High-strength, highly transparent nanocrystalline glass, preparation method therefor, and use thereof

Abstract

A high-strength, highly transparent nanocrystalline glass, a preparation method therefor, and a use thereof. The high-strength, highly transparent nanocrystalline glass uses precursor minerals mainly comprising synthetic aluminum-rich feldspar-like ceramic glass material, β-spodumene material, cordierite material, synthetic β-dicalcium silicate material, and magnesium aluminum spinel material for the main body of a feldspar-like matrix glass having a stable structure. Ultrafine zirconia powder having a particle size of less than 10 nm is used as a nucleating agent and microcrack damping and pinning agent, to control the formation of nanocrystals smaller than 100 nm in the glass body formed after melting. The volume percentage content of the nanocrystals is 50%-95%, and the nanocrystals together with the matrix glass form a high-strength, highly transparent nanocrystalline glass having a uniform microstructure. The obtained nanocrystalline glass has high hardness, high fracture toughness and high light transmittance, and is suitable for manufacturing various types of optical glass.

Description

High-strength and high-transparency nano-ceramic glass and its preparation method and application Technical Field

[0001] The present invention belongs to the field of material technology and relates to a high-strength and high-transparency nano-ceramic glass and a preparation method and application thereof. Background Art

[0002] As smartphone applications expand, performance requirements are also increasing. In particular, requirements for the hardness, strength, fracture toughness, light transmittance, and corrosion resistance of smartphone panels are becoming increasingly stringent. For example, the cover or back glass of electronic devices such as 5G phones must not only have the excellent light transmittance of optical glass (i.e., a transmittance of ≥90%), but also possess relatively high fracture toughness, surface hardness, and corrosion resistance. However, the touch panel glass currently used in mobile phones and other PDA displays has a low surface hardness, is easily abraded, and easily scratched. It also has poor fracture toughness, resulting in panel cracking when the phone is dropped from less than 1 meter, and its drop resistance is insufficient, affecting normal use. Furthermore, it has poor surface corrosion resistance, making the panel susceptible to sweat erosion and fogging when the phone is frequently held in the hand, affecting both light transmission performance and aesthetics.

[0003] Summary of the Invention

[0004] The technical problem addressed by this invention is to address the aforementioned shortcomings of existing glass materials by providing a high-strength, highly transparent nano-glass-ceramics, its preparation method, and its application. The resulting nano-glass-ceramics exhibit high transmittance, mechanical strength, surface hardness, fracture toughness, corrosion resistance, a transmittance of ≥90%, and a low thermal expansion coefficient. They can be widely used in the manufacture of optical glass, including mobile phone covers and back panels, cover glass for high-end electronic products, windshields and side windows for high-speed trains and aircraft, and window glass for high-end instruments and equipment.

[0005] The technical solution adopted to solve the technical problem of the present invention is:

[0006] In one aspect, the present invention provides a high-strength and high-transparency nano-microcrystalline glass, which uses a synthetic aluminum-rich feldspar ceramic glass material, β-spodumene or β-spodumene solid solution material, cordierite material, synthetic β-dicalcium silicate material, i.e., synthetic β-Ca2SiO4, and magnesium-aluminum spinel material as precursor mineral materials with a structurally stable feldspar matrix glass as the main body, and uses zirconium oxide micropowder with a particle size of less than 10nm (or yttria-stabilized zirconia micropowder, such as 3-10nm zirconium oxide micropowder or 3-10nm yttria-stabilized zirconia micropowder) as a crystal nucleating agent and microcrack damping pinning agent to control the generation of nano-crystals less than 100nm in the glass body formed after melting, wherein the volume percentage of the nano-crystals is 50%-95%, and they co-exist with the matrix glass to form a high-strength and high-transparency nano-microcrystalline glass with uniform microstructure.

[0007] The synthetic aluminum-rich feldspar ceramic glass material refers to a ceramic glass material made from synthetic aluminum-rich feldspar minerals. The feldspar minerals described in the present invention include orthoclase, plagioclase (which is further divided into albite, oligoclase, andesine, labradorite, calcite, and anorthite), and their feldspar-like minerals and various variants (such as orthoclase variants of sanudite and potassium microcline). The feldspar-like minerals include analcime, cancrinite, leucite, nepheline, cesium garnet, scapolite, calcite, calcite, and sodalite, all of which are alkaline aluminum silicate minerals. The aluminum-rich feldspar minerals refer to minerals such as calcium feldspar, barium feldspar, and lithium feldspar, whose aluminum oxide (Al2O3) content exceeds the aluminum oxide (Al2O3) content in normal sodium feldspar. In order to increase the aluminum oxide (Al2O3) content in feldspar minerals, the value of X in K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2 is synthetically adjusted to be 1.1≤X≤2.4 and the value of Y is 2≤Y≤6 (which can make the silicon dioxide content lower than the normal content in feldspar minerals), even if the aluminum oxide (Al2O3) content exceeds the normal sodium feldspar mineral content, it becomes a synthetic aluminum-rich feldspar mineral.

[0008] The controlled melting and post-molding glass body generates nanocrystals smaller than 100 nm and the mass percentage of the nanocrystals accounts for 50%-95%, which is mainly achieved by adding zirconium oxide powder smaller than 10 nm (or 3-10 nm yttria-stabilized zirconium oxide powder) as a crystal nucleating agent, while strictly controlling the nucleation temperature and time, crystallization temperature and time of the microcrystalline glass to obtain nanocrystals with the required grain fineness and amount of crystallites.

[0009] Preferably, the chemical formula of the synthetic aluminum-rich feldspar ceramic glass material is K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, 1.1≤X≤2.4, Y=2-6, which represents a composite ceramic glass material of one or two or more of synthetic aluminum-rich potassium feldspar, synthetic aluminum-rich sodium feldspar, synthetic aluminum-rich lithium feldspar, synthetic aluminum-rich calcium feldspar, and synthetic aluminum-rich barium feldspar.

[0010] Among them, the two or more types of synthetic aluminum-rich feldspar composite ceramic glass materials at least include synthetic aluminum-rich sodium feldspar composite ceramic glass material.

[0011] Preferably, the synthetic β-dicalcium silicate material is prepared by determining the amounts of limestone or calcite or calcium oxide and quartz in the synthetic raw materials based on the theoretical weight ratio of CaO to SiO2 in the wollastonite molecular formula CaOSiO2. The two raw materials are uniformly mixed and calcined at a calcination temperature of 1320-1360°C to obtain synthetic wollastonite, i.e., CaSiO3. The synthesized CaSiO3 is then ground into a powder with a mineralizer of 0.5-1.5% by mole of CaSiO3, and the powder is calcined at 1280-1320°C to obtain a stable synthetic β-dicalcium silicate material, i.e., β-Ca2SiO4 or β-2CaOSiO2.

[0012] Preferably, the high-strength and high-transparency nano-glass-ceramics is mainly composed of mineral raw materials and also includes quartz powder and glass melting clarifier. The content of each raw material component is as follows in percentage by mass:

[0013] Wherein: the synthetic β-dicalcium silicate is β-2CaO.SiO2, namely β-Ca2SiO4, and β-Ca2SiO4 is a toughening agent that can improve the toughness strength of nano-ceramic glass and overcome its brittleness.

[0014] Preferably, the chemical composition of the high-strength and high-transparency nano-ceramic glass comprises, by mass percentage:

[0015] It is further preferred that, according to the chemical formula of the synthetic aluminum-rich feldspar ceramic glass material R2O / ROXAl2O3YSiO2, 1.1≤X≤2.4, Y=2-6, when R2O is K2O / Na2O / Li2O, Y≤6, when RO is CaO / BaO, Y≥2, when both R2O / RO corresponding feldspar are present, Y=2-6, and the corresponding potassium / sodium / lithium / calcium / barium feldspar refined raw materials are used in proportion (after removing iron and impurities, the iron content is less than 10ppm), and Alumina powder equivalent to 10%-140% of the Al2O3 content in the feldspar raw material is added to prepare the ingredients, which are crushed and ground evenly to 300-1000 mesh, and then subjected to calcination and thermal synthesis; or corresponding potassium / sodium / lithium / calcium / barium carbonate chemical raw materials, 300-1000 mesh alumina powder equivalent to 110%-240% of the Al2O3 content in the feldspar raw material, and 300-1000 mesh high-purity quartz powder are used to prepare the ingredients, which are stirred evenly and subjected to calcination and thermal synthesis to obtain the synthetic aluminum-rich feldspar ceramic glass material.

[0016] Preferably, the synthetic alumina-rich feldspar ceramic glass material contains both K2O and Li2O, then the content of K2O+Li2O is 2-6% (in the synthetic alumina-rich feldspar ceramic glass material), K2O:Li2O=4-5:1 or 1:4-5, forming a mixed alkali effect, which is beneficial to lowering the melting temperature and improving chemical stability.

[0017] Preferably, when the synthetic aluminum-rich feldspar ceramic glass material is a sodium pyroxene aluminum-rich feldspar ceramic glass material of Na2OXAl2O32SiO2, in order to improve the strength, the raw materials also include 0.2-0.5% of rare earth or rare metal oxides that do not color the glass, such as oxides of metals such as niobium, scandium, gallium, lanthanum, yttrium, and hafnium.

[0018] Preferably, the raw materials used also include yttria Y2O3 as a stabilizer for the zirconia ultrafine powder, with the amount used being zirconia:yttria = 90-95:5-10, or yttria-stabilized zirconia raw material powder (having the same ratio of zirconia:yttria = 90-95:5-10) is directly used instead of zirconia fine powder. When yttria-stabilized zirconia returns to a low temperature such as room temperature after being subjected to high temperatures (above 1173°C), the stable phase of zirconia remains a tetragonal phase, and no crystal phase transition occurs, thereby maintaining volume stability. The yttria-stabilized zirconia raw material is commercially available. In order to prevent the agglomeration of zirconium oxide powder with a particle size of less than 10nm or yttria-stabilized zirconia raw materials of 3-10nm, graphene oxide dispersant is added to zirconium oxide at a ratio of 1:3 (i.e., the amount of graphene oxide dispersant is 3 times the amount of zirconium oxide). After ball milling, the mixture is added to the glass batch and ball milled together, so that the zirconium oxide powder with a particle size of less than 10nm will not agglomerate in the glass batch but can be dispersed and evenly distributed.

[0019] Preferably, the raw materials used also include boron phosphate BO4P as a network strengthening raw material, accounting for 0-5% by mass percentage, which can introduce P2O5 component. Boron phosphate BO4P can use commercially available raw materials.

[0020] Preferably, the raw materials also include phosphates: the phosphates used are calcium zirconium phosphate CaZr(PO4)2 and calcium phosphate Ca3(PO4)2, and the content of CaZr(PO4)2+Ca3(PO4)2 is 0-5%, CaZr(PO4)2:Ca3(PO4)2 = 5:1 - 2:1, which can improve stability and strength.

