阅读说明：本技术 光学玻璃元件的制备方法及具有光吸收层的光学玻璃元件 (Method for manufacturing optical glass element and optical glass element with light absorption layer ) 是由 孙勇 贾金升 郑京明 吕学良 李开宇 曹振博 李自金 石钰 张洋 刘娟 孔壮 于 2020-05-18 设计创作，主要内容包括：本发明是关于一种光学玻璃元件的制备方法及具有光吸收层的光学玻璃元件。该制备方法包括：制备光学玻璃,所述光学玻璃中含有0.01～30mol％的掺杂金属离子；在还原气体气氛下,对所述的光学玻璃进行还原处理,使光学玻璃表层形成色心或所述掺杂金属离子被还原成金属单质,形成光吸收层；对还原处理后的光学玻璃进行后处理,得到光学玻璃元件。该光学玻璃元件包括光学玻璃基体和光吸收层,所述光吸收层位于所述光学玻璃基体的周边部,所述光吸收层与所述光学玻璃基体之间的界面反射率小于1％；其中,所述光吸收层为自基底光吸收层,所述光吸收层的光吸收率大于99％。该制备方法解决了难以在光学玻璃表面制备光吸收层的问题。(The invention relates to a preparation method of an optical glass element and the optical glass element with a light absorption layer. The preparation method comprises the following steps: preparing optical glass, wherein the optical glass contains 0.01-30 mol% of doped metal ions; reducing the optical glass in a reducing gas atmosphere to form a color center on the surface layer of the optical glass or reduce the doped metal ions into a metal simple substance to form a light absorption layer; and carrying out post-treatment on the optical glass after the reduction treatment to obtain the optical glass element. The optical glass element comprises an optical glass substrate and a light absorption layer, wherein the light absorption layer is positioned at the peripheral part of the optical glass substrate, and the interface reflectivity between the light absorption layer and the optical glass substrate is less than 1%; the light absorption layer is a self-substrate light absorption layer, and the light absorption rate of the light absorption layer is more than 99%. The preparation method solves the problem that the light absorption layer is difficult to prepare on the surface of the optical glass.)

1. A method for producing an optical glass element, comprising:

preparing optical glass, wherein the optical glass contains 0.01-30 mol% of doped metal ions;

reducing the optical glass in a reducing gas atmosphere to form a color center on the surface layer of the optical glass or reduce the doped metal ions into a metal simple substance to form a light absorption layer;

and carrying out post-treatment on the optical glass after the reduction treatment to obtain the optical glass element.

2. The method for producing an optical glass element according to claim 1,

in the process of preparing the optical glass, the doping metal ions are introduced into the optical glass component in the form of simple substance, oxide, hydroxide, salt or organic matter.

3. The method for producing an optical glass element according to claim 1 or 2,

the doped metal ions comprise at least one of scandium ions, zinc ions, cadmium ions, gallium ions, indium ions, thallium ions, tin ions, arsenic ions, antimony ions, titanium ions, niobium ions, tantalum ions, platinum ions and gold ions.

4. The method for producing an optical glass element according to claim 1,

the reducing gas comprises H₂、CO、CH₄NO and C₂H₂In (1)At least one of them.

5. A method for producing an optical glass element according to claim 1, wherein the temperature T of the reduction treatment satisfies: tg < T < Tf.

6. The method for producing an optical glass element according to claim 1, wherein the pressure of the reduction treatment is 0MPa to 15 MPa.

7. The method for producing an optical glass element according to claim 1, wherein the time for the reduction treatment is 0.5 to 500 hours.

8. A method for producing an optical glass element according to claim 1, characterized in that the post-treatment comprises:

and cutting, grinding and polishing the processed optical glass according to requirements.

9. An optical glass element having a light absorbing layer, comprising: the optical glass comprises an optical glass substrate and a light absorption layer, wherein the light absorption layer is positioned at the peripheral part of the optical glass substrate, and the interface reflectivity between the light absorption layer and the optical glass substrate is less than 1%; the light absorption layer is a self-substrate light absorption layer, and the light absorption rate of the light absorption layer is more than 99%;

the optical glass element is produced by the production method according to any one of claims 1 to 8.

10. The optical glass element with a light-absorbing layer as claimed in claim 9, wherein the light-absorbing layer has a thickness of 0.1 to 1 mm.

