Raw glass, microcrystalline glass, chemically strengthened glass, glass cover plate, display screen, electronic device and structural member

Abstract

The present application relates to the field of glass. Provided in the present application are raw glass, microcrystalline glass, chemically strengthened glass, a glass cover plate, a display screen, an electronic device and a structural member. In the present application, MgO-ZrO2-SiO2-system glass having good performance can be formed by rationally regulating the molar ratio of all the oxides in the components of the raw glass and the microcrystalline glass and replacing Al2O3 with ZrO2, wherein 4%≤ZrO2≤15%, and 0%≤Al2O3≤2%. Compared with traditional Al2O3-SiO2-system glass, the MgO-ZrO2-SiO2-system glass can exhibit a better coefficient of volume expansion and better elastic modulus, which helps to form a more effective ion transport channel. After a treatment by means of an ion exchange process, chemically strengthened glass having better drop resistance can be obtained. The raw glass, the microcrystalline glass or the chemically strengthened glass provided in the embodiments of the present application can better meet the use requirements of glass materials.

Description

Raw glass, microcrystalline glass, chemically strengthened glass, glass covers, displays, electronic equipment and structural components

[0001] This application claims priority to Chinese Patent Application No. 202411466707.1, filed on October 18, 2024, with the invention titled "Raw Glass, Microcrystalline Glass, Chemically Strengthened Glass, Glass Cover, Display Screen, Electronic Device and Structural Component", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of glass, and more particularly to a raw glass, microcrystalline glass, chemically strengthened glass, glass cover, display screen, electronic device and structural component. Background Technology

[0003] As smartphones, tablets, and other electronic devices become larger and thinner, higher demands are placed on the mechanical properties of protective glass for these devices. Oxide glass possesses excellent optical, chemical, and processability properties, and is widely used as screen covers in mobile consumer electronics products, particularly smartphones. However, due to its high brittleness and low resistance to crack propagation, microcracks introduced during manufacturing, processing, and use can rapidly propagate under external forces, ultimately leading to fracture failure. Traditional methods typically employ ion exchange to chemically strengthen oxide glass, replacing small-radius alkali metal ions on the glass surface with larger-radius alkali metal ions, introducing a surface compressive stress field. The higher the compressive stress level on the surface of chemically strengthened glass, the higher its drop resistance. The compressive stress level on the surface of chemically strengthened glass is positively correlated with the volumetric expansion coefficient and elastic modulus of the original glass (i.e., the glass before the ion exchange process). Therefore, it is necessary to develop a raw glass with a high volumetric expansion coefficient and elastic modulus. Summary of the Invention

[0004] This application provides a raw glass material, microcrystalline glass, chemically strengthened glass, glass cover, display screen, electronic device, and structural component.

[0005] In a first aspect, embodiments of this application provide a raw glass material. The raw glass material, by molar percentage, comprises the following components: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% ≤ K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0006] It is understandable that this application achieves superior performance by rationally controlling the molar ratio of each oxide in the raw glass composition, thus forming a MgO-ZrO2-SiO2 raw glass. In the traditional Al2O3-SiO2 system, an aluminum-oxygen tetrahedron carries a Li+ ion to form a LiAlO2 structure. This application uses ZrO2 instead of Al2O3 in its raw glass, allowing ZrO2 to react with free Li+ ions. + / Na + Stable ZrO6 octahedral clusters are formed. Each ZrO6 octahedron carries two Li groups. + Forming a stable structure of Li₂ZrO₆, carrying Li + The number of atoms is twice that of aluminum-oxygen tetrahedra, which helps the raw glass to form more efficient ion transport channels.

[0007] Furthermore, the raw glass contains 0% ≤ Al2O3 ≤ 2%. No raw materials containing Al2O3 (alumina) are intentionally added during the preparation of the raw glass. However, since the raw materials of each component are not pure substances, they may contain trace amounts of Al2O3. The Al2O3 content in the raw glass can be within a low range and will not affect the forming of the MgO-ZrO2-SiO2 raw glass.

[0008] In some possible implementations, the Young's modulus of the raw glass is in the range of 85 GPa to 110 GPa. Young's modulus is a physical quantity that describes the ability of a solid material to resist deformation. The larger the Young's modulus, the less likely the solid material is to deform under external force.

[0009] Understandably, the Young's modulus of traditional Al2O3-SiO2 system raw glass is generally less than or equal to 80 GPa. The Young's modulus of the MgO-ZrO2-SiO2 raw glass in this application is in the range of 85 GPa to 110 GPa, significantly higher than that of traditional Al2O3-SiO2 system raw glass. Increasing the ZrO2 content in the raw glass can significantly increase bonding strength and structural density, thus significantly improving the Young's modulus. A high Young's modulus is beneficial in two ways: firstly, it helps ensure the stiffness and strength of the chemically strengthened glass obtained after chemical strengthening; secondly, it also helps the chemically strengthened glass achieve a high compressive stress value, thereby improving its drop resistance and impact resistance.

[0010] In some possible implementations, the coefficient of volume expansion B (Na) of the original glass is... + →Li + The coefficient of thermal expansion (CTE) is in the range of 0.06 to 0.1; and / or, the coefficient of thermal expansion (CTE) of the original glass is within the range of 0.06 to 0.1. + →Na +The coefficient of volumetric expansion B (Na) is in the range of 0.09 to 0.17. + →Li + ) is a description of material Na + →Li + The physical quantity of ion exchange capacity, the volume expansion coefficient B(Na) + →Li + The larger the ) is, the more Na of the material + ->Li + The better the ion exchange capacity, the better the volume expansion coefficient B(K). + →Na + ) is a description of material K + →Na + The physical quantity of ion exchange capacity, the volume expansion coefficient B(K) + →Na + The larger the K value, the greater the material's K value. + →Na + The better the ion exchange capacity.

