High-strength and high-transmittance nano microcrystalline glass as well as preparation method and application thereof

Abstract

The invention relates to the technical field of microcrystalline glass, in particular to high-strength and high-transmittance nano microcrystalline glass and a preparation method and application thereof.The preparation method comprises the following steps that raw materials are placed in a crucible to be evenly mixed, melted and clarified, and molten glass liquid is obtained; forming the molten glass into a glass sheet, and cooling to obtain base glass; carrying out microstructure pretreatment on the basic glass, cleaning and drying; carrying out ion exchange strengthening on the pretreated base glass; and carrying out two-stage heat treatment on the reinforced glass to obtain the nano microcrystalline glass, the preparation method comprises the following steps: plating an anti-reflection film layer on nano-glass ceramics through magnetron sputtering to obtain high-transmittance nano-glass ceramics; and transferring the high-transmittance nano glass ceramics into a fluorocarbon silane solution, and forming an anti-fingerprint layer through fluorine chain interfacial polymerization to obtain the anti-fingerprint hydrophobic nano glass ceramics. The nano microcrystalline glass prepared by the invention has high strength and high light transmittance, and can meet the requirements of different industries.

Description

Technical Field

[0001] The present invention relates to the technical field of microcrystalline glass, and in particular to a high-strength, high-transmittance nano-microcrystalline glass and a preparation method and application thereof. Background Art

[0002] Amid the rapid development of optoelectronic displays, aerospace, and new energy, the market demand for advanced materials that combine high strength and high transmittance is becoming increasingly urgent. Traditional soda-lime glass, due to its brittleness and poor impact resistance, struggles to meet the requirements of flexible screens or ultra-thin devices. Furthermore, my country's long-standing reliance on imported high-performance optical glass materials presents the dual challenges of technological barriers and high costs.

[0003] Current research on optical glass focuses on balancing mechanical and optical properties through nanocrystalline phase regulation (such as β-quartz solid solution). However, existing processes generally have problems such as unstable grain size control and stress concentration caused by interface defects, which restrict its application in scenarios such as large-size ultra-thin cover plates (<0.5mm) and optical windows in extreme environments.

[0004] Therefore, there is a need for a preparation method and application of high-strength and high-transmittance nano-ceramic glass with stable grain size control. Summary of the Invention

[0005] The main purpose of the present invention is to provide a high-strength, high-transmittance nano-microcrystalline glass and its preparation method and application, aiming to solve the problems of unstable grain size control and stress concentration caused by interface defects in nano-microcrystalline glass in existing technical means.

[0006] To achieve the above objectives, the present invention provides a method for preparing high-strength and high-transmittance nano-glass-ceramics, which comprises the following steps:

[0007] The raw materials are placed in a crucible for uniform mixing, and the mixed raw materials are melted and clarified in the crucible to obtain molten glass liquid;

[0008] The molten glass liquid is formed into a glass sheet with a thickness of 0.3-1.2 mm by a casting method, a calendering method or an overflow down-draw method, and the temperature is reduced to 550°C to 600°C for heat preservation annealing to obtain a basic glass;

[0009] The base glass was transferred into a beaker containing a 10-15% HF solution, and the surface of the base glass was subjected to a microstructure pretreatment for 20-40 seconds. The pretreated base glass was ultrasonically cleaned in deionized water for 10 minutes and then dried.

[0010] The pretreated base glass is moved into a high-temperature mixed molten salt containing LiNO3 and AgNO3 for ion exchange strengthening;

[0011] The strengthened glass is moved to an oxidizing atmosphere for preheating, and then subjected to a two-stage heat treatment. The first stage is to heat up to the nucleation temperature and then keep the temperature. The second stage is to heat up to the crystallization temperature and then keep the temperature. The temperature is then cooled at a certain rate to 350℃~450℃ and kept at the temperature. Finally, it is cooled to room temperature to obtain nano-ceramic glass.

