Lithium aluminosilicate glass and its preparation method and application

Abstract

The present invention discloses a lithium aluminum silicate glass, a preparation method and an application thereof. The preparation method of the lithium aluminum silicate glass comprises: using a solution for synthesizing copper whiskers to form a periodically distributed wire grid structure on a lithium aluminum silicate base glass, heating under a parallel electric field, and reducing. The method grows copper whiskers in situ on the surface of the base glass, utilizes the diffusion of alkali metal ions in the base glass to improve the adhesion of the copper whiskers to the glass surface, and directs and arranges the copper whiskers in an orderly manner through an auxiliary electric field combined with a temperature field. The method of the present invention can simplify the preparation process of polarized glass and solve the problem of limited size of polarized glass, thereby obtaining lithium aluminum silicate-based polarized glass of large size and excellent polarization performance.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium aluminosilicate glass, and in particular to lithium aluminosilicate glass and a preparation method and application thereof. Background Art

[0002] Light can be used as an information carrier, giving rise to optoelectronics and the booming development of optoelectronic information technology. Light as an information carrier will be a key driver of technological development, but simply having a high-performance light source is not enough; efficient light control components are also required. Optical polarizing glass, with its compact structure, stable performance, and excellent heat resistance, is an important material for manufacturing components that control the propagation of light. It has been widely used in fields such as optical displays, optical communications, and optical detection. With the unprecedented development of optoelectronic technology, these fields have placed increasing demands on polarization devices for excellent optical performance, low cost, large-scale production, and stable physical and chemical properties.

[0003] Traditional polarizing glass is a glass-based composite material composed of granular metal nanoparticles uniformly distributed in an oriented manner within a glass matrix. The key factors affecting the polarization performance of polarizing glass are the formation and orientation of the granules within the glass matrix. Currently, the most common method for preparing optical polarizing glass still follows the traditional manufacturing process, which involves crystallizing the melted metal-containing glass, then stretching or rolling it, and then reducing it in a strongly reducing atmosphere or through exposure to light to form the oriented, granular metal nanostructures.

[0004] However, the polarizing glass produced using this process is small, limiting its application to optical communications and other fields, failing to meet the requirements for applications such as three-dimensional displays and vehicle glare eliminators. Furthermore, the process is complex, the polarization effect is difficult to control, and the yield rate is low, seriously hindering the widespread application of polarizing glass. Therefore, there is an urgent need to research the production technology of large-scale polarizing glass. Summary of the Invention

[0005] In view of this, the main purpose of the present invention is to provide a lithium aluminum silicate glass and its preparation method and application. The technical problem to be solved is to break the limitations of existing process technology on the size of polarized glass, realize the production of large-size lithium aluminum silicate-based polarized glass above the meter level, while maintaining excellent optical properties, thereby meeting the industry development requirements for glass polarization performance.

[0006] The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions. According to the present invention, a method for preparing lithium aluminosilicate glass is proposed, which comprises:

[0007] A solution for synthesizing copper whiskers is used to form a periodically distributed wire grid structure on a lithium aluminum silicate base glass, which is then heated and reduced under a parallel electric field to obtain the lithium aluminum silicate glass.

[0008] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0009] Preferably, the method for preparing the lithium aluminosilicate glass comprises the following steps:

[0010] 1) preparing the solution for synthesizing copper whiskers by a soft template method;

[0011] 2) arranging a wire grid mold on the surface of the lithium aluminum silicate base glass;

[0012] 3) applying the solution on the surface of the glass provided with the wire grid mold;

[0013] 4) placing the glass obtained in step 3) in an oven with the parallel electric field and heating it;

[0014] 5) The glass obtained in step 4) is placed in a reducing atmosphere for reduction to obtain the lithium aluminosilicate glass.

[0015] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 2), the lithium aluminosilicate base glass contains alkali metal ions, and the content of the alkali metal ions is 5-20 wt%, based on the total weight of the lithium aluminosilicate base glass.

[0016] Preferably, in the above-mentioned method for preparing lithium aluminosilicate glass, in step 2), the alkali metal ions include Li + .

