CN111533465B - Anti-halation step glass and preparation method and application thereof - Google Patents

Anti-halation step glass and preparation method and application thereof Download PDF

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CN111533465B
CN111533465B CN202010421569.0A CN202010421569A CN111533465B CN 111533465 B CN111533465 B CN 111533465B CN 202010421569 A CN202010421569 A CN 202010421569A CN 111533465 B CN111533465 B CN 111533465B
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glass
antihalation
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CN111533465A (en
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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
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China building materials Photon Technology Co.,Ltd.
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China Building Materials Academy CBMA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/0055—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ion implantation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment

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Abstract

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.

Description

Anti-halation step glass and preparation method and application thereof
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 preparation method of the anti-halation step glass, in step 1), the parameters of the metal ion implantation are set as follows: accelerating voltage of 5-100kV, and vacuum degree of system of (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.
In the specific implementation, in the step 1), the halo-proof step glass blank is selected from borosilicate glass or quartz glass, preferably 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.
In specific implementation, in the step 1), the implanted metal ions are at least one selected from Cu ions, Ni ions, Fe ions, Mn ions, Cr ions, V ions, Ag ions, and Au ions; preferably Ag ions. The implantation dosage of the metal ions in the metal ion doped glass is 1 multiplied by 1017～5×1018ions·cm-2(ii) a Preferably 3X 1018ions·cm-2The injection dosage of the metal is too small, the generated black layer is incomplete, and the black transmittance is too high; the injection dosage of the metal is too high, the black transmittance is not changed greatly, and resources are wasted.
In specific implementation, in step 1), the metal ion implantation process conditions are as follows: accelerating voltage of 5-100kV, and vacuum degree of system of (1.0-8.0) × 10-4Pa, the beam intensity is 1.0-10.0mA, and the ion injection time is 2-20 hours; preferably, the acceleration voltage is 80kV, and the system vacuum degree is 6.0X 10-4Pa, the beam intensity is 8.0mA, and the ion implantation time is 16 h. The metal ion implantation is performed in an ion implanter. Accelerating voltage, system vacuum degree, beam intensity, ion implantation time and other parameters influence the thickness of the black layer, so that the black transmittance is influenced; the parameter is too high, the black transmittance is not changed greatly, and resources are wasted.
In a specific implementation, in step 2), the thermal reduction includes: 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. The thermally reduced gas is selected from one of hydrogen, carbon monoxide and methane, preferably hydrogen; this is because the hydrogen atom radius is small, the permeability on the glass surface is high, and the effect is good.
In the specific implementation, in the step 2), the flow rate of the gas for thermal reduction is 0.1L/min-2L/min, preferably 1.2L/min, the flow rate is too low, the permeability on the surface of the glass is low, and the reduction effect is poor; the flow is too high, the glass surface is saturated, the reduction effect is not improved, and resources are wasted.
In the specific implementation, in the step 2), the preheating temperature is 200-300 ℃, and the time of impurity removal treatment is 1-5 h; preferably, the preheating temperature is 240 ℃, and the time of impurity removal treatment is 3 h.
In the specific implementation, in the step 2), the blackening temperature is 500-700 ℃, and the blackening time is 50-2000 h; preferably, the blackening temperature is 600 ℃, and the blackening treatment time is 1200 h. (low blackening temperature, small thickness of black layer, high black transmittance; high blackening temperature, sample deformation.
The average light transmittance of the anti-halation step glass in the transparent glass area with large and small surfaces ground off is more than 90 percent in the wavelength range of 380 nm-900 nm, the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is less than 1 percent, and the surface pressure stress is 720-800 MPa.
Example 1
The embodiment provides a preparation method of anti-halation step glass, which comprises the following steps:
injecting metal ions into a glass substrate, wherein the glass substrate is borosilicate glass, and the process of injecting the metal ions comprises the following steps: performing ion implantation in an ion implanter with silver target as metal target and silver ion implantation dosage of 5 × 1018ions·cm-2Acceleration voltage of 100kV and vacuum degree of system of 8 × 10-4Pa, beam intensity of 10.0mA, ion injection time of 20 hours, and obtaining silver ion doped glass;
putting the silver ion doped glass into a closed reducing atmosphere high-temperature furnace, and introducing H with the purity of 99.99 percent2(ii) a By controlling H2A pressure reducing valve at the gas source maintains the gas pressure in the reducing atmosphere furnace in a micro-positive pressure state of 0.01MPa, and the gas flow is controlled within the range of 2L/min; the furnace temperature is firstly raised from room temperature to 300 ℃, and is kept at 300 ℃ for 5h, so that impurities on the surface of the blank are completely decomposed and volatilized, because the impurities on the surface of the glass occupy the position of the surface and form a high surface potential barrier, and therefore, the furnace temperature is completely raised, and the temperature of the furnace is not lowered, so that the glass is not damaged, and the glass is not damagedImpurities on the surface must be removed; secondly, heating to 700 ℃ from 300 ℃, wherein the blackening time is 2000h, and obtaining a glass blank with a blackened surface layer;