[0021] Preferably, the β-spodumene raw material or β-spodumene solid solution is based on the theoretical mass ratio of Li2O, Al2O3 and SiO2 in the β-spodumene chemical formula Li2OAl2O3nSiO2, n = 4-8 (when n = 4, it is β-spodumene, when 4 < n ≤ 8, it is β-spodumene solid solution). The precursor raw material Li2O source uses LiCO3, the alumina source uses alumina powder, and the SiO2 source uses high-purity quartz powder, and it is synthesized by sintering at a firing temperature of 1300°C - 1390°C, or β-spodumene is directly obtained by calcining spodumene concentrate powder at 1300°C;

[0022] The cordierite material is based on the theoretical mass ratio of MgO, Al2O3 and SiO2 in the cordierite chemical formula 2MgO2Al2O35SiO2. The precursor raw material MgO source uses talc concentrate powder or MgO analytical pure chemical raw material, the alumina source uses alumina powder, and the SiO2 source uses high-purity quartz powder, and it is synthesized by sintering at 1300°C - 1400°C.

[0023] Preferably, the nano-crystals include aluminosilicate nano-crystals, β-spodumene nano-crystals or β-spodumene solid solution nano-crystals, cordierite nano-crystals, β-dicalcium silicate nano-crystals, magnesium aluminate spinel nano-crystals, mullite nano-crystals (the aluminous part reacts with part of SiO2 and quartz in the corresponding feldspar to form mullite), zirconia nano-crystals or zirconia / yttrium oxide solid solution nano-crystals (with yttrium oxide Y2O3 as a stabilizer).

[0024] More preferably, the volume percentage content of each of the above nano-crystals in the total nano-crystals is:

[0025] Furthermore, it also includes diopside nano-crystals (formed by aluminous and β-dicalcium silicate) 0.5% - 2%, and the magnesium aluminate spinel nano-crystals include composite magnesium aluminate spinel nano-crystals such as ROMgOAl2O3 spinel nano-crystals, and RO is CaO and / or BaO, etc.

[0026] Among them, the aluminum-rich feldspar nanocrystals are the main crystal phase of the nano-crystalline glass, and the high-strength feldspar matrix glass skeleton provides the basis for the high strength of the nano-crystalline glass. The number of the feldspar nanocrystals accounts for more than 50% of the total crystals, and the aluminum-rich feldspar nanocrystals are continuous with the residual glass phase components, and the refractive index is close to the same, so that the nano-crystalline glass has a high transmittance in the visible light region; β-spodumene nanocrystals or β-spodumene solid solution nanocrystals and cordierite nanocrystals in the nano-crystalline glass have the dual effect of reducing the thermal expansion coefficient of the crystal glass, thereby improving thermal stability and thermal shock resistance; the synthetic β-dicalcrystals are ring-shaped The microcrystals are combined with aluminum-rich feldspar nanocrystals to form interlocking, producing synergistic effects and greatly improving the fracture toughness of nano-microcrystalline glass and strengthening the surface hardness of aluminum-rich feldspar nanocrystals; the effect of magnesium-aluminum spinel nanocrystals is good thermal shock resistance and high high-temperature compressive strength; mullite nanocrystals improve the hardness and impact strength of nano-microcrystalline glass, good thermal shock resistance and high chemical stability, zirconium oxide or zirconium oxide / yttrium oxide solid solution nanocrystals can improve toughness, can pin and rivet the microcracks in the glass and the grain boundaries and prevent their expansion, and at the same time have toughening effect on β-dicalcrystals. The two have synergistic effects and effects.

[0027] Among them, the aluminum-rich feldspar nanocrystals include one or two or more mixed crystals of aluminum-rich potassium feldspar nanocrystals, aluminum-rich sodium feldspar nanocrystals, aluminum-rich lithium feldspar nanocrystals, aluminum-rich calcium feldspar nanocrystals, and aluminum-rich barium feldspar nanocrystals, forming a framework-like long-chain structure in the nanocrystalline glass, and synthesizing β-dicalcrystals β-2CaO.SiO2 as ring-shaped structure buckles, so that one or more long-chain aluminum-rich feldspar nanocrystals are surrounded and buckled by β-dicalcrystals to form locked crystals. The locked crystals are also surrounded and buckled by β-2CaO.SiO2 nanocrystals through the long-chain structure of aluminum-rich feldspar nanocrystals, forming a three-dimensional locked crystal space structure, strengthening the framework-like main crystal phase, and zirconia nanocrystals or zirconia / yttrium oxide solid solution nanocrystals pin and rivet the glass microcracks, greatly improving the fracture toughness.

[0028] Preferably, the content of K2O+Na2O+BaO is 6-14%, wherein:

[0029] When the aluminum-rich feldspar nanocrystals are mainly aluminum-rich potassium feldspar nanocrystals,

[0030] K2O 4%-9%, Na2O 2%-7%, BaO 0-2%

[0031] When the aluminum-rich feldspar nanocrystals are mainly aluminum-rich sodium feldspar nanocrystals,

[0032] K2O 0.85%-4%, Na2O 6%-12%, BaO 0%-1%,

[0033] When the aluminum-rich feldspar nanocrystals contain aluminum-rich celsius nanocrystals,

[0034] BaO 2%-6%, K2O 0.85%-2%, Na2O 6%-10%

[0035] It is further preferred that when the aluminum-rich feldspar nanocrystals further contain aluminum-rich lithium feldspar nanocrystals,

[0036] Li2O 2%-5%, Na2O 6%-9%, K2O 0.85%-3% BaO 0%-2%

[0037] When the aluminum-rich feldspar nanocrystals described above also contain aluminum-rich calcium feldspar nanocrystals,

[0038] CaO 2%-5%, Na2O 6%-9%, K2O 0.85%-3% BaO 0-2%.

[0039] Preferably, the magnesium-aluminum spinel raw material comprises synthetic composite magnesium-aluminum spinel.

[0040] It is further preferred that the synthesized composite magnesium-aluminum spinel includes different metal oxides in addition to magnesium-aluminum spinel, which respectively react with aluminum oxide at the synthesis temperature to form a composite spinel crystal structure. The different metal oxides include calcium oxide and barium oxide, which can respectively generate calcium-aluminum spinel and barium-aluminum spinel, as well as one or two or more of these spinels, at least including barium-aluminum spinel (barium-aluminum spinel is beneficial for reducing the synthesis temperature for forming spinel, reducing the synthesis temperature to 1260°C-1360°C) and magnesium-aluminum spinel to form a composite magnesium-aluminum spinel.

[0041] The raw material used for glass melting clarifier is Sb2O5 as clarifier.

[0042] Preferably, the high-strength and high-transparency nano-ceramic glass undergoes one or two chemical strengthenings, with a Mohs hardness of 6.0-8.0 before strengthening and 7.0-9.0 after strengthening, and a fracture toughness of 4.8-8 MPa m before strengthening. 1 / 2 , after strengthening 10-12MPam 1 / 2 , light transmittance 91%-96%, ring-on-ring strength: 0.4mm thick glass plate, 3200Mpa after strengthening, 0.6mm thick glass plate, 5600Mpa after strengthening, that is, the ring-on-ring strength after strengthening is 3200MPa-5600MPa.

[0043] A second aspect of the present invention provides a method for preparing high-strength and high-transparency nano-ceramic glass, comprising:

[0044] Preparation of synthetic raw materials: synthesizing the raw materials in accordance with the above-mentioned ratio of synthetic raw materials in the high-strength and high-transparency nano-glass-ceramics to obtain the corresponding synthetic mineral materials;

[0045] Formula batching: batch the synthetic materials with other raw materials according to the formula ratio requirements;

[0046] Processing and mixing: crush the raw materials to the required fineness, such as 200-300 mesh, mix and evenly mix to obtain dry powder glass raw material batch;

[0047] Melting molding: Add the dry powder batch material into the glass melting (melting) equipment, melt, clarify, and homogenize it, and use appropriate molding methods according to product requirements;

[0048] Nucleation and crystallization: The formed glass products are nucleated at the nucleation temperature, and then crystallized by controlling the temperature and time to control the grain growth to the required fineness of nano-crystals and micro-crystals;

[0049] Annealing: Anneal the crystallized product to eliminate the thermal stress in the glass to obtain high-strength and high-transparency nano-ceramic glass products.

[0050] Preferably, the method further comprises: performing a strengthening treatment after further molding the nano-glass-ceramic product to obtain a desired structure.

[0051] It is further preferred that the strengthening of the nano-ceramic glass product includes physical strengthening or chemical strengthening.

[0052] The chemical strengthening is a single chemical strengthening or a double chemical strengthening, and the depth of the surface compressive stress layer generated by ion exchange after strengthening is 20-120 μm. For example, the depth of the surface compressive stress layer of a 0.4-0.6 mm thick thin transparent nano-ceramic glass after chemical strengthening is 120 μm.

[0053] The secondary chemical strengthening is a secondary step ion exchange strengthening, and its approach is that the primary strengthening is Na + →Li + (Sodium ions replace lithium ions, and heat preservation at 380℃-420℃ molten salt liquid temperature for 6-10 hours), secondary strengthening is K + →Na + (Potassium ions replace sodium ions and keep the temperature of molten salt solution at 470℃-500℃ for 8-15 hours), thereby greatly improving the mechanical strength of glass microcrystals.

[0054] The synthetic raw materials mentioned above include: synthetic aluminum-rich feldspar glass-ceramic materials, synthetic β-dicalcium silicate, synthetic (composite) magnesium-aluminum spinel materials, synthetic cordierite, or synthetic β-spodumene or β-spodumene solid solution (if necessary).

[0055] Preferably, the dry powder batch material is added to the glass melting equipment during the fusion molding process by adding the dry powder batch material to a sagger for melting glass (i.e., in the case of nano-glass-ceramics produced using a sagger in-situ growth method, the dry powder batch material is loaded into the sagger and the glass is produced in an oxidizing atmosphere or an oxidizing-reducing atmosphere, or in the case of colored backplane nano-glass-ceramics produced in an oxidizing atmosphere), and the sagger is placed in a high-temperature furnace in an oxidizing atmosphere or an oxidizing-reducing atmosphere for melting, clarification, and homogenization. The thermal expansion coefficient of the sagger used should be substantially consistent with that of the matrix glass.

[0056] Further preferably, the sagger is a magnesium aluminum spinel sagger or an α-corundum-mullite sagger or an α-corundum-quartz glass sagger.

[0057] Further preferably, the magnesia-alumina-spinel sagger is a synthetic composite magnesia-alumina-spinel sagger.

[0058] Preferably, the nucleation crystallization adopts an in-situ growth method, that is, the glass is formed directly by shaping the shape of the sagger, and the sagger together with the glass in the sagger is directly nucleated and crystallized in a kiln and then annealed to obtain transparent nano-ceramic glass.

[0059] More preferably, the transparent nano-glass-ceramics obtained by the in-situ nucleation and crystallization method are separated from the sagger, and further formed and processed to obtain the desired structural parts, and then strengthened. The cut sagger waste and glass-ceramics waste are recycled as secondary materials.

[0060] Preferably, in the melt molding, the dry powder batch material is added into a glass melting furnace for melting, clarifying and homogenizing, and the molding is performed by using a casting method, a calendering method or an overflow method.

[0061] Preferably, the melting (processing) temperature is 1500-1600°C, and the clarifying temperature is 1550-1600°C. That is, the melting and clarifying are heating the dry powder batch material to 1500-1600°C for melting for 2-8 hours, and clarifying at 1550-1600°C for 2-6 hours.