[0012] The nano-ceramic glass is coated with an anti-reflection film layer by magnetron sputtering to obtain a high-transmittance nano-ceramic glass;

[0013] The highly transparent nano-microcrystalline glass is moved into a fluorocarbon silane solution, and then an anti-fingerprint layer is formed through the interfacial polymerization of fluorine chains to obtain an anti-fingerprint hydrophobic nano-microcrystalline glass.

[0014] Furthermore, the melting temperature is 1550°C to 1650°C, the melting time is 2 to 4 hours, the clarification temperature is 1600°C to 1700°C, and the clarification time is 1 to 2 hours.

[0015] Furthermore, the cooling rate is 3-5°C / min, and the holding time is 1-2h.

[0016] Furthermore, the temperature of the high-temperature mixed molten salt containing LiNO3 and AgNO3 is 350°C to 450°C, the exchange time is 4 to 12 hours, and the depth of the ion exchange layer is 20 to 50 μm.

[0017] Furthermore, in the two-stage heat treatment, the preheating temperature is 300°C~400°C, the heating rate of the first stage is 3~5°C / min, the nucleation temperature is 640°C~720°C, the nucleation holding time is 2~4h, the heating rate of the second stage is 3~5°C / min, the crystallization temperature is 760°C~800°C, the crystallization holding time is 0.5~2h, and the cooling rate is 3~5°C / min.

[0018] Furthermore, the grain size of the nano-glass-ceramics is 50-70 nm.

[0019] Furthermore, the anti-reflection film layer is a multilayer film formed by alternating deposition of SiO2 and Si3N4, with a total number of layers of 7-10 and a single layer thickness of 80-200 nm.

[0020] Furthermore, the reaction temperature of the fluorocarbon silane solution is 80-150° C., the reaction time is 10-60 minutes, and an anti-fingerprint layer with a thickness of 1-10 nm is formed, and the water contact angle is ≥110°.

[0021] To achieve the above objectives, the present invention also provides a high-strength, high-transmittance nano-ceramic glass prepared by the above preparation method.

[0022] Furthermore, the present invention also proposes the application of the high-strength, high-transmittance nano-ceramic glass in the field of mobile phone flat glass cover plates.

[0023] The present invention adopts a technical solution of sequentially performing surface microstructuring pretreatment, ion exchange strengthening, two-stage heat treatment under an oxidizing atmosphere, and a coating process to achieve etching of nano-scale concave-convex structures on the glass surface, increase the depth of the ion exchange layer, increase the assembly density, and avoid the precipitation of Ag particles during the exchange process that causes the glass to turn yellow and affect the transmittance of the glass, thereby solving the problems of low surface crystallinity, coarse grains, insufficient strength and transmittance of nano-microcrystalline glass in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the processes shown in these drawings without paying any creative work.

[0025] Figure 1 A schematic flow chart of the method for preparing the high-strength and high-transmittance nano-glass-ceramics provided by the present invention;

[0026] Figure 2 This is an SEM image of the uncoated nano-glass-ceramics provided in comparative example 5 of the present invention. DETAILED DESCRIPTION

[0027] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0028] It should be noted that all directional indications (such as up, down, left, right, front, back, etc.) in the embodiments of the present invention are only used to explain the relative position relationship, movement status, etc. between the various components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0029] In addition, the descriptions of "first", "second", etc. in the present invention are for descriptive purposes only and should not be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of such features. In addition, the technical solutions between the various embodiments can be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in this field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0030] In the traditional direct ion exchange process, ions diffuse only through the "planar interface" of the glass surface. The exchange efficiency is limited to the single surface contact area, and the ion concentration gradient shows a simple distribution of "monotonically decreasing from the surface to the inside". In order to increase the ion exchange area, the present invention uses surface microstructure pretreatment to make the glass surface before ion exchange evenly distributed with nano-concave and convex structures, thereby increasing the contact area of ​​ion exchange, providing more reaction sites for ion exchange, increasing the embedding depth of ions in subsequent ion exchange, and improving the compressive stress on the glass surface and thus improving the drop resistance.