grinding and removing the black glass layers (light absorption layers) on the upper surface and the lower surface of the glass blank after the heat treatment to expose the transparent glass inside (the specific steps comprise placing the anti-halation step glass in a grinding disc, introducing small-particle-size polishing powder into a polishing machine, circularly polishing the anti-halation step glass by using a fine grinding polishing pad, wherein the polishing time is 4min/m, the pressure is 3Mpa, the black glass layers (light absorption layers) on the upper surface and the lower surface are ground and removed to expose the transparent glass inside), and simultaneously reserving the black glass layers on the step surface to obtain the anti-halation input window glass with the structure shown in the figure 1, wherein the transparent glass part 1 is completely transparent colorless glass, the black glass layer 2 can absorb spectrums in ultraviolet, visible and near infrared regions, and the anti-halation input window can be used for eliminating stray light. The antihalation prepared above was input into a window glass and the transmittance of the glass was measured with an instrument to obtain the performance test results shown in fig. 2 and 3. As shown in fig. 2, the average light transmittance of the transparent glass region of the antihalation step glass in the wavelength range of 380nm to 900nm is about 95%; as shown in fig. 3, the light transmittances of the black glass layer of the antihalation step glass in the wavelength range of 380nm to 900nm are all about 0.1%; the surface pressure stress of the antihalation step glass is 800 MPa.
Example 2
The embodiment provides a preparation method of anti-halation step glass, which comprises the following steps:
injecting metal ions into a glass substrate, wherein the glass substrate is borosilicate glass, and the process of injecting the metal ions comprises the following steps: performing ion implantation in an ion implanter, wherein the metal target of the ion implanter is a nickel target, and the dosage of the nickel ion implantation is 1 × 1017ions·cm-2Accelerating voltage of 5kV and vacuum degree of 1.0 × 10-4Pa, beam intensity of 1.0mA, and ion injection time of 2 hours to obtain the glass doped with nickel ions;
putting the glass doped with nickel ions into a closed reducing atmosphere high-temperature furnace, and introducing H with the purity of 99.99 percent2(ii) a By controlling H2A pressure reducing valve at the gas source maintains the gas pressure in the reducing atmosphere furnace in a micro-positive pressure state of 0.01MPa, and the gas flow is controlled within the range of 0.1L/min; the furnace temperature is firstly raised from room temperature to 200 ℃, and is kept at 200 ℃ for 1h, so that impurities on the surface of the blank are completely decomposed and volatilized, because the impurities on the surface of the glass occupy the position of the surface and form a high surface potential barrier, the impurities on the surface must be removed; and secondly, heating from 200 ℃ to 500 ℃ and blackening for 50h to obtain the glass blank with the blackened surface layer.
Grinding and removing the black glass layers (light absorption layers) on the upper surface and the lower surface of the glass blank after the heat treatment to expose the transparent glass inside (the specific steps comprise that the anti-halation step glass is placed in a grinding disc, small-particle-size polishing powder is introduced into a polishing machine, the anti-halation step glass is circularly polished by using a fine grinding polishing pad, the polishing time is 4min/m, the pressure is 3Mpa, the black glass layers (light absorption layers) on the upper surface and the lower surface are ground and removed to expose the transparent glass inside), and meanwhile, the black glass layer on the step surface is kept to obtain the anti-halation input window glass, wherein 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 about 91%, and the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is about 0.9%; the surface pressure stress of the antihalation step glass is 720 MPa.
Example 3
The embodiment provides a preparation method of anti-halation step glass, which comprises the following steps:
injecting metal ions into a glass substrate, wherein the glass substrate is borosilicate glass, and the process of injecting the metal ions comprises the following steps: performing ion implantation in an ion implanter, wherein the metal target of the ion implanter is copper target, and the dosage of copper ion implantation is 3 × 1018ions·cm-2Accelerating voltage of 80kV and system vacuum degree of 4X 10-4Pa, beam intensity of 5.0mA, and ion injection time of 10 hours to obtain copper ion doped glass;
placing the glass doped with copper ions into a closed reducing atmosphere high-temperature furnace, and introducing H with the purity of 99.99 percent2(ii) a By controlling H2A pressure reducing valve at the gas source maintains the gas pressure in the reducing atmosphere furnace in a micro-positive pressure state of 0.01MPa, and the gas flow is controlled within the range of 1L/min; the furnace temperature is firstly increased from room temperature to 270 ℃, and is kept at 270 ℃ for 3h, so that impurities on the surface of the blank are completely decomposed and volatilized, because the impurities on the surface of the glass occupy the position of the surface and form a high surface barrier, the impurities on the surface must be removed; and secondly, heating from 270 ℃ to 600 ℃, wherein the blackening time is 1000h, and obtaining the glass blank with the blackened surface layer.
Grinding and removing the black glass layers (light absorption layers) on the upper surface and the lower surface of the glass blank after the heat treatment to expose the transparent glass inside (the specific steps comprise that the anti-halation step glass is placed in a grinding disc, small-particle-size polishing powder is introduced into a polishing machine, the anti-halation step glass is circularly polished by using a fine grinding polishing pad, the polishing time is 4min/m, the pressure is 3Mpa, the black glass layers (light absorption layers) on the upper surface and the lower surface are ground and removed to expose the transparent glass inside), and meanwhile, the black glass layer on the step surface is kept to obtain the anti-halation input window glass, wherein 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 about 93%, and the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is about 0.2%; the surface pressure stress of the antihalation step glass is 760 MPa.
