CN118184137B

CN118184137B - Long-service-life halation-preventing glass and preparation method and application thereof

Info

Publication number: CN118184137B
Application number: CN202410409303.2A
Authority: CN
Inventors: 贾金升; 吕学良; 韩玉; 曹振博; 李自金; 洪升; 刘蕊; 魏东萌; 王可; 吕海风; 张洋
Original assignee: China Building Materials Photon Technology Co ltd
Current assignee: China Building Materials Photon Technology Co ltd
Priority date: 2024-04-07
Filing date: 2024-04-07
Publication date: 2024-11-08
Anticipated expiration: 2044-04-07
Also published as: CN118184137A

Abstract

The present application provides a long-life anti-halation glass and a preparation method and application thereof. The glass composition of the long-life anti-halation glass, in terms of mass percentage, comprises SiO ₂ 40-60%, B ₂ O ₃ 10-30%, Bi ₂ O ₃ 3-5%, CaO 3-5%, BaO 0.1-2%, Al ₂ O ₃ 0-3%, MgO 3-8%, ZnO 0-4% and CeO ₂ 0-4%. The glass has good transmittance, good anti-crystallization performance, good chemical stability, good cathode sensitivity and low cathode decay rate, and has a long service life.

Description

Long-service-life halation-preventing glass and preparation method and application thereof

Technical Field

The application relates to a special glass material, in particular to long-life halation-preventing glass and a preparation method and application thereof.

Background

Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

With the rapid development of technology, low-light night vision technology has become an important component in a plurality of fields such as military, safety monitoring, search and rescue and the like. Especially in the day and night monitoring of armed police and frontier defense, and the searching and rescuing operation of an urban space net monitoring system and an underground mine, the low-light night vision equipment plays a vital role. In addition, the technology is increasingly applied to high-end fields such as high-performance cameras, space vision imaging detection systems and the like, and the wide application and the importance of the technology in modern technology are shown. To meet the special requirements of these applications, higher standards are being put on the performance of critical materials used in low-light night vision equipment, especially anti-halation glass.

The vignetting prevention glass is used as a key material of super second-generation and third-generation low-light night vision devices, and the effect of the vignetting prevention glass is not quite variable. The material is mainly characterized by high light transmittance in ultraviolet light, visible light and near infrared spectrum ranges, and can effectively improve the imaging quality of the night vision device. However, conventional anti-halation glass has a number of technical difficulties while providing the necessary light transmission properties. For example, to achieve an anti-halation effect, it is often necessary to apply a specific anti-halation coating to the glass surface. The treatment mode not only can reduce the transmittance of the glass, but also can shorten the service life of the product because the adhesiveness between the coating and the glass is not strong.

More seriously, the existing anti-halation glass component often contains heavy metal elements such As As ₂O₃、Sb₂O₃, pbO and the like, and the substances have obvious negative effects on the cathode sensitivity of an optical instrument and are visually called As 'poisoning'. The poison effect seriously affects the visible light transmittance and the service life of the anti-halation glass, and further affects the performance and the reliability of the whole night vision system.

Disclosure of Invention

Therefore, the application aims to provide a glass composition and a glass material prepared from the glass composition, wherein the glass material can not only effectively prevent halation, but also keep high light transmittance and no heavy metal pollution, has good chemical stability and lower cathode decay rate, has longer service life, and can be widely applied to the technical field of intelligent vision technology or photoelectric information processing as an anti-halation glass material.

Specifically, the present invention provides the following technical features, and one or more of the following technical features are combined to form the technical scheme of the present invention.

In a first aspect of the invention, there is provided a glass composition comprising or consisting of ：SiO₂ 40-60％、B₂O₃ 10-30％、Bi₂O₃ 3-5％、CaO 3-5％、BaO 0.1-2％、Al₂O₃ 0-3％、MgO 3-8％、ZnO 0-4％ and CeO ₂ in mass percent 0-4%.

The selection of the components of the glass composition and the interaction and balance among the components are important, and the combination and the interaction among the components enable the glass with the composition of the glass composition to have good anti-halation effect, including better light transmittance, lower cathode decay rate, better crystallization resistance, better chemical stability and longer service life. In the invention, by carefully introducing and adjusting the contents of SiO ₂、B₂O₃, baO and CeO ₂, glass with uniform inner quality and stable components can be prepared, and has excellent transmittance and chemical stability. Meanwhile, the content of Bi ₂O₃ is introduced and controlled, so that the stray light eliminating performance of the glass is improved. And, the introduction and content adjustment of Al ₂O₃, mgO, znO, caO and B ₂O₃ not only can reduce the viscosity and molding difficulty of glass melting, but also can accelerate the melting process, reduce crystallization tendency, improve the chemical stability and mechanical property of glass, and facilitate processing and manufacturing.