[0031] It is understandable that ion exchange and oxidizing atmosphere cooperate with the medium to achieve a systematic improvement in the performance of glass materials through multi-dimensional coupling of composition regulation, crystal nucleus activation and stress strengthening. + Replacement of Na on the glass surface + / K + On the one hand, the surface composition is adjusted to the lithium-rich area to reduce the crystal activation energy; on the other hand, the lithium-rich area on the surface precipitates β-spodumene with a very low thermal expansion coefficient after subsequent heat treatment, while the interior is composed of components with a higher thermal expansion coefficient. This difference causes the outer layer of the glass to shrink less and the inner layer to shrink more during the cooling process, thus forming a compressive stress layer on the surface of the glass with a depth of up to 20~50μm. At the same time, the introduced Ag + Oxidation reaction occurs in an oxidizing atmosphere (Ag + →AgO), is converted into a nano-scale crystal nucleating agent, which increases the density of crystal nuclei on the glass surface and increases the surface compressive stress.

[0032] The oxidizing atmosphere involved in the present invention has an oxygen concentration of 21-90 vol% and an oxygen flow rate of 5-20 L / min.

[0033] Based on this, an embodiment of the present application provides a high-strength, high-transmittance nano-ceramic glass, the components of which, by mass percentage, include: SiO2 57%~64%, Al2O3 14%~21%, Na2O 10%~18%, MgO 3%~7%, K2O0.5%~1.5%, and TiO2 1%~2%.

[0034] The present invention also proposes a method for preparing high-strength and high-transmittance nano-ceramic glass. Figure 1 As shown, the steps of the preparation method are as follows:

[0035] Step S10, placing the raw materials in a crucible for uniform mixing, and melting and clarifying the mixed raw materials in the crucible to obtain molten glass;

[0036] Step S20, forming the molten glass into a glass sheet with a thickness of 0.3-1.2 mm by a casting method, a rolling method or an overflow down-draw method, and cooling the molten glass to 550° C. to 600° C. for heat preservation annealing to obtain a base glass;

[0037] Step S30, moving the base glass into a beaker filled with a 10-15% HF solution, performing a microstructure pretreatment on the surface of the base glass for 20-40 seconds, ultrasonically cleaning the pretreated base glass in deionized water for 10 minutes, and then drying;

[0038] Step S40, moving the pretreated base glass into a high-temperature mixed molten salt containing LiNO3 and AgNO3 for ion exchange strengthening;

[0039] Step S50: The strengthened glass is moved to an oxidizing atmosphere for preheating. After preheating, a two-stage heat treatment is performed. The first stage is heating to the nucleation temperature and then holding the temperature. The second stage is heating to the crystallization temperature and then holding the temperature. The temperature is then cooled at a certain rate to 350°C to 450°C and then held. Finally, the temperature is cooled to room temperature to obtain nano-ceramic glass.

[0040] Step S60, coating the nano-ceramic glass with an anti-reflection film by magnetron sputtering to obtain a high-transmittance nano-ceramic glass;

[0041] In step S70 , the highly transparent nano-ceramic glass is moved into a fluorocarbon silane solution, and then an anti-fingerprint layer is formed by interfacial polymerization of fluorine chains to obtain an anti-fingerprint hydrophobic nano-ceramic glass.

[0042] Specifically, during the two-step heat treatment process described above, the nucleation stage, at low temperatures, promotes the uniform precipitation of nanoscale nuclei within the glass matrix. These nanocrystal nuclei act as "strengthening particles" and are evenly distributed throughout the glass. The crystallization stage, at high temperatures, controls the directional growth of the crystals into nanoscale grains. These nanoscale grains are significantly smaller than the wavelength of visible light, thus preventing light scattering and improving the transmittance of the nano-ceramic glass. Furthermore, when the glass is subjected to external forces, the fine, uniform nanocrystal network forms an "interlocking structure," hindering crack propagation and enhancing the glass's strength.

