阅读说明：本技术 一种防光晕台阶玻璃及其制备方法和应用 (Anti-halation step glass and preparation method and application thereof ) 是由 孔壮 贾金升 郑京明 孙勇 曹振博 李自金 吕学良 李开宇 洪升 那天一 于 2020-05-18 设计创作，主要内容包括：本发明涉及一种防光晕台阶玻璃及其制备方法和应用,所述防光晕台阶玻璃的制备方法,包括：在防光晕台阶玻璃毛坯的衬底上进行金属离子注入,得到金属离子掺杂的玻璃；将得到的金属离子掺杂的玻璃的表面进行热还原,得到表层黑化的玻璃毛坯；将得到的玻璃毛坯上下表面的黑玻璃层研磨除去,露出内部的透明玻璃,同时保留台阶面的黑玻璃层,即得到防光晕输入窗玻璃。本发明在玻璃配方不变的情况下,黑玻璃层的厚度取决于高温黑化的时间,一定范围内高温黑化的时间越长,黑玻璃层的厚度越厚。采用离子注入工艺,玻璃表面形成纳米孔道,增加了还原气体在玻璃中的扩散,减少黑化的高温时间,缩短了黑化所需的时间,进而加快防光晕台阶玻璃的黑化周期。(The invention relates to anti-halation step glass and a preparation method and application thereof, wherein the preparation method of the anti-halation step glass comprises the following steps: performing metal ion implantation on a substrate of the antihalation step glass blank to obtain metal ion doped glass; carrying out thermal reduction on the surface of the obtained metal ion doped glass to obtain a glass blank with a blackened surface layer; and grinding and removing the black glass layers on the upper and lower surfaces of the obtained glass blank to expose the internal transparent glass, and simultaneously reserving the black glass layers on the step surfaces to obtain the antihalation input window glass. Under the condition that the glass formula is not changed, the thickness of the black glass layer depends on the high-temperature blackening time, and the longer the high-temperature blackening time in a certain range is, the thicker the thickness of the black glass layer is. By adopting the ion implantation process, the nano-pore channel is formed on the surface of the glass, the diffusion of reducing gas in the glass is increased, the high-temperature time of blackening is reduced, the time required by blackening is shortened, and the blackening period of the anti-halation step glass is further accelerated.)

1. The preparation method of the antihalation step glass is characterized by comprising the following steps of:

1) performing metal ion implantation on a substrate of the antihalation step glass blank to obtain metal ion doped glass;

2) carrying out thermal reduction on the surface of the metal ion doped glass obtained in the step 1) to obtain a glass blank with a blackened surface layer;

3) grinding and removing the black glass layers on the upper and lower surfaces of the glass blank obtained in the step 2), exposing the transparent glass inside, and simultaneously keeping the black glass layers on the step surfaces to obtain the antihalation input window glass.

2. The method for producing an antihalation step glass according to claim 1, wherein in the step 1), the antihalation step glass blank is selected from borosilicate glass or quartz glass; the implanted metal ions are selected from at least one of Cu ions, Ni ions, Fe ions, Mn ions, Cr ions, V ions, Ag ions, and Au ions.

3. The method for preparing the anti-halation step glass according to claim 2, wherein the anti-halation step glass blank is selected from borosilicate glass, the borosilicate glass comprises 70-80% of silicon oxide, 6-20% of boron oxide, 0-1% of sodium oxide, 0-5% of aluminum oxide, 0-2% of barium oxide and 0-2% of calcium oxide by weight, and the implantation dosage of metal ions in the metal ion doped glass is 1 × 10¹⁷～5×10¹⁸ions·cm^-2。

4. The method for preparing an anti-halation step glass as defined in claim 3, wherein the parameters of the metal ion implantation are set such that the accelerating voltage is 5-100kV, the system vacuum degree is (1.0-8.0) × 10^-4Pa, beam intensity of 1.0-10.0mA, and ion implantation time of 2-20 hours.

5. The method for producing an antihalation step glass according to claim 1, wherein in step 2), the thermal reduction comprises: and heating the reducing furnace from room temperature to preheating temperature, removing impurities from the anti-halation step glass blank, and heating to blackening temperature for blackening.

6. The method for producing an antihalation step glass according to claim 5, wherein in the step 2), the thermally reduced gas is selected from one of hydrogen, carbon monoxide and methane; the flow rate of the gas for thermal reduction is 0.1L/min-2L/min.