[0017] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 2), the alkali metal ions further include Na + , K + At least one of .

[0018] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 2), the period of the wire grid mold is 100-500 nm, and the width is 100-300 nm.

[0019] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 4), the parallel electric field is an electrostatic field parallel to the surface of the glass.

[0020] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 4), the electrostatic field strength of the parallel electric field loading is 500-800 V / mm, and the time is 30-60 min.

[0021] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 4), the heating temperature is 200-300° C. and the heating time is 30-60 min.

[0022] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 5), the reducing atmosphere comes from at least one of hydrogen and carbon monoxide or a mixture thereof with an inert gas.

[0023] Preferably, in the aforementioned method for preparing lithium aluminosilicate glass, in step 5), the pressure of the gas is 0.3-1.0 MPa, and the reduction time is 3-6 hours.

[0024] The purpose of the present invention and the solution to its technical problems are also achieved by adopting the following technical solutions. According to the present invention, a lithium aluminosilicate glass is provided, which comprises:

[0025] Lithium aluminosilicate based glass; and

[0026] Copper whiskers grown on the lithium aluminum silicate base glass have a periodically distributed wire grid structure.

[0027] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0028] Preferably, the aforementioned lithium aluminosilicate glass is prepared by any of the methods described above.

[0029] Preferably, the aforementioned lithium aluminosilicate glass, wherein the length and width of the lithium aluminosilicate glass are independently greater than 1 mm.

[0030] Preferably, the aforementioned lithium aluminosilicate glass has an extinction ratio of 60 dB or more and a transmittance of light in the wavelength range of 190-1100 nm of 76% or more.

[0031] The purpose of the present invention and the solution to its technical problems are also achieved by the following technical solutions: A polarization device proposed in the present invention includes a polarizer, an analyzer or an attenuator, wherein the polarizer, analyzer or attenuator comprises any of the above-mentioned lithium aluminosilicate glasses.

[0032] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0033] Preferably, the aforementioned polarization device is an optical isolator, an optical magnetic disk signal detection sensor, an optical voltage sensor, an optical fiber connector or a liquid crystal display.

[0034] By means of the above technical solution, the lithium aluminosilicate glass of the present invention and its preparation method and application have at least the following beneficial effects:

[0035] The method for preparing lithium aluminosilicate glass of the present invention first prepares a solution for synthesizing copper whiskers, then applies the solution to the glass surface with a wire grid mold, and then applies a parallel electric field and a temperature field. After reduction, copper whiskers with directional arrangement are grown in situ on the glass surface. This can greatly simplify the subsequent processing of the base glass, effectively reduce the complexity of the preparation, avoid the difficulties existing in the high-temperature stretching process of the glass, and shorten the process time. In addition, the alkali metal ions (such as Li + 、Na + , K + ) can diffuse into the copper whiskers, anchoring the whiskers to the glass surface and improving the adhesion of the copper whiskers to the glass surface, thereby achieving the preparation of lithium aluminum silicate-based polarizing glass with controllable polarization properties under low temperature conditions. In addition, by introducing directional metallic copper elements into the lithium aluminum silicate base glass through in-situ growth, the problem of introducing metallic copper elements during the preparation process of the base glass, which causes turbidity or coloration of the base glass, can also be avoided. In particular, this method can solve the problem of small size in the preparation of traditional polarizing glass, and can produce large-sized, highly polarizing lithium aluminum silicate glass, thereby greatly expanding the application field of lithium aluminum silicate glass.

[0036] The method for preparing lithium aluminosilicate glass of the present invention can use a soft template method to prepare a solution for synthesizing copper whiskers to in-situ grow copper whiskers on the glass surface. As a result, the aspect ratio of the copper whiskers can be adjusted by controlling the solution ratio. Plasmon resonance absorption is also used to enable the copper whiskers to selectively absorb light waves vibrating in different directions, wherein light waves vibrating parallel to the long axis are absorbed by the metal particles, while light waves vibrating perpendicular to the long axis are less strongly absorbed.