[0011] It is understandable that the volume expansion coefficient B(Na) of the original glass in the traditional Al2O3-SiO2 system is... + →Li + The coefficient of volume expansion B(Na) of the MgO-ZrO2-SiO2 raw glass in this application is generally less than 0.06. + →Li + The coefficient of thermal expansion (C / Na) is significantly higher than that of traditional Al2O3-SiO2 system raw glass in the range of 0.06 to 0.1. + →Li + Increasing the ZrO2 content in the raw glass material can significantly improve the coefficient of volume expansion B(Na). + →Li + ), to improve the Na content of the raw glass + →Li + Ion exchange capacity is beneficial for subsequent chemical strengthening of the raw glass.

[0012] The coefficient of volume expansion (K) of the raw glass in the traditional Al2O3-SiO2 system + →Na + The coefficient of volume expansion B(K) of the MgO-ZrO2-SiO2 raw glass in this application is generally less than 0.08. + →Na + The coefficient of thermal expansion (B(K)) is in the range of 0.09 to 0.17, which is significantly higher than that of the bulk expansion coefficient B(K) of the traditional Al2O3-SiO2 system of raw glass. + →Na + Increasing the ZrO2 content in raw glass can significantly improve the coefficient of volumetric expansion, B(K). + →Na+ ), improve the K of the raw glass + →Na + Ion exchange capacity is beneficial for subsequent chemical strengthening of the raw glass.

[0013] In some possible implementations, the fracture toughness of the raw glass is 0.8 MPa. 0.5 Up to 1.1 MPa 0.5 Within a certain range. Fracture toughness is a physical quantity that describes the resistance of a solid material to crack propagation and brittle fracture. The greater the fracture toughness, the less likely the material is to crack under external force.

[0014] It is understandable that the fracture toughness of the original glass in the traditional Al2O3-SiO2 system is less than or equal to 0.75 MPa. 0.5 The fracture toughness of the MgO-ZrO2-SiO2 raw glass in this application is 0.8 MPa. 0.5 Up to 1.1 MPa 0.5 Within the specified range, the fracture toughness of the raw glass is significantly higher than that of the traditional Al2O3-SiO2 system. The raw glass of this application has high fracture toughness. High fracture toughness improves the intrinsic damage resistance of the raw glass and enhances its resistance to crack propagation and bifurcation. This, in turn, helps to improve the tensile stress limit of the chemically strengthened raw glass, which can help improve the drop resistance and impact resistance of chemically strengthened glass.

[0015] Secondly, embodiments of this application provide a microcrystalline glass. The microcrystalline glass comprises the following components by molar percentage: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% ≤ K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0016] It is understood that, in this embodiment, by reasonably controlling the molar ratio of each oxide in the microcrystalline glass composition, a high-performance MgO-ZrO2-SiO2 microcrystalline glass was formed. The microcrystalline glass uses ZrO2 to replace Al2O3, and ZrO2 can react with free Li... + / Na + Stable ZrO6 octahedral clusters are formed. Each ZrO6 octahedron carries two Li groups. + Forming a stable structure of Li₂ZrO₆, carrying Li + The number of atoms is twice that of aluminum-oxygen tetrahedra, which is beneficial for microcrystalline glass to form more efficient ion transport channels.

[0017] In some possible implementations, the crystals in the glass-ceramic include Zr. 4+ Solid solution of β-quartz, Mg 2+ One or more of the following: solid-solution β-quartz, magnesium silicate, zirconium silicate, and lithium zirconate.

[0018] In some possible implementations, the grain size of the crystals in the glass-ceramic is in the range of 1 nm to 100 nm.

[0019] It is understandable that the crystal grain size of glass-ceramics is much smaller than the wavelength of visible light, resulting in less scattering of visible light and thus contributing to the higher transmittance of glass-ceramics.

[0020] In some possible implementations, the crystallinity of the glass-ceramic is between 1% and 90%.

[0021] It is understandable that adjusting the crystallinity of glass-ceramics within this range can control the hardness, Young's modulus, light transmittance, and other properties of glass-ceramics, resulting in superior overall performance.

[0022] Thirdly, embodiments of this application provide a chemically strengthened glass. By molar percentage, the chemically strengthened glass comprises the following components: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% < K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0023] It is understood that the chemically strengthened glass can be obtained by ion exchange (i.e., chemical strengthening) of the raw glass or microcrystalline glass described in the embodiments of this application. After ion exchange, a strengthening layer (i.e., compressive stress layer) of a certain depth is formed on the surface of the raw glass, which has higher surface compressive stress and further improves mechanical properties, such as surface hardness and fracture toughness, thereby greatly improving its ability to resist external forces.

[0024] In some possible implementations, the surface compressive stress CS of the chemically strengthened glass is ≥800MPa.

[0025] It is understandable that the surface compressive stress (CS) of the traditional Al2O3-SiO2 system chemically strengthened glass is less than 800 MPa. The MgO-ZrO2-SiO2 chemically strengthened glass provided in this application has a higher surface compressive stress, which enables the chemically strengthened glass to have higher hardness and fracture toughness, and thus gives it excellent drop resistance.

[0026] In some possible implementations, the Young's modulus E of the chemically strengthened glass is ≥85 GPa; and / or, the shear modulus G of the chemically strengthened glass is ≥30 GPa.

[0027] Understandably, chemically strengthened glass exhibits higher Young's modulus and shear modulus. A higher Young's modulus results in better stiffness and strength, leading to superior drop resistance and impact resistance. A higher shear modulus helps improve the structural stiffness of chemically strengthened glass, ensuring its dimensional accuracy.

[0028] In some possible implementations, the CS50 of the chemically strengthened glass satisfies: 120MPa≤CS50≤400MPa. Here, 50μm is the depth of the strengthening layer measured from its surface, specifically the compressive stress value at a distance of 50μm from the surface of the strengthening layer within the chemically strengthened glass.

