce the viscosity of the glass during high-temperature melting and make the glass easy to melt. It is a good flux. If too much is introduced, it will increase the thermal expansion coefficient of the glass and reduce the chemical stability, thermal stability and mechanical strength of the glass.

[0013] At the same time, the present invention adjusts B 2 O 3 、Na 2 O and K 2 The component content of O is to solve the problem of SiO 2 The extremely high content of Mg leads to the problem of melting difficulty.

[0014] The Al in the present invention 2 O 3 It is an intermediate oxide. When Na 2 O and Al 2 O 3 When the molar ratio of Na is greater than 1, aluminum-oxygen tetrahedrons are formed and form a continuous structural network with silicon-oxygen tetrahedrons. 2 O and Al 2 O 3 When the molar ratio of Al is less than 1, an octahedron is formed, which is a network outside body and is located in the hole of the silicon oxygen structure network. 2 O 3 It can reduce the crystallization tendency of glass and improve the chemical stability, thermal stability, mechanical strength, hardness and refractive index of glass. However, adding too much will significantly increase the viscosity of the glass and increase the difficulty of melting.

[0015] CaO and BaO are divalent alkaline earth metal oxides, both of which are network exosome oxides. The main function of CaO in the glass of the present invention is a stabilizer, that is, to increase the chemical stability and mechanical strength of the glass. However, when the content is high, the crystallization tendency of the glass can be increased, and the glass can be easily brittle. BaO can increase the refractive index, density, gloss and chemical stability of the glass. In addition, the addition of 1 to 5 parts of BaO in the present invention can accelerate the melting of the glass.

[0016] The present invention adds Bi 2 O 3 、Ag 2 O and In 2 O 3In the anti-halation optoelectronic glass of the present invention, it mainly plays the role of making the glass produce a light absorption layer. Bi 2 O 3 can significantly reduce the viscosity of the glass and increase the refractive index of the glass. However, due to Bi 2 O 3 seriously erodes the crucible and significantly reduces the chemical stability of the glass, so the amount of Bi 2 O 3 added in the present invention is 0 - 2 parts. Ag 2 When O is added to the glass, colloidal particles of silver can precipitate during melting. The addition of an appropriate amount of Ag 2 O can effectively improve the thermal conductivity and mechanical properties of the glass. If the addition amount is too much, the glass is likely to turn light yellow after heating. Therefore, the amount of Ag 2 O added in the present invention is 0 - 2 parts. In 2 O 3 can improve the thermal conductivity and mechanical properties of the glass material; when the indium content is low, the thermal stability and heat resistance of the glass can be effectively improved; while when the indium content increases, the density and refractive index of the glass will also increase. However, too much In 2 O 3 content is also likely to cause serious discoloration of the glass; therefore, the amount of In 2 O 3 added in the present invention is 0 - 2 parts.

[0017] The addition of CeO 2 in the present invention can improve the ability of the glass to absorb ultraviolet rays. The glass containing CeO 2 does not change color under strong radiation. At the melting temperature of the glass, CeO 2 can decompose and release oxygen, which is an environmentally friendly glass fining agent and can effectively improve the transmittance of the glass.

[0018] Second aspect, a preparation method of the heat-resistant high-strength environmentally friendly anti-halation optoelectronic glass described in the first aspect of the present invention, comprising the following steps:

[0019] Mix each glass raw material evenly according to the component ratio to obtain a mixture;

[0020] Melt the mixture, and then homogenize the glass liquid by stirring;

[0021] Carry out clarification on the homogenized glass liquid, and then draw and form it.

[0022] Third aspect, an application of the heat-resistant high-strength environmentally friendly anti-halation optoelectronic glass described in the first aspect of the present invention in a low-light level image intensifier, the low-light level image intensifier includes an anti-halation glass input window, and the anti-halation glass input window is composed of the heat-resistant high-strength environmentally friendly anti-halation optoelectronic glass.

[0023] The beneficial effects of the present invention are as follows:

[0024] 1. For the heat-resistant, high-strength, environmentally friendly anti-halo optoelectronic glass provided by the present invention, by adjusting the composition and content of its glass system, the transmittance in the effective region can be made ≥ 92.5% within the wavelength range of 350 - 1000 nm, and the transmittance of the black light absorption layer ≤ 1.5% within the wavelength range of 350 - 1000 nm. It has good light transmission and stray light elimination performance, can effectively eliminate the halo formed by strong light sources, and improve the image contrast.