Technical Field

The invention relates to the technical field of optical glass processing, in particular to a preparation method of an optical glass element and the optical glass element with a light absorption layer.

Background

In addition to receiving target signals, other stray light and stray light formed by refraction, interface reflection and the like of the optical system are also provided in the use process of the optical imaging and detecting system. The existence of stray light can affect the imaging precision of an optical system and restrict the observation precision and the resolution. Therefore, the elimination of stray light from the optical system plays a crucial role in the optical imaging and detection system.

The conventional stray light eliminating technology for optical systems mainly comprises: coating an optical absorption layer; optimizing the optical structure design and using a stray light eliminating diaphragm; and manufacturing threads on the inner wall of the lens. The latter two technologies have less application due to the problems of complex process, increased optical system volume and the like. The technique of applying an optically absorbing layer is currently the most common one. However, although the technology is simple, there are some disadvantages: for example: an interface exists between the coating layer and the lens, so that interface reflection can be generated, the imaging definition of a space optical system is influenced, and the observation precision is reduced; secondly, the difference between the expansion coefficients of the coating layer and the optical lens is large, and when the lens bears a certain high-low temperature environment or high-magnitude mechanical vibration, the coating layer is easy to fall off from the edge of the lens, so that the normal work of an optical system is influenced, and even the system is scrapped. Therefore, the stray light eliminating technology with simple exploration process and high stability is widely concerned by researchers at home and abroad.

In recent years, a process of performing high-temperature reduction treatment on an optical lens has been proposed to solve the problem of stray light, but at present, the types of optical glasses satisfying this condition are very limited, and the problem of optical crosstalk of only a very small number of optical glasses is solved.

Disclosure of Invention

The invention mainly aims to provide a method for preparing an optical glass element and the optical glass element with a light absorption layer, and the technical problem to be solved is that the light absorption layer is difficult to form on the surface of the optical glass.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the invention, the preparation method of the optical glass element comprises the following steps:

preparing optical glass, wherein the optical glass contains 0.01-30 mol% of doped metal ions;

reducing the optical glass in a reducing gas atmosphere to form a color center on the surface layer of the optical glass or reduce the doped metal ions into a metal simple substance to form a light absorption layer;

and carrying out post-treatment on the optical glass after the reduction treatment to obtain the optical glass element.

The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.

Preferably, in the method for producing an optical glass element, the doped metal ions are introduced into the optical glass component in the form of a simple substance, an oxide, a hydroxide, a salt or an organic substance during the production of the optical glass.

Preferably, in the method for producing an optical glass element, the doping metal ions include at least one of scandium ions, zinc ions, cadmium ions, gallium ions, indium ions, thallium ions, tin ions, arsenic ions, antimony ions, titanium ions, niobium ions, tantalum ions, platinum ions, and gold ions.

Preferably, the above-mentioned method for producing an optical glass element, wherein the reducing gas comprises H₂、CO、CH₄NO and C₂H₂At least one of (1).

Preferably, in the above method for producing an optical glass element, the temperature T of the reduction treatment satisfies: tg < T < Tf.

Preferably, in the method for producing an optical glass element, the pressure of the reduction treatment is 0MPa to 15 MPa.

Preferably, in the method for producing an optical glass element, the time for the reduction treatment is 0.5 to 500 hours.

Preferably, the method for producing an optical glass element described above, wherein the post-treatment comprises:

and cutting, grinding and polishing the processed optical glass according to requirements.

The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the present invention, an optical glass device with a light absorption layer comprises: the optical glass comprises an optical glass substrate and a light absorption layer, wherein the light absorption layer is positioned at the peripheral part of the optical glass substrate, and the interface reflectivity between the light absorption layer and the optical glass substrate is less than 1%; the light absorption layer is a self-substrate light absorption layer, and the light absorption rate of the light absorption layer is more than 99%; the optical glass element is prepared by the preparation method of any one of the preceding methods.

The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.

Preferably, the optical glass element having the light absorption layer has a thickness of 0.1 to 1 mm.

By the technical scheme, the preparation method of the optical glass element and the optical glass element with the light absorption layer provided by the invention at least have the following advantages:

1. the preparation method of the optical glass element provided by the invention mainly comprises two steps: firstly, in the process of preparing the optical glass, doping metal ions are introduced into the optical glass in the form of simple substances, oxides, hydroxides, salts or organic matters, and then the optical glass containing the doping metal ions is subjected to reduction treatment to form a light absorption layer on the surface of the optical glass. The preparation of the optical glass from the substrate light absorption layer is realized by introducing doped metal ions into the optical glass, and the stray light absorption layer meeting the requirements is obtained.