[0037] The preparation method of the lithium aluminum silicate glass described in the present invention can add an electrostatic field during the growth of copper whiskers. Compared with the temperature field, the control of the electrostatic field loading intensity and time is easier and more precise. Therefore, under the action of an auxiliary electric field parallel to the glass surface, the loaded electrostatic field can be used to control the arrangement of the copper whiskers on the glass surface, so that they form an ordered chain-like directional arrangement structure along the direction of the electric field. The size of the chain-like arrangement structure is adjusted by controlling the electric field intensity and loading time, thereby achieving a high degree of order and obtaining lithium aluminum silicate-based polarizing glass with a high extinction ratio.

[0038] The lithium aluminosilicate glass described in the present invention is not limited by the conventional polarizing glass manufacturing process and can be controlled within a wide range from a few millimeters to hundreds of meters. Its extinction ratio can reach more than 60dB, and its transmittance for light with a wavelength between 190-1100nm can reach more than 76%.

[0039] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention. DETAILED DESCRIPTION

[0040] To further illustrate the technical means and effectiveness of the present invention in achieving its intended objectives, the following describes in detail the specific implementations, structures, features, and effectiveness of the polarizing glass, its preparation method, and its applications according to the present invention, in conjunction with preferred embodiments. In the following description, different references to "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.

[0041] In the examples of the present invention, unless otherwise specified, the materials and reagents involved are commercially available products familiar to those skilled in the art; unless otherwise specified, the methods involved are methods well known in the art. Unless otherwise defined, the technical or scientific terms used shall have the same meaning as those of ordinary skill in the art to which this invention belongs.

[0042] The present invention provides a method for preparing lithium aluminosilicate glass, which comprises:

[0043] A solution for synthesizing copper whiskers is used to form a periodically distributed wire grid structure on a lithium aluminum silicate base glass, which is then heated and reduced under a parallel electric field to obtain the lithium aluminum silicate glass.

[0044] In the prior art, the preparation of polarized glass requires the introduction of metallic elements into the glass components beforehand, followed by a crystallization heat treatment after melting and forming, and finally a drawing process to form a structure containing rod-shaped silver nanoparticles with directional arrangement. However, the silver-containing polarized glass drawn using this technology suffers from problems such as uneven distribution of silver colloid particles, difficulty in controlling the particle size ratio and a wide range, resulting in a low extinction ratio, poor polarization performance, and a time-consuming and energy-intensive subsequent processing process. Furthermore, the resulting glass is small in size, typically only on the millimeter scale. In view of this, the present invention grows copper whiskers on a base glass without the introduction of metallic elements beforehand, using a soft template method, etc., to impart a plasma oscillation absorption effect to the glass. Furthermore, the lithium aluminum silicate base glass contains alkali metals. Since alkali metal ions are very active and easily mobile, they can diffuse into the copper whiskers and fill the gaps in the copper structure, thereby improving the bonding strength between the copper whiskers and the glass surface, thereby solving the problem of insufficient whisker adhesion to the glass surface. At the same time, the preparation process does not require a drawing process and does not impose any restrictions on the size of the glass. Therefore, meter-level polarized glass can be prepared under low-temperature conditions, thereby solving the problem of preparing large-size, high-polarization performance lithium aluminum silicate glass, and can meet the industry's development requirements for glass polarization performance.

[0045] In some embodiments, the method comprises the following steps:

[0046] 1) preparing the solution for synthesizing copper whiskers by a soft template method;

[0047] 2) arranging a wire grid mold on the surface of the lithium aluminum silicate base glass;

[0048] 3) applying the solution on the surface of the glass provided with the wire grid mold;

[0049] 4) placing the glass obtained in step 3) in an oven with the parallel electric field and heating it;

[0050] 5) The glass obtained in step 4) is placed in a reducing atmosphere for reduction to obtain the lithium aluminosilicate glass.