[0062] Preferably, the nucleation crystallization process is performed at a temperature of 600°C-650°C for 2-4 hours, and at a crystallization temperature of 650°C-750°C for 2-6 hours. Strict control of the nucleation crystallization temperature and time is required to achieve a nanocrystallite fineness below 100 nanometers, a majority of crystallites between 10-30 nm, and a nanocrystallite content between 50% and 95%.

[0063] Preferably, the annealing temperature is 500°C to 550°C, the heating rate is no more than 0.5°C / min, the annealing holding time is 1-4 hours, and the cooling rate from the annealing holding temperature to room temperature is 0.2°C to 0.4°C / min.

[0064] Preferably, before the nucleation and crystallization, the formed glass product is pre-annealed, wherein the temperature of the glass product is first raised to 650°C-750°C and held at this temperature for 2-5 hours, then the temperature is lowered to 550°C-600°C at a rate of 0.2°C-0.3°C / min for the pre-annealing, the pre-annealing holding time being 2-3 hours, then the temperature is lowered to 500°C at a rate of 0.2°C-0.3°C / min and held at this temperature for 2-3 hours, then the temperature is raised to the nucleation temperature at a rate of no more than 0.5°C / min, and the subsequent nucleation, crystallization and annealing are performed.

[0065] The third aspect of the present invention provides an application of high-strength and high-transparency nano-microcrystalline glass. The high-strength and high-transparency nano-microcrystalline glass is used to make various optical glasses, including mobile phone covers and back panels, cameras, cover glass of high-end electronic products, and high-speed trains, aircraft windshields and side window glass, high-end instrument and equipment window glass, vehicle-mounted control screens, quantum radar panels, etc.

[0066] The high-strength and high-transparency nano-ceramic glass of the present invention meets the following technical performance indicators: Drop height test: a glass piece with a length and width of 5X5cm and a thickness of 0.5mm does not break when dropped vertically from a height of 2.5 meters; fracture toughness: 5-8MPa before strengthening 1 / 2 , after strengthening 10-12MPam 1 / 2 Hardness: Mohs hardness before strengthening 7-8, Mohs hardness after strengthening 8-9, Optical properties: 1. Refractive index: 1.51-1.53; 2. Visible light transmittance 90% ≤ <95%; 3. Haze: <0.1%. Mechanical properties include: 1. Poisson's ratio: 0.21-0.23; 2. Young's modulus after strengthening: 11.5-14.1Mpsi; 3. Vickers hardness before strengthening ≥660kgf / mm 2 , after strengthening, Vickers hardness ≥780kgf / mm 2; 4. The bending strength before strengthening is greater than 550MPa, the bending strength after strengthening is greater than 800Mpa, and the ring-on-ring strength after strengthening (glass plate thickness 0.4-0.6mm) is 3200Mpa-5000Mpa. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] FIG1 is a microstructure diagram of the high-strength and high-transparency nano-ceramics glass-ceramics manufactured in Preparation Example 8 in Table 2 of Example 1 of the present invention, obtained by a 20KV transmission electron microscope at 1.2 million times magnification (a microstructure diagram of the transparent nano-ceramics glass-ceramics after chemical strengthening);

[0068] Figure 2 X-ray diffraction pattern of preparation example 15 of nano-glass crystals in Table 2 Example 1. DETAILED DESCRIPTION

[0069] To further illustrate the technical means and effects of the present invention, the following is a detailed description with reference to the preferred embodiments of the present invention and the accompanying drawings.

[0070] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the embodiments described are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without making creative efforts shall fall within the scope of protection of this application.

[0071] In the description of this application, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more features. In the description of this application, "plurality" means two or more, unless otherwise specifically defined.

[0072] In this application, the word "exemplary" is used to mean "serving as an example, illustration, or illustration." Any embodiment described in this application as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. The following description is given to enable any person skilled in the art to implement and use the present application. In the following description, details are listed for the purpose of explanation. It should be understood that one of ordinary skill in the art can recognize that the present application can be implemented without using these specific details. In other instances, well-known structures and processes are not elaborated in detail to avoid obscuring the description of the present application with unnecessary details. Therefore, the present application is not intended to be limited to the embodiments shown, but is consistent with the widest scope consistent with the principles and features disclosed in this application.

[0073] To produce glass-ceramics with high strength, excellent light transmittance, and high chemical stability, a high-strength matrix glass system must be selected. This invention utilizes feldspar minerals with high Al₂O₃ content as the matrix glass system. Feldspar-based glass melted at 1500°C-1600°C is inherently transparent and possesses high strength and hardness, primarily due to the high Al₂O₃ content in the feldspar. Glass-ceramics, also known as ceramic glass, are a hard, dense, and uniform composite material composed of crystalline phases and glass, produced by microcrystallization of matrix glass. Clearly, producing glass-ceramics with feldspar as the matrix will yield even greater strength and hardness. By incorporating other technical measures into the microcrystallization process, glass-ceramics with feldspar as the matrix can be made transparent. The present invention uses feldspar-based glass raw materials as a hard template material for crystallization, and further increases the amount of Al2O3 to improve glass strength. To make the glass-ceramics transparent, the crystallite size is smaller than the wavelength of visible light (360nm-950nm), even if the crystallite size reaches the nanometer level. To achieve higher levels of transmittance, such as visible light transmittance greater than 90%, the crystallite size must be controlled within the nanometer range of less than 100 nanometers. The refractive index of the glass matrix, nanocrystals, and solid solution must be substantially uniform, and the crystallite content must reach 50%-95% to achieve high strength. The resulting glass-ceramics is a nano-crystalline transparent glass with high strength, high hardness, and high transparency.

[0074] Based on this, the present invention 1. synthesizes aluminum-rich feldspar glass-ceramic materials by strengthening the Al2O3 content in feldspar mineral raw materials, forming a synthetic aluminum-rich feldspar glass-ceramic material with a chemical formula of K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, 1.1≤X≤2.4, Y=2-6, that is, alumina powder equivalent to 10%-140% by mass of the Al2O3 content in feldspar is combined with the corresponding feldspar raw materials to synthesize aluminum-rich feldspar to form a network frame glass, which can also be formed according to the chemical formula (K2O / Na2O / Li2 O / CaO / BaO)XAl2O32SiO2 uses corresponding chemical raw materials to synthesize aluminum-rich feldspar, and melts the corresponding synthetic aluminum-rich feldspar into a network frame glass, which is a typical hard basic glass with good chemical stability; 2. As a preferred example, a synthetic aluminum-rich feldspar ceramic glass material: a nepheline (crystallized nepheline) symbiotic with aluminum-rich sodium potassium feldspar matrix glass, small nano-sized ultrafine crystallites, and a composite material with "near-range order and long-range uniformity" and high transparency, with a Mohs hardness of 7-8 and a fracture toughness of 5-8MPam 1 / 2; 3. In the above-mentioned network frame microcrystalline glass structure space, there are also "ring-shaped" microcrystals of synthetic β-dicalcrystals to reinforce the frame-shaped main crystal phase; 4. In order to prevent the expansion of glass microcracks under external force, nano ZrO2 / Y2O3 (yttria-stabilized zirconia solid solution) and MgAlO4-stabilized grains with a size of less than 10 nanometers are introduced for pinning and riveting to form a toughening solid solution. Nano ZrO2 with a size of less than 10 nanometers also acts as a crystal nucleating agent and is uniformly and continuously distributed in the network frame glass body. In situ nucleation and growth are achieved, with fast nucleation and a short time for the nucleus to grow into nano-scale crystals, which is easy to control (by controlling the nucleation temperature and time, the crystallization temperature and time). 5. To improve the thermodynamic stability of the glass-ceramics, nanocrystalline solid solutions formed from β-spodumene and cordierite and / or nanocrystalline solid solutions formed from lithium feldspar and cordierite are introduced, resulting in a low thermal expansion coefficient and mitigating thermal shock vibrations. 6. A small amount of phosphates, such as tricalcium phosphate (Ca3(PO4)2) and boron phosphate (BO4P), are introduced into the exemplary sodium alumina-potassium feldspar glass with a low-interruption R2O composition to effectively activate the migration and flow of the glass solution, ensuring the material properties (fluidity and molding viscosity) of the glass after clarification in a temperature range of 1550°C-1600°C.

[0075] 7. The present invention uses the following synthetic materials:

[0076] ①Synthetic β-dicalcium silicate material

[0077] ②β-spodumene (solid solution) materials, cordierite materials

[0078] ③ Composite magnesium aluminum spinel material

[0079] ④Synthetic aluminum-rich feldspar materials

[0080] ⑤Yttria-stabilized zirconia material

[0081] 8. The innovative in-situ growth production method for high-strength, high-transparency nano-glass-ceramics employs a magnesia-alumina spinel sagger, a α-corundum-mullite sagger, or a α-corundum-quartz glass sagger. This method is fully applicable to the commercial production of high-end optical glass-ceramics and multi-colored glass-ceramics cover plates.

[0082] 9. The transparent nano-microcrystalline glass of the present invention is a high-strength and high-transparency nano-microcrystalline glass with a feldspar mineral matrix material as a mineral template; 10. In order to achieve chemical strengthening, sodium feldspar (or nepheline) minerals are used as the necessary raw materials for synthesizing aluminum-rich feldspar ceramic glass materials (or synthesized using precursor chemical raw materials for preparing sodium feldspar or nepheline), so that the obtained transparent nano-microcrystalline glass can be subjected to secondary step ion exchange strengthening. + →Li + (sodium replaces lithium) and K + →Na+ (potassium replaces sodium); 11. In order to achieve high strength, the following technical means are mainly adopted: (1) The basic matrix glass is feldspar glass, (2) The microcrystals in the microcrystalline glass are nano-microcrystals below 100nm, and the microcrystal content is 50%-95%; (3) Reducing microcracks: The in-situ growth method of the box body greatly reduces the amount of bubbles in the glass liquid after clarification, and the microcracks are greatly reduced. At the same time, the use of nano ZrO2 / Y2O3 and MgAlO4 spinel stable grains below 10 nanometers can pin and rivet the microcracks to form a toughening solid solution, preventing the glass from cracking. The expansion of microcracks in the glass body greatly improves the mechanical strength; (4) Synthetic β-dicalcrystals with a ring-shaped structure form locked crystals, and the aluminum-rich feldspar nanocrystals with a long-chain structure are surrounded and locked by synthetic β-dicalcrystals, which are linked together to strengthen the continuous spatial frame structure. The surface layer is like a carpet-like dense woven structure (as shown in Figure 1), and the fracture toughness is greatly improved; (5) The influence of magnesium-aluminum (or composite magnesium-aluminum) spinel materials on strength (6) Chemical strengthening: The depth of the surface compressive stress layer generated by ion exchange after strengthening is 20-120μm. Chemical strengthening is a secondary step ion exchange strengthening, and its path is that the primary strengthening is Na + →Li + , the secondary reinforcement is K + →Na +, thereby significantly improving the mechanical strength of the glass microcrystals. 12. In order to achieve nano-crystals below 100nm in nano-crystal glass, the following technical means are adopted: zirconium oxide powder with a particle size of less than 10nm is used as a nucleating agent. In order to ensure that the zirconium oxide powder with a particle size of less than 10nm is evenly, continuously and densely dispersed and does not agglomerate, yttrium oxide Y2O3 is added as a stabilizer for zirconium oxide. At the same time, a dispersant is added to prevent the agglomeration of zirconium oxide powder with a particle size of less than 10nm or yttrium oxide stabilized zirconium oxide raw materials of 3-10nm. Graphene oxide dispersant is added in a ratio of 1:3 to zirconium oxide (i.e., the amount of graphene oxide dispersant is 3 times the amount of zirconium oxide). After ball milling and mixing evenly, it is added to the glass batch and ball milled together to mix evenly, so that the zirconium oxide powder with a particle size of less than 10nm does not agglomerate in the glass batch but can be dispersed and evenly distributed. It ensures that zirconium oxide powder less than 10nm is uniformly and continuously dispersed in the glass raw material batch with synthetic aluminum-rich feldspar ceramic glass material as the main raw material, and easily generates uniform, continuous and densely dispersed crystal nuclei in the glass body after melt forming and annealing; then, at the temperature of crystallite growth, the temperature and time of nucleation and crystallization are controlled by technical means to control the growth of nano-crystals below 100nm (mainly nano-crystals of 10-30nm). 13. The sagger in-situ growth method is used to produce nano-crystal glass. The sagger uses a spinel sagger, preferably a magnesium-aluminum spinel sagger or an ɑ-corundum-mullite sagger or an ɑ-corundum-quartz glass sagger. It is further preferred to use a composite magnesium-aluminum spinel sagger to reduce the production cost of the spinel sagger and the cost of disposable use of the spinel sagger.

