Optical absorption glass for high-resolution and high-uniformity fiber image inverters and its preparation method

Abstract

The present invention discloses a light absorption glass for a high-resolution and high-uniformity fiber image inverter and a preparation method thereof. The light absorption glass is composed of the following components in mole percentage: SiO2 71-80.0%, Al2O3 0.5-5.0%, B2O3 1.0-5.0%, Na2O 1.0-11.0%, K2O 6.0-11.0%, MgO 0.1-2.0%, CaO 0.1-2.0%, BaO 0-0.04%, TiO2 0-1.0%, Co2O3 0.1-0.4%, NiO 0.1-1.0%, MnO 1.0-5.0%, V2O5 0.1-1.0%, CeO2 0-0.2%, CuO 0-0.05%. Using the light absorption glass of the present invention can improve the contrast and clarity of the image formed by the fiber image inverter.

Description

Technical Field

[0001] The present invention relates to the field of manufacturing fiber optic image transmission elements, and particularly to a light absorption glass for a high-resolution and high-uniformity fiber optic image inverter and a preparation method thereof. Background Art

[0002] The image transmission mechanism of a fiber optic image inverter is realized by using the total reflection principle of optical fibers. The optical fibers constituting the fiber optic image inverter are prepared by hot melt pressing using a rod-tube combination and vacuum drawing process with a low-refractive-index skin glass tube, a high-refractive-index core glass rod, and light absorption glass filaments. Since the optical fibers are completely fused together tightly by the skin glass, the adjacent optical fibers are close to each other, resulting in crosstalk between adjacent fibers. For example, problems such as uneven wall thickness of the skin glass tube caused by uneven temperature field or drawing stress during the preparation process may lead to light penetration during total reflection, causing light leakage, or the core or skin contact interface of the optical fiber being damaged due to defects or contaminants, destroying the total reflection condition of light, and causing light scattering here. These scattered lights entering adjacent fibers will also cause crosstalk, and crosstalk is an important factor directly affecting the imaging quality of the contrast and clarity of fiber optic image transmission elements.

[0003] To solve the problem of crosstalk in fiber optic image inverters, usually, the method of filling light absorption glass filaments in the gaps between adjacent optical fibers is adopted to absorb stray light to reduce crosstalk. The method of inserting absorption filaments can effectively eliminate stray light. The light absorption glass is drawn into absorption filaments and inserted into the gaps between the arranged optical fibers, thereby playing roles such as absorbing crosstalk and light leakage. However, complete optical insulation cannot be achieved, and the key lies in the problem of light absorption glass. The role of the light absorption glass is to absorb the stray light that penetrates the skin of the optical fiber to achieve optical insulation and improve the contrast of the image. Light absorption glass is an important type of optical glass, mainly achieving the absorption effect of interfering stray light and improving the performance such as clarity and contrast of optical elements. However, with the expansion of the application field, in recent years, the requirements for ultra-thin, high clarity, and high contrast have become higher and higher. Therefore, it is also required that the light absorption effect of the light absorption glass is better, the absorption of stray light is more thorough, and it should cover the wavelength range from ultraviolet to visible to near infrared.

[0004] Ordinary light absorption glass still has a relatively high transmittance in the visible light range at a thickness of 0.5 mm. As the thickness decreases, the transmittance will gradually increase. The light absorption materials of traditional fiber optic image transmission elements generally have problems such as low absorption efficiency of stray light and poor imaging contrast. This is because most of the light absorption coloring agents in the light absorption material are Fe2O3, and the main light absorption coloring agent is iron(III) oxide Fe2O3. Although Fe 3+Ions have good light absorption properties, but they are mainly concentrated in the infrared region. In the visible light region, their light absorption properties are poor. Moreover, when using Fe 3+ ions as light absorbers, it is difficult for them to maintain an oxidized state in glass. Especially for optical fiber filaments with a filament diameter less than 6 μm, the coloring of iron oxide Fe2O3 will be unstable or even fade during the high-temperature wire drawing process. More seriously, the coloring ions will diffuse into the cladding glass of the optical fiber, weakening or disappearing the total reflection mechanism of the optical fiber, poisoning the photocathode material, and having a serious impact on improving the image transmission quality of the fiber optic image inverter. A reducing atmosphere is also required to obtain good light absorption effects. And because Fe 3+ ions are variable-valence element ions, it is very easy for them to change the ion valence state at high temperatures, directly affecting the light absorption effect. Especially for the light absorption glass used in fiber optic image inverters, it cannot meet the application requirements of high-definition and high-contrast fiber optic image inverters. Summary of the Invention