[0051] In step 1) of some embodiments, the solution for synthesizing copper whiskers is prepared by a soft template method. The soft template method can be implemented by the following steps: 1) dissolving 50-75g of copper sulfate, 100g of sodium hydroxide and 50g of polyvinylpyrrolidone in 100ml of a mixed solvent of deionized water and ethanol, and ultrasonicating for 10-15min; 2) adding 1-50g of a surfactant hexadecyltrimethylammonium bromide and stirring for 30-60min; 3) adding 40-80ml of hydrazine hydrate and continuing to stir for 30min to obtain a solution for synthesizing copper whiskers. In addition to the above method, the solution for synthesizing copper whiskers described in the present invention can also be prepared by other methods, as long as a copper whisker precursor solution suitable for the subsequent steps of the method described in the present invention can be obtained, and the present invention does not impose any special restrictions on this.

[0052] In step 2) of some embodiments, the lithium aluminum silicate base glass contains alkali metal ions, and the alkali metal ions include Li + , and may also include Na + , K + In the method of the present invention, the alkali metal ions (such as Li + 、Na + , K +) diffuses into the copper whiskers under a suitable temperature field, so that the copper whiskers are anchored to the glass surface, thereby improving the adhesion of the copper whiskers to the glass surface. The content of the alkali metal ions is 5-20wt%, based on the total weight of the lithium aluminum silicate base glass. If the content of alkali metal ions is lower than 5wt%, the anchoring effect of the alkali metal ions on the copper whiskers is not obvious, and the expected adhesion improvement effect cannot be achieved; if the content of alkali metal ions is higher than 20wt%, the thermal expansion coefficient of the glass will be increased, and the thermal stability, chemical stability and mechanical strength of the glass will be reduced. In this regard, the alkali metal ion content range described in the present invention can be applied to the composition of existing lithium aluminum silicate glass. Therefore, the method described in the present invention can be achieved by cleverly utilizing known conventional lithium aluminum silicate glass without specifically changing the content of alkali metal ions in the glass.

[0053] In step 2) of some embodiments, the alkali metal ions further include Na + , K + When two or three alkali metals are added to the glass, a mixed alkali effect is generated, which is beneficial for reducing the thermal expansion coefficient of the glass and improving the chemical stability.

[0054] In step 2) of some embodiments, the period of the wire grid mold is 100-500nm, and the width is 100-300nm. The purpose of setting the wire grid mold is to form a periodically distributed copper whisker body wire grid when the copper whiskers grow on the glass surface. Since copper is a metal material with high photostability, when light is irradiated on the copper whisker wire grid, the electrons in the wire grid can only move along the direction of the whiskers. The vibration direction of the light wave electric vector is parallel to the direction of the whiskers and will be absorbed by the electrons in the wire grid whiskers, while the vibration direction of the light wave electric vector is perpendicular to the direction of the whiskers and can pass through the lithium aluminum silicate glass. If the period of the wire grid mold is greater than 500nm or the width is less than 100nm, the copper whisker wire grid formed is too sparse and the polarization performance is low; if the period of the wire grid mold is less than 100nm or the width is greater than 300nm, the copper whisker wire grid formed is too dense, affecting the light transmittance of the glass.

[0055] In step 2) of some embodiments, the wire grid mold is covered on the surface of the lithium aluminosilicate base glass.

[0056] In step 4) of some embodiments, the parallel electric field is an electrostatic field parallel to the surface of the glass, and the electrostatic field strength of the parallel electric field loading is 500-800V / mm, and the time is 30-60min. Under the action of the electrostatic field parallel to the glass surface, the direction of growth and arrangement of the copper whiskers on the glass surface is controlled by loading the electrostatic field. If the electrostatic field strength is lower than 500V / mm, the copper whiskers in the glass cannot be arranged along the direction of the electric field; if the electrostatic field strength is higher than 800V / mm, the copper whiskers in the glass will agglomerate instead of forming an orderly arrangement, thereby failing to achieve a polarization effect. If the loading time is less than 30min, the copper whiskers do not have sufficient time to be oriented; if the loading time is greater than 60min, the copper whiskers have been arranged, and further increasing the time will result in energy waste.