[0083] The following are non-limiting examples of the present invention:

[0084] Example 1

[0085] A high-strength and high-transparency nano-microcrystalline glass comprises a synthetic aluminum-rich feldspar ceramic glass material, β-spodumene or β-spodumene solid solution material, cordierite material, synthetic β-dicalcium silicate material, and magnesium-aluminum (or composite magnesium-aluminum) spinel material as precursor mineral raw materials with a structurally stable feldspar matrix glass as the main body, and zirconium oxide micropowder with a particle size of less than 10nm as a crystal nucleating agent and microcrack damping and pinning agent. Nano-microcrystals with a mass percentage of 50%-95% are controlled to coexist with the matrix glass to form a high-strength and high-transparency nano-microcrystalline glass with a uniform microstructure.

[0086] The chemical formula of the synthetic aluminum-rich feldspar ceramic glass material is K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, 1.1≤X≤2.4, Y=2-6, which represents a composite ceramic glass material of one or two or more synthetic aluminum-rich feldspars selected from the group consisting of synthetic aluminum-rich potassium-sodium feldspar, synthetic aluminum-rich sodium feldspar, synthetic aluminum-rich lithium feldspar, synthetic aluminum-rich calcium feldspar, and synthetic aluminum-rich barium feldspar. The two or more synthetic aluminum-rich feldspar composite ceramic glass materials include at least a synthetic aluminum-rich sodium feldspar composite ceramic glass material.

[0087] The synthetic aluminum-rich feldspar ceramic glass material is prepared according to the chemical formula K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, with the weight percentages of K2O / Na2O / Li2O / CaO / BaO, Al2O3, and SiO2 being determined. The corresponding precursor raw materials containing K2O / Na2O / Li2O / CaO / BaO, Al2O3, and SiO2 are prepared into a batch material, which is then ground through a 300-1000 mesh sieve. The resulting dry powder is sintered and thermally synthesized at a firing temperature of 1200°C-1300°C to obtain the synthetic aluminum-rich feldspar ceramic glass material.

[0088] Preferably, according to the chemical formula of the synthetic aluminum-rich feldspar ceramic glass material K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, 1.1≤X≤2.4, Y=2-6, the corresponding precursor raw materials containing K2O / Na2O / Li2O / CaO / BaO, Al2O3, and SiO2 are made of the corresponding refined raw materials of potassium / sodium / lithium / calcium / barium feldspar in proportion, and alumina powder equivalent to 10%-140% of the Al2O3 content in the feldspar raw material is added to prepare the ingredients, and the powder is The raw materials are ground uniformly to 300-1000 mesh and then calcined for thermal synthesis. Alternatively, the raw materials are prepared from corresponding potassium / sodium / lithium / calcium / barium carbonates, i.e., the raw materials contain K2O, Na2O, Li2O, CaO, BaO, Al2O3, and SiO2 in the required proportions. The K2O, Na2O, Li2O, CaO, and BaO sources are carbonate raw materials such as potassium carbonate, sodium carbonate, lithium carbonate Li2CO3, calcium carbonate, and barium carbonate. The alumina source is alumina powder, and the SiO2 source is high-purity quartz powder. The alumina powder is a 300-1000 mesh alumina fine powder, the high-purity quartz powder is a 300-1000 mesh high-purity quartz fine powder, and the potassium carbonate, sodium carbonate, lithium carbonate Li2CO3, calcium carbonate, and barium carbonate are powders of 300-1000 mesh. The synthetic aluminum-rich feldspar ceramic glass material is obtained by mixing 300-1000 mesh alumina powder equivalent to 110%-240% of the Al2O3 content in the feldspar raw material and 300-1000 mesh high-purity quartz powder into ingredients, stirring them evenly, and calcining them for thermal synthesis.

[0089] Thus, according to the chemical formula of the synthetic aluminum-rich feldspar ceramic glass material K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, the weight percentages (Wt%) of the chemical components of K2O / Na2O / Li2O / CaO / BaO, Al2O3, and SiO2 required in the formulations of each preparation example in this embodiment are calculated when the K2O / Na2O / Li2O / CaO / BaO contents are different and 1.1≤X≤2.4, Y=2-6, respectively, as shown in the following table:

[0090] Table 1 Chemical composition of ingredients for synthetic alumina-rich feldspar ceramic glass materials (wt%)

[0091] Table 1 shows 17 examples of preparing synthetic alumina-rich feldspar ceramic glass materials. The raw material batches were prepared according to the above chemical component ratios, and then the raw material batches were crushed by high-speed grinding. The dry powder evenly passed through a 200-mesh sieve was loaded into a sealed sagger with a lid and fired in a kiln. The desired synthetic alumina-rich feldspar ceramic glass materials were obtained by sintering synthesis.

[0092] Preferably, when the synthetic alumina-rich feldspar ceramic glass material contains both K2O and Li2O, the content of K2O+Li2O is 2-4% (the content in the synthetic alumina-rich feldspar, see Preparation Examples S16 and S17 in Table 1), K2O:Li2O=4-5:1 or 1:4-5, and the mixed alkali effect is beneficial to lowering the glass melting temperature and improving chemical stability.

[0093] Preferably, when the synthetic aluminum-rich feldspar ceramic glass material is an aluminum-rich sodium feldspar (see Preparation Examples S13-S14 in Table 1) of Na2OXAl2O32SiO2 or a synthetic nepheline (see Preparation Example S15 in Table 1), 0.2-0.5% niobium oxide (Nb2O5) is added to the raw materials to improve strength and acid and alkali resistance. Natural nepheline minerals contain a high content of impurities, making them unsuitable for producing high-end glass such as optical glass and high-strength glass. By preparing synthetic nepheline according to its chemical formula, a high-purity synthetic mineral raw material is obtained, which is also a high-aluminum (aluminum-rich) synthetic mineral raw material.

[0094] Preferably, the synthetic β-dicalcium silicate material is prepared by determining the amounts of limestone or calcite or calcium oxide and quartz in the synthetic raw materials based on the theoretical weight ratio of CaO to SiO2 in the wollastonite molecular formula CaOSiO2. The two raw materials are uniformly mixed and calcined at a calcination temperature of 1320-1360°C to obtain synthetic wollastonite, i.e., CaSiO3. The synthesized CaSiO3 is then ground into a powder with a mineralizer of 0.5-1.5% by mole of CaSiO3, and the powder is calcined at 1280-1320°C to obtain a stable synthetic β-dicalcium silicate material, i.e., β-Ca2SiO4 or β-2CaOSiO2.

[0095] Preferably, the raw materials used also include yttria (Y2O3) as a stabilizer for the zirconium oxide powder, with the ratio of zirconium oxide to yttria being 90-95:5-10. Alternatively, yttria-stabilized zirconia raw material powder (having the same ratio of zirconium oxide to yttria = 90-95:5-10) can be directly used in place of the zirconium oxide powder to obtain a stable zirconium oxide-containing powder. Yttria-stabilized zirconia raw material can be commercially available. To prevent agglomeration of zirconium oxide powder with a particle size less than 10 nm or yttria-stabilized zirconia raw material with a particle size of 3-10 nm, a graphene oxide dispersant is added at a ratio of 1:3 to zirconium oxide (i.e., the amount of graphene oxide dispersant is three times the amount of zirconium oxide). After ball milling, the mixture is then added to the glass batch and milled together, ensuring that the zirconium oxide powder with a particle size less than 10 nm is dispersed evenly in the glass batch without agglomeration.

[0096] Preferably, the raw materials used also include boron phosphate BO4P, a network reinforcement raw material, accounting for 0-5% by mass, which can introduce P2O5 components. Boron phosphate BO4P can be a commercially available raw material.

[0097] Preferably, the raw materials also include phosphates: calcium zirconium phosphate [CaZr(PO4)2] and calcium phosphate [Ca3(PO4)2], with the CaZr(PO4)2 + Ca3(PO4)2 content being 0-5%, and the CaZr(PO4)2:Ca3(PO4)2 ratio being 5:1-2:1, to improve stability and strength. Calcium zirconium phosphate [CaZr(PO4)2] is a synthetic raw material produced by reacting zirconium hydrogen phosphate (Zr(HPO4)2H2O) with calcium oxide (CaO).

[0098] Preferably, the raw materials used may also include zinc borate ZB. Zinc borate has the function of limiting the growth of crystallites. Multiple measures are taken to limit the growth of crystallites to ensure that they are nano-crystals.

[0099] Preferably, the β-spodumene raw material or β-spodumene solid solution is based on the theoretical mass ratio of Li2O, Al2O3, and SiO2 in the β-spodumene chemical formula Li2OAl2O3nSiO2, where n = 4 - 8 (when n = 4, it is β-spodumene; when 4 < n ≤ 8, it is β-spodumene solid solution). Its precursor raw material Li2O source uses LiCO3, the alumina source uses alumina powder, and the SiO2 source uses high-purity quartz powder, and it is synthesized by sintering at a firing temperature of 1300°C - 1390°C; or the β-spodumene directly uses spodumene concentrate powder calcined at 1300°C.

[0100] The cordierite material is based on the theoretical mass ratio of MgO, Al2O3, and SiO2 in the cordierite chemical formula 2MgO2Al2O35SiO2. Its precursor raw material MgO source uses talc concentrate powder (calcined at 1300°C) or MgO analytical pure chemical raw material, the alumina source uses alumina powder, and the SiO2 source uses high-purity quartz powder, and it is synthesized by sintering at 1300°C - 1350°C.