[0043] In more detail, the surface of the nano-crystalline glass prepared by the present invention is coated with 7 to 10 layers of AR film (Anti-Reflective Film) with a single layer thickness of 80 to 200 nm. The thickness of the film is controlled to 1 / 4 of the wavelength of the incident light. Destructive interference occurs to greatly reduce the intensity of the reflected light, thereby enhancing the transmittance of the nano-crystalline glass. In addition, the AR film itself has high hardness and wear resistance. The alternating coating of multiple layers of SiO2 and Si3N4 films can be tightly combined with the nano-crystalline glass substrate, reducing damage to the glass surface and the expansion of cracks.

[0044] The present invention further discloses the following six groups of embodiments and five groups of comparative embodiments. The specific implementation of each embodiment is as follows:

[0045] Example 1

[0046] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0047] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch, after etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, the strengthened glass is ultrasonically cleaned again, ultrasonically cleaned and dried, and then placed in a platinum crucible and placed in a high-temperature furnace, and passed through High-purity nitrogen was added for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 h for preheating treatment. Subsequently, the temperature was raised to 680 ° C at a rate of 3 ° C / min for nucleation, and the nucleation was kept warm for 4 h. The temperature was then raised to 780 ° C at a rate of 5 ° C / min for crystallization, and the crystallization was kept warm for 1 h. Finally, the temperature was lowered to 400 ° C at a rate of 5 ° C / min and kept warm for 1 h. Then, it was cooled to room temperature to obtain nano-ceramic glass.

[0048] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0049] Example 2:

[0050] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0051] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch, after etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, the strengthened glass is ultrasonically cleaned again, ultrasonically cleaned and dried, and then placed in a platinum crucible and placed in a high-temperature furnace, and passed through High-purity nitrogen was added for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 hours for preheating treatment. Subsequently, the temperature was raised to 660 ° C at a rate of 3 ° C / min for nucleation, and the nucleation was kept warm for 4 hours. Then the temperature was raised to 780 ° C at a rate of 5 ° C / min for crystallization, and the crystallization was kept warm for 1 hour. Finally, the temperature was lowered to 400 ° C at a rate of 5 ° C / min and kept warm for 1 hour. Then, it was cooled to room temperature to obtain nano-microcrystalline glass.

[0052] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0053] It can be seen that Example 2 lowers the nucleation temperature compared to Example 1.

[0054] Example 3:

[0055] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0056] Step S2, preparation of nano-microcrystalline glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 35°C for etching for 30 seconds. After etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, and the strengthened glass is ultrasonically cleaned again. After ultrasonic cleaning and drying, it is placed in a platinum crucible and then placed in a high-temperature furnace, and passed through High-purity nitrogen was added for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 hours for preheating treatment. Subsequently, the temperature was raised to 700 ° C at a rate of 3 ° C / min for nucleation, and the nucleation was kept warm for 4 hours. Then the temperature was raised to 780 ° C at a rate of 5 ° C / min for crystallization, and the crystallization was kept warm for 1 hour. Finally, the temperature was lowered to 400 ° C at a rate of 5 ° C / min and kept warm for 1 hour. Then, it was cooled to room temperature to obtain nano-ceramic glass.

[0057] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0058] It can be seen that Example 3 further improves the nucleation temperature compared with Example 2 and Example 1.

[0059] Example 4:

[0060] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0061] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch, after etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, the strengthened glass is ultrasonically cleaned again, ultrasonically cleaned and dried, and then placed in a platinum crucible and placed in a high-temperature furnace, and passed through High-purity nitrogen was added for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 h for preheating treatment. Subsequently, the temperature was raised to 680 ° C at a rate of 3 ° C / min for nucleation, and the nucleation was kept warm for 2 h. The temperature was then raised to 780 ° C at a rate of 5 ° C / min for crystallization, and the crystallization was kept warm for 2 h. Finally, the temperature was lowered to 400 ° C at a rate of 5 ° C / min and kept warm for 1 h. Then, it was cooled to room temperature to obtain nano-ceramic glass.

[0062] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0063] It can be seen that Example 4 shortens the crystallization time compared with Example 1.