[0057] In step 4) of some embodiments, the heating temperature is 200-300°C and the time is 30-60 minutes. The purpose of heating is to promote the formation of copper whiskers and remove ethanol in the solution so that the copper whiskers can be fixed on the glass surface. If the heating temperature is lower than 200°C, the temperature is too low to promote the growth of copper whiskers, and the ethanol volatilization rate is too slow. At the same time, the alkali metal ions (Li + 、Na + and K + ) is difficult to diffuse into the copper whiskers. If the heating temperature exceeds 300°C, the copper whiskers grow too quickly, affecting the expected aspect ratio, and the alkali metal ions diffuse too quickly, affecting the plasma oscillation effect of the copper whiskers. If the heating time is less than 30 minutes, the copper whiskers will not grow completely, the ethanol will not be completely removed, and the alkali metal ions will not diffuse sufficiently. If the heating time exceeds 60 minutes, the reaction is already complete, and further increase in heating time will result in energy waste.

[0058] In step 4) of some embodiments, the oven is a vacuum oven.

[0059] In step 5) of some embodiments, the reducing atmosphere is from at least one of hydrogen, carbon monoxide or a mixture thereof with an inert gas, the pressure of the gas is 0.3-1.0 MPa, and the reduction time is 3-6 hours. The whiskers synthesized by methods such as the soft template method are cuprous oxide whiskers, and the cuprous oxide whiskers are reduced to copper whiskers using a reducing gas. If the gas pressure is less than 0.3 MPa, the degree of reduction reaction is low, and the number of copper whiskers generated is small; if the gas pressure is greater than 1.0 MPa, the reduction reaction rate is too fast, and the copper whiskers grow too fast, affecting the reduction quality of the copper whiskers, while increasing the requirements for equipment and the preparation cost. If the reduction time is less than 3 hours, the copper whiskers are not completely reduced; if the reduction time is more than 6 hours, the reaction is complete, and continuing to increase the time will lead to reduced efficiency.

[0060] The present invention also provides a lithium aluminosilicate glass, which includes a lithium aluminosilicate base glass and copper whiskers grown on the lithium aluminosilicate base glass, wherein the copper whiskers have a periodically distributed wire grid structure.

[0061] In some embodiments, the lithium aluminosilicate glass is prepared by any of the methods described above.

[0062] In some embodiments, the lithium aluminosilicate glass has an extinction ratio of 60 dB or greater, and a transmittance of light in the wavelength range of 190-1100 nm of 76% or greater.

[0063] As previously mentioned, the lithium aluminosilicate glass preparation method of the present invention is performed by in-situ directional growth of copper whiskers on the surface of a lithium aluminosilicate base glass. Therefore, the lithium aluminosilicate glass prepared by this method is not subject to the glass size limitations of conventional polarizing glass manufacturing processes. In other words, because it allows the use of readily available base glass, the lithium aluminosilicate glass prepared by the method of the present invention can achieve a size comparable to that of the base glass, enabling the controllable preparation of polarizing glass with sizes ranging from millimeters to meters, or even hundreds of meters.

[0064] Therefore, the length and width of the lithium aluminosilicate glass of the present invention can be independently and controllably adjusted within a range of, for example, 0.1-100,000 mm. For example, the upper limits of the length and width of the lithium aluminosilicate glass include, but are not limited to, 100,000 mm, 80,000 mm, 50,000 mm, 30,000 mm, 10,000 mm, 8,000 mm, 5,000 mm, 3,000 mm, 1,000 mm, 800 mm, 500 mm, 300 mm, 100 mm, 800 mm, 500 mm, 300 mm, 100 mm, 80 mm, 50 mm, 30 mm, 10 mm, 80 mm, 50 mm, 30 mm, 10 mm, 8 mm, 5 mm, 3 mm, 1 mm, 0.8 mm, 0.5 mm, and 0.3 mm. mm; the lower limits of the length and width of the lithium aluminosilicate glass include but are not limited to 80000mm, 50000mm, 30000mm, 10000mm, 8000mm, 5000mm, 3000mm, 1000mm, 800mm, 500mm, 300mm, 100mm, 80mm, 50mm, 30mm, 10mm, 8mm, 5mm, 3mm, 1mm, 0.8mm, 0.5mm, 0.3mm and 0.1mm.