[0029] It is understandable that the CS50 of traditional Al2O3-SiO2 system chemically strengthened glass is less than 100MPa. The MgO-ZrO2-SiO2 chemically strengthened glass provided in this application has a higher CS50 value, which can effectively suppress the initiation and expansion of surface defects in chemically strengthened glass, and is conducive to ensuring that chemically strengthened glass has higher strength and better drop resistance.

[0030] In some possible implementations, the relationship between the depth DOL of the strengthening layer of the chemically strengthened glass and the thickness D of the chemically strengthened glass satisfies: DOL / D≥10%.

[0031] As can be understood, the reinforcement layer depth (DOL) refers to the depth of the reinforcement layer on one side of the chemically strengthened glass, that is, the distance from the surface of the chemically strengthened glass to the point where the compressive stress value is 0. A larger reinforcement layer depth (DOL) reflects that the chemically strengthened glass has better drop resistance and can better improve the reliability of electronic devices.

[0032] In some possible implementations, the average tensile stress CT.av in the tensile stress zone of the chemically strengthened glass satisfies: 50MPa≤CT.av≤250MPa.

[0033] Understandably, chemically strengthened glass has a higher average tensile stress (CT.av) in the tensile stress zone, and therefore exhibits better drop resistance and impact resistance.

[0034] In some possible implementations, the composite fracture toughness of chemically strengthened glass satisfy:

[0035] It is understandable that the composite fracture toughness of chemically strengthened glasses based on the traditional Al2O3-SiO2 system is limited. 1.1 MPa·m 0.5 Clearly, the MgO-ZrO2-SiO2 chemically strengthened glass provided in this application has high composite fracture toughness. Chemically strengthened glass has better drop resistance and impact resistance.

[0036] In some possible implementations, the drop height H of chemically strengthened glass satisfies: 1.5m ≤ H ≤ 4.5m. It is understood that a larger drop failure height H indicates better drop resistance and impact resistance in chemically strengthened glass.

[0037] In some possible implementations, the thickness T of the chemically strengthened glass is ≤ 2 mm. It is understood that a smaller thickness facilitates the use of chemically strengthened glass in the manufacture of thinner glass covers.

[0038] Fourthly, embodiments of this application provide a chemically strengthened glass. The chemically strengthened glass is obtained by ion exchange of the raw glass described in the first aspect; or, the chemically strengthened glass is obtained by ion exchange of the microcrystalline glass described in the second aspect.

[0039] Chemically strengthened glass, by molar percentage, comprises the following components: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% < K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0040] In some possible implementations, the ion exchange treatment is a two-step ion exchange process. It is understood that in a two-step ion exchange process, ion diffusion can proceed sufficiently, while stress relaxation can be greatly suppressed, which is beneficial for obtaining chemically strengthened glass with high-pressure stress.

[0041] Fifthly, embodiments of this application provide a glass cover. The glass cover is made of the raw glass described in the first aspect, or of the microcrystalline glass described in the second aspect, or of the chemically strengthened glass described in the third aspect, or of the chemically strengthened glass described in the fourth aspect. It is understood that the raw glass, microcrystalline glass, or chemically strengthened glass is a MgO-ZrO2-SiO2 system glass. Compared to traditional Al2O3-SiO2 system glass, the glass of this application can have greater stiffness and strength, therefore the prepared glass cover also has better drop resistance and impact resistance.

[0042] Sixthly, embodiments of this application provide a display screen. The display screen includes a display panel and a glass cover, the glass cover being fixed to the display surface of the display panel. It is understood that the glass cover has better drop resistance and impact resistance, and can better protect the display panel.

[0043] Seventhly, embodiments of this application provide an electronic device. The electronic device includes a housing and a display screen, with the display screen mounted on the housing. It is understood that the display screen has a strong glass cover, resulting in better drop resistance of the electronic device and reducing the likelihood of the display effect being affected by drops or other reasons, thus providing a better user experience.

[0044] Eighthly, embodiments of this application provide a structural component. The structural component includes a frame and a glass cover plate, the glass cover plate being fixed to the frame. It is understood that the glass cover plate of the fifth aspect can be used not only in devices with display functions, but also in other non-electronic devices, or electronic devices without display functions. For example, lenses for telescopes, microscopes, myopia glasses, or automobile windshields. Attached Figure Description

[0045] To illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments of this application will be described below.

[0046] Figure 1 is a schematic diagram of one embodiment of the electronic device provided in this application;

[0047] Figure 2 is a partially exploded schematic diagram of the electronic device shown in Figure 1;

[0048] Figure 3a is a schematic diagram of the atomic structure of ZrO6 octahedral cluster ions;

[0049] Figure 3b is a schematic diagram of the ionic atomic structure of an aluminum-oxygen tetrahedron;

[0050] Figure 4 is a schematic diagram of a chemically strengthened glass provided in an embodiment of this application;

[0051] Figure 5 shows the stress variation curves with depth for the embodiment shown in the table. Detailed Implementation

[0052] For ease of understanding, the English abbreviations and related technical terms used in the embodiments of this application will be explained and described below.

[0053] Chemically strengthened glass, Ion-exchanged glasses, IXG;

[0054] Surface compressive stress (CS);

[0055] Depth of Compressive Layer (DOL)

[0056] Compressive stress at a depth of 50 μm, CS50;

[0057] Average tensile stress in the central region, CT.av;

[0058] The maximum tensile stress in the central region, CT.cv;

[0059] Molecular dynamics simulation (MD);

[0060] Large-scale Atomic / Molecular Massively Parallel Simulator (LAMMPS);

[0061] Cover glass, CG.

[0062] The embodiments of this application are described below with reference to the accompanying drawings. The embodiments described herein with reference to the accompanying drawings are exemplary and intended to explain this application, and should not be construed as limiting this application.