[0064] Example 5:

[0065] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0066] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch, after etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, the strengthened glass is ultrasonically cleaned again, ultrasonically cleaned and dried, and then placed in a platinum crucible and placed in a high-temperature furnace, and passed through High-purity nitrogen was added for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 hours for preheating treatment. Subsequently, the temperature was raised to 680 ° C at a rate of 3 ° C / min for nucleation, and the nucleation was kept warm for 4 hours. Then the temperature was raised to 760 ° C at a rate of 5 ° C / min for crystallization, and the crystallization was kept warm for 1 hour. Finally, the temperature was lowered to 400 ° C at a rate of 5 ° C / min and kept warm for 1 hour. Then, it was cooled to room temperature to obtain nano-ceramic glass.

[0067] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0068] It can be seen that Example 5 has a lower crystallization temperature than Example 1.

[0069] Example 6:

[0070] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0071] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch, after etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, the strengthened glass is ultrasonically cleaned again, and after ultrasonic cleaning and drying, it is placed in a platinum crucible and then placed in a high-temperature furnace, and then heated to 400°C. High-purity nitrogen was introduced for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 hours for preheating treatment, and then the temperature was raised to 680 ° C at 5 ° C / min for nucleation, and the nucleation was kept warm for 4 hours. Then the temperature was raised to 780 ° C at 5 ° C / min for crystallization, and the crystallization was kept warm for 1 hour. Finally, the temperature was lowered to 400 ° C at a cooling rate of 5 ° C / min and kept warm for 1 hour, and then cooled to room temperature to obtain nano-ceramic glass.

[0072] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0073] It can be seen that Example 6 improves the nucleation heating rate compared with Example 1.

[0074] Comparative Example 1:

[0075] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0076] Step S2, preparation of nano-microcrystalline glass: place the base glass in a platinum crucible and then place it in a high-temperature furnace, introduce high-purity nitrogen for 10 minutes to expel the air in the furnace, and then adjust the gas to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stabilize the ventilation for 5 minutes before heating to 300°C and keeping it warm for 0.5 hours for preheating treatment. Subsequently, heat it to 680°C at 3°C / min for nucleation, keep it warm for 4 hours, and then heat it to 780°C at 5°C / min for crystallization, keep it warm for 1 hour, and finally cool it to 400°C at a cooling rate of 5°C / min and keep it warm for 1 hour, and then cool it to room temperature to obtain nano-microcrystalline glass.

[0077] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0078] It can be seen that compared with Example 1, Control Example 1 lacks surface microstructure pretreatment and ion exchange strengthening treatment.

[0079] Comparative Example 2:

[0080] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0081] Step S2, preparation of nano-microcrystalline glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for etching for 20 seconds. After etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, and the strengthened glass is ultrasonically cleaned again. After ultrasonic cleaning and drying, it is placed in a platinum crucible and then placed in a high-temperature furnace, heated to 300°C and kept warm for 0.5h for preheat treatment, and then heated to 680°C at 3°C / min for nucleation, kept warm for 4h, and then heated to 780°C at 5°C / min for crystallization, kept warm for 1h, and finally cooled to 400°C at a cooling rate of 5°C / min and kept warm for 1h, and then cooled to room temperature to obtain nano-microcrystalline glass.

[0082] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0083] It can be seen that, compared with Example 1, in Comparative Example 2, there is no oxidizing atmosphere treatment in the heat treatment step.

[0084] Comparative Example 3:

[0085] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0086] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch. After etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, and the strengthened glass is ultrasonically cleaned again. After ultrasonic cleaning and drying, it is placed on a platinum plate. The gold crucible was then placed in a high-temperature furnace, and high-purity nitrogen was introduced for 10 minutes to expel the air in the furnace. The gas was then adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol% and an oxygen flow rate of 10 L / min. After stable ventilation for 5 minutes, the temperature was raised to 300°C and kept warm for 0.5 hours for preheating treatment. Subsequently, the temperature was raised to 680°C at a rate of 3°C / min for heat treatment and kept warm for 5 hours. Finally, the temperature was lowered to 400°C at a rate of 5°C / min and kept warm for 1 hour, and then cooled to room temperature to obtain nano-crystalline glass.