[0005] The object of the present invention is to provide a light absorption glass for a high-resolution and high-uniformity fiber optic image inverter with improved imaging contrast and clarity, aiming at the defects of the above-mentioned existing technologies.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A light absorption glass for a high-resolution and high-uniformity fiber optic image inverter, which is composed of the following components in mole percentage:

[0008]

[0009]

[0010] The present invention also provides a preferred technical solution. A light absorption glass for a high-resolution and high-uniformity fiber optic image inverter, which is composed of the following components in mole percentage:

[0011]

[0012] The present invention also provides a more preferred technical solution. A light absorption glass for a high-resolution and high-uniformity fiber optic image inverter, which is composed of the following components in mole percentage:

[0013]

[0014]

[0015] The present invention also provides a method for preparing a light absorption glass for a high-resolution and high-uniformity fiber optic image inverter using the above composition, including the following steps:

[0016] (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture;

[0017] (2) Glass melting: Put the raw material mixture into a crucible for melting. After the raw material mixture melts and clarifies, pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, light absorption material glass is obtained.

[0018] The melting temperature is 1450 - 1550 °C; the melting time is 7 - 10 hours, and the raw material mixture is stirred 2 - 3 times during the melting process.

[0019] The clarification temperature is 1350 - 1450 °C; the clarification time is 2 - 4 hours.

[0020] The present invention also provides a light absorption glass for a high-resolution and high-uniformity fiber optic image inverter, which is prepared according to the described method.

[0021] The present invention further provides an application of the described light absorption glass for a high-resolution and high-uniformity fiber optic image inverter on a fiber optic image transmission element.

[0022] The light absorption material glass of the present invention is suitable for use as an outer-wall absorption glass material for glass fibers when preparing fiber optic image transmission elements. Fiber optic image transmission elements include fiber optic panels, fiber optic image inverters, fiber optic light cones, fiber optic image bundles, etc.

[0023] Since the wavelength of the phosphor used in the fluorescent screen for low-light level night vision devices is in the range of 510 - 560 nm, mainly dominated by the green light wavelength, the light absorption material glass of the present invention has strong and uniform light absorption ability and spectral absorption effect in the wavelength range of 510 - 660 nm at a thickness of 0.5 ± 0.01 mm, the spectral transmittance ≤ 3.0%, and has good adjustment of the contrast performance of the fiber optic image inverter; the thermal expansion coefficient of the light absorption material glass of the present invention is (85 ± 5) × 10 -7 / °C; and has good chemical stability and anti-crystallization performance, does not crystallize or phase-separate after being kept at 850 - 900 °C for 6 hours, and has excellent anti-crystallization performance and excellent chemical stability.

[0024] In the light absorbing glass composition of the present invention, SiO2 is the main component of the glass skeleton and plays a major role in the glass skeleton. The molar percentage (mol.%) of SiO2 is 71.0-80.0. When the SiO2 content is lower than 71.0 mol.%, it is difficult to obtain a thermal expansion coefficient similar to that of the leather glass, and the chemical resistance of the glass will be reduced; when the SiO2 content is higher than 80.0 mol.%, the high temperature viscosity of the glass will increase, resulting in an excessively high melting temperature of the glass.

[0025] Al2O3 is an intermediate oxide of glass. 3+ There are two coordination states, namely, located in tetrahedron or octahedron. When there is enough oxygen in the glass, aluminum oxygen tetrahedron [AlO4] is formed, forming a continuous network with silicon oxygen tetrahedron. When there is insufficient oxygen in the glass, aluminum oxygen octahedron [AlO6] is formed, which is an external body of the network and is located in the cavities of the silicon oxygen structure network. Therefore, within a certain content range, it can be the main body of the glass network formed with SiO2. The molar percentage (mol.%) of Al2O3 is 0.5-5.0. Al2O3 content greater than 5.0 mol.% will significantly increase the high temperature viscosity of the glass and increase the melting temperature of the glass.