[0065] In addition, the thickness of the lithium aluminosilicate glass can be controllably adjusted within a range of, for example, 15-60 mm. For example, the upper limit of the thickness of the lithium aluminosilicate glass includes, but is not limited to, 60 mm, 55 mm, 50 mm, 45 mm, 40 mm, 35 mm, 30 mm, 25 mm, and 20 mm; the lower limit of the thickness of the lithium aluminosilicate glass includes, but is not limited to, 55 mm, 50 mm, 45 mm, 40 mm, 35 mm, 30 mm, 25 mm, 20 mm, and 15 mm.

[0066] In some embodiments, the length and width of the lithium aluminosilicate glass are independently greater than 1 mm.

[0067] In some specific embodiments, the dimensions of the lithium aluminosilicate glass are, for example, 1500 mm in length×1500 mm in width×(25-50) mm in thickness.

[0068] The present invention also provides a polarization device, which includes a polarizer, an analyzer or an attenuator, wherein the polarizer, the analyzer or the attenuator comprises any of the lithium aluminosilicate glasses described above.

[0069] In some embodiments, the polarization device is an optical isolator, an optical magnetic disk signal detection sensor, an optical voltage sensor, an optical fiber connector, a liquid crystal display, or the like. The optical isolator can be used in fields such as optical fiber communications and optical fiber sensing systems; the optical voltage sensor can be used in power system energy metering and relay protection; and the optical magnetic disk signal detection sensor can be used in power system high voltage and high current measurement or electronic anti-theft detectors.

[0070] The present invention will be further described below with reference to specific embodiments, but these embodiments should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0071] Extinction Ratio Test: A semiconductor laser beam of various wavelengths was collimated using a fiber collimator. This beam was then incident perpendicularly on the lithium aluminosilicate polarizing glass prepared in the following examples via a phase compensator and a Glan-Thompson prism. The lithium aluminosilicate polarizing glass was then rotated in a plane perpendicular to the optical axis. The minimum transmitted light intensity, P1, was first measured. The maximum transmitted light intensity, P2, was then measured by rotating the lithium aluminosilicate polarizing glass 90°. The extinction ratio was calculated using the formula: Extinction Ratio (dB) = -10Log(P1 / P2).

[0072] Transmittance test: test the luminous flux or luminous energy of the incident light after passing through the object, and compare the test value with the total luminous flux or luminous energy of the incident light itself to obtain the transmittance of the object. First, the luminous flux or luminous energy of the incident light is directly tested without passing through the sample to obtain reference light data; then the luminous flux or luminous energy of the incident light after passing through the object is tested to obtain test light data. Specifically, the incident light is irradiated on the lithium aluminum silicate-based polarizing glass prepared in each embodiment covering the light inlet, and the light after passing through each lithium aluminum silicate-based polarizing glass is collected, and then enters the detector through the detection port, and the detector is used to detect the outgoing light data, wherein the wavelength of the incident light used for the test is in the range of 190-1100nm.

[0073] The lithium aluminum silicate base glass used in the following embodiments and comparative examples has the following chemical composition: 62 wt% SiO2, 15 wt% Al2O3, 10 wt% Li2O, 5 wt% B2O3, 4 wt% Na2O, 3 wt% ZnO2 and 1 wt% Sb2O3.

[0074] Example 1

[0075] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 200°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminosilicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 62 dB and a light transmittance of 78% within the wavelength range of 190-1100 nm. The prepared lithium aluminosilicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0076] Example 2

[0077] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 75g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 200°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 64 dB and a light transmittance of 78% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0078] Example 3

[0079] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 500nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 200°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 61 dB and a light transmittance of 79% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0080] Example 4

[0081] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 100nm was attached to the surface of a lithium aluminosilicate base glass. The prepared solution was then coated onto the surface of the lithium aluminosilicate base glass with the wire grid mold attached. The glass was then heated at 300°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 60 dB and a light transmittance of 79% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0082] Example 5

[0083] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 300°C for 30 minutes in an oven with a parallel electric field strength of 800V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 66 dB and a light transmittance of 78% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0084] Example 6

[0085] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 300°C for 60 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 67 dB and a light transmittance of 77% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0086] Example 7