In the present invention, siO ₂ (silica) is a main component of the glass-forming body, and forms the basis of the glass skeleton. The high content of the modified glass in the glass is beneficial to reducing the thermal expansion coefficient and improving the thermal stability, chemical stability and heat resistance of the glass. In an embodiment of the invention, the content of SiO ₂ is 40-60% by mass. In some embodiments of the present invention, the SiO ₂ content, in mass%, may also be selected from or be any of the following ranges: 40-55%, 40-58%, 40-60%, 55-58%, 55-60%, 58-60%, etc. In some preferred embodiments of the invention, the content of SiO ₂ is 40-58%, preferably 55-58% by mass.

In the present invention, B ₂O₃ (diboron trioxide) is also a glass former oxide that not only improves the thermal and chemical stability of the glass, but also, in some aspects, can replace SiO ₂ to enhance the stability of the glass network. However, the content of B ₂O₃ cannot be excessive, otherwise, the tetrahedral BO ₄ structure cannot be formed completely, and the tetrahedral BO ₄ structure exists in the form of a triangle BO ₃, so that the continuity of a network is broken, and the chemical stability of glass is reduced. In an embodiment of the invention, the content of B ₂O₃ is 10-30% by mass. In some embodiments of the present invention, the content of B ₂O₃ in mass percent may also be selected from the following ranges or ranges consisting of any of the values therein or any of the values ：10.0-14.0％、10.0-24.6％、10.0-27.0％、10.0-30.0％、14.0-24.6％、14.0-27.0％、14.0-30.0％、24.6-27.0％、24.6-30.0％、27.0-30.0％, therein, and the like. In some preferred embodiments of the invention, the content of B ₂O₃ is 10-27% or 20-30% or 14.5-30% by mass.

In some embodiments of the invention, the SiO ₂ content is not less than 1.3 times the B ₂O₃ content, such as a ratio of SiO ₂ to B ₂O₃ content of 1.33-6, preferably 1.33-4, more preferably 1.33-2.5 or 2.3-6.

In the invention, bi ₂O₃ (bismuth trioxide) is introduced as a regulating oxide to influence the thickness of a reduced layer (black layer) and the stray light eliminating performance after the reduction of the glass, and although Bi ₂O₃ has less toxic effect on a photoelectric cathode, the cathode sensitivity of the glass can be reduced due to improper use. In the embodiment of the invention, the content of Bi ₂O₃ is 3-5% by mass percent. In some embodiments of the present invention, the content of Bi ₂O₃ in mass percent may also be selected from or be any of the following ranges or ranges of compositions between any of the following values: 3.0-4.0%, 3.0-4.9%, 3.0-5.0%, 4.0-4.9%, 4.0-5.0%, 4.9-5.0%, etc. In some preferred embodiments of the invention, the Bi ₂O₃ is present in an amount of 3.5 to 5%, preferably 3.5 to 4.9% or 4 to 5% by mass.

In some embodiments of the invention, the content of SiO ₂ is not less than 8 times the content of Bi ₂O₃, such as a ratio of SiO ₂ to Bi ₂O₃ of 8-20, preferably 8-15, more preferably 8-12 or 11-14.5.

In the present invention, caO (calcium oxide) and BaO (barium oxide) are oxides of the network structure exosomes. The CaO content should not be too high, which would otherwise reduce the chemical resistance of the glass and increase the devitrification tendency. BaO provides free oxygen to promote glass melting, and proper use can increase transmittance, but excessive BaO reduces chemical stability. In an embodiment of the present invention, the content of CaO is 3 to 5% by mass. In some embodiments of the present invention, the CaO content, in mass percent, may also be selected from or be any of the following ranges: 3.0-4.8%, 3.0-5.0%, 4.8-5.0%, etc. In some preferred embodiments of the present invention, the CaO content is 3-4.8% or 4.8-5% by mass.

In an embodiment of the present invention, the content of BaO is 0.1 to 2% by mass. In some embodiments of the present invention, the BaO content may also be selected from or be any of the following ranges or ranges between any of the following values in mass percent: 0.1-0.6%, 0.1-1.2%, 0.1-1.5%, 0.1-2.0%, 0.6-1.2%, 0.6-1.5%, 0.6-2.0%, 1.2-1.5%, 1.2-2.0%, 1.5-2.0%, etc. In some preferred embodiments of the invention, the content of BaO is 0.1 to 1.5%, preferably 0.1 to 1.2% or 0.1 to 0.5% by mass.

In the present invention, al ₂O₃ (aluminum oxide) and MgO (magnesium oxide) are added as conditioning oxides, which can reduce the crystallization tendency and expansion coefficient of glass and improve the thermal stability, chemical stability and mechanical strength. However, excessive Al ₂O₃ content increases the viscosity of the melt, making melting and fining difficult and increasing the crystallization tendency. Also, too much MgO can have a negative effect on the glass properties, increasing the devitrification tendency, increasing the annealing temperature, and increasing the manufacturing cost. In an embodiment of the present invention, the content of Al ₂O₃ is 0 to 3% by mass. In some embodiments of the present invention, the content of Al ₂O₃ in mass percent may also be selected from or be any of the following ranges: 0-0.6%, 0-2.0%, 0-2.4%, 0-3.0%, 0.6-2.0%, 0.6-2.4%, 0.6-3.0%, 2.0-2.4%, 2.0-3.0%, 2.4-3.0%, 0, etc. In some preferred embodiments of the present invention, the content of Al ₂O₃ is 0.5-3% or 0-2%, preferably 2-3% or 0.5-2% or 0, by mass%.