[0025] ≥ 92.5%, and the transmittance of the black light absorption layer ≤ 1.5% within the wavelength range of 350 - 1000 nm, having good light transmission and stray light elimination performance, can effectively eliminate the halo formed by strong light sources, and improve the image contrast.

[0026] 2. For the heat-resistant, high-strength, environmentally friendly anti-halo optoelectronic glass provided by the present invention, the thermal expansion coefficient at 30°C - 300°C is (50 ± 2) × 10 -7 / °C, the transformation temperature Tg ≥ 570°C, and the softening point temperature Tf ≥ 675°C, having good chemical stability.

[0027] 3. It is difficult to improve the heat resistance such as the baking resistance temperature and thermal stability, and the mechanical properties such as impact resistance, drop resistance, and flexural strength of the existing anti-halo optoelectronic glass. Through the selection and adjustment of the types and ratios of raw materials, and the synergistic effect generated by the mixing of several special ionic components, the anti-halo glass not only has high optical transmittance performance and stray light elimination performance, but also can simultaneously improve its high-temperature resistance and mechanical properties. Its thermal conductivity coefficient ≥ 1.8 W / (m·K), the thermal stability ≥ 200°C, and the flexural strength ≥ 155 MPa, which can meet the use requirements of future advanced image intensifiers and other high-performance anti-halo glass materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The attached drawings of the specification constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention.

[0029] Figure 1 It is a comparison diagram of the transmittance of the effective region and the black light absorption region of the glass of Example 2 and Comparative Example 5 within the range of 350 - 1000 nm.

[0030] Figure 2 It is a comparison diagram of the thermal conductivity coefficients of the glass materials of Examples 1 - 9.

[0031] Figure 3 It is a comparison diagram of the thermal conductivity coefficients of the glass materials of Comparative Examples 1 - 10.

[0032] Figure 4 It is a comparison diagram of the flexural strengths of the glass materials of Examples 1 - 9 and Comparative Examples 1 - 10. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] It should be noted that the following detailed description is exemplary and is intended to provide further illustration of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention pertains.

[0034] It should be noted that the terms used herein are merely for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular forms are also intended to include the plural forms. In addition, it should also be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0035] In view of the fact that it is difficult for existing anti-halation optoelectronic glass to simultaneously have excellent optical transmittance performance, strength, and heat resistance, the present invention proposes a heat-resistant, high-strength, and environmentally friendly anti-halation optoelectronic glass, its preparation method, and its application.

[0036] A typical embodiment of the present invention provides a heat-resistant, high-strength, and environmentally friendly anti-halation optoelectronic glass, which is composed of the following components in parts by mass: SiO 2 75 - 85 parts, B 2 O 3 4 - 7 parts, Al 2 O 3 1 - 6 parts, Na 2 O 1 - 4 parts, K 2 O 1 - 7 parts, BaO 1 - 5 parts, CaO 0.5 - 1 part, Bi 2 O 3 0 - 2 parts, Ag 2 O0 - 2 parts, In 2 O 3 0 - 2 parts, CeO 2 0.1 - 0.2 part;

[0037] Among them, Bi 2 O 3 、Ag 2 O、In 2 O 3 are not all 0 at the same time.

[0038] In some embodiments, SiO 2 80 - 85 parts, B 2 O 3 5 - 7 parts, Al 2 O 3 1 - 4 parts, Na 2 O 2 - 4 parts, K 2O 1 to 4 parts, BaO 1 to 3 parts, CaO 0.5 to 0.9 parts, Bi 2 O 3 0 to 2 parts, Ag 2 O 0 to 2 parts, In 2 O 3 0 to 2 parts, CeO 2 0.1 to 0.15 parts. Research shows that the glass has better properties under this composition ratio.