2. The optical glass element prepared by the method has a self-substrate light absorption layer, and the light absorption efficiency of the light absorption layer is detected to be more than 99 percent, so that the optical glass element reduces the optical crosstalk caused by the optical glass. Because the light absorption layer is generated by the reduction reaction of the optical glass from the substrate, the absorption layer and the base glass are originally integrated, the interface reflectivity between the light absorption layer and the optical glass base is less than 1 percent, the interface reflection is prevented, and the problem of falling off after being heated or receiving external acting force does not exist, thereby being more suitable for practical use.

3. The method also comprises a step of correcting the optical glass, the corrected optical glass cannot cause the performance change due to the introduction of doped metal ions, the preparation method can be suitable for most brands of optical glass elements on the market, and the technical problem that the surface layer of the optical glass is difficult to reduce is solved.

The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.

Drawings

Fig. 1 shows a schematic view of a manufacturing method of an optical glass element according to an embodiment of the present invention.

Detailed Description

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the specific implementation, structure, features and effects of the method for manufacturing an optical glass device and the optical glass device with a light absorption layer according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

As shown in fig. 1, a method for manufacturing an optical glass element according to an embodiment of the present invention specifically includes the following steps:

s1, preparing optical glass, wherein the optical glass contains 0.01-30 mol% of doped metal ions; to implement step S1, it is necessary to introduce doping metal ions into the glass batch when preparing the optical glass. Then the optical glass is melted by the processes of feeding, clarifying, homogenizing, pouring and the like.

In step S1, the present application does not limit the type and form of the doped metal ions, and the preparation method can be implemented as long as the doped metal ions are easily reduced by the reducing gas to form the light absorption center during the post-reduction treatment. The doping metal ions are introduced in the form of simple substance, oxide, hydroxide, salt or organic substance, and include, but are not limited to, at least one of scandium ions, zinc ions, cadmium ions, gallium ions, indium ions, thallium ions, tin ions, arsenic ions, antimony ions, titanium ions, niobium ions, tantalum ions, platinum ions and gold ions. When the glass is used, proper doped metal ions can be selected according to actual needs and the type of glass, one doped metal ion can be selected, and mixed ions of multiple doped metals can also be selected.

In step S1, the optical glass contains 0.01 to 30 mol% of doped metal ions, and the doped metal ions are contained in the optical glass at this concentration, so that sufficient light absorption centers can be generated during the reduction reaction, and the formed light absorption layer has an absorption rate of 99% or more to eliminate the stray light influence at the boundary of the optical glass element. The doped metal ions preferably contain 0.1-10 mol%, more preferably 0.5-5 mol%, and the doped metal ions in this range can ensure that the thickness of the formed light absorption layer is sufficiently thick and durable, and avoid introducing excessive doped metal ions, which can cause great influence on the performance of the optical glass and increase the difficulty of later-stage correction of the optical glass.

The specific process for melting the optical glass is determined according to a glass system, and the common preparation process of the optical glass can be used. It should be noted that when the component doped with metal ions is introduced, the original refractive index and dispersion of the optical glass are changed, and the optical performance of the optical glass needs to be adjusted by adjusting other components of the glass or introducing other elements according to the index of the brand optical glass. Therefore, the optical glass after melting can be optically corrected as required. The optical correction mainly comprises: firstly, the optical performance of the melted optical glass is tested and compared with the standard index, the components of the glass are further finely adjusted, and the optical performance of the optical glass is corrected until the index requirement of the brand optical glass is met. The optical property correction of the optical glass can be calculated by empirical formulas of the method of the Arabic and the method of the dry happiness, and the experiments prove that the optical property correction of the optical glass can be realized.

Step S2, carrying out reduction treatment on the optical glass after pretreatment in a reducing gas atmosphere to form a color center on the surface layer of the optical glass or reduce the doped metal ions into a metal simple substance to form a light absorption layer; in this step, the kind of reducing gas is not limited, and a gas having reducing property is selected so long as reduction of the relevant group in the optical glass can be achievedI.e., the reducing atmosphere includes, but is not limited to, H₂、CO、CH₄NO and C₂H₂At least one of (1). It should be noted that when the reducing gas is hydrogen, the hydrogen combines with oxygen in the glass to generate water, and the water is pumped out in time to avoid affecting the subsequent reaction.