[0026] B2O3 is a glass-forming oxide and a component of the glass skeleton. It is also a flux that reduces the viscosity of the glass. Boron oxide triangles [BO3] and boron oxide tetrahedrons [BO4] are structural components. Boron may exist in the form of triangles [BO3] or boron oxide tetrahedrons [BO4] under different conditions. Under high-temperature melting conditions, it is generally difficult to form boron oxide tetrahedrons, and can only exist in the form of trihedrons. However, at low temperatures, under certain conditions, B 3+ It has a tendency to capture free oxygen to form tetrahedrons, making the structure compact and increasing the low-temperature viscosity of the glass. However, due to its characteristics of reducing the viscosity of the glass at high temperatures and increasing the viscosity of the glass at low temperatures, it is also the main component that reduces the refractive index of the glass, which determines that its content range is relatively small. The molar percentage (mol.%) of B2O3 is 1.0-5.0. If the content of B2O3 is greater than 5.0mol.%, the phase separation tendency of the glass will increase.

[0027] Na2O is an oxide outside the glass structure network. The molar percentage (mol.%) of Na2O is 1.0-11.0. When the content of Na2O is greater than 11.0 mol.%, the thermal expansion coefficient of the glass will increase.

[0028] K2O is an oxide outside the glass structure network. The molar percentage (mol.%) of K2O is 6.0-11.0. When the content of K2O is greater than 11.0 mol.%, the thermal expansion coefficient of the glass will increase.

[0029] MgO is an external oxide of the glass structure network and is used to adjust the crystallization temperature of the glass. The molar percentage (mol.%) of MgO is 0.1 - 2.0. When the content of MgO is greater than 2.0 mol.%, it will increase the crystallization tendency of the glass.

[0030] CaO is an external oxide of the glass structure network. The molar percentage (mol.%) of CaO is 0.1 - 2.0. When the content of CaO is greater than 2.0 mol.%, it will reduce the chemical stability of the glass and increase the crystallization tendency of the glass.

[0031] BaO is an external oxide of the glass structure network and is used to adjust the crystallization temperature of the glass. The molar percentage (mol.%) of BaO is 0 - 0.04. When the content of BaO is greater than 0.04 mol.%, it will reduce the chemical stability of the glass and increase the crystallization tendency of the glass.

[0032] TiO2 is used to adjust the chemical stability and crystallization of the glass. The molar percentage (mol.%) of TiO2 is 0 - 1.0. When the content of TiO2 is greater than 1.0 mol.%, it will reduce the chemical resistance of the glass and increase the crystallization tendency.

[0033] Co2O3 is a colorant for light-absorbing glass. The molar percentage (mol.%) of Co2O3 is 0.1 - 0.4. Co2O3 has a lower melting point than CoO, which enables Co2O3 to combine with other coloring ions and form a stable form in the glass, thus making the coloring of the light-absorbing material more stable. When the content of Co2O3 is greater than 0.4 mol.%, it will reduce the chemical stability of the glass and increase the crystallization tendency of the glass.

[0034] NiO is a colorant for light-absorbing glass. The molar percentage (mol.%) of NiO is 0.1 - 1.0, and Ni 2+ has a good absorption effect in the visible light region. When the content of NiO is greater than 1.0 mol.%, it will reduce the chemical stability of the glass and increase the crystallization tendency of the glass.

[0035] MnO is a colorant for light-absorbing glass. In the present invention, MnO is the main light absorber. MnO has a higher melting point temperature than MnO2, and Mn 2+ has a stable light absorption ability between 400 - 700 nm and can form stable coloring in the glass. The molar percentage (mol.%) of MnO is 1.0 - 5.0. When the content of MnO is greater than 5.0 mol.%, it will reduce the chemical stability of the glass and increase the crystallization tendency of the glass.

[0036] V2O5 is a colorant for light-absorbing glass. The molar percentage (mol.%) of V2O5 is 0.1 - 1.0. V2O5 can solidify the coloring of manganese ions, making the coloring of the light-absorbing material more stable. When the content of V2O5 is greater than 1.0 mol.%, it will reduce the chemical stability of the glass and increase the crystallization tendency of the glass.