[0063] In the description of the embodiments of this application, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation" and "connection" should be interpreted broadly. For example, "connection" can be a detachable connection or a non-detachable connection; it can be a direct connection or an indirect connection through an intermediate medium. It should be understood that in this application, "electrical connection" can be understood as components physically contacting and conducting electricity; it can also be understood as a form of connection between different components in a circuit structure through physical lines that can transmit electrical signals, such as copper foil or wires on a printed circuit board (PCB). "Connection" and "connected" can both refer to a mechanical connection relationship or a physical connection relationship. For example, A connecting to B or A being connected to B can mean that there are fastening components (such as screws, bolts, rivets, etc.) between A and B, or that A and B are in contact with each other and are difficult to separate.

[0064] Furthermore, the term "fixed" in this document should be interpreted broadly. For example, "fixed" can mean direct fixing or indirect fixing through an intermediate medium. "Fixed" refers to connections where the relative positional relationship remains unchanged after connection. The directional terms used in the embodiments of this application, such as "upper" and "lower," are merely for reference to the directions in the accompanying drawings. Therefore, the directional terms used are for better and clearer explanation and understanding of the embodiments of this application, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the embodiments of this application. "Multiple" refers to two or more.

[0065] In the description of the embodiments of this application, unless otherwise stated, " / " means "or". For example, A / B can mean A or B. The "and / or" in the text is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, and B exists alone. In addition, in the description of the embodiments of this application, "multiple" means two or more.

[0066] In the embodiments of this application, the terms "first," "second," "third," and "fourth" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined with "first," "second," "third," and "fourth" may explicitly or implicitly include one or more of that feature.

[0067] The embodiments of this application are described below with reference to the accompanying drawings.

[0068] Figure 1 is a schematic diagram of one embodiment of the electronic device 1000 provided in this application. It should be noted that Figure 1 only schematically shows some components included in the electronic device 1000; the actual size, location, and structure of these components are not limited by Figure 1. Similarly, the following figures only schematically show some components; the actual size, location, and structure of these components are not limited by the following figures. Specific details will not be elaborated further below.

[0069] As shown in Figure 1, this application provides an electronic device 1000. The electronic device 1000 can be a mobile phone, tablet personal computer, laptop computer, personal digital assistant (PDA), personal computer, laptop computer, in-vehicle equipment, wearable device, augmented reality (AR) glasses, AR headset, virtual reality (VR) glasses, VR headset, monitor, speaker, automobile, and headphones, etc., and is an electronic device 1000 with a glass structure related to mobile office, smart home, sports and health, audio-visual entertainment, and smart travel. The electronic device 1000 in the embodiment shown in Figure 1 is illustrated using a mobile phone as an example.

[0070] Figure 2 is a partially exploded schematic diagram of the electronic device 1000 shown in Figure 1.

[0071] As shown in Figures 1 and 2, the electronic device 1000 includes a display screen 100, a housing 200, and electronic components (not shown). The housing 200 can serve as a structural support component for the electronic components. This application does not specifically limit the structure of the housing 200.

[0072] For example, the display screen 100 is mounted on the housing 200. The display screen 100 may be within the internal space of the electronic device 1000 enclosed by the housing 200. The display screen 100 may be a flat screen, i.e., the edges of the display screen 100 are not curved to form an arc surface. Alternatively, the display screen 100 may be a curved screen, i.e., the edges of the display screen 100 are curved to form an arc surface. In addition, the display screen 100 may be a non-foldable rigid screen or a foldable screen.

[0073] For example, the electronic device may be located inside the electronic device 1000. The electronic device may be a camera module, a fingerprint module, a home button, a handset, or a speaker, etc.

[0074] As shown in Figure 2, exemplarily, the display screen 100 includes a glass cover plate 10 and a display panel 20. The glass cover plate 10 is fixed to the display surface of the display panel 20. The glass cover plate can be used to protect the display panel. The display panel 20 can be an organic light-emitting diode (OLED) panel, a quantum dot light-emitting diode (QLED) panel, etc. This embodiment uses an OLED display panel 20 as an example for description.

[0075] For example, the housing 200 may include a mid-frame 210 and a rear cover 220. The mid-frame 210 may be fixedly connected between the rear cover 220 and the glass cover 10. The display panel 20 may be fixedly connected to the side of the glass cover 10 near the rear cover 220. In some embodiments, the rear cover 220 may be made of glass. In this way, the rear cover 220 may have a better appearance.

[0076] In traditional technical solutions, the various protective glasses used in electronic devices 1000, such as the glass cover 10 and the back cover 220, are still mainly Al2O3-SiO2 system glass. However, the current Al2O3-SiO2 system glass has a low Young's modulus and a low coefficient of volume expansion, resulting in a low stress level. Its drop resistance in practical application scenarios still cannot meet expectations, nor can it support the evolution of thinner and lighter products such as mobile phones.

[0077] Therefore, this application provides a raw glass material with high Young's modulus and coefficient of volume expansion. The raw glass material is chemically strengthened to obtain chemically strengthened glass, which can possess high modulus, high fracture toughness, and a high coefficient of volume expansion. The raw glass material or chemically strengthened glass can be used to manufacture various protective glasses for electronic devices (e.g., glass covers 10 and 220 for mobile phones, or protective covers for watches), providing good protection for various components of electronic devices.

[0078] In some embodiments, the raw glass comprises, by molar percentage, the following components: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% ≤ K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0079] It is understandable that by rationally controlling the molar ratio of each oxide in the raw glass component, a high-performance MgO-ZrO2-SiO2 raw glass is formed. The main network components of the raw glass in this application may include SiO2 and ZrO2.

[0080] The content of SiO2 (silicon dioxide) affects the connectivity of the glass network structure. Too low a SiO2 content results in a weaker network structure, leading to poorer glass forming and reduced stability. Too high a SiO2 content not only increases the viscosity of the molten glass and higher melting costs but also reduces the mechanical properties of the raw glass. Considering all these factors, the molar percentage of SiO2 in this application is controlled between 50% and 80%. Specifically, the molar percentage of SiO2 can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.