In an embodiment of the present invention, the MgO content is 3 to 8% by mass. In some embodiments of the present invention, the MgO content may also be selected from or be any of the following ranges or ranges between any of the following values in mass percent: 3.0-6.0%, 3.0-7.0%, 3.0-8.0%, 6.0-7.0%, 6.0-8.0%, 7.0-8.0%, etc. In some preferred embodiments of the present invention, the MgO content is 3-6.5% or 7.5-8% by mass.

In the invention, znO serves as a network intermediate in the glass structure, and can exist by taking a [ ZnO ₆ ] octahedron as a network exosome to improve the alkali resistance of the glass, and can also be formed into a glass network forming body by taking a [ ZnO ₄ ] structure. Meanwhile, the glass can replace Al ₂O₃, the introduction amount of coloring oxides in raw materials is properly reduced, and the transmittance of the glass is improved. But the ZnO content should not be too high, otherwise the coefficient of expansion of the glass would be increased, while the tendency of the glass to phase separate would be increased. In an embodiment of the present invention, the content of ZnO is 0 to 4% by mass. In some embodiments of the present invention, the ZnO content may also be selected from or be any of the following ranges or ranges between any of the following values: 0-0.5%, 0-1.4%, 0-3.5%, 0-4.0%, 0.5-1.4%, 0.5-3.5%, 0.5-4.0%, 1.4-3.5%, 1.4-4.0%, 3.5-4.0%, 0, etc. In some preferred embodiments of the present invention, the content of ZnO is 0 to 3.5% or 0.5 to 4%, preferably 0 to 1.5% or 0.5 to 3.5% by mass.

In some embodiments of the invention, the content of Al ₂O₃ is not less than 0.4 times the content of ZnO.

In the invention, ceO ₂ (cerium oxide) can be used as a clarifying agent to promote the removal of bubbles in glass liquid at high temperature, improve the clarity and transparency, and can also be used as a valence-variable oxide to inhibit the generation of color centers and improve the glass performance. In an embodiment of the present invention, the content of CeO ₂ is 0 to 4% by mass. In some embodiments of the present invention, the content of CeO ₂ in mass percent may also be selected from or be any of the following ranges: 0-0.9%, 0-1.9%, 0-3.0%, 0-4.0%, 0.9-1.9%, 0.9-3.0%, 0.9-4.0%, 1.9-3.0%, 1.9-4.0%, 3.0-4.0%,0, etc. In some preferred embodiments of the present invention, the content of CeO ₂ is 0-3.5% or 0.5-4%, preferably 0-2% or 0.5-2% by mass.

In some embodiments of the present invention, glass prepared from the glass compositions according to the present invention may have an average optical transmission of greater than or equal to 85%, > or equal to 86%, > or equal to 89%, > or equal to 90%, or even greater than or equal to 93%, e.g., in some embodiments, the glass has an average optical transmission of from 85% to 93%, more preferably from 90% to 93%, at 400 nm to 1000 nm.

In some embodiments of the invention, glass prepared from glass compositions according to the invention may have an average cathode sensitivity of ≡754. Mu.A/lm, ≡760. Mu.A/lm, 770. Mu.A/lm, and ≡778. Mu.A/lm. For example, in some embodiments, the glass has an average cathode sensitivity of 754 to 778 μA/lm, preferably 760 to 778 μA/lm, and more preferably 770 to 778 μA/lm.

In some embodiments of the invention, glass produced from the glass compositions of the invention has a cathodic decay rate of 4.5% or less, further 4% or less, and still further 3% or less. For example, in some embodiments, the glass has a print decay rate of 3 to 4.5%, preferably 3 to 4%.

In some embodiments of the present invention, glass prepared from the glass compositions of the present invention have a coefficient of thermal expansion of (87.4-92.6) x 10 ^-7/°c, at 20 ℃ to 300 ℃.

In some embodiments of the present invention, the glass produced from the glass composition according to the present invention may have a reduced layer thickness as low as 492 μm after reduction, and may be less than or equal to 553 μm, less than or equal to 549 μm, less than or equal to 534 μm, for example, in some embodiments, the reduced layer thickness may be 492-553 μm. A relatively higher absorption rate (lower transmittance) can be achieved by a relatively thinner reduction layer.

In some embodiments of the present invention, the glass prepared from the glass composition according to the present invention may have a reduced layer transmittance of as low as 0.07% at 400-1000nm, as low as 0.09%, 0.1%, 0.15%, 0.2%, and 0.3% after reduction. For example, in some embodiments, the resulting reduced layer may have a transmittance of 0.07 to 0.3%, 0.07 to 0.2%, 0.07 to 0.15%, 0.07 to 0.1% at 400 to 1000 nm.