Through detection, part of doped metal ions in the surface layer of some optical glass are reduced to form metal simple substances, some of the doped metal ions form color centers, and the concentration of the doped metal ions is gradually reduced from the outer surface to the inner surface of the optical glass.

During the reduction treatment, it is necessary to determine the temperature, pressure and time of the reduction treatment according to the properties of the optical glass and the required thickness of the light absorbing layer. The higher the density of the optical glass, the higher the temperature and pressure required, and the longer the treatment time, the thicker the light absorbing layer under the same conditions, for different types of optical glass.

In some embodiments, the temperature T of the reduction treatment satisfies: tg < T < Tf, Tg being the glass transition temperature of the optical glass; tf is the melting temperature of the optical glass, and the Tg-Tf is in a high-elastic state, so that the reducing gas is favorable for reducing easily reducible substances in the optical glass in the high-elastic state. Different optical glasses correspond to different reduction temperatures, and although the reduction treatment temperatures of the optical glasses have larger differences, most optical glasses can undergo reduction reaction at the temperature of between 100 and 1500 ℃.

In some embodiments, the pressure of the reduction treatment is 0MPa to 15MPa, preferably 0.1 to 0.5MPa, and the pressure of the reduction treatment in the method of the present invention is relatively mild compared to the reduction treatment at high temperature and high pressure, and the method has no high requirement on equipment, and is easier to implement.

In some embodiments, the time of the reduction treatment is 0.5 to 500 hours, and the time of the reduction treatment is related to the composition (the degree of easy reduction of the contained components) and the performance (such as compactness), temperature, pressure, thickness of the absorption layer required, and other conditions of the optical glass, and in actual operation, the time needs to be selected as required. For example ZK9 glass, a reduction temperature of 670 ℃ and a reducing gas H₂The pressure of reducing gas is 0.1MPa, and the reducing time is 10000 min. For example ZF4 glass, a reduction temperature of 450 ℃, a reducing gas H₂The pressure of the reducing gas is 0.1MPa, and the reducing time is 3000 min. In principle, in the same optical glass, the longer the time of the reduction reaction, the thicker the light absorbing layer of the optical glass formed, when the temperature and pressure are constant.

If the reducing gas is hydrogen, step S2 further includes, after the reduction treatment, evacuating the reduced system, and pumping out water generated by the reaction between hydrogen and glass in time to avoid affecting the surface quality of glass, and then cooling the glass to a certain temperature and keeping the temperature for a period of time in order to anneal the glass and eliminate stress.

And step S3, after the reduction reaction, cooling the optical glass after the reduction treatment to room temperature in a nitrogen atmosphere, and then cutting, grinding and polishing the optical glass after the treatment according to requirements to obtain the optical glass element.

In order to use the optical glass, the light-absorbing layer of the optical glass thus obtained needs to be further processed. Firstly, processing a blank, and carrying out high-temperature reduction on the blank to generate a light absorbing layer on the periphery. And further processing at the later stage, and removing the light absorption layer in the light transmission region. So that the formed light absorbing layer is located at the peripheral portion of the optical glass substrate and the intermediate portion is used for receiving a target optical signal, and therefore, there are two processing methods in which a coating film or a protective paste is coated on the optical region of the optical glass before processing the optical glass so that it cannot be oxidized at high temperature and high pressure; alternatively, the surface layer of the optical glass is subjected to reduction treatment, after the light absorbing layer is formed on the surface layer of the optical glass, the light absorbing layer in the optical region of the optical glass is polished, and the light absorbing layer on the surface layer is removed by grinding, polishing or the like.

In the embodiment of the present invention, the optical glass element is produced mainly in two steps: firstly, in the process of preparing the optical glass, doping metal ions are introduced into the optical glass in the form of simple substances, oxides, hydroxides, salts or organic matters, and then the optical glass containing the doping metal ions is subjected to reduction treatment to form a light absorption layer on the surface of the optical glass. The doped metal ions are introduced into the optical glass, so that the optical glass is prepared from the substrate light absorption layer, a better reduction effect is achieved, and a stray light absorption layer which is more in line with the standard is manufactured. Experiments prove that the preparation method has reasonable theoretical basis and feasible operation process. The method solves the problem that the traditional high-temperature reduction process cannot meet the requirement of preparing the light absorption layer in the optical glass with a compact structure.