[0081] Zirconia (ZrO2) not only affects the network connectivity of glass but also the ion exchange capacity of the raw glass. Generally, the higher the ZrO2 content, the higher the network connectivity of the glass, and the higher the stability and mechanical properties of the glass. However, if the ZrO2 content is too high, although the stability of the glass network structure increases, the glass melting becomes more difficult. Taking into account all the effects, the molar percentage of ZrO2 in this application is controlled between 4% and 15%. Specifically, the molar percentage of ZrO2 can be 4%, 5%, 7%, 10%, 12%, 13%, 15%, etc.

[0082] The network outer layer of the raw glass in this application may include Li₂O (lithium oxide), Na₂O (sodium oxide), and K₂O (potassium oxide). These alkali metal ions (Li₂O, Na₂O, and K₂O) are important carriers for achieving chemical strengthening and introducing compressive stress. Higher alkali metal ion content results in better ion exchange performance of the glass; however, excessively high alkali metal ion content can lead to structural instability, poor glass formation, and difficulty in molding. Therefore, rationally controlling the content of alkali metal oxides in the glass composition can enable the raw glass to undergo efficient ion exchange, achieving a deeper strengthening layer and higher surface compressive stress, thereby secondary enhancement of the raw glass's strength and ultimately obtaining excellent mechanical properties such as drop resistance and scratch resistance.

[0083] For example, in this application embodiment, the molar percentage of Li2O is controlled between 5% and 20%. Specifically, the molar percentage of Li2O can be 5%, 8%, 10%, 12%, 15%, 17%, 20%, etc.

[0084] For example, this application controls the molar percentage of Na2O to be between 1% and 10%. Specifically, the molar percentage of Na2O can be 1%, 2%, 3%, 4%, 6%, 7%, 8%, 9%, 10%, etc.

[0085] For example, this application controls the molar percentage of K2O to be between 0% and 5%. Specifically, the molar percentage of K2O can be 0%, 1%, 2%, 3%, 4%, 5%, etc.

[0086] The main intermediates in the network of the raw glass in this application may include MgO (magnesium oxide) and ZnO (zinc oxide). MgO and ZnO can further increase the Young's modulus. At the same time, increasing the percentage of MgO and / or ZnO can also lower the melting temperature and high-temperature viscosity, effectively dissolve ZrO2, improve the glass-forming ability of the system, reduce the tendency to crystallize, and improve the forming ability of the high ZrO2 glass system.

[0087] For example, in this application embodiment, the molar percentage of MgO is controlled between 5% and 15%. Specifically, the molar percentage of MgO can be 5%, 6%, 8%, 10%, 12%, 14%, 15%, etc.

[0088] For example, in this application embodiment, the molar percentage of ZnO is controlled between 0% and 5%. Specifically, the molar percentage of ZnO can be 0%, 1%, 2%, 3%, 4%, 5%, etc.

[0089] The raw glass in this application also includes B2O3 and P2O5. It is understood that ZrO2 has a high melting point and low solubility in aluminosilicates. B2O3 and P2O5 can act as fluxes; adding appropriate amounts of B2O3 and P2O5 can lower the melting temperature and high-temperature viscosity, improving the fluidity of the raw glass during the forming process, which is beneficial for the forming of MgO-ZrO2-SiO2 raw glass. For example, the forming temperature for preparing conventional Al2O3-SiO2 system glass is generally around 1620℃. ZrO2 has a high melting point, and as the ZrO2 content in the glass raw materials increases, the forming temperature required for the raw glass also rises accordingly, exceeding 1650℃, which causes significant damage to the equipment. When appropriate amounts of B2O3 and P2O5 are added, the melting temperature can be reduced by 30℃ to 50℃. Therefore, the forming temperature of the raw glass, which increases due to the increased ZrO2 content, can be lowered to around 1600℃, which helps reduce damage to the preparation equipment, extend equipment life, and improve production efficiency.

[0090] For example, in this application embodiment, the molar percentage of B2O3 is controlled between 0% and 3%. Specifically, the molar percentage of B2O3 can be 0%, 1%, 2%, 3%, etc.

[0091] For example, in this application embodiment, the molar percentage of P2O5 is controlled between 0% and 5%. Specifically, the molar percentage of P2O5 can be 0%, 1%, 2%, 3%, 4%, 5%, etc.

[0092] The raw glass of this application contains 0% ≤ Al2O3 ≤ 2%. It is understood that raw materials containing Al2O3 (alumina) are not intentionally added during the preparation of the raw glass. However, since the raw materials of each component are not pure substances, they may contain trace amounts of Al2O3. The Al2O3 content in the raw glass can be within a low range and will not affect the forming of the MgO-ZrO2-SiO2 raw glass. For example, the molar percentage of Al2O3 can be 0%, 0.0001%, 0.001%, 0.1%, 0.3%, 0.6%, 1%, 1.3%, 1.6%, 1.7%, 2%, etc.

[0093] In some embodiments of this application, the raw glass may further include a clarifying agent. The addition of a clarifying agent can reduce bubbles, streaks, etc., in the molten glass during the glass melting process, thereby achieving a better melting effect. The clarifying agent includes one or more of the following: Sb₂O₃ (antimony trioxide), As₂O₃ (arsenic oxide), SnO₂ (tin dioxide), Na₂SO₄ (sodium sulfate), K₂SO₄ (potassium sulfate), Li₂SO₄ (lithium sulfate), NaNO₃ (sodium nitrate), Ba(NO₃)₂ (barium nitrate), CaF₂ (calcium fluoride), and Na₂SiF₆ (sodium fluorosilicate), but is not limited to these.