In a second aspect of the invention, there is provided a glass blank made from the glass composition described in the first aspect above.

In some embodiments of the invention, the method of making a glass blank comprises: mixing the raw materials, melting at 1400-1480deg.C, stirring, clarifying, and molding at 1110-1150 deg.C to obtain glass blank.

In some embodiments of the invention, the melting time is from 5 to 20 hours.

In some embodiments of the invention, the stirring speed is 20-50r/min and the stirring time is 8-16h.

In some embodiments of the invention, the molding time is 5-30 minutes. The generation of secondary bubbles and impurities is prevented by rapid molding of glass.

In the embodiment of the invention, the uniformity and clarity of the feed liquid can be improved by melting and stirring. The low clarity of the feed solution can result in bubbles in the formed glass, which can reduce the quality of the glass. When the uniformity of the feed liquid is low, the feed liquid is easy to generate layering or agglomeration, so that glass is difficult to melt, clarify and homogenize, and even streak or calculus defects can be generated in severe cases.

The method for preparing the blank has process stability, and the glass material prepared by the process method can show stable characteristics and cannot cause non-negligible fluctuation of glass performance due to the increase or decrease of the process in the range. Of course, it is understood that within this process, some higher temperatures can shorten the preparation process compared to lower temperatures. If desired to reduce the time costs as much as possible, one skilled in the art can select a relatively higher temperature within the temperature range disclosed herein when operating. In a third aspect of the present invention there is provided a long life anti-halation glass comprising a light transmissive active area of glass composition as described in the first aspect above or made from the glass blank as described in the second aspect above.

In some embodiments of the invention, the long life antihalation glass further comprises a reduction layer that is obtained from the light transmissive effective area glass after reduction treatment.

In some embodiments of the invention, the reducing layer is located on the glass surface of the light transmissive active region.

In some embodiments of the invention, the reduction treatment is performed in a reducing atmosphere (such as hydrogen) where the reduction temperature is 550-650 ℃, the reduction time is 13500-14500min, and the reduction pressure is 0.01-0.5 MPa.

In some embodiments of the invention, the thickness of the reduction layer may be as low as 492 μm, may be less than or equal to 553 μm, less than or equal to 549 μm, less than or equal to 534 μm, for example, in some embodiments, the thickness of the reduction layer may be 492-553 μm. The long life antihalation glass of the present invention is capable of achieving a relatively higher absorptivity (lower transmittance) through a relatively thinner reduction layer.

In some embodiments of the invention, the reduction layer may have a transmittance of as low as 0.07% at 400-1000nm, as low as 0.09%, 0.1%, 0.15%, 0.2%, 0.3%. For example, in some embodiments, the reduction layer may have a transmittance of 0.07 to 0.3%, 0.07 to 0.2%, 0.07 to 0.15%, 0.07 to 0.1% at 400 to 1000 nm.

In some embodiments of the invention, the average optical transmission of the light transmissive active region at 400-1000nm may be ≡85%,. Gtoreq.86%,. Gtoreq.89%,. Gtoreq.90%, or even ≡93%, for example, in some embodiments, the average optical transmission of the glass at 400-1000nm is 85-93%, more preferably 90-93%.

In some embodiments of the invention, the long life antihalation glass has an average cathode sensitivity of ≡754. Mu.A/lm, ≡760. Mu.A/lm, ≡778. Mu.A/lm. For example, in some embodiments, the glass has an average cathode sensitivity of 754 to 778 μA/lm, preferably 760 to 778 μA/lm, and more preferably 770 to 778 μA/lm.

In some embodiments of the invention, the long life antihalation glass has a cathode fall-off of 4.5% or less, further 4% or less, still further 3% or less. For example, in some embodiments, the glass has a print decay rate of 3 to 4.5%, preferably 3 to 4%.

In some embodiments of the invention, the long life antihalation glass has a coefficient of thermal expansion of (87.4-92.6) x 10 ^-7/°c at 20 ℃ to 300 ℃. In a fourth aspect of the present invention, there is provided a method for preparing the long life anti-halation glass of the third aspect described above, comprising:

Mixing the raw materials uniformly, melting at 1400-1480deg.C, stirring, clarifying, and molding at 1110-1150 deg.C to obtain glass blank;

after the glass blank is annealed, the blank is machined and then reduced.

After the reduction treatment, the glass may be subjected to a surface treatment to properly expose the light-transmitting effective region.

In the embodiment of the invention, the annealing to eliminate the internal stress of the glass meets the requirement of the later mechanical processing, and the annealing temperature is 500-620 ℃.