[0101] Thus, according to the above, the (mineral) raw materials used to make the matrix glass of the high-strength and high-transparency nanocrystalline glass of the present invention include synthetic aluminum-rich feldspar ceramic glass materials, β-spodumene materials, cordierite raw materials, β-dicalcium silicate materials, (composite) magnesium-aluminum spinel materials, alumina powder, high-purity quartz powder, zirconia micropowder with a particle size less than 10 nm as a nucleating agent, and yttrium oxide Y2O3 or yttrium-stabilized zirconia raw material as a stabilizer for the zirconia micropowder, as well as calcium zirconium phosphate [CaZr(PO4)2] and calcium phosphate, glass network strengthening raw material boron phosphate, and glass melting clarifier. By mass percentage, the content of each raw material component is as follows:

[0102] Zirconia micropowder with a particle size less than 10 nm: 1% - 6% (plus 0.05% - 0.6% yttrium oxide stabilizer, or directly use yttrium-stabilized zirconia with a particle size less than 10 nm)

[0103] Preferably, the chemical composition of the high-strength and high-transparency nanocrystalline glass, by mass percentage, includes:

[0104] The above-mentioned glass melting clarifier can use Sb2O5, the β-dicalcium silicate material can use a synthetic β-dicalcium silicate material (the β-dicalcium silicate material is prepared according to the method described in Chinese Patent No.: ZL201310374914.X), and the β-spodumene can be prepared by using the precursor raw material according to the synthesis method in Chinese Patent No.: China Patent No.: ZL 202011586411.5 to obtain β-spodumene (β-spodumene solid solution when n=4 or n>4). The cordierite raw material can use a precursor raw material for generating cordierite. According to the theoretical mass ratio of MgO to Al2O3 and SiO2 in the cordierite chemical formula 2MgO2Al2O35SiO2, talc concentrate powder is used as the MgO source, alumina powder is used as the alumina source, and high-purity quartz powder is used as the SiO2 source, and thermal synthesis is carried out at 1300°C. CaZr(PO4)2:Ca3(PO4)2=5:1-2:1.

[0105] Based on the 17 preparation examples of the synthetic alumina-rich feldspar ceramic glass material in Table 1 described above in this embodiment and the component ranges of the (mineral) raw materials used in the matrix glass for manufacturing the high-strength and high-transparency nano-glass-ceramics of the present invention described above, the raw material batch formulas for the 17 implementation preparation examples of the (mineral) raw materials used in preparing the matrix glass listed in Table 2 below are obtained:

[0106] Table 2 Example of Preparation of Matrix Glass of Glass-Ceramics Raw Material Formula (wt%)

[0107] In Table 2: S1:55 in Preparation Example 1 indicates that 55% of the synthetic aluminum-rich feldspar ceramic glass material of Preparation Example S1 in Table 1 is used to prepare the synthetic aluminum-rich feldspar ceramic glass material, and the same meaning applies to other preparation examples; the amount of zirconium oxide + yttrium oxide used is according to zirconium oxide: yttrium oxide = 95:5, or yttrium oxide is directly used to stabilize the zirconium oxide raw material powder, and yttrium oxide Y2O3 is a zirconium oxide stabilizer; Sb2O5 is used as a clarifier, and boron phosphate is BO4P, which is a commercially available raw material.

[0108] The matrix glass obtained by melting the matrix glass raw material batch formula of the microcrystalline glass described in the embodiment of Table 2 is subjected to thermodynamic nano-crystallization treatment to obtain nano-crystallites less than 100 nm in the glass body, and the mass percentage of the nano-crystals accounts for 50%-95%.

[0109] Preferably, the nanocrystals include aluminum-rich feldspar nanocrystals, β-spodumene nanocrystals or β-spodumene solid solution nanocrystals, cordierite nanocrystals, β-dicalcrystals, magnesium-aluminum (or composite magnesium-aluminum) spinel nanocrystals, mullite nanocrystals (the aluminum-rich portion reacts with SiO2 in the corresponding feldspar and quartz to form mullite), and zirconium oxide (or yttria-stabilized zirconium oxide solid solution) nanocrystals. See FIG2 for an X-ray diffraction pattern of the nanocrystals obtained by crystallizing the matrix glass obtained from the raw material formulation of Preparation Example 15 in Table 2 of Nanocrystals Glass Example 1. The diffraction peaks shown in the figure are primarily aluminum-rich feldspar nanocrystals, nepheline crystals, and secondary phases of mullite crystals, β-dicalcrystals, and zirconium oxide (or yttria-stabilized zirconium oxide solid solution) nanocrystals. Crystal particles of other minerals do not exhibit prominent diffraction peaks in Preparation Example 15 due to their relatively low content.

[0110] It is further preferred that the volume percentage of each of the nanocrystals in the total nanocrystals is:

[0111] Aluminum-rich feldspar nanocrystals, i.e., K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2 nanocrystals 50%-80%, 1.1≤X≤2.4, Y=2-6

[0112] Among them, the aluminum-rich feldspar nanocrystals are nanocrystals of one or two or more mixed crystals of aluminum-rich potassium feldspar nanocrystals, aluminum-rich sodium feldspar nanocrystals (including nepheline nanocrystals), aluminum-rich lithium feldspar nanocrystals, aluminum-rich calcium feldspar nanocrystals, and aluminum-rich barium feldspar nanocrystals, forming a framework-like long-chain structure in the nanocrystalline glass. The β-dicalcrystals are ring-shaped buckles, so that one or more aluminum-rich feldspar nanocrystals with long-chain structures are surrounded and buckled by the β-dicalcrystals to form locked crystals. The locked crystals are also surrounded and buckled by the β-dicalcrystals with long-chain structures through the aluminum-rich feldspar nanocrystals with long-chain structures to form a three-dimensional locked crystal space structure, which strengthens the framework-like main crystal phase. The zirconium oxide nanocrystals pin and rivet the glass microcracks, greatly improving the fracture toughness.

[0113] Preferably, the content of K2O+Na2O+BaO is 6%-14%, wherein:

[0114] When the aluminum-rich feldspar nanocrystals are mainly aluminum-rich potassium feldspar nanocrystals,

[0115] K2O 4%-9%, Na2O 2%-7%, BaO 0-2%

[0116] When the aluminum-rich feldspar nanocrystals are mainly aluminum-rich sodium feldspar nanocrystals,

[0117] K2O 0.85%-4%, Na2O 6%-12%, BaO 0-1%,

[0118] When the aluminum-rich feldspar nanocrystals contain aluminum-rich celsius nanocrystals,

[0119] BaO 2%-6%, K2O 0.85%-2%, Na2O 6%-10%

[0120] It is further preferred that when the aluminum-rich feldspar nanocrystals further contain aluminum-rich lithium feldspar nanocrystals,

[0121] Li2O 2%-5%, Na2O 6%-9%, K2O 0.85%-3% BaO 0-2%,

[0122] When the aluminum-rich feldspar nanocrystals also contain aluminum-rich calcium feldspar nanocrystals,

[0123] CaO 2%-5%, Na2O 6%-9%, K2O 0.85%-3% BaO 0-2%.

[0124] Preferably, the magnesium-aluminum spinel raw material comprises synthetic composite magnesium-aluminum spinel.

[0125] It is further preferred that the synthesized composite magnesium-aluminum spinel includes different metal oxides in addition to magnesium-aluminum spinel, which respectively react with aluminum oxide at the synthesis temperature to form a composite spinel crystal structure. The different metal oxides include calcium oxide and barium oxide, which can respectively generate calcium-aluminum spinel and barium-aluminum spinel, as well as a composite magnesium-aluminum spinel generated by combining one or two or more of these spinels, at least barium-aluminum spinel (which is beneficial for reducing the synthesis temperature for forming spinel, reducing the synthesis temperature to 1260°C-1360°C) and magnesium-aluminum spinel.

[0126] The raw materials used also include 0.5%-2% Sb2O5 as a clarifier.

[0127] The microcrystalline glass obtained as described above is high-strength and high-transparency nano-microcrystalline glass.

[0128] Preferably, the high-strength and high-transparency nano-ceramic glass is subjected to one or two chemical strengthening steps to make the high-strength and high-transparency nano-ceramic glass have a Mohs hardness of 8.0-9.0 and a fracture toughness of 10-12 MPa m. 1 / 2 , light transmittance 91%-96%, 3200Mpa-5600Mpa after ring-on-ring strengthening (glass plate thickness 0.4-0.6mm).

[0129] Example 2

[0130] This embodiment is a method for manufacturing high-strength and high-transparency nano-ceramic glass.

[0131] To manufacture high-strength and high-transparency nano-microcrystalline glass, the required synthetic raw materials must first be prepared according to Example 1, including synthetic aluminum-rich feldspar ceramic glass materials, β-spodumene materials, cordierite materials, β-calcium silicate materials, and (composite) magnesium-aluminum spinel materials. Then, the matrix glass raw material batch is prepared according to the preparation example formula in Table 2 of Example 1, and the materials are melted, formed, microcrystal nucleated, the crystal nuclei are grown into nano-microcrystals, annealed, and high-strength and high-transparency nano-microcrystalline glass is obtained.

[0132] Thus, a method for preparing high-strength and high-transparency nano-ceramic glass comprises:

[0133] 1. Preparation of synthetic raw materials: First, prepare the required synthetic raw materials, and synthesize the required type of aluminum-rich feldspar ceramic glass material according to the chemical composition table and raw material ratio of the ingredients for synthesizing aluminum-rich feldspar ceramic glass materials in Table 1 of Example 1, that is, according to the corresponding precursor raw materials containing K2O / Na2O / Li2O / CaO / BaO, Al2O3, and SiO2, use the corresponding potassium / sodium / lithium / calcium / barium feldspar raw materials in proportion, and add alumina powder equivalent to 10%-140% of the Al2O3 content in the feldspar raw materials to prepare the ingredients, and powder The raw materials are ground uniformly to a size of 300-1000 mesh and then calcined for thermal synthesis. Alternatively, the raw materials are prepared from corresponding potassium / sodium / lithium / calcium / barium carbonates, i.e., the raw materials contain K2O, Na2O, Li2O, CaO, BaO, Al2O3, and SiO2 in the required proportions. The K2O, Na2O, Li2O, CaO, and BaO sources are carbonate raw materials such as potassium carbonate, sodium carbonate, lithium carbonate Li2CO3, calcium carbonate, and barium carbonate. The alumina source is alumina powder, and the SiO2 source is high-purity quartz powder. The alumina powder is a 300-1000 mesh alumina fine powder, the high-purity quartz powder is a 1000-2000 mesh high-purity quartz fine powder, and the potassium carbonate, sodium carbonate, lithium carbonate Li2CO3, calcium carbonate, and barium carbonate are powders of 300-1000 mesh. Alumina powder of 300-1000 mesh, which is equivalent to 110%-240% of the Al2O3 content in the feldspar raw material, and high-purity quartz powder of 1000-2000 mesh are prepared into ingredients, stirred evenly, and subjected to calcination and thermal synthesis to obtain the synthetic mineral raw material for the synthetic aluminum-rich feldspar ceramic glass material. Take the aluminum-rich sodium feldspar (feldspar) ceramic glass material Na2OXAl2O36SiO2 (X=1.8) of Preparation Example S14 in Table 1 as an example: add 80% by weight of aluminum oxide powder equivalent to the amount of aluminum oxide in the sodium feldspar to 1 weight part of refined sodium feldspar powder, crush and grind evenly to 600 mesh, and calcine at 1300°C to obtain the synthetic mineral material for the aluminum-rich sodium feldspar ceramic glass material. Or

[0134] According to the weight percentage ratios of Na2O, Al2O3, and SiO2 in the chemical formula of the aluminous anorthite-based ceramic glass material of Preparation Example S14, i.e., Na2OXAl2O36SiO2 (X = 1.8), the carbonate raw material sodium carbonate of 400-mesh powder, alumina powder of 1000-mesh fine alumina powder, and 1000-mesh high-purity quartz powder are respectively used to prepare the ingredients, which are stirred evenly and then thermally synthesized by calcination at 1100 °C to obtain the synthetic mineral material Na2O1.8Al2O36SiO2 of the synthetic aluminous anorthite ceramic glass material.