[0087] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 300°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 1.0MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminosilicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 64 dB and a light transmittance of 80% within the wavelength range of 190-1100 nm. The prepared lithium aluminosilicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0088] Example 8

[0089] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 300°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 1.0MPa for 6 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 64 dB and a light transmittance of 78% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0090] Example 9

[0091] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 300°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 6 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminum silicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, with an extinction ratio of 63 dB and a light transmittance of 79% within the wavelength range of 190-1100 nm. The prepared lithium aluminum silicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0092] Example 10

[0093] Copper sulfate, sodium hydroxide, and polyvinylpyrrolidone were weighed in a mass ratio of 50g:100g:50g and dissolved in 100ml of a 50:50 deionized water / ethanol mixture. Ultrasonication was then performed for 10 minutes. 20g of hexadecyltrimethylammonium bromide was added and stirred for 30 minutes. Then, 40ml of hydrazine hydrate was added and stirred for 30 minutes to prepare a solution for synthesizing copper whiskers. A wire grid mold with a period of 100nm and a width of 300nm was attached to a lithium aluminosilicate base glass surface. The prepared solution was then coated onto the lithium aluminosilicate base glass surface with the wire grid mold. The glass was then heated at 300°C for 30 minutes in an oven with a parallel electric field strength of 500V / mm. Finally, the glass was reduced in a hydrogen atmosphere at a gas pressure of 0.3MPa for 3 hours to obtain the lithium aluminosilicate polarizing glass. Tests showed that the prepared lithium aluminosilicate polarizing glass has dimensions of 1500 mm long, 1500 mm wide, and 50 mm thick, with an extinction ratio of 64 dB and a light transmittance of 76% within the wavelength range of 190-1100 nm. The prepared lithium aluminosilicate polarizing glass can be used in polarizers, analyzers, or attenuators in optical isolators.

[0094] Comparative Example 1

[0095] This comparative example differs from Example 1 in that no wire grid mold is attached to the lithium aluminosilicate base glass; otherwise, the same as Example 1 is used. Testing revealed that the prepared lithium aluminosilicate-based glass had dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, an extinction ratio of 19 dB, and a light transmittance of 68% within the 190-1100 nm wavelength range.

[0096] Comparative Example 2

[0097] This comparative example differs from Example 1 in that no parallel electric field is applied; otherwise, all other aspects are the same as Example 1. Testing revealed that the prepared lithium aluminosilicate glass had dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, an extinction ratio of 13 dB, and a light transmittance of 70% within the wavelength range of 190-1100 nm.

[0098] Comparative Example 3

[0099] This comparative example differs from Example 1 in that no heat treatment was performed; otherwise, all other aspects were the same as Example 1. Testing revealed that the prepared lithium aluminosilicate-based glass had dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, an extinction ratio of 31 dB, and a light transmittance of 71% within the wavelength range of 190-1100 nm.

[0100] Comparative Example 4

[0101] This comparative example differs from Example 1 in that no reduction treatment was performed; otherwise, all other aspects were the same as Example 1. Testing revealed that the prepared lithium aluminosilicate-based glass had dimensions of 1500 mm long, 1500 mm wide, and 25 mm thick, an extinction ratio of 34 dB, and a light transmittance of 72% within the wavelength range of 190-1100 nm.

[0102] It can be seen from the test data of the above embodiments 1-10 that the size of the lithium aluminum silicate-based polarizing glass prepared by the method of the present invention can reach a length of 1500 mm × a width of 1500 mm × a thickness of (20-50) mm, the extinction ratio can reach more than 60 dB, and the light transmittance in the wavelength range of 190-1100 nm can reach more than 76%.

[0103] From the test data of the above-mentioned comparative examples 1-4, it can be seen that in comparative example 1, no wire grid mold was attached, and the extinction ratio of the prepared lithium aluminum silicate-based glass was 19dB, and the light transmittance in the wavelength range of 190-1100nm was 68%. In comparative example 2, no parallel electric field was loaded, and the extinction ratio of the prepared lithium aluminum silicate-based glass was 13dB, and the light transmittance in the wavelength range of 190-1100nm was 70%. In comparative example 3, no heat treatment was performed, and the extinction ratio of the prepared lithium aluminum silicate-based glass was 31dB, and the light transmittance in the wavelength range of 190-1100nm was 71%. In comparative example 4, no reduction treatment was performed, and the extinction ratio of the prepared lithium aluminum silicate-based glass was 34dB, and the light transmittance in the wavelength range of 190-1100nm was 72%.