In embodiments of the present invention, the machining may include essentially one or more of grinding, polishing, engraving, chamfering, cutting, etc. conventional machining processes aimed at obtaining glass of a certain size, shape and surface condition. The appropriate treatment may be selected as desired. For example, in some embodiments of the present invention, the step glass may be obtained by subjecting the annealed glass blank to the machining steps of rounding, slicing and stepped opening.

In embodiments of the present invention, the surface treatment includes, but is not limited to, sanding, polishing and cutting, polishing, etc., to adjust the surface state of the glass, such as flatness and finish, etc. The appropriate treatment may be selected as desired. For example, in some embodiments of the present invention, the step glass obtained by the mechanical processing is subjected to a reduction treatment, a reduction layer is formed on the surface of the step glass, and then the reduction layers on the upper and lower surfaces of the step glass are ground and polished to leak out a transparent glass portion (i.e., to expose the light-transmitting effective region glass) while leaving the (step surface) reduction layer on the remaining surface, thereby obtaining the step-shaped long-life anti-halation glass.

In a fifth aspect of the present invention, there is provided an optical element made of the glass composition described in the above first aspect or the glass blank described in the above second aspect, or comprising the long-life antihalation glass described in the above third aspect.

In some embodiments of the invention, the optical element is an optical window. In particular, in some embodiments, the optical window may be a cathode glass window or an anti-halation photovoltaic glass input window.

In a sixth aspect of the present invention, there is provided the use of a glass composition according to the first aspect or a glass blank according to the second aspect, or a long life anti-halation glass comprising the third aspect, in the field of smart vision technology or electro-optical information processing technology.

The intelligent vision technical field combines various technologies such as optical imaging, photoelectric detection, image processing, artificial intelligence and the like, and is used for realizing perception, understanding and interaction of the environment. The fusion of these techniques enables the relevant devices to capture not only high quality images, but also to analyze and process the images through intelligent algorithms to provide more rich and accurate information. For example: in the field of safety monitoring, the urban space network monitoring system utilizes a high-definition camera and an intelligent image analysis technology to conduct face recognition, behavior analysis and the like so as to realize automatic monitoring of public safety. Low-light night vision devices and high-performance cameras can provide clear visual information even in very low light conditions through advanced image enhancement techniques and intelligent noise reduction algorithms. The space vision imaging detection system is used for a plurality of fields such as a geographic information system, environment monitoring, interstellar exploration and the like by intelligently processing image data captured from space. The underground mine searching and rescuing device combines photoelectric detection technology and intelligent image analysis, and helps a searching team to quickly locate trapped personnel in a complex underground environment. The development of intelligent vision technology, especially in combination with the progress of artificial intelligence and machine learning, is continuously expanding its application in the wide fields of industrial automation, medical imaging, environmental monitoring, consumer electronics, etc., and becomes an important direction in the development of modern technology. In these mentioned fields, such as in some embodiments of the invention, the application is as an optical window in fields such as low light night vision devices, high performance cameras, space vision imaging detection systems, urban space net surveillance systems, underground mine search and rescue, high-end personal equipment, etc., such as optical input windows, cathode glass windows or key components of optical lenses to reduce halation and stray light, improve light transmittance and image clarity, thereby ensuring that these devices capture optimal visual information under low light conditions or in situations where high image quality is required.

For example, in these applications, the primary functions and roles of the antihalation glass may include:

improving image definition and contrast: by reducing the halation effect due to light scattering and reflection, it is ensured that the imaging system is able to obtain a clearer, higher contrast image.

Enhancing photoelectric conversion efficiency: for devices that need to convert optical signals into electrical signals (e.g., photomultiplier tubes in low-light night vision devices), the anti-halation glass can ensure that as much of the effective light as possible is captured and converted, improving the sensitivity and performance of the device.

Protection of optical and optoelectronic components: as an external interface to the device, the anti-halation glass not only provides optical functionality, but also helps to protect the internal optical and optoelectronic components from physical damage and environmental effects.

Adapt to specific environmental requirements: in some special environments (such as space vision imaging detection, underground mine search and rescue), the anti-halation glass also needs to have specific physical and chemical stability to adapt to extreme temperature, pressure or corrosive environments.

By the above functions, the antihalation glass plays an irreplaceable role in these high-end application fields, and is a key material for ensuring device performance and image quality.

The specific features described in all the embodiments of the above aspects of the present invention may be combined in any suitable manner, without contradiction, and in order to avoid unnecessary repetition, the present invention will not be described in any detail with respect to the various possible combinations.

The numerical ranges recited herein include all numbers within the range and include any two values within the range, unless specifically stated otherwise. For example, 0-3.5%, which includes all values between 0-3.5%, and any number of values within the range (e.g., 0%, 0.1%, 2.9%) and possible combinations thereof (e.g., 0-0.1%, 0-2.9%, 0.1-2.9%); the different values of the same index appearing in all embodiments of the invention can be combined arbitrarily to form a range value.