[0039] In some embodiments, SiO 2 80 to 85 parts, B 2 O 3 5 to 7 parts, Al 2 O 3 1 to 4 parts, Na 2 O 2 to 4 parts, K 2 O 1 to 4 parts, BaO 1 to 3 parts, CaO 0.5 to 0.9 parts, Bi 2 O 3 0.1 to 1 part, Ag 2 O 0.1 to 1 part, In 2 O 3 0.1 to 1 part, CeO 2 0.1 to 0.15 parts. Research shows that the glass has better properties under this composition ratio.

[0040] In some embodiments, SiO 2 83 to 85 parts, B 2 O 3 6 to 7 parts, Al 2 O 3 1 to 2 parts, Na 2 O 3 to 4 parts, K 2 O 1 to 2 parts, BaO 1 to 2 parts, CaO 0.5 to 0.6 parts, Bi 2 O 3 0.1 to 0.2 part, Ag 2 O 0.1 to 0.2 part, In 2 O 3 0.1 to 0.3 part, CeO 2 0.1 to 0.12 parts. Research shows that the glass has better properties under this composition ratio.

[0041] In some embodiments, the content of B 2 O 3 is greater than the content of Al 2 O 3 Research shows that B 2 O 3 compared with Al 2 O3 It can reduce the expansion coefficient and melting viscosity to a greater extent. Therefore, under this compositional condition, the processing performance is better and the glass properties are better.

[0042] In some embodiments, Bi 2 O 3 , Ag 2 O and In 2 O 3 have a mass ratio of 1:0.9 to 1.1:1.8 to 2.2. Research shows that the glass properties are better under this compositional condition.

[0043] In some embodiments, the sum of the contents of Bi 2 O 3 , Ag 2 O and In 2 O 3 is not greater than 5 parts. Adding too much easily causes the glass to discolor, and the glass properties are better under this compositional condition.

[0044] In some embodiments, the sum of the contents of Bi 2 O 3 , Ag 2 O and In 2 O 3 is less than one percent of the content of SiO 2 . Under this compositional condition, the glass is not prone to devitrification, and the glass properties are better under this compositional condition.

[0045] By controlling the contents of compounds such as SiO 2 , B 2 O 3 , Na 2 O and K 2 O, an anti-halation optoelectronic glass with a low thermal expansion coefficient was prepared, and its thermal expansion coefficient at 30°C - 300°C is (50 ± 2) × 10 -7 / °C, and it has good transmittance and chemical stability.

[0046] By controlling the contents of SiO 2 , Al 2 O 3 , K 2 O, Li 2 O, CaO, BaO and MgO, an anti-halation optoelectronic glass with a transformation temperature Tg ≥ 570°C (specifically 570 - 580°C, more specifically 570 - 577°C) and a softening point temperature Tf ≥ 675°C (specifically 675 - 680°C, more specifically 675 - 678°C) was prepared, improving the hot processing performance of the glass, and the glass has good chemical stability, thermal stability and mechanical strength.

[0047] In some embodiments, it includes a light-transmitting effective area and / or a black light absorption area; wherein, the light-transmitting effective area has good transmittance, and its minimum optical transmittance in the wavelength range of 350 - 1000 nm ≥ 90.5% (preferably 90.5 - 92.0%, more preferably 91.3 - 91.8%); the black light absorption area has a light absorption layer with good light absorption effect, and its maximum optical transmittance in the wavelength range of 350 - 1000 nm ≤ 1.8% (preferably 1.2 - 1.8%, more preferably 1.7 - 1.8%). The black light absorption area is obtained by reduction treatment, and in addition to the change in light-transmitting performance before and after the reduction treatment of the glass system of the present invention, other properties (such as thermal properties, mechanical properties, etc.) do not change.

[0048] The second embodiment of the present invention provides a preparation method of the above-mentioned heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass, including the following steps:

[0049] Mix each glass raw material evenly according to the component ratio to obtain a mixture;

[0050] Melt the mixture, and then homogenize the glass melt by stirring;

[0051] Clarify the homogenized glass melt, and then draw it into shape.

[0052] In some embodiments, the melting temperature is 1400 - 1550 °C. Specifically, the melting time is 25 - 35 °C. At this melting time, it helps to clarify the glass melt.