[0037] CeO2 is a rare earth oxide, which mainly regulates the crystallization performance of the glass and acts as a glass fining agent. The molar percentage (mol.%) of CeO2 is 0 - 0.2. When the content of CeO2 is greater than 0.2 mol.%, it will increase the crystallization tendency of the glass.

[0038] CuO is a colorant for light-absorbing glass and can combine with Ni 2+ , Co 3+ , Mn 2+ etc. to form stable coloring in the glass. By using the composite absorption effect, it can ensure the absorption of stray light in the wavelength range of 400 nm - 700 nm, obtain a good light absorption effect, and make the light absorption curve not show obvious transmission peaks in the visible light region. The molar percentage (mol.%) of CuO is 0 - 0.05. However, when the content of CuO is greater than 0.05 mol.%, it will increase the crystallization tendency of the glass.

[0039] Compared with the prior art, the light-absorbing glass of the present invention has the following advantages:

[0040] (1) It has good performance in adjusting the contrast of the fiber optic image inverter. At a thickness of 0.5 ± 0.01 mm, it has strong and uniform light absorption ability and spectral absorption effect in the wavelength range of 510 - 660 nm, and the spectral transmittance ≤ 3.0%.

[0041] (2) The thermal expansion coefficient of the light-absorbing glass of the present invention is (85 ± 5) × 10 -7 / ℃;

[0042] (3) It has good chemical stability and anti-crystallization performance. It does not crystallize or phase-separate after being kept at 850 - 900 °C for 6 hours, and has excellent anti-crystallization performance and excellent chemical stability.

[0043] Using the light-absorbing glass of the present invention has good chemical stability and anti-crystallization performance. After the light-absorbing glass is melted, there are no stones, no bubble holes inside. When applied to the fiber optic image inverter, it can effectively improve the absorption of stray light between optical fibers to reduce the cross-talk between fibers, thereby achieving the effect of improving the imaging contrast and clarity of the fiber optic image inverter. The obtained fiber optic image inverter has the characteristics of high resolution and high uniformity.

[0044] The light-absorbing glass of the present invention can be applied to an ultra-narrow twisted wire area fiber image inverter, which can be applied to a low-light image intensifier to improve the miniaturization, light weight, and high-definition imaging level of the low-light image intensifier. Description of the Drawings

[0045] Figure 1 It is the transmittance curve of the light-absorbing glass provided by the embodiment of the present invention. Detailed Embodiments

[0046] To make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes in detail the embodiments of the present invention.

[0047] See Figure 1 , which is the transmittance curve of the light-absorbing material. It can be seen from it that in the wavelength range of 510 - 660 nm, it has a strong and uniform light absorption ability and spectral absorption effect, and the spectral transmittance ≤ 3.0%. It can be seen that the light absorption effect on visible light is very obvious.

[0048] In this article, all "mole percentages mol.%" are based on the total mole amount of the final glass composition, and the glass chemical composition (mol.%) of the embodiments is listed in detail in Table 1.

[0049] The parameters measured for the light-absorbing glass for the high-resolution and high-uniformity fiber image inverter of the present invention, as well as the measurement methods and instruments, are as follows:

[0050] (1) The transmittance of the glass is measured using a transmittance tester;

[0051] (2) The average linear thermal expansion coefficient α 30 / 300 [×10 -7 / °C] is measured using a horizontal dilatometer and measured by the method specified in GB / T 16920 - 2015.

[0052] Table 1 shows the chemical composition (mol.%) and properties of the light-absorbing glass embodiments

[0053]

[0054]

[0055] Example 1

[0056] Select raw materials according to the glass composition of Example 1 in Table 1 to make the batching meet the glass chemical composition in Table 1, and then prepare the light-absorbing glass according to the following steps:

[0057] (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture;

[0058] (2) Glass melting: Put the raw material mixture into a crucible and melt it at 1550 °C for 7 hours. Stir it twice during the melting process. After the raw material mixture is melted, clarify it at 1450 °C for 2 hours. Pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, light absorption material glass is obtained.