Through one or more of the above technical means, the following beneficial effects can be achieved:

The invention provides a glass composition, the glass prepared by the glass composition has good transmittance, the average optical transmittance within the range of 400-1000nm is more than or equal to 85%, and the optimal transmittance can be more than or equal to 93%; has proper melting temperature (1400-1480 ℃) and proper thermal expansion coefficient, has the thermal expansion coefficient of (87.4-92.6) multiplied by 10 ^-7/DEG C at 20-300 ℃, has good crystallization resistance and good chemical stability. Meanwhile, the invention also provides the long-life anti-halation glass, which has good optical transmittance and good cathode sensitivity, particularly has very low cathode decay rate, the cathode decay rate within 12 months can be less than or equal to 4%, and the problems of low transmittance and short service life of the existing anti-halation glass in a wide wavelength range are solved.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Embodiments of the present application are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 is a graph of average transmission over a range of 400-1000nm for a glass article of the present invention versus a comparative glass article.

FIG. 2 is a graph of the photocathode sensitivity of the glass article of the present invention versus a comparative glass article over time.

Detailed Description

The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present application may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present application. The preferred methods and materials described herein are presented for illustrative purposes only.

The performance parameters in the following examples were measured as follows:

the coefficient of thermal expansion of the glass samples was measured using a model DIL 402 coefficient of expansion tester, a company of resistance, germany. Sample preparation, the glass sample was ground and polished to a cylindrical glass rod of Φ6×50mm with the two end faces parallel. The temperature rising speed is set to be 5 ℃/min, and the data acquisition period is set to be 20ms. And drawing a relation curve of the temperature and linear expansion by the data, and obtaining the glass transition temperature and the expansion softening temperature by a tangent method. (GB/T7962.16-2010)

Transmittance was measured with an ultraviolet-visible infrared spectrophotometer. And (3) preparing a sample, wherein the sample is larger than the effective light transmission caliber, the thickness is 20mm, and parameters such as a wavelength range, a scanning speed and the like are input during double-sided polishing and testing, so that the transmittance of the sample is tested. (GB/T7962.12-2010)

The acid and alkali resistance of the glass samples were tested according to GB/T7962.14-2010 and GB/T7962.21-2019. The acid resistance stability test is to process a sample into a size of 20×20×10mm, polish one surface of the sample, and use a solution having acidity of ph=2.9, ph=4.6, and ph=6.0 as a measurement medium. After the surface of the polished glass sample is corroded by a measuring medium, observing the time of occurrence of purple-blue interference color on the surface of the glass or the time of occurrence of variegation or shedding of the surface under an incandescent lamp, and carrying out descending classification on the acid-resistant stability of the colorless optical glass according to the time; the alkali resistance stability test is to process a glass sample into 30×30×2mm, polish all surfaces of the sample, have surface roughness ra=0.012, put the polished sample into a sodium hydroxide test solution with a temperature of 50 ℃ and a concentration of 0.01mol/L for a specified time to erode, weigh and measure the mass loss of the sample, and calculate the erosion depth according to the density of the glass. And judging the alkali resistance stability level of the glass to be tested according to the time t _0.1 required for the corrosion depth to reach 0.1 mu m and the change of the surface of the sample to be tested after the corrosion is finished. The thickness of the reduction layer of the glass sample is measured by using a body microscope, the reduced glass black sheet is required to be free from tingling, sagging and deformation, the thickness of the black layer is 0.5-0.6 mm, and the transmittance is less than 1%.

The light sensitivity of the anti-halation photoelectric glass is tested according to GJB 7351-2011, and the cathode attenuation rate is characterized by calculating the light sensitivity before and after attenuation. The test was performed on a super second generation image intensifier tube. The super second-generation image intensifier tube applies a prescribed voltage. A tungsten filament lamp with a color temperature of 2856 K+/-50K is used as a light source, a specified luminous flux is uniformly distributed in a specified area of a photocathode in parallel with an input optical axis, the spectral characteristics of input light radiation are not changed when a dimmer is used, and the current of the cathode at the moment is measured; the cathode current was measured after switching off the light source when no radiation was input to the photocathode. The light sensitivity is calculated according to formula (1):

S＝(I₁-I₂)/Φ (1)

wherein:

s-photosensitivity, μA/lm;

I ₁, which is the cathode current when light radiation is input, is the sum of photocurrent caused by the light radiation and I ₂, and is mu A;

I ₂, namely cathode current when no radiation is input, which is the sum of photocathode dark current and internal and external leakage current, and mu A;

Φ—the input luminous flux lm.

The cathode decay rate of the anti-halation photoelectric glass is calculated by the formula (2):

wherein:

S ₁ -initial cathode light sensitivity, μA/lm;

s ₂ -cathode light sensitivity after a period of use, μA/lm.

The invention is further illustrated below with reference to examples.

Example 1

The glass composition and physical properties of this example are shown in Table 1.