According to the basic principle of glass technology, glass is an amorphous material and has a network structure, and gaps exist in the middle of the network. Therefore, small molecules or atoms of the reducing gas can gradually diffuse into the glass interior to undergo redox reactions with the ions. Therefore, the concentration of the light absorption centers reduced in the glass decreases from the surface layer to the inside, and the concentration of the light absorption centers on the surface becomes the maximum.

According to the diffusion reaction kinetics, the depth of the reducing gas entering the glass depends on the reduction treatment conditions, the pressure, the temperature and the time have an influence on the depth of the reducing gas entering the glass, the greater the pressure, the greater the depth of the reducing gas entering the glass, and the thicker the glass containing the reduced metal; the higher the temperature, the greater the depth of the reducing gas into the glass, and the thicker the thickness of the glass containing the reduced doped metal; also, the longer the time, the greater the depth of the reducing gas into the glass, and the greater the thickness of the reduced metal containing glass, so that the pressure, temperature and time can be controlled to control the thickness of the reduced metal containing glass.

According to the thermodynamic principle of redox reaction, the reduction temperature cannot be too low and is lower than the Tg of glass, and the activation energy of the reduction reaction is insufficient, so that the redox reaction cannot occur or the occurrence rate is extremely low; the reduction temperature is not too high and is higher than Tf of glass, and the higher temperature is easy to cause surface defects such as deformation, chap and the like of the glass surface.

In the process of reduction treatment, the conditions of reduction treatment are controlled to reduce enough doped metal ions to generate light absorption centers with enough concentration on the glass surface, and meanwhile, the reduction treatment is controlled not to generate too thick light absorption layers to influence the optical performance of the whole structure. Therefore, it is necessary to select the conditions for the reduction treatment according to actual needs.

The light absorption layer obtained by the method has the property of absorbing light, and doped metal ions in the optical glass generate light absorption centers after reduction treatment, so that the light absorption layer has the property of absorbing light.

The light absorption layer obtained by the method has the property of absorbing light, and the reaction mechanisms possibly generated in the reduction process are mainly two types: (1) the reducing gas reacts with oxygen in the glass to generate an oxygen vacancy color center, which absorbs visible light. (2) The reducing gas reacts with the doped metal ions to generate a coloring center, which absorbs visible light.

Different optical glass components and different compactness require different reduction reaction conditions, so that different optical glass has different reduction reaction conditions, such as ZK9 glass with a reduction temperature of 670 ℃ and ZF4 glass with a reduction temperature of 450 ℃. Because most of optical glass has higher density, the reduction reaction gradually weakens from the surface layer of the optical glass to the inside, the surface layer of the optical glass is strongest, and the condition of light absorption can be met as long as the light absorption layer can reach the light absorption rate of more than 99%.

In principle, the process is suitable for most brands of optical glass on the market, and other types of non-optical special glass can be used for manufacturing functional layers which are more durable or meet various other standards, so that the glass is multifunctional.

As shown in fig. 1, another embodiment of the present invention provides an optical glass element, including: the optical glass comprises an optical glass substrate 1 and a light absorption layer 2, wherein the light absorption layer 2 is positioned at the peripheral part of the optical glass substrate 1, and the interface reflectivity between the light absorption layer 2 and the optical glass substrate 1 is less than 1%; the light absorption layer 2 is a self-substrate light absorption layer.

The self-substrate light absorption layer referred to herein means that the light absorption layer is formed by reduction reaction of optical glass from a substrate, and the light absorption layer and the optical glass substrate are integrated. Through reduction treatment on the optical glass, a light absorption layer with the thickness of about 0.1-1 mm, preferably 0.2-0.7 mm, is generated on the surface of a non-light-transmitting area of the optical glass, the light absorption layer with the thickness can meet the effect of light absorption, can be easily obtained through reduction reaction of the optical glass from a substrate, and does not occupy too much optical area. The light absorption layer and the optical glass substrate are of an integrated structure, and the problem of falling off caused by heating or external acting force does not exist. Meanwhile, the interface reflectivity between the light absorption layer and the optical glass substrate can be kept below 1 percent. The light absorption layer has a light absorption rate of greater than 99%.

In some embodiments, the method for producing an optical glass element is produced by the method for producing an optical glass element described above.

The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.