7. The method for preparing antihalation step glass according to claim 5, wherein in the step 2), the preheating temperature is 200 ℃ to 300 ℃, the time of impurity removal treatment is 1h to 5h, the blackening temperature is 500 ℃ to 700 ℃, and the time of blackening treatment is 50h to 2000 h.

8. The halo-proof step glass is characterized in that the average light transmittance of a transparent glass region of the halo-proof step glass in the wavelength range of 380 nm-900 nm is more than 90%, the light transmittance of a black glass layer in the wavelength range of 380 nm-900 nm is less than 1%, and the surface compressive stress is 720-800 MPa.

9. The antihalation step glass according to claim 8, wherein the antihalation step glass is prepared by the method according to any one of claims 1 to 7.

10. A single stage image intensifier comprising an input window formed from the antihalation step glass of claim 8 or 9.

Technical Field

The invention relates to the field of optical materials, in particular to anti-halation step glass and a preparation method and application thereof.

Background

The antihalation step glass is a kind of transparent glass with black glass layer on the surface, and is mainly used in the image intensifier of low-light level night vision device as the input window of single-stage image intensifier to eliminate stray light and deposit multi-alkali photocathode. The black glass layer can absorb the light rays incident and reflected to the surface of the black glass layer, so that scattered light generated by stripes, bubbles and other defects and reflected light of a light path system can be eliminated, and the image resolution and the sensitivity of the low-light level night vision device are greatly improved. The antihalation step glass is mainly prepared by the following methods:

the glass is doped with colouring ions or valence-changing ions (Pb, Bi, Co, Fe, Mn, Cr, V, etc.) and then treated with high-temp. H₂The reduction blackens the surface. In this way, the glass formula needs to be modified, and the existing glass cannot be blackened.

The ion exchange hydrogen reduction method is characterized in that the components in the glass formula contain a certain amount of univalent cation (Li)⁺、Na⁺、K⁺) Under certain conditions, the silver in the silver nitrate is melted⁺Exchanged and then passed through H₂Reducing the glass into Ag simple substance at high temperature to blacken the surface of the glass. The method can only be used for the glass containing alkali metal in the glass formula, and can not perform blackening treatment on other glass.

The surface coating method is to select low-melting point glass powder matched with the expansion coefficient of the antihalation step glass blank, dope coloring ion oxide according to a certain proportion, mix the mixture evenly with water, coat the mixture on the surface of the step glass blank, dry the mixture in the shade and sinter the mixture to obtain a step glass semi-finished product with black surface. By adopting the method, the low-melting-point glass powder with matched expansion coefficients of the antihalation step glass blanks is required to be selected, and the requirements of glass application cannot be met.

The sol-gel method comprises soaking the antihalation step glass blank in sol containing coloring ions (Fe, Mn, Cr, V, etc.), taking out, and sintering at high temperature to obtain the step glass semi-finished product with black glass layer on the surface. Due to the immersion method, the thickness of the obtained black glass layer is not uniform, and has a great difference from the expected thickness.

Therefore, the development of the antihalation step glass with good blackening treatment effect has important market prospect.

Disclosure of Invention

In view of the above, the main objective of the present invention is to provide an anti-halation step glass, and a preparation method and an application thereof, and a technical problem to be solved is to provide an anti-halation step glass with a good blackening treatment effect, which is more suitable for practical applications.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.

The preparation method of the anti-halation step glass provided by the invention comprises the following steps:

1) performing metal ion implantation on a substrate of the antihalation step glass blank to obtain metal ion doped glass;

2) carrying out thermal reduction on the surface of the metal ion doped glass obtained in the step 1) to obtain a glass blank with a blackened surface layer;

3) grinding and removing the black glass layers on the upper and lower surfaces of the glass blank obtained in the step 2), exposing the transparent glass inside, and simultaneously keeping the black glass layers on the step surfaces to obtain the antihalation input window glass.

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 preparing the anti-halation step glass, in step 1), the anti-halation step glass blank is selected from borosilicate glass or quartz glass.

Preferably, in the method for preparing the anti-halation step glass, the anti-halation step glass blank is selected from borosilicate glass; the borosilicate glass comprises 70-80% of silicon oxide by weight percentage; 6-20% of boron oxide; 0-1% of sodium oxide; 0-5% of alumina; 0-2% of barium oxide; 0-2% of calcium oxide.

Preferably, in the above method for producing an anti-halation step glass, wherein in step 1), the implanted metal ions are selected from at least one of Cu ions, Ni ions, Fe ions, Mn ions, Cr ions, V ions, Ag ions, and Au ions.