[0135] The β-spodumene raw material can be prepared according to the oxides Li2O, Al2O3, and SiO2 in the chemical formula of the β-spodumene (Li2OAl2O3nSiO2, n = 4 - 8) raw material, respectively using the corresponding precursor raw materials of the oxide sources to prepare the ingredients, which are stirred evenly and then obtained by thermal synthesis through calcination. For example, the β-spodumene (when n = 4) or β-spodumene solid solution (when 4 < n ≤ 8) is prepared by the synthesis method in Chinese Patent No.: ZL 202011586411.5. The β-spodumene raw material can also directly use the spodumene concentrate powder calcined at 1300 °C.

[0136] The cordierite raw material can use commercially available raw materials, or can be prepared according to the oxides Al2O3, SiO2, and MgO in the chemical formula of the cordierite 2MgO2Al2O35SiO2 raw material, respectively using the corresponding precursor raw materials of the oxide sources to prepare the ingredients, which are stirred evenly and then thermally synthesized by calcination at 1350 °C.

[0137] The β-dicalcium silicate β-2CaOSiO2 material is prepared by the synthesis method in Chinese Patent No.: ZL201310374914.X. That is, first, according to the theoretical weight ratio of CaO to SiO2 in the wollastonite molecular formula CaOSiO2, the amounts of limestone or calcite and quartz in the synthetic raw materials are determined. After mixing these two raw materials evenly, they are fired at a firing temperature of 1320 - 1360 °C to obtain the synthesized CaSiO3, i.e., wollastonite. Then, the synthesized CaSiO3 and 0.5 - 1.5% of the mineralizer B2O3 based on the molar amount of CaSiO3 are ground into powder together and fired at 1280 - 1320 °C to obtain the stable β-Ca2SiO4, i.e., β-dicalcium silicate β-2CaOSiO2.

[0138] The composite magnesium-aluminum spinel material is prepared by the synthesis method in Chinese Patent No.: ZL202210579939.2 or Chinese Patent Application No.: 202311261078.4, and a composite magnesium-aluminum spinel material of calcium oxide / barium oxide / magnesium oxide can be synthesized. The composite magnesium-aluminum spinel material in this embodiment adopts a ratio of 0.34CaO 0.58MgO 0.06BaO 0.56Al2O3, wherein the CaO is calcined limestone, the MgO is light-burned magnesium powder or magnesia, and the BaO is barium oxide powder. The raw materials of the formula are crushed to 200-360 mesh, mixed evenly, and calcined. The sintering temperature is 1200-1300°C for 1-2h to obtain a synthetic composite magnesium-aluminum spinel material (CaOMgOBaO)Al2O3.

[0139] Synthesis of calcium zirconium phosphate: Calcium zirconium phosphate [CaZr(PO4)2] is a synthetic raw material, which is synthesized by the reaction of zirconium hydrogen phosphate Zr(HPO4)2H2O and calcium oxide CaO.

[0140] 2. Formula and ingredients: The synthetic raw materials and other raw materials are mixed according to the formula ratio requirements, and the ingredients are mixed according to the raw material mixing formula table of the matrix glass preparation example of the microcrystalline glass in Table 2 of Example 1. Taking the raw material mixing formula in Preparation Example 14 in Table 2 as an example, 60% of the S14 aluminum-rich sodium feldspar (feldspar) ceramic glass material prepared in the above synthetic raw material preparation, 10% of β-spodumene, 5% of cordierite, 5% of β-dicalcium silicate (β-Ca2SiO4), 5% of high-purity quartz powder, 6% of composite magnesium aluminum spinel, 4.5% of zirconium oxide micropowder with a particle size of less than 10nm (plus 0.4% of yttrium oxide as a zirconium oxide stabilizer), 0.6% of calcium zirconium phosphate and calcium phosphate (the ratio of CaZr(PO4)2:Ca3(PO4)2=2:1, i.e. 0.4% of calcium zirconium phosphate and 0.2% of calcium phosphate), 1.5% of boron phosphate, and 2% of clarifier Sb2O5 are mixed. The chemical composition of each raw material in the formula is shown in Table 3 below.

[0141] 3. Processing and mixing: crush the raw materials to the required particle size of 200-300 mesh, mix and mix evenly to obtain dry powder glass raw material batch;

[0142] 4. Melting and molding: Add the dry powder glass raw material batch into the glass melting equipment, melt, clarify, and homogenize it, and use appropriate molding methods according to product requirements;

[0143] The glass has a melting temperature of 1500°C to 1600°C, and a clarification temperature of 1550°C to 1600°C. The raw material batch formulations for the matrix glass preparation examples in Table 2 of Example 1 are different, and the melting and clarification temperatures of the matrix glass are different. In this example, Preparation Example 14 in Table 2 is used as an example. The melting temperature of the matrix glass is determined by heating the dry powder batch to a temperature of 1500°C to 1600°C for 2-4 hours, and then clarifying the dry powder batch at a temperature of 1550°C to 1600°C for 3-5 hours.

[0144] Preferably, in the melting process of the melt forming of this embodiment, the dry powder batch material is added into a sagger for melting glass, and the sagger is placed in a high temperature furnace for melting, clarifying and homogenizing;

[0145] It is further preferred that the sagger is a magnesia-alumina spinel sagger; it is further preferred that the magnesia-alumina spinel sagger is a synthetic composite magnesia-alumina spinel sagger; it is further preferred to use the synthetic composite magnesia-alumina spinel sagger described in Chinese Patent No.: ZL202210579939.2, that is, a composite magnesia-alumina spinel sagger prepared by the synthesis method of Chinese Patent No.: ZL202210579939.2.

[0146] Alternatively, this embodiment may also adopt another glass melting method, in which the melting in the fusion molding is to add the dry powder batch material into a glass melting furnace for melting, clarification, and homogenization.

[0147] The molding is performed using an appropriate molding method according to product requirements, including a flat drawing method, a calendering method, a tape casting method, an overflow method, and a sagger in-situ shaping method. The sagger in-situ shaping method is a method in which the glass raw material batch is melted in a sagger and then shaped directly in-situ in the sagger. This is the basis for the microcrystalline nucleation in-situ growth method after subsequent annealing. The molding method used in this embodiment is selected from the sagger in-situ shaping method, the tape casting method, and the overflow method according to product requirements.

[0148] 5. Nucleation and crystallization: The formed glass products are heated to the nucleation temperature for nucleation, and then crystallized by controlling the temperature and time to control the growth of the grains into nano-crystals to obtain high-strength and high-transparency nano-crystal glass products.

[0149] Preferably, the formed product is subjected to nucleation and crystallization, and the nucleation and crystallization temperature is: nucleation at a temperature of 600°C-650°C, nucleation time: 2-4 hours, crystallization temperature 650°C-700°C, crystallization time: 2-6 hours.

[0150] According to the raw material formulation of the matrix glass of the embodiment micro-ceramic glass in Table 2 of Example 1, taking Preparation Example 14 as an example, the temperature regime for the nucleation crystallization thermodynamic treatment of the obtained matrix glass is as follows: the nucleation crystallization is performed on the formed glass product, and the temperature of the formed glass product is about 700°C.

[0151] (1) 700°C → 650°C, cooling rate 0.5°C / min, holding at 650°C for 2 hours for nucleation;

[0152] (2) 650°C → 700°C, heating rate 0.5°C / min, keeping at 700°C for 2-5 hours for crystallization.

[0153] 6. Annealing: Anneal the crystallized product to eliminate the thermal stress in the glass body and obtain high-strength and high-transparency nano-ceramic glass products.

[0154] The annealing temperature system is as follows: the crystallized product is heated from room temperature to 600℃~650℃, with a heating rate of 0.4℃-1.0℃ / min, kept at 600℃~650℃ for 2-5 hours, and annealed, and then cooled from the annealing holding temperature to room temperature at a cooling rate of 0.2℃-0.5℃ / min.

[0155] According to the different raw material formulations of the matrix glass preparation examples of the example microcrystalline glass in Table 2 of Example 1, the specific operations of the annealing temperature system of the obtained matrix glass are different. This embodiment still takes Preparation Example 14 as an example, and the annealing temperature system of the obtained matrix glass is: after the molding, the product is kept at 700°C for 2 hours and then cooled from 700°C to 650°C at a cooling rate of 0.5°C / min, and then kept at 650°C for 3 hours to 5 hours for annealing; then, the annealing is carried out from the annealing holding temperature of 650°C to room temperature at a cooling rate of 0.4°C / min (this is a single annealing mode).

[0156] Preferably, before the nucleation and crystallization, the formed glass product may be pre-annealed, wherein the temperature of the glass product is first raised to 650°C-700°C and held at this temperature for 2-5 hours, then the temperature is lowered to 550°C-600°C at a rate of 0.2°C-0.3°C / min for the pre-annealing, the pre-annealing holding time being 2-3 hours, then the temperature is lowered to 500°C at a rate of 0.2°C-0.3°C / min and held at this temperature for 2-3 hours, then the temperature is raised to the nucleation temperature at a rate of no more than 0.5°C / min, and the subsequent nucleation, crystallization and annealing are performed (this is a two-step annealing mode).

[0157] Further preferably, when the matrix glass is formed using the in-situ shaping method using a sagger, the annealing and nucleation crystallization adopt an in-situ growth method, that is, after the glass is formed directly by shaping the shape of the sagger, the sagger together with the matrix glass in the sagger is directly placed in a crystallization furnace for nucleation crystallization and then annealed in an annealing kiln to obtain transparent nano-glass-ceramics. The mode of nucleation crystallization and annealing heat treatment can be a single annealing mode or a double annealing mode as described above. The temperature regime of the nucleation crystallization and annealing heat treatment is the same as described above.

[0158] Further preferably, the in-situ growth method is used to nucleate and crystallize the transparent nano-glass-ceramics, the nano-glass-ceramics are separated from the sagger, and further formed and processed to obtain the desired structural components, followed by strengthening. After the sagger is separated, the waste sagger and waste glass are recycled and reused.

[0159] Preferably, after obtaining the transparent nano-crystalline glass as described above, the process further includes: further molding and processing the transparent nano-crystalline glass product to obtain the desired structure, and then performing a strengthening treatment. As described above in this embodiment, the nano-crystalline glass and the sagger are separated to obtain a glass ingot (or the glass liquid coming out of the glass kiln is formed into a glass ingot, which is then subjected to nucleation, crystallization and annealing to obtain a transparent nano-crystalline glass ingot), and the glass ingot is then cut into 0.2-0.5mm thick mobile phone panel (or back panel) glass sheets using a diamond wire cutter. In order to further increase the strength, the nano-crystalline glass product is subjected to a strengthening treatment. The strengthening includes physical strengthening or chemical strengthening.