[0094] In some embodiments, the Young's modulus of the raw glass can range from 85 gigapascals (GPa) to 110 GPa. Young's modulus is a physical quantity describing the resistance of a solid material to deformation; a higher Young's modulus indicates that the solid material is less prone to deformation under external force. It is understood that the Young's modulus of the raw glass in the traditional Al2O3-SiO2 system is generally less than or equal to 80 GPa. The Young's modulus of the MgO-ZrO2-SiO2 raw glass of this application is in the range of 85 GPa to 110 GPa, which is significantly higher than that of the raw glass in the traditional Al2O3-SiO2 system. Increasing the ZrO2 content in the raw glass can significantly increase the bonding strength and structural density, thereby significantly improving the Young's modulus of the raw glass. A high Young's modulus is beneficial in two ways: firstly, it helps to ensure the stiffness and strength of chemically strengthened glass after the original glass is chemically strengthened; secondly, it helps to obtain a high compressive stress value in the chemically strengthened glass, which in turn helps to improve the drop resistance and impact resistance of the chemically strengthened glass.

[0095] In some embodiments, the coefficient of volume expansion B (Na) of the original glass is... + →Li + The coefficient of volumetric expansion (B(Na)) can be in the range of 0.06 to 0.1. + →Li + ) is a description of material Na + →Li+ The physical quantity of ion exchange capacity, the volume expansion coefficient B(Na) + →Li + The larger the ) is, the more Na of the material + ->Li + The better the ion exchange capacity, the better. It's understandable that the volume expansion coefficient B(Na) of the raw glass in the traditional Al2O3-SiO2 system is... + →Li + The coefficient of volume expansion B(Na) of the MgO-ZrO2-SiO2 raw glass in this application is generally less than 0.06. + →Li + The coefficient of thermal expansion (C / Na) is significantly higher than that of traditional Al2O3-SiO2 system raw glass in the range of 0.06 to 0.1. + →Li + Increasing the ZrO2 content in raw glass can significantly improve the coefficient of volume expansion B(Na). + →Li + ), to improve the Na content of the raw glass + →Li + Ion exchange capacity is beneficial for subsequent chemical strengthening of the raw glass.

[0096] In some embodiments, the coefficient of volume expansion B(K) of the original glass is... + →Na + The coefficient of volumetric expansion (B(K)) can range from 0.09 to 0.17. + →Na + ) is a description of material K + →Na + The physical quantity of ion exchange capacity, the volume expansion coefficient B(K) + →Na + The larger the K value, the greater the material's K value. + →Na + The better the ion exchange capacity, the better. It's understandable that the coefficient of volume expansion (K2) of the raw glass in the traditional Al2O3-SiO2 system is. + →Na + The coefficient of volume expansion B(K) of the MgO-ZrO2-SiO2 raw glass in this application is generally less than 0.08. + →Na + The coefficient of thermal expansion (B(K)) is in the range of 0.09 to 0.17, which is significantly higher than that of the bulk expansion coefficient B(K) of the traditional Al2O3-SiO2 system of raw glass. + →Na + Increasing the ZrO2 content in raw glass can significantly improve the coefficient of volumetric expansion, B(K). + →Na + ), improve the K of the raw glass +→Na + Ion exchange capacity is beneficial for subsequent chemical strengthening of the raw glass.

[0097] In some implementations, the fracture toughness of the raw glass can reach 0.8 MPa per meter. 0.5 ) to 1.1 MPa 0.5 Within a certain range. Fracture toughness is a physical quantity describing the resistance of a solid material to crack propagation and brittle fracture. The greater the fracture toughness, the less likely the material is to crack under external force. It is understandable that the fracture toughness of the original glass material in the traditional Al2O3-SiO2 system is less than or equal to 0.75 MPa. 0.5 The fracture toughness of the MgO-ZrO2-SiO2 raw glass in this application is 0.8 MPa. 0.5 Up to 1.1 MPa 0.5 Within the specified range, the fracture toughness of the raw glass is significantly higher than that of the traditional Al2O3-SiO2 system. The raw glass of this application has high fracture toughness. High fracture toughness improves the intrinsic damage resistance of the raw glass and enhances its resistance to crack propagation and bifurcation. This, in turn, helps to improve the tensile stress limit of the chemically strengthened raw glass, which can help improve the drop resistance and impact resistance of chemically strengthened glass.

[0098] The following section explains in detail the principle that ZrO2 can improve the ion exchange capacity of raw glass using the ball-and-stick model of ion atoms. Figure 3a is a schematic diagram of the ionic atomic structure of ZrO6 octahedral clusters. Figure 3b is a schematic diagram of the ionic atomic structure of aluminum-oxygen tetrahedra.

[0099] As shown in Figures 3a and 3b, in the traditional Al2O3-SiO2 system of raw glass, an aluminum-oxygen tetrahedron carries a Li₂O₃ atom. + This forms a LiAlO2 structure. The MgO-ZrO2-SiO2 raw glass material provided in this application allows ZrO2 to react with free Li... + / Na + Stable ZrO6 octahedral clusters are formed. For example, one ZrO6 octahedron carries two Li groups. + Forming a stable structure of Li₂ZrO₆, carrying Li + The number of MgO-ZrO2-SiO2 is twice that of aluminum-oxygen tetrahedra, thus forming more efficient ion transport channels. Therefore, compared with the traditional Al2O3-SiO2 system glass, the novel MgO-ZrO2-SiO2 system raw material glass of this application has a significantly higher coefficient of volume expansion, thus having greater strengthening potential, as well as better fracture toughness and Young's modulus, and superior intrinsic mechanical properties.

[0100] It is understandable that by rationally controlling the molar ratio of each oxide in the raw glass component, a high-performance MgO-ZrO2-SiO2 raw glass is formed. Furthermore, by rationally controlling the content of alkali metal oxides in the glass component, the raw glass can undergo efficient ion exchange, achieving a deeper strengthening layer and higher surface compressive stress, thus further enhancing the strength of the raw glass and ultimately obtaining excellent mechanical properties such as drop resistance and scratch resistance. In addition, while possessing good mechanical properties, the raw glass remains transparent in the visible light band, which is beneficial for its application in the field of electronic devices. Therefore, the raw glass provided in this application embodiment can effectively combine excellent mechanical properties (high Young's modulus) and high ion exchange performance, thereby better meeting the application requirements of protective glass materials in fields such as electronic devices.