[0053] Mechanical stirring can accelerate the homogenization process of the glass melt. Stirring can continuously divide the inhomogeneous regions and thick stripes in the glass melt into very fine and short stripes, increasing their contact area, so as to facilitate the mutual dissolution and diffusion between the glass melt and the stripes, thereby gradually disappearing or reducing the stripes.

[0054] In some embodiments, compressed air is introduced into the glass melt from the bottom of the glass melt to achieve clarification. Specifically, the time for introducing compressed air is 9 - 11 h.

[0055] In some embodiments, the forming temperature is 1200 - 1300 °C, and the forming time is 10 - 15 min. By shortening the forming time, the generation of secondary bubbles and impurities, etc. can be reduced.

[0056] In some embodiments, it also includes a reduction treatment, in which the leak-molded glass is subjected to a reduction treatment. Specifically, the reduction treatment is carried out in a reducing atmosphere, the temperature of the reduction treatment is 550-650°C (preferably 580-620°C), the pressure is 0.01-0.5MPa (preferably 0.1-0.5MPa, more preferably 0.11-0.5MPa, and more preferably 0.11-0.3MPa), and the time is 3000-15000min. More specifically, it also includes a surface treatment, in which the surface treatment is to grind and remove the light absorption layer on the surface preset as the light-transmitting effective area and polish it, leaking out the transparent glass part, while retaining the light absorption layer on the surface preset as the black light absorption area.

[0057] A third embodiment of the present invention provides an application of the above-mentioned heat-resistant, high-strength, environmentally friendly, anti-halo photoelectric glass in a low-light image intensifier, wherein the low-light image intensifier comprises an anti-halo glass input window, and the anti-halo glass input window is composed of the heat-resistant, high-strength, environmentally friendly, anti-halo photoelectric glass.

[0058] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in combination with specific embodiments and comparative examples.

[0059] Example 1

[0060] The components of the heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass of this embodiment, the weight percentage of each component, and the physical properties of the glass obtained are shown in Table 1. The symbol "-" in the technical effect of Table 1 means not measured.

[0061] The preparation method of heat-resistant high-strength environmentally friendly anti-halation photoelectric glass is as follows: using quartz sand, boric acid, aluminum hydroxide, sodium nitrate, potassium nitrate, barium nitrate, calcium carbonate, bismuth trioxide, silver nitrate, indium oxide and cerium oxide as raw materials, after fully mixing, high-temperature melting at 1400°C for 35 hours, mechanical stirring (15r / min, 15 hours), auxiliary high-temperature clarification (compressed air is introduced into the bottom of the glass liquid at a pressure of 0.20MPa for 10 hours), and leak molding at 1200°C (molding time is 10 minutes) to obtain a plate glass blank.

[0062] A plate-shaped glass blank is placed in a sealed container and heated to 600°C, and hydrogen is introduced with a hydrogen pressure of 0.20 MPa. The hydrogen treatment time is 60 hours, and the hydrogen in the sealed container is replaced every 15 hours. A light absorption layer is generated on the surface of the glass blank after the reduction treatment, and the light absorption layer on the surface preset as the light-transmitting effective area is ground and removed and polished to expose the transparent glass part, while the light absorption layer on the surface preset as the black light absorption area is retained to obtain the anti-halation photoelectric glass.

[0063] The transmittance was measured using a UV-Vis-NIR spectrophotometer.

[0064] The thermal expansion coefficient of the glass sample was measured using a Netzsch DIL 402 dilatometer. Sample preparation: The glass sample was ground and polished into a cylindrical glass rod with a diameter of Φ6 mm and a length of 50 mm, and both end faces were made parallel. The heating rate was set at 5 °C / min, and the data acquisition period was 20 ms. The relationship curve between temperature and linear expansion was plotted, and the glass transition temperature and dilatometric softening temperature were obtained by the tangent method. (GB / T7962.16~2010)

[0065] The softening point temperature of the glass sample was measured using a Model PPV-1000 / 1200 plate viscometer produced by Orton. Sample preparation: The glass sample was ground and polished into a cylindrical glass rod with a diameter of Φ6 mm and a length of 6 mm, and both end faces were made parallel. The glass sample was placed on the top plate, a heat-resistant metal alloy disc with a diameter of 44 mm and a thickness of 6 mm, which was connected to the bottom of the probe rod, and a heat-resistant metal alloy disc below (also with a diameter of 44 mm and a thickness of 6 mm). 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 upper and lower heat-resistant metal discs to facilitate sampling and sample placement. (GB / T 7962.16-2010)