[0104] Compared to the aforementioned comparative examples, in the embodiments of the present invention (e.g., Example 1), after applying a solution for synthesizing copper whiskers onto a lithium aluminosilicate base glass with a wire grid mold, a combined heating, electric field, and reduction process was used to prepare lithium aluminosilicate polarizing glass. The resulting lithium aluminosilicate polarizing glass exhibited an extinction ratio of 62 dB and a light transmittance of 78% within the 190-1100 nm wavelength range, significantly improving its optical performance.

[0105] The technical features in the claims and / or the specification of the present invention may be combined, and the manner of combination is not limited to the combination obtained by reference in the claims. Technical solutions obtained by combining the technical features in the claims and / or the specification are also within the scope of protection of the present invention.

[0106] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention still falls within the scope of the technical solution of the present invention.

Claims

1. A method for preparing lithium aluminosilicate glass, characterized in that: include: Using a solution for synthesizing copper whiskers to form a periodically distributed wire grid structure on a lithium aluminum silicate base glass, heating and reducing the solution under a parallel electric field to obtain the lithium aluminum silicate glass; The specific steps include: 1) preparing the solution for synthesizing copper whiskers by a soft template method; 2) arranging a wire grid mold on the surface of the lithium aluminum silicate base glass; 3) applying the solution on the surface of the glass provided with the wire grid mold; 4) placing the glass obtained in step 3) in an oven with the parallel electric field and heating it; 5) The glass obtained in step 4) is placed in a reducing atmosphere for reduction to obtain the lithium aluminosilicate glass.

2. The method according to claim 1, characterized in that In step 2), the lithium aluminum silicate base glass contains alkali metal ions, and the content of the alkali metal ions is 5-20 wt %, based on the total weight of the lithium aluminum silicate base glass.

3. The method according to claim 2, characterized in that In step 2), the alkali metal ions include Li + .

4. The method according to claim 3, characterized in that In step 2), the alkali metal ions also include Na + , K + At least one of .

5. The method according to claim 1, characterized in that In step 2), the wire grid mold has a period of 100-500 nm and a width of 100-300 nm.

6. The method according to claim 1, wherein In step 4), the parallel electric field is an electrostatic field parallel to the surface of the glass, the electrostatic field strength of the parallel electric field is 500-800 V / mm, and the time is 30-60 min.

7. The method according to claim 1, characterized in that In step 4), the heating temperature is 200-300° C. and the heating time is 30-60 min.

8. The method according to claim 1, characterized in that In step 5), the reducing atmosphere is from at least one of hydrogen and carbon monoxide or a mixture thereof with an inert gas, the pressure of the gas is 0.3-1.0 MPa, and the reduction time is 3-6 h.

9. A lithium aluminosilicate glass, characterized in that: Prepared by the method according to any one of claims 1 to 8, comprising: Lithium aluminosilicate based glass; and Copper whiskers grown on the lithium aluminum silicate base glass have a periodically distributed wire grid structure.

10. The lithium aluminosilicate glass according to claim 9, characterized in that The length and width of the lithium aluminosilicate glass are independently greater than 1 mm.

11. The lithium aluminosilicate glass according to claim 9, characterized in that The lithium aluminosilicate glass has an extinction ratio of more than 60 dB and a transmittance of more than 76% for light in the wavelength range of 190-1100 nm.

12. A polarization device, characterized in that: It comprises a polarizer, an analyzer or an attenuator, wherein the polarizer, the analyzer or the attenuator comprises the lithium aluminosilicate glass according to any one of claims 9 to 11.

13. The polarization device according to claim 12, characterized in that: The polarization device is an optical isolator, an optical disk signal detection sensor, an optical voltage sensor, an optical fiber connector or a liquid crystal display.