[0101] The term "ion exchange" used in this application refers to what is commonly known as "chemical fortification." Its main principle is to transfer larger ions (such as K+) from a molten salt into the ion exchange medium. + Na + ) and smaller ions in glass (such as Na) + Li + The ion exchange layer (also known as the strengthening layer or compressive stress layer) is formed on the glass surface through the "squeezing effect" by exchanging ions with the glass.

[0102] This application also provides a method for preparing the aforementioned raw glass, comprising:

[0103] The raw materials corresponding to the components of the raw glass are mixed according to the composition of the raw glass, and then melted, shaped, and annealed to obtain the raw glass. The components of the raw glass, in molar percentage, include: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% ≤ K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0104] It is understood that, by adjusting the appropriate component ratio of the raw glass, the embodiments of this application can prepare glass raw materials with high Young's modulus, high fracture toughness, and high ion exchange capacity, so as to meet the high performance requirements of glass products in fields such as electronic devices.

[0105] Although the components in the aforementioned raw glass are expressed in oxide terms, in actual manufacturing, the raw materials corresponding to each component can be various forms of materials available in the glass manufacturing field. For example, the aforementioned SiO2 can be silica sand, the aforementioned ZrO2 can be ZrO2, zirconium silicate, etc., the aforementioned MgO can be dolomite, basic magnesium carbonate, light magnesium oxide, etc., the aforementioned Li2O can be Li2CO3, the aforementioned Na2O can be Na2CO3, the aforementioned ZnO can be ZnO, zinc silicate, etc., and the aforementioned SiO2, Li2O, ZnO, and MgO can be added together in the form of silicate materials. The form of raw materials corresponding to each glass component is not limited, as long as the proportions of these materials, after being converted into oxides, can meet the aforementioned oxide content requirements.

[0106] Specifically, melting involves melting the raw materials corresponding to each component to form a molten glass. The melting temperature can be between 1600 degrees Celsius (°C) and 1680°C, for example, 1600°C, 1630°C, 1650°C, 1670°C, 1680°C, etc. In some embodiments, after melting, a clarification and homogenization treatment is performed to shape the uniformly mixed and clarified molten glass.

[0107] Forming is the process of transforming molten glass into a geometrically shaped product (i.e., raw glass) at a certain temperature. In some embodiments, the raw glass is in the form of a plate / block, such as glass sheets or glass bricks. Its thickness can be selected according to application requirements. Forming methods may include, but are not limited to, casting, calendering, float glass, overflow drawing, and slot-pull forming.

[0108] The purpose of annealing after molding is to minimize or eliminate thermal stress generated in the glass. In this embodiment, the annealing temperature can be in the range of 500℃-750℃, for example, 550℃, 560℃, 580℃, 600℃, 620℃, 650℃, 670℃, 700℃, 720℃, 750℃, etc.

[0109] Understandably, prolonged annealing near the glass transition temperature yields stress-free raw glass. This raw glass then undergoes multiple processing steps, including cutting, rough grinding, CNC machining, and polishing, to ultimately obtain glass samples with the target dimensions.

[0110] The preparation method of the above-mentioned raw glass provided in this application embodiment is simple and suitable for industrial production.

[0111] This application also provides a microcrystalline glass, which has a high Young's modulus and coefficient of volume expansion. The microcrystalline glass can be chemically strengthened to obtain chemically strengthened glass. The microcrystalline glass can also be used to prepare various protective glasses for electronic devices (e.g., glass covers 10 and 220 for mobile phones, or protective covers for watches), providing good protection for various components of electronic devices. Exemplarily, in molar percentage, the microcrystalline glass comprises the following components: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% ≤ K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0112] Understandably, by rationally controlling the molar ratio of each oxide in the glass-ceramic composition, a high-performance MgO-ZrO2-SiO2 glass-ceramic is formed. The glass-ceramic uses ZrO2 to replace Al2O3, and ZrO2 can react with free Li... + / Na + Stable ZrO6 octahedral clusters are formed. Each ZrO6 octahedron carries two Li groups. + Forming a stable structure of Li₂ZrO₆, carrying Li + The number of atoms is twice that of aluminum-oxygen tetrahedra, which is beneficial for microcrystalline glass to form more efficient ion transport channels.

[0113] In some embodiments, the crystals of the glass-ceramic may include Zr. 4+ / Mg 2+ Solid-solution β-quartz, magnesium silicate, zirconium silicate, lithium zirconate, or one or more of these.

[0114] In some embodiments, the grain size of the glass-ceramic crystals can range from 1 nanometer (nm) to 100 nm. It is understood that the grain size of the glass-ceramic crystals is much smaller than the wavelength of visible light, resulting in less scattering of visible light and thus contributing to the high transmittance of the glass-ceramic.

[0115] In some embodiments, the crystallinity of the glass-ceramic is between 1% and 90%. Adjusting the crystallinity within this range allows for control over the glass-ceramic's hardness, Young's modulus, light transmittance, and other properties, resulting in superior overall performance. For example, the crystallinity of the glass-ceramic can be 1%, 5%, 10%, 14%, 20%, 27%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc.

[0116] In some embodiments, microcrystalline glass can be obtained by nucleation and crystallization treatments on the aforementioned glass raw materials. The nucleation treatment temperature is generally in the range of 700°C to 800°C, and the time is generally in the range of 2 hours to 48 hours. The crystallization treatment temperature is generally in the range of 750°C to 1050°C, and the time is generally in the range of 2 hours to 48 hours.