[0087] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0088] It can be seen that, compared with Example 1, in the heat treatment step of Control Example 3, one-step heat treatment is used instead of two-step heat treatment.

[0089] Comparative Example 4:

[0090] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0091] Step S2, preparation of nano-microcrystalline glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for etching for 20 seconds. After etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, and the strengthened glass is ultrasonically cleaned again. After ultrasonic cleaning and drying, it is placed in a platinum crucible and then placed in a high-temperature furnace, and high-purity nitrogen is introduced for 10 minutes to discharge the air in the furnace, and then the gas is adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and after stable ventilation for 5 minutes, the temperature is raised to 680°C at 3°C / min for nucleation, and the nucleation is kept warm for 4 hours, and then the temperature is raised to 780°C at 5°C / min for crystallization, and the crystallization is kept warm for 1 hour, and finally cooled to room temperature to obtain nano-microcrystalline glass.

[0092] Step S3, coating process: the prepared nano-microcrystalline glass is cleaned with ultrasonic wave, and a total of 7 layers of SiO2 and Si3N4 films with a thickness of 80nm are alternately coated by magnetron sputtering to obtain anti-reflective nano-microcrystalline glass, and then the anti-reflective nano-microcrystalline glass is immersed in a 100°C fluorocarbon silane solution to react for 1h to form a 1nm anti-fingerprint layer.

[0093] It can be seen that, compared with Example 1, Control Example 4 does not have a pre-burning treatment before the heat treatment and does not have an annealing and heat-holding treatment after the heat treatment.

[0094] Comparative Example 5:

[0095] Step S1, preparation of basic glass: weigh raw materials in the following proportions, calculated by mass fraction percentage: SiO2 62%, Al2O3 17%, Na2O 14%, MgO 5%, K2O 1%, and TiO2 1%, with a total mass of 200 g of raw materials. After mixing the raw materials evenly, put them into a platinum crucible and place them in a high-temperature furnace, heat them to 800°C and preheat them for 1 hour; after preheating, put them into a melting furnace and heat them to 1600°C to melt them into glass liquid, and keep them at this temperature for 3 hours, stirring them twice (5 minutes each time); then heat them to 1650°C to clarify them, keep them at this temperature for 1.5 hours, and remove bubbles; form the glass liquid into a glass substrate with a thickness of 1 mm by using a casting method, a calendering method, or an overflow down-draw method, and then cool them to 600°C at a rate of 3°C / min and anneal them at this temperature for 2 hours to obtain basic glass.

[0096] Step S2, preparation of nano-crystal glass: immerse the base glass in a beaker filled with HF solution, and place the beaker in a constant temperature water bath at 25°C for 20 seconds to etch, after etching, move the base glass into deionized water for ultrasonic cleaning for 10 minutes, and then dry it after ultrasonic cleaning for 10 minutes to complete the pretreatment; the pretreated base glass is immersed in a mixed molten salt containing LiNO3 and AgNO3 at 370°C for ion exchange strengthening, the strengthened glass is ultrasonically cleaned again, ultrasonically cleaned and dried, and then placed in a platinum crucible and placed in a high-temperature furnace, and passed through High-purity nitrogen was added for 10 minutes to expel the air in the furnace, and then the gas was adjusted to an oxygen-nitrogen mixed gas with an oxygen concentration of 50 vol%, an oxygen flow rate of 10 L / min, and stable ventilation was carried out for 5 minutes. The temperature was raised to 300 ° C and kept warm for 0.5 h for preheating treatment. Subsequently, the temperature was raised to 680 ° C at a rate of 3 ° C / min for nucleation, and the nucleation was kept warm for 4 h. The temperature was then raised to 780 ° C at a rate of 5 ° C / min for crystallization, and the crystallization was kept warm for 1 h. Finally, the temperature was lowered to 400 ° C at a rate of 5 ° C / min and kept warm for 1 h. Then, it was cooled to room temperature to obtain nano-ceramic glass.

[0097] It can be seen that, compared with Example 1, Control Example 5 does not have a coating process.