[0160] The chemical strengthening is one-time chemical strengthening or multiple-time chemical strengthening. The depth of the surface compressive stress layer generated by ion exchange after strengthening is 20-120 μm.

[0161] The multiple chemical strengthening is a secondary step ion exchange strengthening, and the method is that the first strengthening is Na + →Li + , the secondary reinforcement is K + →Na + , greatly improving the mechanical strength of glass microcrystals.

[0162] The highly transparent nano-ceramic glass of Example 14 of this embodiment was chemically strengthened by placing the highly transparent nano-ceramic glass in a mixed salt bath of 15 wt% NaNO3 and 85 wt% KNO3 for enhanced ion exchange at a temperature of 420°C for 8 hours. + →Li + The depth of the compressive stress layer generated by the exchange is 30μm-90μm.

[0163] Secondary reinforcement is K +→Na + , the ion exchange temperature is 500℃, and the exchange time is 12 hours. + →Na + The depth of the compressive stress layer generated by the exchange is 20-50μm.

[0164] The high-strength and high-transparency nano-ceramic glass of the present invention has achieved the following technical performance indicators after testing:

[0165] Anti-drop height test: The glass piece does not break when dropped vertically from a height of 2-2.6 meters;

[0166] For example, a tempered glass sheet with a length and width of 5×5 cm and a thickness of 0.5 mm will not break if dropped vertically from a height of 2.5 meters.

[0167] Fracture toughness: 5-8MPa*m before strengthening 1 / 2 , after strengthening 10-12MPa*m 1 / 2 After strengthening, the deeper the ion exchange layer (the thicker the thickness), the higher the fracture toughness strength;

[0168] Hardness: Mohs hardness before strengthening 7-8, Mohs hardness after strengthening 8-9;

[0169] Ring-on-ring strength after strengthening (glass plate thickness 0.4-0.6mm) 3200Mpa-5000Mpa;

[0170] Chemically strengthened compressive stress layer thickness: 20-120μm;

[0171] Thermal expansion coefficient: 1.5×10 -6 / ℃~5.2×10 -6 / ℃, softening point: 850~930℃(viscosity η=1.5×10 9 -3.5×10 9 Poise), annealing point: 630℃~680℃(viscosity η=1.0×10 13 ~2.5×10 13 Poise), strain point: 580℃~620℃(viscosity η=1.0×10 14.5 moor);

[0172] Optical properties: 1. Refractive index: 1.51-1.53; 2. 91% < visible light transmittance ≤ 96%; 3. Haze: < 0.1%;

[0173] Mechanical properties include: 1. Poisson's ratio: 0.21-0.23; 2. Young's modulus after strengthening: 11.5-14.1Mpsi; 3. Vickers hardness before strengthening ≥720kgf / mm 2 , after strengthening, Vickers hardness ≥780kgf / mm 2; 4. The bending strength before strengthening is greater than 550MPa, and the bending strength after strengthening is greater than 850Mpa;

[0174] Nanocrystal size: The main nanocrystals are 5-30nm (the largest of the remaining nanocrystals is less than 100nm). As can be seen from the 1.2 million-magnification microstructure image of a 20KV transmission electron microscope in Figure 1, the nanocrystals are approximately 5-30nm in size and are interconnected like a densely woven carpet, which also explains why high-strength and high-transparency nanocrystal glass has high fracture toughness.

[0175] Types of nanocrystals: Nanocrystals include aluminum-rich feldspar nanocrystals, β-spodumene nanocrystals, cordierite nanocrystals, synthetic β-dicalcrystals, mullite nanocrystals, magnesium-aluminum / composite magnesium-aluminum spinel nanocrystals, zirconium oxide / yttrium oxide solid solution nanocrystals, and diopside nanocrystals;

[0176] Total nanocrystal content: 50%-95%. As shown in Figure 1, a 20kV transmission electron microscope micrograph at 1.2 million magnification, nanocrystals, primarily 5-30nm in size, are interconnected like a densely woven carpet, with a dense distribution of nanocrystals. Testing of the 17 preparation examples listed in Table 2 of the Examples shows that the nanocrystal content ranges from 50%-95%, symbiotically weaving with the residual matrix glass to form a uniform, high-strength, and highly transparent nanocrystal glass-ceramics.

[0177] Tyndall Effect Test: When a beam of visible red light passes through a glass-ceramic plate perpendicular to its thickness, a bright red beam of light, known as the Tyndall Effect beam, can be seen on the glass's flat surface. This indicates that the glass-ceramic contains microcrystals with a diameter d between 1 and 100 nm, which is smaller than the wavelength of the incident light (the wavelength of visible light is approximately between 360 and 700 nm). Therefore, when visible light passes through the glass-ceramic, it produces a significant scattering effect. The intensity of the scattered light increases with the concentration of nanocrystal particles in the dispersed system. The stronger the scattered light, the greater the diameter of the nanocrystals (5-30 nm as shown in Figure 1), indicating that scattering occurs, and the higher the proportion of nanocrystals (50%-95%).

[0178] Example 3

[0179] This embodiment is an application of high-strength and high-transparency nano-ceramic glass.

[0180] The high-strength and high-transparency nano-microcrystalline glass of the present invention is used to make mobile phone covers and back panels: due to its high surface hardness, the mobile phone panel made of it has good wear resistance, the surface is not easily scratched or fogged, it has high fracture toughness and bending strength, and high light transmittance, and can be made into 3D panel glass. It can also be used to make mobile phone back panels, has no shielding effect on radio waves, is conducive to the arbitrary arrangement of mobile phone antennas in the machine, and the reception and transmission of signals are not affected by the panel and back panel.

[0181] Used in optical glass: Due to the synergistic effect of various nano-crystals, the strength of micro-crystal glass is improved. At the same time, the refractive index of various nano-crystals is close to that of residual glass, and the light transmittance is high, which can meet the use requirements of optical glass. It has high hardness, wear resistance, no fogging, and no mold. It is used for cameras, glasses glass, window glass and shells of high-end instruments and equipment, etc.

[0182] It can also be used for cover glass of high-end electronic products, as well as windshields and side windows of high-speed trains and aircraft, vehicle control screens, and quantum radar panels.

Claims

1. A high-strength and highly transparent nanocrystalline glass, characterized in that, Adopt a precursor mineral material with a structure-stable feldspar-based glass as the main body, including synthetic aluminous feldspar-like ceramic glass material, β-spodumene or β-spodumene solid solution material, cordierite material, synthetic β-dicalcium silicate material, and magnesium aluminate spinel material. Use zirconia micropowder with a particle size less than 10 nm as the crystal nucleating agent and microcrack damping pinning agent to control the formation of nanocrystals with a size less than 100 nm in the vitreous body formed after melting. The volume percentage content of the nanocrystals accounts for 50%-95%, and they coexist with the matrix glass to form a high-strength and highly transparent nanocrystalline glass with a uniform microstructure.

2. The high-strength and high-transparency nanocrystalline glass according to claim 1, characterized in that, The chemical formula of the synthetic aluminous feldspar-like ceramic glass material is K2O / Na2O / Li2O / CaO / BaOXAl2O3YSiO2, where 1.1 ≤ X ≤ 2.4 and Y = 2 - 6. It represents a composite ceramic glass material of one or more of synthetic potassium aluminosilicate, synthetic sodium aluminosilicate, synthetic potassium-sodium aluminosilicate, synthetic lithium aluminosilicate, synthetic calcium aluminosilicate, and synthetic barium aluminosilicate. Among them, the composite ceramic glass material of two or more synthetic aluminous feldspars includes at least a synthetic sodium aluminosilicate composite ceramic glass material.

3. The high-strength and high-transparency nano-crystalline glass according to claim 1, wherein The synthetic β-dicalcium silicate material is determined according to the theoretical weight ratio of CaO to SiO2 in the wollastonite molecular formula CaOSiO2. The amounts of limestone or calcite or calcium oxide and quartz in the synthetic raw materials are determined. After mixing these two raw materials evenly, they are fired at a firing temperature of 1320 - 1360 °C to obtain synthetic wollastonite, i.e., CaSiO3. Then, the synthetic CaSiO3 is ground into powder together with 0.5 - 1.5% of the mineralizer B2O3 based on the molar amount of CaSiO3 and fired at 1280 - 1320 °C to obtain the stable synthetic β-dicalcium silicate material, i.e., β-Ca2SiO4.

4. The high-strength and high-transparency nanocrystalline glass according to claim 2, characterized in that, The high-strength and highly transparent nanocrystalline glass has mineral raw materials as the main body, and also includes quartz and glass melting clarifying agents. By mass percentage, the content of each raw material component is as follows:

5. The high-strength and high-transparency nanocrystalline glass according to claim 4, characterized in that, The chemical composition of the high-strength and high-transparency nano-crystalline glass includes, by mass percentage:

6. The high-strength and high-transparency nanocrystalline glass according to claim 2, wherein, According to the chemical formula of the synthetic aluminous feldspar-like ceramic glass material R2O / ROXAl2O3YSiO2, where 1.1 ≤ X ≤ 2.4 and Y = 2 - 6. When R2O is K2O / Na2O / Li2O, Y ≤ 6; when RO is CaO / BaO, Y ≥ 2; when there are corresponding feldspars with R2O / RO at the same time, Y = 2 - 6. Proportionally adopt the refined raw materials of the corresponding potassium / sodium / lithium / calcium / barium feldspars, and add alumina powder equivalent to 10%-140% of the Al2O3 content in the feldspar raw materials to make a formulation, crush and grind it evenly to 300 - 1000 mesh, and then carry out calcination heat synthesis; or use the corresponding carbonate chemical raw materials of potassium / sodium / lithium / calcium / barium, 300 - 1000 mesh alumina powder equivalent to 110%-240% of the Al2O3 content in the feldspar raw materials, and 300 - 1000 mesh high-purity quartz powder to make a formulation, stir it evenly, and carry out calcination heat synthesis to obtain the synthetic aluminous feldspar-like glass ceramic material.

7. The high-strength and highly transparent nanocrystalline glass according to claim 2, characterized in that, If the synthetic aluminous feldspar-like ceramic glass material contains both K2O and Li2O at the same time, the content of K2O + Li2O is 2 - 6%, and K2O:Li2O = 4 - 5:1 or 1:4 - 5.

8. The high-strength and highly transparent nano-crystalline glass according to claim 2, wherein When the synthesized aluminosilicate-based ceramic glass material is a albite aluminosilicate-based ceramic glass material of Na2OXAl2O36SiO2, in order to improve the strength, it also includes 0.2-0.5% of rare earth or rare metal oxides that do not color the glass.

9. The high-strength and highly transparent nano-crystalline glass according to claim 4, characterized in that, The raw materials used also include yttrium oxide Y2O3 as a stabilizer for zirconia fine powder, and the amount used is calculated as zirconia:yttrium oxide = 90-95:5-10, or directly use yttrium oxide-stabilized zirconia raw material fine powder to replace zirconia fine powder.