The preparation method comprises the following steps: quartz sand, boric acid, kaolin, bismuth nitrate, zinc nitrate, magnesium nitrate, barium oxide and calcium oxide are taken as raw materials, a clarifying agent CeO ₂ is added, the weight of the clarifying agent accounts for 4.0% of the weight of the high-transmittance long-service-life anti-halation glass, and glass blanks are obtained after full mixing, through high-temperature melting at 1430 ℃ for 9 hours, mechanical stirring (25 r/min,10 hours), auxiliary high-temperature clarification and 1120 ℃ leakage or casting molding (molding time is 5 minutes).

And (3) machining the glass blank to obtain stepped glass, and then carrying out reduction treatment in a hydrogen reduction atmosphere, wherein the reduction temperature is 637 ℃, the reduction time is 14000min, and the reduction pressure is 0.18MPa. And (3) forming a reducing layer on the surface of the glass after the reduction treatment, grinding and polishing the upper and lower surfaces of the step-type glass with the reducing layer on the surface, removing the reducing layer to expose the transparent glass part, and reserving the reducing layers on the other surfaces to obtain the halation-preventing glass.

Example 2

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 0.9% of the weight of the high-transmittance long-service-life anti-halation glass; the melting temperature is 1450 ℃, and the melting time is 15 hours; mechanical stirring (30 r/min,13 h), molding temperature of 1130℃and molding time of 20min, and other preparation steps and parameters were the same as in example 1.

Example 3

The composition and physical properties of the glass of this example are shown in Table 1.

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 1.9% of the weight of the high-transmittance long-service-life anti-halation glass; the melting temperature is 1440 ℃, and the melting time is 18 hours; mechanical stirring (30 r/min,15 h), molding temperature 1140℃and molding time 25min, and other preparation steps and parameters were the same as in example 1.

Example 4

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 3.0% of the weight of the high-transmittance long-service-life anti-halation glass; the melting temperature is 1440 ℃, and the melting time is 11h; mechanical stirring (30 r/min,15 h), molding temperature 1140℃and molding time 20min, and other preparation steps and parameters were the same as in example 1.

Example 5

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 4.0% of the weight of the high-transmittance long-service-life anti-halation glass; the melting temperature is 1480 ℃ and the melting time is 18 hours; mechanical stirring (40 r/min,15 h), molding temperature 1130℃and molding time 25min, and other preparation steps and parameters were the same as in example 1.

Example 6

In the preparation method, a glass clarifying agent is not added; the melting temperature is 1440 ℃, and the melting time is 15 hours; mechanical stirring (35 r/min,15 h), molding temperature 1140℃and molding time 25min, and other preparation steps and parameters were the same as in example 1.

Comparative examples 1 to 4

The compositions and physical properties of the glasses of comparative examples 1 to 4 are shown in Table 1.

The glasses of comparative examples 1 to 4 were prepared in the same manner as in example 1.

TABLE 1 Components, contents and physical Properties of glasses according to examples 1 to 6 and comparative examples of the present invention

The glass articles of examples 1-6 have better optical transmittance, less "poisoning" effect on the cathode, and can increase the service life of the antihalation glass. As can be seen from Table 1, the glass products prepared in examples 1 to 6 of the present invention have an average optical transmittance of 400 to 1000nm of not less than 85%, a cathode sensitivity of not less than 754. Mu.A/lm, and a cathode decay rate of less than 4.5%, while having good chemical stability.

The foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A long-life anti-halation glass, comprising a light-transmitting effective area and a reduction layer, wherein the reduction layer is obtained by reducing the glass in the light-transmitting effective area, wherein the light-transmitting effective area is composed of the following components in terms of mass percentage: SiO ₂ 40-60%, B ₂ O ₃ 20-30%, Bi ₂ O ₃ 3-5%, CaO 3-5%, BaO 0.1-2%, Al ₂ O ₃ 0-3%, MgO 3-8%, ZnO 0-4% and CeO ₂ 0-4%.

2. The long-life anti-halation glass according to claim 1, characterized in that the content of _SiO2 is not less than 1.3 times _the content of _B2O3 .

3. The long-life anti-halation glass according to claim 1, characterized in that the content of _SiO2 is not less than 8 times _the content of _Bi2O3 .

4. The long-life anti-halation glass according to claim 1, characterized in that the content of _Al2O3 is not less than 0.4 times the content of _ZnO .

5. The long-life anti-halation glass according to claim 1, characterized in that the content of _SiO2 is 40-58% by mass percentage.

6. The long-life anti-halation glass according to claim 1, characterized in that the content of _SiO2 is 55-58% by mass percentage.

7. The long-life anti-halation glass according to claim 1, characterized in that the content of _Bi2O3 _is 3.5-5% by mass percentage.

8. The long-life anti-halation glass according to claim 1, characterized in that the content of _Bi2O3 _is 4-5% by mass percentage.

9. The long-life anti-halation glass according to claim 1, characterized in that the content of CaO is 3-4.8% by mass percentage.

10. The long-life anti-halation glass according to claim 1, characterized in that the content of CaO is 4.8-5% by mass.

11. The long-life anti-halation glass according to claim 1, characterized in that the content of BaO is 0.1-1.5% by mass.