[0098] The present invention also discloses performance tests, which are as follows:

[0099] The present invention performs performance tests on the nano-ceramic glass obtained in the above examples and comparative examples. The surface compressive stress is tested using a surface stress tester. The impact resistance height of each example product when struck by a steel ball weighing 55g and 20mm in diameter is measured using a drop ball tester. The average value of the nine points is taken as the drop resistance height of the sample glass. The light transmittance of the glass in the range of 400-750nm is measured using a spectrophotometer. The specific results are shown in the following table:

[0100] surface Properties of the nano-ceramic glass prepared in each embodiment and comparative example

[0101] Group Surface compressive stress / MPa Drop ball height / cm Transmittance / % Example 1 977.56 176 92.42 Example 2 966.18 169 91.76 Example 3 970.54 167 90.81 Example 4 962.98 155 90.47 Example 5 969.14 151 90.36 Example 6 971.65 153 90.11 Comparative Example 1 767.75 129 90.18 Comparative Example 2 805.84 144 89.15 Comparative Example 3 807.89 148 87.26 Comparative Example 4 814.79 130 89.14 Comparative Example 5 756.48 124 88.45

[0102] Surface compressive stress refers to the compressive stress generated on the glass surface due to ion exchange. It is a core indicator of ion exchange strengthening. Surface compressive stress can offset externally applied tensile stress (such as stress generated by impact and friction) and slow the growth of microcracks. The higher the surface compressive stress, the greater the glass's ability to resist surface damage.

[0103] Specifically, the performance test results of the nano-ceramic glass provided in Examples 1, 2, 3, and 5 show that the optimal nucleation temperature and optimal crystallization temperature of the prepared base glass are around 680°C and 780°C, respectively. The performance test results of the nano-ceramic glass provided in Examples 1, 4, and 6 show that shortening the nucleation time and extending the crystallization time reduce the light transmittance of the glass: from 91.42% to 90.47%, and from 91.42% to 90.11%, respectively, and also reduce the surface compressive stress and drop resistance.

[0104] From the comparison of the performance test results of the nano-ceramic glass provided by Examples 1-6 and Comparative Examples 1-4, it can be seen that the surface compressive stress and drop resistance of the nano-ceramic glass of Examples 1-6 are stronger, and the light transmittance is also improved, which shows that the preheating process, surface microstructuring pretreatment, ion strengthening (Li + With Ag + ), two-step heat treatment and annealing treatment in an oxidizing atmosphere can comprehensively improve the surface compressive stress, drop resistance and transmittance of nano-microcrystalline glass, and significantly improve the performance of nano-microcrystalline glass.

[0105] In summary, compared with the traditional single ion exchange or one-step heat treatment process, the present invention uses surface microstructure pretreatment, dual ion exchange (Li + / Ag + The performance of nano-ceramic glass is improved by the synergistic mechanism of synergistic replacement), preheating (300-400℃ / 0.5-2h), and two-step heat treatment in an oxidizing atmosphere (nucleation 640-720℃ / 2-4h, crystallization 760-800℃ / 0.5-2h). Preheating promotes the opening of ion diffusion channels by reducing the viscosity of the glass, making Li + / Ag + The replacement is more uniform and, at the same time, the residual stress after ion exchange is reduced.

[0106] In the present invention, reference is made to Figure 2 As shown, Figure 2The SEM image of the uncoated nano-microcrystalline glass provided in one embodiment of the present invention clearly shows that the uncoated nano-microcrystalline glass has the following significant defects: decreased strength, local stress concentration will occur at the edges of the pores when subjected to force, and the generated cracks will initiate and expand from the pores; poor wear resistance: the pores are easy to harbor dirt and become "weak areas" when worn, accelerating surface damage; decreased corrosion resistance: corrosive media (such as water, acid and alkali) can penetrate into the interior through the pores, destroying the crystal phase-glass phase structure, etc.