Example 4
The embodiment provides a preparation method of anti-halation step glass, which comprises the following steps:
injecting metal ions into a glass substrate, wherein the glass substrate is borosilicate glass, and the process of injecting the metal ions comprises the following steps: performing ion implantation in an ion implanter with gold target material of 50keV energy and gold ion implantation dosage of 1 × 1018ions·cm-2Acceleration voltage of 60kV and vacuum degree of 3X 10-4Pa, the beam intensity is 6.0mA, the ion injection time is 8 hours, and the glass doped with gold ions is obtained;
placing the glass doped with gold ions into a closed reducing atmosphere high-temperature furnace, and introducing H with the purity of 99.99 percent2(ii) a By controlling H2A pressure reducing valve at the gas source maintains the gas pressure in the reducing atmosphere furnace in a micro-positive pressure state of 0.01MPa, and the gas flow is controlled within the range of 1.2L/min; the furnace temperature is firstly increased from room temperature to 240 ℃, and is kept at 240 ℃ for 4h, so that impurities on the surface of the blank are completely decomposed and volatilized, because the impurities on the surface of the glass occupy the position of the surface and form a high surface potential barrier, the impurities on the surface must be removed; and secondly, heating from 240 ℃ to 600 ℃, wherein the blackening time is 800h, and obtaining the glass blank with the blackened surface layer.
Grinding and removing the black glass layers (light absorption layers) on the upper surface and the lower surface of the glass blank after the heat treatment to expose the transparent glass inside (the specific steps comprise that the anti-halation step glass is placed in a grinding disc, small-particle-size polishing powder is introduced into a polishing machine, the anti-halation step glass is circularly polished by using a fine grinding polishing pad, the polishing time is 4min/m, the pressure is 3Mpa, the black glass layers (light absorption layers) on the upper surface and the lower surface are ground and removed to expose the transparent glass inside), and meanwhile, the black glass layer on the step surface is reserved to obtain the anti-halation input window glass, wherein 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 about 93%, and the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is about 0.5%; the surface pressure stress of the antihalation step glass is 740 MPa.
Comparative example 1
The comparative example provides a preparation method of anti-halation step glass, which comprises the following steps:
directly placing borosilicate glass into a closed reducing atmosphere high-temperature furnace, and introducing H with the purity of 99.99 percent2(ii) a By controlling H2A pressure reducing valve at the gas source maintains the gas pressure in the reducing atmosphere furnace in a micro-positive pressure state of 0.01MPa, and the gas flow is controlled within the range of 2L/min; the furnace temperature is firstly increased from room temperature to 300 ℃, and is kept at 300 ℃ for 5h, so that impurities on the surface of the blank are completely decomposed and volatilized, because the impurities on the surface of the glass occupy the position of the surface and form a high surface potential barrier, the impurities on the surface must be removed; secondly, heating the mixture from 300 ℃ to 700 ℃ and blackening the mixture for 2000 hours to obtain the black pigmentThe surface layer is blackened;
grinding and removing the black glass layers (light absorbing layers) on the upper and lower surfaces of the glass blank after the heat treatment to expose the transparent glass inside (the specific steps comprise placing the anti-halation step glass in a grinding disc, introducing small-particle-size polishing powder into a polishing machine, circularly polishing the anti-halation step glass by using a fine polishing pad for 4min/m under 3Mpa for removing the black glass layers (light absorbing layers) on the upper and lower surfaces to expose the transparent glass inside), and simultaneously retaining the black glass layers on the step surfaces, and obtaining the antihalation input window glass, wherein the average light transmittance of the transparent glass region of the antihalation step glass in the wavelength range of 380 nm-900 nm is about 95%, the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is about 10%, and the surface pressure stress of the antihalation step glass is 510 MPa.
Comparing the data of example 1 with that of comparative example 1, it was found that: through silver ion implantation and the same reduction process, the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is reduced from 10% to 0.1%; the surface compressive stress is increased from 510MPa to 800 MPa. The reason is that the ion implantation process is adopted, the nano-pore channel is formed on the surface of the glass, the diffusion of reducing gas in the glass is increased, the blackening of the antihalation step glass is further accelerated, and the light transmittance of the black glass layer in the wavelength range of 380 nm-900 nm is reduced. Due to the intense atomic collisions and temperature rise of the target during ion implantation, precipitate phases may form in the matrix to further strengthen the matrix structure. In addition, the intense collision also causes the refinement of crystal grains in the matrix, and the grain boundary is increased correspondingly, thereby inhibiting the movement of dislocation and improving the surface compressive stress of the material.
The recitation of numerical ranges herein includes all numbers subsumed within that range and includes any two numbers subsumed within that range. For example, "SiO2Is 61-67 w% ", which includes all values between 61-67, and includes any two values (e.g., 50, 60) within the range (50-60); the different values of the same index, which appear in all embodiments of the invention, can be combined arbitrarily,composition range values.
In the description of the present invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (8)