[0066] The thermal stability test method is as follows: Take 6 pieces of each of the three annealed specimens, with the sample size of 10 mm×10 mm×4 mm. The cut surfaces of the specimens need to be ground and polished. Place the three specimens on refractory bricks and put them into an annealing furnace. Set the initial holding temperature at 120 °C, and set the heating time so that the heating rate is controlled at 4±1 °C / min. After the temperature of the annealing furnace rises to 120 °C, hold for 60 min. After the holding is completed, immerse the specimens in ice water. Check in the water at least 10 s later. Wipe the specimens that are not damaged after inspection clean with alcohol and put them back into the annealing furnace. Raise the temperature by 10 °C compared with the previous time, and repeat the test according to the above steps until all the specimens are broken. Calculate the thermal stability ΔT of each specimen using the following formula:

[0067]

[0068] where ΔT 1 , ΔT 2 , ΔT 3 , ……ΔT i is the temperature difference between the furnace temperature and the water temperature during each measurement, and N 1 , N 2 , N 3 , ……N i is the number of specimens broken during each measurement.

[0069] The thermal conductivity of the glass material was tested with reference to the national standard GB / T 38712-2020. The processed size of the glass sample was 50mm×50mm×4mm.

[0070] The flexural strength of the glass material was tested with reference to the national standard GB / T 37781-2019. The processed size of the glass sample was 120mm×20mm×10mm, and the test method was the three-point bending method.

[0071] Example 2

[0072] The components of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in this example, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0073] In the preparation method of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass, the melting temperature was 1550°C, and the melting time was 25h; mechanical stirring (45r / min, 30h), the forming temperature was 1300°C, and the forming time was 15min. Other preparation steps, parameters, and test processes were the same as those in Example 1.

[0074] Example 3

[0075] The components of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in this example, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0076] In the preparation method of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in this example, the melting temperature was 1420°C, and the melting time was 27h; mechanical stirring (40r / min, 22h), the forming temperature was 1250°C, and the forming time was 12min. Other preparation steps, parameters, and test processes were the same as those in Example 1.

[0077] Example 4

[0078] The components of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in this example, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0079] In the preparation method of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in this example, the melting temperature was 1540°C, and the melting time was 32h; mechanical stirring (25r / min, 18h), the forming temperature was 1270°C, and the forming time was 14min. Other preparation steps, parameters, and test processes were the same as those in Example 1.

[0080] Example 5

[0081] The components of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in this example, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0082] In the preparation method of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass in this embodiment, the melting temperature is 1430 °C and the melting time is 31 h; mechanical stirring (25 r / min, 18 h), the forming temperature is 1260 °C and the forming time is 13 min. Other preparation steps, parameters and testing processes are the same as those in Embodiment 1.

[0083] Example 6

[0084] The components of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0085] In the preparation method of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass in this embodiment, the melting temperature is 1520 °C and the melting time is 32 h; mechanical stirring (24 r / min, 17 h), the forming temperature is 1270 °C and the forming time is 14 min. Other preparation steps, parameters and testing processes are the same as those in Embodiment 1.

[0086] Example 7

[0087] The components of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0088] In the preparation method of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass in this embodiment, the melting temperature is 1510 °C and the melting time is 22 h; mechanical stirring (20 r / min, 15 h), the forming temperature is 1270 °C and the forming time is 11 min. Other preparation steps, parameters and testing processes are the same as those in Embodiment 1.

[0089] Example 8

[0090] The components of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0091] In the preparation method of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass in this embodiment, the melting temperature is 1500 °C and the melting time is 17 h; mechanical stirring (17 r / min, 15 h), the forming temperature is 1220 °C and the forming time is 12 min. Other preparation steps, parameters and testing processes are the same as those in Embodiment 1.

[0092] Example 9

[0093] The components of the heat-resistant, high-strength, environmentally friendly and anti-halation optoelectronic glass, the weight percentage of each component, and the physical properties of the obtained glass are shown in Table 1.