[0059] Example 2

[0060] Select raw materials according to the glass composition of Example 2 in Table 1 to make the ingredients meet the glass chemical composition in Table 1, and then prepare light absorption material glass according to the following steps:

[0061] (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture;

[0062] (2) Glass melting: Put the raw material mixture into a crucible and melt it at 1450 °C for 10 hours. Stir it three times during the melting process. After the raw material mixture is melted, clarify it at 1350 °C for 4 hours. Pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, light absorption material glass is obtained.

[0063] Example 3

[0064] Select raw materials according to the glass composition of Example 3 in Table 1 to make the ingredients meet the glass chemical composition in Table 1, and then prepare light absorption material glass according to the following steps:

[0065] (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture;

[0066] (2) Glass melting: Put the raw material mixture into a crucible and melt it at 1480 °C for 8 hours. Stir twice during the melting process. After the raw material mixture is melted, clarify it at 1370 °C for 4 hours. Then carry out melting. After the raw material mixture is melted and clarified, pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, the light-absorbing material glass is obtained.

[0067] Example 4

[0068] Select raw materials according to the glass composition of Example 4 in Table 1 to make the batching meet the glass chemical composition in Table 1. Then prepare the light-absorbing material glass according to the following steps:

[0069] (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture;

[0070] (2) Glass melting: Put the raw material mixture into a crucible and melt it at 1460 °C for 9 hours. Stir three times during the melting process. After the raw material mixture is melted, clarify it at 1400 °C for 3 hours. Pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, the light-absorbing material glass is obtained.

[0071] Example 5

[0072] Select raw materials according to the glass composition of Example 5 in Table 1 to make the batching meet the glass chemical composition in Table 1. Then prepare the light-absorbing material glass according to the following steps:

[0073] (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture;

[0074] (2) Glass melting: Put the raw material mixture into a crucible and melt it at 1530 °C for 7 hours. Stir three times during the melting process. After the raw material mixture is melted, clarify it at 1420 °C for 3 hours. Pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, the light-absorbing material glass is obtained.

[0075] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A composition of light-absorbing glass for a high-resolution and high-uniformity fiber image inverter, characterized in that, Composed of components with the following molar percentages:

2. The composition according to claim 1, wherein Composed of components with the following molar percentages:

3. A method for preparing a light-absorbing glass for a high-resolution and high-uniformity fiber image inverter using the composition according to claim 1 or 2, characterized in that, Including the following steps: (1) Raw material preparation: Weigh quartz sand, alumina, boric acid or boric anhydride, sodium carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate, titanium dioxide, cobalt sesquioxide, nickel monoxide, manganese monoxide, vanadium pentoxide, cerium oxide and copper oxide according to the ratio, and mix them evenly to obtain a raw material mixture; (2) Glass melting: Put the raw material mixture into a crucible for melting. After the raw material mixture is melted and clarified, pour the melted and clarified glass liquid into a preheated mold to form a specified specification. After the glass liquid cools and solidifies, light absorption material glass is obtained.

4. The method according to claim 3, wherein The temperature of the melting is 1450 - 1550 °C; the time of the melting is 7 - 10 hours, and the raw material mixture is stirred 2 - 3 times during the melting process.

5. The method according to claim 3 or 4, characterized in that, The temperature of the clarification is 1350 - 1450 °C; the time of the clarification is 2 - 4 hours.

6. An optical absorption glass for a high-resolution and high-uniformity fiber image inverter, characterized in that, Prepared by the method according to any one of claims 3 - 5.

7. The light absorption glass for a high-resolution and high-uniformity fiber image inverter according to claim 6, wherein The light-absorbing glass has strong and uniform light absorption ability and spectral absorption effect in the wavelength range of 510 - 660 nm at a thickness of 0.5 ± 0.01 mm, and the spectral transmittance ≤ 3.0%; the thermal expansion coefficient of the light-absorbing glass is (85 ± 5) × 10 -7 / ℃; it does not crystallize or phase-separate after being kept at 850 - 900 °C for 6 hours.

8. Application of the light absorption glass for a high-resolution and high-uniformity fiber image inverter according to claim 6 or 7 on a fiber image transmission element.

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