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; the injected 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; the implantation dosage of the metal ions in the metal ion doped glass is 1 multiplied by 1017～5×1018 ions·cm -2；
The parameters of the metal ion implantation are set as follows: accelerating voltage of 5-100kV, and vacuum degree of system of (1.0-8.0) × 10-4Pa, the beam intensity is 1.0-10.0mA, and the ion injection time is 2-20 hours;
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 surface to obtain the antihalation step glass;
the average light transmittance of the transparent glass region of the antihalation 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.
2. The method for producing an antihalation step glass according to claim 1, wherein in step 1), the antihalation step glass blank is selected from borosilicate glass and quartz glass.
3. The method of claim 2, wherein the antihalation step glass blank is selected from the group consisting of 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.
4. 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.
5. The method for producing an antihalation step glass according to claim 4, 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.
6. The method for preparing antihalation step glass according to claim 4, 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.
7. 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; the antihalation step glass is prepared by the method of any one of claims 1 to 6.
8. A single stage image intensifier comprising an input window comprised of the antihalation step glass of claim 7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050635A (en) * 2009-11-03 2011-05-11 北京东方新材科技有限公司 Integral coloring method for glass ceramics
CN104591539A (en) * 2015-01-29 2015-05-06 中国建筑材料科学研究总院 Borosilicate glass with high transmittance at far ultraviolet band and preparation method thereof
CN109704555A (en) * 2019-01-22 2019-05-03 广州宏晟光电科技股份有限公司 A kind of fire polishing melanism preparation method of antihalation step glass
CN109963821A (en) * 2016-04-12 2019-07-02 旭硝子欧洲玻璃公司 Blue reflecting glass substrate and its manufacturing method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030097858A1 (en) * 2001-11-26 2003-05-29 Christof Strohhofer Silver sensitized erbium ion doped planar waveguide amplifier
US20060210783A1 (en) * 2005-03-18 2006-09-21 Seder Thomas A Coated article with anti-reflective coating and method of making same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050635A (en) * 2009-11-03 2011-05-11 北京东方新材科技有限公司 Integral coloring method for glass ceramics
CN104591539A (en) * 2015-01-29 2015-05-06 中国建筑材料科学研究总院 Borosilicate glass with high transmittance at far ultraviolet band and preparation method thereof
CN109963821A (en) * 2016-04-12 2019-07-02 旭硝子欧洲玻璃公司 Blue reflecting glass substrate and its manufacturing method
CN109704555A (en) * 2019-01-22 2019-05-03 广州宏晟光电科技股份有限公司 A kind of fire polishing melanism preparation method of antihalation step glass

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