10. The high-strength and highly transparent nano-crystalline glass according to claim 1, wherein The raw materials used also include boron phosphate as a network strengthening raw material, accounting for 0.1%-2% by mass percentage, introducing P2O5 component.

11. The high-strength and high-transparency nano-crystalline glass according to claim 10, characterized in that, The raw materials also include phosphates: The phosphates used are calcium zirconium phosphate CaZr(PO4)2 and calcium phosphate Ca3(PO4)2, and the content of CaZr(PO4)2+Ca3(PO4)2 is 0.1-2%, and CaZr(PO4)2:Ca3(PO4)2 = 5:1-2:

1.

12. The high-strength and high-transparency nanocrystalline glass according to claim 1, characterized in that, The β-spodumene or β-spodumene solid solution material is synthesized according to the theoretical mass ratio of Li2O, Al2O3 and SiO2 in the β-spodumene or β-spodumene solid solution chemical formula Li2OAl2O3nSiO2, n = 4-8. The Li2O source uses LiCO3, the alumina source uses alumina powder, and the SiO2 source uses high-purity quartz powder, and is sintered and synthesized at a firing temperature of 1300°C-1390°C, or β-spodumene is directly obtained by calcining spodumene concentrate powder at 1300°C; The cordierite material is based on the theoretical mass ratio of MgO, Al2O3 and SiO2 in the cordierite chemical formula 2MgO2Al2O35SiO2. The MgO source uses talc concentrate powder or MgO analytical pure chemical raw material, the alumina source uses alumina powder, and the SiO2 source uses high-purity quartz powder, and is sintered and synthesized at 1300 °C-1400 °C.

13. The high-strength and highly transparent nanocrystalline glass according to claim 5, wherein The nanocrystals include aluminosilicate-based nanocrystals, β-spodumene or β-spodumene solid solution nanocrystals, cordierite nanocrystals, synthesized β-dicalcium silicate nanocrystals, magnesium aluminate spinel nanocrystals, mullite nanocrystals, zirconia or zirconia / yttrium oxide solid solution nanocrystals.

14. The high-strength and highly transparent nanocrystalline glass according to claim 13, characterized in that, The volume percentage content of each of the nanocrystals in the total nanocrystals is as follows:

15. The high-strength and highly transparent nano-crystalline glass according to claim 14, characterized in that, The aluminosilicate-based nanocrystals include one or two or more mixed crystals of potassium aluminosilicate nanocrystals, sodium aluminosilicate nanocrystals, lithium aluminosilicate nanocrystals, calcium aluminosilicate nanocrystals, barium aluminosilicate nanocrystals, etc., forming a framework long-chain structure in the nanocrystalline glass. The synthesized β-dicalcium silicate nanocrystal β-2CaO.SiO2 is a ring buckle of a cyclic structure, so that one or more long-chain aluminosilicate-based nanocrystals are surrounded and buckled by the synthesized β-dicalcium silicate nanocrystals, forming a locked crystal. The locked crystals are also surrounded and buckled by the β-2CaO.SiO2 nanocrystals through the long-chain aluminosilicate-based nanocrystals, forming a three-dimensional locked crystal space structure, strengthening the framework main crystal phase, and the zirconia nanocrystals or zirconia / yttrium oxide solid solution nanocrystals pin and rivet the glass microcracks.

16. The high-strength and high-transparency nano-crystalline glass according to claim 15, wherein, The content of K2O+Na2O+BaO is 6%-14%, where: When the aluminous feldspar - type nanocrystals are mainly potassium - rich aluminous feldspar nanocrystals, K2O 4% - 9%, Na2O 2% - 7%, BaO 0 - 2% When the aluminous feldspar - type nanocrystals are mainly sodium - rich aluminous feldspar nanocrystals, K2O 0.85% - 4%, Na2O 6% - 12%, BaO 0 - 1%, When the aluminous feldspar - type nanocrystals contain barium - rich aluminous feldspar nanocrystals, BaO 2% - 6%, K2O 0.85% - 2%, Na2O 6% - 10% 17. The high-strength and highly transparent nano-crystalline glass according to claim 16, characterized in that, When the aluminous feldspar - type nanocrystals also contain lithium - rich aluminous feldspar nanocrystals, Li2O 2% - 5%, Na2O 6% - 9%, K2O 0.85% - 3% BaO 0 - 2% When the aluminous feldspar - type nanocrystals also contain calcium - rich aluminous feldspar nanocrystals, CaO 2% - 5%, Na2O 6% - 9%, K2O 0.85% - 3% BaO 0 - 2%.

18. The high-strength and highly transparent nano-crystalline glass according to claim 1, characterized in that, The magnesia - alumina spinel raw material includes synthetic composite magnesia - alumina spinel.

19. The high-strength and highly transparent nanocrystalline glass according to claim 18, wherein The synthetic composite magnesia - alumina spinel, in addition to magnesia - alumina spinel, includes different metal oxides that respectively form composite spinel crystal structures with alumina at the synthesis temperature. The different metal oxides include calcium oxide and barium oxide, which can respectively form calcium - alumina spinel and barium - alumina spinel, and one or two or more of these spinels, at least including the composite magnesia - alumina spinel formed by combining barium - alumina spinel and magnesia - alumina spinel into one body.

20. The high-strength and highly transparent nano-crystalline glass according to claim 1, wherein The high-strength and highly transparent nanocrystalline glass is chemically strengthened once or twice. Before strengthening, its Mohs hardness is 6.0 - 8.0, and after strengthening, it is 7.0 - 9.

0. Its fracture toughness before strengthening is 4.8 - 8 MPam 1 / 2 , and after strengthening, it is 10 - 12 MPam 1 / 2 , its light transmittance is 91% - 96%, and the ring-to-ring strength after strengthening is 3200 MPa - 5600 MPa.

21. A method for preparing high - strength and high - transparency nanocrystalline glass, comprising: Synthesis raw material preparation: Synthesize according to the synthesis raw material ratio in the high - strength and high - transparency nanocrystalline glass described in any one of claims 1 to 20 to obtain the corresponding synthetic mineral materials; Formula batching: Batch the synthetic materials and other raw materials according to the formula ratio requirements; Processing and mixing: Crush the raw materials of the batch to the required fineness, mix and homogenize to obtain a dry - powder glass green batch; Melting and forming: Add the dry - powder batch into a glass melting device, perform melting, clarification, and homogenization, and use an appropriate forming method for forming according to product requirements; Nucleation and crystallization: For the formed glass product, perform nucleation at the nucleation temperature, and then control the temperature and time for crystallization to control the grain growth into nanocrystals and microcrystal amounts with the required fineness; Annealing: Anneal the crystallized product to eliminate the thermal stress in the glass body to obtain a high - strength and high - transparency nanocrystalline glass product.

22. The method for preparing high-strength and highly transparent nanocrystalline glass according to claim 21, wherein It also includes: After further forming and processing the nanocrystalline glass product to obtain the required structure, perform strengthening treatment.

23. The method for preparing high-strength and highly transparent nanocrystalline glass according to claim 22, wherein The strengthening of the nanocrystalline glass product includes physical strengthening or chemical strengthening.

24. The method for preparing high-strength and highly transparent nano-crystalline glass according to claim 23, characterized in that, The chemical strengthening is primary chemical strengthening or secondary chemical strengthening, and the depth of the surface compressive stress layer generated by ion exchange after strengthening is 20 - 120μm.

25. The method for preparing high-strength and high-transparency nanocrystalline glass according to claim 24, characterized in that, The secondary chemical strengthening is secondary stepped ion exchange strengthening. The process is that the first strengthening is Na + →Li + , and the second strengthening is K + →Na + .

26. The method for preparing high-strength and highly transparent nano-crystalline glass according to claim 21, wherein, In the melting and forming, adding the dry - powder batch into the glass melting device means adding the dry - powder batch into the crucible for melting glass, and placing the crucible in a high - temperature furnace for melting, clarification, and homogenization in an oxidizing atmosphere or an oxidizing - reducing atmosphere.

27. The method for preparing high-strength and high-transparency nano-crystalline glass according to claim 26, characterized in that, The sagger is a magnesia-aluminum spinel sagger or an α-alumina-mullite sagger or an α-alumina-quartz glass sagger.

28. The method for preparing high-strength and highly transparent nano-crystalline glass according to claim 27, wherein The magnesia-aluminum spinel sagger is a synthetic composite magnesia-aluminum spinel sagger.

29. The method for preparing high-strength and highly transparent nanocrystalline glass according to claim 26, wherein, The nucleation and crystallization adopt the in-situ growth method, that is, the forming of the glass is directly shaped in-situ through the shape of the sagger, and the sagger together with the glass in the sagger is directly nucleated, crystallized and then annealed in the kiln to obtain transparent nano-crystalline glass.

30. The method for preparing high-strength and high-transparency nanocrystalline glass according to claim 29, characterized in that, The transparent nano-crystalline glass obtained by the in-situ growth method of nucleation and crystallization is separated from the sagger, and then further formed and processed to obtain the required structural parts, and then strengthened.

31. The method for preparing high-strength and highly transparent nanocrystalline glass according to claim 21, wherein, In the melt forming, the melting is to add the dry powder batch into the kiln for melting glass, and carry out melting, clarification and homogenization. The forming is carried out by the casting method, or the rolling method, or the overflow method.

32. The method for preparing high-strength and high-transparency nanocrystalline glass according to claim 21, characterized in that, The melting temperature is 1500°C to 1600°C, and the clarification temperature is 1550°C to 1600°C.

33. The method for preparing high-strength and highly transparent nanocrystalline glass according to claim 21, wherein, The formed product is nucleated and crystallized. The temperature of the nucleation and crystallization is: nucleation at a temperature of 600°C - 650°C, nucleation time: 2 - 4h, crystallization temperature 650°C - 750°C, crystallization time: 2 - 6h.

34. The method for preparing high-strength and high-transparency nano-crystalline glass according to claim 21, wherein The annealing temperature is: 500°C to 550°C, the heating rate is 0.5°C - 1°C / min, the annealing holding time is 1 - 4 hours, and the cooling rate from the annealing holding temperature to room temperature is 0.2°C - 0.4°C / min.

35. The method for preparing high-strength and highly transparent nanocrystalline glass according to claim 33, characterized in that, Before the nucleation and crystallization, the formed glass product is pre-annealed first, and the process is as follows: First, the temperature of the glass product is raised to 650°C - 750°C, the holding time is: 2 - 5h, and then the temperature is lowered to 550°C - 600°C at a rate of 0.2°C - 0.3°C / min for the pre-annealing. The pre-annealing holding time is 2 - 3 hours, and then the temperature is lowered to 500°C at a rate of 0.2°C - 0.3°C / min, the holding time is 2 - 3 hours, and then the temperature is raised to the nucleation temperature at a rate not greater than 0.5°C / min for the subsequent nucleation, crystallization and annealing.

36. Application of high-strength and highly transparent nanocrystalline glass, characterized in that The high-strength and high-transparency nano-crystalline glass according to any one of claims 1 - 20 is used to make various optical glasses, including mobile phone cover surfaces and cover backplates, cameras, cover glasses for high-end electronic products, windshield and side window glasses for high-speed trains and airplanes, view window glasses and shells for high-end instrument and equipment, in-vehicle control screens, and quantum radar panels.

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