[0107] The present invention constructs a lithium-rich layer on the glass surface through ion exchange, preferentially induces lithium disilicate crystallization, and forms a gradient structure of large surface grains and fine internal grains. In an oxidizing atmosphere, Ag + Oxidized to high-valent Ag 2+ (By Ag + The nanocrystalline glass undergoes a two-step heat treatment, including preheat treatment, surface microstructure pretreatment, double ion exchange, and oxidation atmosphere treatment. The surface compressive stress, drop strength, and light transmittance of the nanocrystalline glass are significantly higher than those of the nanocrystalline glass treated with a single ion exchange treatment, and are also higher than those of the nanocrystalline glass treated with only a single heat treatment.

[0108] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformation made by using the contents of the present description and drawings under the inventive concept of the present invention, or directly / indirectly applied in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. A method for preparing high-strength and high-transmittance nano-glass-ceramics, characterized in that: The following steps are involved: The raw materials are placed in a crucible for uniform mixing, and the mixed raw materials are melted and clarified in the crucible to obtain molten glass liquid; The molten glass liquid is formed into a glass sheet with a thickness of 0.3-1.2 mm by a casting method, a calendering method or an overflow down-draw method, and the temperature is reduced to 550°C to 600°C for heat preservation annealing to obtain a basic glass; The base glass was transferred into a beaker containing a 10-15% HF solution, and the surface of the base glass was subjected to a microstructure pretreatment for 20-40 seconds. The pretreated base glass was ultrasonically cleaned in deionized water for 10 minutes and then dried. The pretreated base glass is moved into a high-temperature mixed molten salt containing LiNO3 and AgNO3 for ion exchange strengthening; The strengthened glass is moved to an oxidizing atmosphere for preheating, and then subjected to a two-stage heat treatment. The first stage is to heat up to the nucleation temperature and then keep the temperature. The second stage is to heat up to the crystallization temperature and then keep the temperature. The temperature is then cooled at a certain rate to 350℃~450℃ and kept at the temperature. Finally, it is cooled to room temperature to obtain nano-ceramic glass. The nano-ceramic glass is coated with an anti-reflection film layer by magnetron sputtering to obtain a high-transmittance nano-ceramic glass; The highly transparent nano-microcrystalline glass is moved into a fluorocarbon silane solution, and then an anti-fingerprint layer is formed through the interfacial polymerization of fluorine chains to obtain an anti-fingerprint hydrophobic nano-microcrystalline glass.

2. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: The melting temperature is 1550° C. to 1650° C., the melting time is 2 to 4 hours, the clarification temperature is 1600° C. to 1700° C., and the clarification time is 1 to 2 hours.

3. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: The cooling rate is 3-5°C / min, and the holding time is 1-2h.

4. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: The temperature of the high-temperature mixed molten salt containing LiNO3 and AgNO3 is 350°C to 450°C, the exchange time is 4 to 12 hours, and the depth of the ion exchange layer is 20 to 50 μm.

5. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: In the two-stage heat treatment, the preheating temperature is 300°C~400°C, the heating rate of the first stage is 3~5°C / min, the nucleation temperature is 640°C~720°C, the nucleation holding time is 2~4h, the heating rate of the second stage is 3~5°C / min, the crystallization temperature is 760°C~800°C, the crystallization holding time is 0.5~2h, and the cooling rate is 3~5°C / min.

6. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: The grain size of the nano-ceramic glass is 50-70 nm.

7. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: The anti-reflection film layer is a multilayer film formed by alternating deposition of SiO2 and Si3N4, with a total number of 7-10 layers and a single layer thickness of 80-200 nm.

8. The method for preparing high-strength and high-transmittance nano-glass-ceramics according to claim 1, wherein: The reaction temperature of the fluorocarbon silane solution is 80-150° C., the reaction time is 10-60 minutes, and an anti-fingerprint layer with a thickness of 1-10 nm is formed, and the water contact angle is ≥110°.

9. The high-strength, high-transmittance nano-ceramic glass prepared by the preparation method according to any one of claims 1 to 8.

10. Application of the high-strength, high-transmittance nano-ceramic glass as claimed in claim 9 in the field of mobile phone flat glass cover plates.

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