12. The long-life anti-halation glass according to claim 1, characterized in that the content of BaO is 0.1-1.2% by mass.

13. The long-life anti-halation glass according to claim 1, characterized in that the content of BaO is 0.1-0.5% by mass.

14. The long-life anti-halation glass according to claim 1, characterized in that the content of _Al2O3 _is 0.5-3% by mass percentage.

15. The long-life anti-halation glass according to claim 1, characterized in that the content of _Al2O3 _is 0-2% by mass percentage.

16. The long-life anti-halation glass according to claim 1, characterized in that the content of _Al2O3 _is 2-3% by mass percentage.

17. The long-life anti-halation glass according to claim 1, characterized in that the content of _Al2O3 _is 0.5-2% by mass percentage.

18. The long-life anti-halation glass according to claim 1, characterized in that the content of _Al2O3 _is 0 in terms of mass percentage.

19. The long-life anti-halation glass according to claim 1, characterized in that the content of MgO is 3-6.5% by mass.

20. The long-life anti-halation glass according to claim 1, characterized in that the content of MgO is 7.5-8% by mass.

21. The long-life anti-halation glass according to claim 1, characterized in that the content of ZnO is 0-3.5% by mass percentage.

22. The long-life anti-halation glass according to claim 1, characterized in that the content of ZnO is 0.5-4% by mass.

23. The long-life anti-halation glass according to claim 1, characterized in that the content of ZnO is 0-1.5% by mass.

24. The long-life anti-halation glass according to claim 1, characterized in that the content of ZnO is 0.5-3.5% by mass.

25. The long-life anti-halation glass according to claim 1, characterized in that the content of _CeO2 is 0-3.5% by mass percentage.

26. The long-life anti-halation glass according to claim 1, characterized in that the content of _CeO2 is 0.5-4% by mass.

27. The long-life anti-halation glass according to claim 1, characterized in that the content of _CeO2 is 0-2% by mass percentage.

28. The long-life anti-halation glass according to claim 1, characterized in that the content of _CeO2 is 0.5-2% by mass percentage.

29. The long-life anti-halation glass according to any one of claims 1 to 28, characterized in that the reducing layer is located on the glass surface in the effective light transmission area.

30. The long-life anti-halation glass according to any one of claims 1 to 28, characterized in that the reduction treatment is carried out in a reducing atmosphere, wherein the reduction temperature is 550-650°C, the reduction time is 13500-14500 min, and the reduction pressure is 0.01-0.5 MPa.

31. The long-life anti-halation glass according to any one of claims 1 to 28, characterized in that the reduction layer has a thickness of 492-553 μm.

32. The long-life anti-halation glass according to any one of claims 1 to 28, characterized in that the optical transmittance of the reducing layer at 400-1000 nm is 0.07-0.3%.

33. The long-life anti-halation glass according to any one of claims 1 to 28, characterized in that the average optical transmittance of the light-transmitting effective area in the range of 400-1000 nm is ≥ 85%.

34. The long-life anti-halation glass according to any one of claims 1 to 28, characterized in that the average cathode sensitivity of the long-life anti-halation glass is 754-778 μA/lm.

35. The long-life anti-corona glass according to any one of claims 1 to 28, characterized in that the cathode decay rate of the long-life anti-corona glass is ≤4.5%.

36. The long-life anti-corona glass according to any one of claims 1 to 28, characterized in that the thermal expansion coefficient of the long-life anti-corona glass at 20°C-300°C is (87.4-92.6) x ^10-7 /°C.

37. A method for preparing the long-life anti-halation glass according to any one of claims 1 to 36, comprising:

After the raw materials are mixed, they are melted at 1400-1480°C, stirred, clarified, and molded at 1110-1150°C to obtain glass blanks;

After the glass blank is annealed at 500-620°C, it is machined, and the obtained glass material is reduced to form a reduction layer on the surface of the glass material.

38. The method according to claim 37, characterized in that the reduction treatment is carried out in a reducing atmosphere, wherein the reduction temperature is 550-650°C, the reduction time is 13500-14500 min, and the reduction pressure is 0.01~0.5 MPa.

39. An optical element comprising the long-life anti-halation glass according to any one of claims 1 to 36.

40. The optical element according to claim 39, characterized in that the optical element is an optical window.

41. The optical element according to claim 40, characterized in that the optical window is a cathode glass window or an anti-halation photoelectric glass input window.

42. Use of the long-life anti-halation glass according to any one of claims 1 to 36 in the field of intelligent vision technology or optoelectronic information processing technology.

43. The application according to claim 42 is characterized in that the application includes being used as an optical window in low-light night vision devices, high-performance cameras, space visual imaging detection systems, urban skynet monitoring systems, and underground mine search and rescue.

44. The use according to claim 43, characterized in that the long-life anti-halation glass is used as a cathode glass window or an anti-halation photoelectric glass input window.