Preferably, in the method for preparing the anti-halation step glass, in step 1), the implantation dose of the metal ions in the glass doped with the metal ions is 1 × 10¹⁷～5×10¹⁸ions·cm^-2。

Preferably, in the method for preparing the anti-halation step glass, in the step 1), the parameters for the metal ion implantation are set as follows, wherein the accelerating voltage is 5-100kV, and the system vacuum degree is (1.0-8.0) × 10^-4Pa, beam intensity of 1.0-10.0mA, and ion implantation time of 2-20 hours.

Preferably, in the above method for preparing an anti-halation step glass, in step 1), the metal ion implantation is performed in an ion implanter.

Preferably, in the above method for preparing an anti-halation step glass, wherein in step 2), the thermal reduction comprises: and heating the reducing furnace from room temperature to preheating temperature, removing impurities from the anti-halation step glass blank, and heating to blackening temperature for blackening.

Preferably, in the above method for producing an anti-halation step glass, wherein in step 2), the thermally reduced gas is selected from one of hydrogen, carbon monoxide and methane.

Preferably, in the above method for preparing anti-halation step glass, in step 2), the flow rate of the gas for thermal reduction is 0.1L/min to 2L/min.

Preferably, in the preparation method of the anti-halation step glass, in the step 2), the preheating temperature is 200-300 ℃, and the time of impurity removal treatment is 1-5 hours.

Preferably, in the preparation method of the anti-halation step glass, in the step 2), the blackening temperature is 500-700 ℃, and the blackening time is 50-2000 h.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme.

According to the anti-halation step glass provided by the invention, the average light transmittance of the transparent glass region of the anti-halation step glass in the wavelength range of 380 nm-900 nm is more than 90%, the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is less than 1%, and the surface compressive stress is 720-800 MPa.

Preferably, in the anti-halation step glass, the anti-halation step glass is prepared by the method.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme.

According to the invention, the single-stage image intensifier is characterized by comprising an input window, wherein the input window is made of the anti-halation step glass.

The invention uses ion implantation technology to implant metal ions into the surface of the glass, and the metal ions implanted in the thermal reduction process can be reduced, thereby achieving the effect of blackening the surface of the glass. Under the condition that the glass composition is unchanged, the thickness of the black glass layer depends on the time of high-temperature blackening, and the longer the time of high-temperature blackening of ion implantation in a certain range is, the thicker the thickness of the black glass layer is.

Compared with the prior art, the invention has the beneficial effects that:

the preparation method of the halo-proof step glass has the advantages of short treatment time, high efficiency and high strength of the obtained black glass layer.

Under the condition that the glass formula is not changed, the thickness of the black glass layer depends on the high-temperature blackening time, and the longer the high-temperature blackening time in a certain range is, the thicker the thickness of the black glass layer is. By adopting the ion implantation process, the nano-pore channel is formed on the surface of the glass, the diffusion of reducing gas in the glass is increased, the high-temperature time of blackening is reduced, the time required by blackening is shortened, and the blackening period of the anti-halation step glass is further accelerated.

According to the invention, ions are injected into the lattice structure of the glass, a compressive stress layer for enhancing the stability is created, and the surface compressive stress of the glass is improved.

The invention can be used for ion implantation of workpieces with complex shapes, and has the advantages of adaptability to low-temperature treatment, capability of performing energy-saving treatment, realization of large-area and large-batch production, low price and the like.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Drawings

FIG. 1 is a schematic view of a blackened antihalation step glass product in example 1 of the present invention;

FIG. 2 is a light transmittance graph of the transparent glass region of the antihalation step glass in the wavelength range of 380nm to 900nm in example 1 of the present invention;

FIG. 3 is a light transmittance diagram of the black glass layer of the antihalation step glass of example 1 of the present invention in the wavelength range of 380nm to 900 nm.

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 given to the specific embodiments, structures, features and effects of an anti-halation step glass, a preparation method thereof and applications thereof according to the present invention in combination with the preferred embodiments.

The following starting materials are available from conventional commercial sources unless otherwise specified.

The invention provides a preparation method of anti-halation step glass, which comprises the following steps:

1) performing metal ion implantation on a substrate of the antihalation step glass blank to obtain metal ion doped glass;

2) carrying out thermal reduction on the surface of the metal ion doped glass obtained in the step 1) to obtain a glass blank with a blackened surface layer;

3) grinding and removing the black glass layers on the upper and lower surfaces of the glass blank obtained in the step 2), exposing the transparent glass inside, and simultaneously keeping the black glass layers on the step surfaces to obtain the antihalation input window glass.