[0094] In the preparation method of the heat-resistant high-strength environmentally friendly anti-halation optoelectronic glass in this embodiment, the melting temperature is 1470 °C, and the melting time is 30 h; mechanical stirring (20 r / min, 19 h), the forming temperature is 1240 °C, and the forming time is 13 min. Other preparation steps, parameters, and testing processes are the same as those in Example 1.

[0095] Comparative Example 1-10

[0096] The component weight percentages of the glass materials in Comparative Example 1-10 and the physical properties of the obtained glass are shown in Table 2. The introduction of the remaining components, the preparation steps, parameters, and testing processes of the glass are the same as those in Example 2.

[0097] Table 1 Components, contents, and physical properties of the glasses in Examples 1-9

[0098]

[0099]

[0100] Table 2 Components, contents, and physical properties of Comparative Example 1-10

[0101]

[0102]

[0103] In Examples 1-9, by reasonably adding corresponding components and controlling the ratio of each component in the raw materials, while ensuring the high transmittance in the effective area of the anti-halation optoelectronic glass and the low transmittance in the black light absorption area, it has better heat resistance and mechanical properties. As can be seen from Table 1, the optical transmittance of the heat-resistant high-strength environmentally friendly anti-halation optoelectronic glass prepared from the glass components in Examples 1-9 of the present invention is as follows: the transmittance in the effective area of the anti-halation glass is ≥92.5% in the wavelength range of 350-1000 nm, the transmittance in the black light absorption area is ≤1.5% in the wavelength range of 350-1000 nm, the thermal conductivity is ≥1.8 W / (m·K), the thermal stability is ≥200 °C, and the flexural strength is ≥155 MPa, with excellent comprehensive performance.

[0104] The heat-resistant high-strength environmentally friendly anti-halation optoelectronic glass provided by the present invention has a thermal expansion coefficient of (50±2)×10 -7 / °C at 30 °C - 300 °C, the glass transition temperature Tg ≥ 570 °C, and the softening point temperature Tf ≥ 675 °C, with good chemical stability.

[0105] Figure 1 It is a comparison chart of the transmittance in the effective area and the black light absorption area of the glass in Example 2 and Comparative Example 6 in the range of 350-1000 nm.

[0106] Figure 2 、3 They are respectively the comparison charts of the thermal conductivity of the glass materials in Examples 1-9 and Comparative Examples 1-10.

[0107] Figure 4 It is the comparison chart of the flexural strength of the glass materials in Examples 1-9 and Comparative Examples 1-10.

[0108] As can be seen from the above, the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass provided in Examples 1-9 of the present invention has excellent heat resistance and mechanical properties, good optical transmittance and thermal properties, and is convenient for preparation and processing. This is because in the preparation of the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass in Examples 1-9 of the present invention, metal oxides Bi 2 O 3 、Ag 2 O and In 2 O 3 are added. The addition of Bi 2 O 3 、Ag 2 O and In 2 O 3 can ensure the anti-scattered light performance of the glass. The addition of Ag 2 O and In 2 O 3 can improve the high-temperature resistance and mechanical properties of the glass, and maintain the content and proportion of some components in the raw materials. At the same time, appropriate melting, forming temperatures and stirring processes are set. Therefore, the heat-resistant, high-strength, environmentally friendly anti-halation optoelectronic glass of the present invention has excellent comprehensive performance and great application potential in the fields of night vision, cameras and optical instruments.

[0109] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A heat-resistant, high-strength, environmentally friendly, anti-halo photoelectric glass, characterized in that: The invention is composed of the following components by weight: SiO2 75-85 parts, B2O3 4-7 parts, Al2O3 1-6 parts, Na2O 1-4 parts, K2O 1-7 parts, BaO 1-5 parts, CaO 0.5-1 parts, Bi2O3 0-2 parts, Ag2O 0-2 parts, In2O3 0-2 parts, CeO2 0.1-0.2 parts; Among them, Bi2O3, Ag2O, and In2O3 are not 0 at the same time.

2. The heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass according to claim 1, characterized in that: SiO2 80-85 parts, B2O3 5-7 parts, Al2O3 1-4 parts, Na2O 2-4 parts, K2O 1-4 parts, BaO 1-3 parts, CaO 0.5-0.9 parts, Bi2O3 0-2 parts, Ag2O0-2 parts, In2O3 0-2 parts, CeO2 0.1-0.15 parts; Or, SiO2 80-85 parts, B2O3 5-7 parts, Al2O3 1-4 parts, Na2O 2-4 parts, K2O 1-4 parts, BaO 1-3 parts, CaO 0.5-0.9 parts, Bi2O3 0.1-1 parts, Ag2O0.1-1 parts, In2O3 0.1-1 parts, CeO2 0.1-0.15 parts; Or, SiO2 83-85 parts, B2O3 6-7 parts, Al2O3 1-2 parts, Na2O 3-4 parts, K2O 1-2 parts, BaO 1-2 parts, CaO 0.5-0.6 parts, Bi2O3 0.1-0.2 parts, Ag2O0.1-0.2 parts, In2O3 0.1-0.3 parts, CeO2 0.1-0.12 parts.

3. The heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass according to claim 1, characterized in that: The content of B2O3 is greater than that of Al2O3; Or, the mass ratio of Bi2O3, Ag2O and In2O3 is 1:0.9-1.1:1.8-2.2; or, the sum of the contents of Bi2O3, Ag2O and In2O3 is not more than 5 parts; Or, the sum of the contents of Bi2O3, Ag2O and In2O3 is less than one percent of the content of SiO2.

4. The heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass according to claim 1, characterized in that: The thermal expansion coefficient at 30℃-300℃ is (50±2)×10 -7 / ℃.

5. The heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass according to claim 1, characterized in that: The transition temperature Tg is ≥570°C, preferably 570-580°C, and more preferably 570-577°C; the softening point temperature Tf is ≥675°C, preferably 675-680°C, and more preferably 675-678°C.

6. The heat-resistant high-strength environmentally friendly anti-halation photoelectric glass according to claim 1, characterized in that: It includes a light-transmitting effective area and / or a black light-absorbing area; wherein the minimum optical transmittance of the light-transmitting effective area is ≥90.5%, preferably 90.5-92.0%, and more preferably 91.3-91.8%; the maximum optical transmittance of the black light-absorbing area in the wavelength range of 350-1000nm is ≤1.8%, preferably 1.2-1.8%, and more preferably 1.7-1.8%.

7. A method for preparing the heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass according to claim 1, characterized in that: The steps include: Mixing glass raw materials except the cerium source according to component proportions, and then adding the cerium source and mixing evenly to obtain a mixture; The mixture is melted, and the glass liquid is homogenized by stirring; The homogenized glass liquid is clarified and then molded into a mold.

8. The method for preparing the heat-resistant high-strength environmentally friendly anti-halation photoelectric glass according to claim 7, characterized in that: The melting temperature is 1400-1550°C, and preferably, the melting time is 25-35h; Alternatively, compressed air is introduced into the molten glass from the bottom to achieve clarification. Preferably, the time for introducing compressed air is 9 to 11 hours; Alternatively, the molding temperature is 1200-1300° C., and the molding time is 10-15 min.

9. The method for preparing the heat-resistant high-strength environmentally friendly anti-halation photoelectric glass according to claim 7, characterized in that: The method further includes a reduction treatment, in which the leak-molded glass is subjected to a reduction treatment; preferably, the reduction treatment is carried out in a reducing atmosphere, the reduction treatment temperature is 550-650°C, preferably 580-620°C, the pressure is 0.01-0.5MPa, preferably 0.1-0.5MPa, further preferably 0.11-0.5MPa, further preferably 0.11-0.3MPa, and the time is 3000-15000min; preferably, the surface treatment is further included, in which the light absorption layer on the surface preset as the light-transmitting effective area is ground off and polished to expose the transparent glass portion, while retaining the light absorption layer on the surface preset as the black light absorption area.

10. Application of the heat-resistant, high-strength, environmentally friendly, anti-halation photoelectric glass according to any one of claims 1 to 7 in a low-light image intensifier, characterized in that: The low-light image intensifier comprises an anti-halation glass input window, and the anti-halation glass input window is composed of the heat-resistant high-strength environmentally friendly anti-halation photoelectric glass.

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