[0117] In some embodiments, the Young's modulus of the glass-ceramic can be in the range of 85 GPa to 110 GPa. Young's modulus is a physical quantity describing the resistance of a solid material to deformation. The higher the Young's modulus, the less likely the solid material is to deform under external force. Young's modulus is a type of elastic modulus. It is understood that the Young's modulus of traditional Al2O3-SiO2 system glass-ceramics is generally less than or equal to 80 GPa. The Young's modulus of the MgO-ZrO2-SiO2 glass-ceramic of this application is in the range of 85 GPa to 110 GPa, which is significantly higher than that of traditional Al2O3-SiO2 system glass-ceramics. Increasing the ZrO2 content in glass-ceramics can significantly increase bonding strength and structural density, thereby significantly improving the Young's modulus. A high Young's modulus is beneficial in two ways: firstly, it helps to ensure the stiffness and strength of chemically strengthened glass obtained after chemical strengthening of microcrystalline glass; secondly, it helps to obtain a high compressive stress value in chemically strengthened glass, which in turn helps to improve the drop resistance and impact resistance of chemically strengthened glass.

[0118] In some embodiments, the volume expansion coefficient B(Na) of the glass-ceramic is... + →Li + The coefficient of volumetric expansion (B(Na)) can be in the range of 0.06 to 0.1. + →Li + ) is a description of material Na + →Li + The physical quantity of ion exchange capacity, the volume expansion coefficient B(Na) + →Li + The larger the ) is, the more Na of the material + ->Li + The better the ion exchange capacity, the better. It's understandable that the volume expansion coefficient B(Na) of the traditional Al₂O₃-SiO₂ system of glass-ceramics is... + →Li + The bulk expansion coefficient B(Na) of the MgO-ZrO2-SiO2 microcrystalline glass of this application is generally less than 0.06. + →Li + The coefficient of volume expansion (B(Na)) is significantly higher than that of traditional Al2O3-SiO2 system glass-ceramics in the range of 0.06 to 0.1. + →Li +Increasing the ZrO2 content in microcrystalline glass can significantly improve the volumetric expansion coefficient B(Na). + →Li + ), to improve the Na content of glass-ceramics + →Li + Ion exchange capacity is beneficial for subsequent chemical strengthening of glass-ceramics.

[0119] In some embodiments, the volume expansion coefficient B(K) of the glass-ceramic is... + →Na + The coefficient of volumetric expansion (B(K)) can range from 0.09 to 0.17. + →Na + ) is a description of material K + →Na + The physical quantity of ion exchange capacity, the volume expansion coefficient B(K) + →Na + The larger the K value, the greater the material's K value. + →Na + The better the ion exchange capacity, the better. It's understandable that the volume expansion coefficient (Kc) of the traditional Al2O3-SiO2 system of glass-ceramics is... + →Na + The volume expansion coefficient B(K) of the MgO-ZrO2-SiO2 microcrystalline glass of this application is generally less than 0.08. + →Na + The coefficient of volume expansion (B(K)) is significantly higher than that of traditional Al2O3-SiO2 glass-ceramics in the range of 0.09 to 0.17. + →Na + Increasing the ZrO2 content in microcrystalline glass can significantly improve the coefficient of volume expansion B(K). + →Na + ), to improve the K of glass-ceramics + →Na + Ion exchange capacity is beneficial for subsequent chemical strengthening of glass-ceramics.

[0120] In some embodiments, the fracture toughness of the glass-ceramic can reach 1.1 MPa. 0.5 Up to 2.0 MPa 0.5 Within a certain range. Fracture toughness is a physical quantity describing the resistance of a solid material to crack propagation and brittle fracture. The greater the fracture toughness, the less likely the material is to crack under external force. It is understandable that the fracture toughness of traditional Al2O3-SiO2 system glass-ceramics is less than or equal to 1.0 MPa. 0.5 The fracture toughness of the MgO-ZrO2-SiO2 microcrystalline glass of this application is 1.1 MPa. 0.5 Up to 2.0 MPa 0.5Within the specified range, the fracture toughness of the microcrystalline glass is significantly higher than that of the traditional Al2O3-SiO2 system. The microcrystalline glass of this application exhibits high fracture toughness, which enhances both the intrinsic damage resistance of the microcrystalline glass and its resistance to crack propagation and bifurcation. This, in turn, helps to increase the tensile stress limit of the chemically strengthened microcrystalline glass, thus contributing to improved drop resistance and impact resistance.

[0121] This application also provides a method for preparing the above-mentioned microcrystalline glass, comprising:

[0122] The raw materials corresponding to the components of the microcrystalline glass are mixed according to the composition of the original glass, and then melted, shaped, and annealed to obtain the microcrystalline glass. The components of the microcrystalline glass, in molar percentage, include: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% ≤ K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0123] It is understood that, by adjusting the appropriate component ratio of the microcrystalline glass and combining it with heat treatment to achieve crystallization, the embodiments of this application can prepare microcrystalline glass with high Young's modulus, high fracture toughness, and high ion exchange capacity, so as to meet the high performance requirements of glass products in fields such as electronic devices.

[0124] This application also provides a chemically strengthened glass, which can be obtained by ion exchange (i.e., chemical strengthening) of the raw glass or microcrystalline glass described in the embodiments of this application. After ion exchange, a strengthening layer (i.e., a compressive stress layer) of a certain depth is formed on the surface of the raw glass, which has higher surface compressive stress and further improves mechanical properties, such as surface hardness and fracture toughness, thereby greatly improving its ability to resist external forces.

[0125] Referring to Figure 4, which is a schematic diagram of a chemically strengthened glass provided in an embodiment of this application, the chemically strengthened glass includes a body layer 11 and a strengthening layer 12 located on the surface of the body layer 11. The body layer 11 can be completely identical to the raw material glass or microcrystalline glass described in the embodiments of this application (including composition and crystal composition, etc.), that is, the body layer 11 includes the raw material glass or microcrystalline glass described in the embodiments of this application. The strengthening layer 12 can be regarded as the product of ion exchange of the raw material glass or microcrystalline glass. After ion exchange, the composition or crystal composition of the strengthening layer 12 changes relative to the body layer 11. The strengthening layer 12 can be formed on one side of the body layer 11 or on opposite sides of the body layer 11.

[0126] In some embodiments, the chemically strengthened glass comprises, by molar percentage, the following components: 4% ≤ ZrO2 ≤ 15%; 5% ≤ MgO ≤ 15%; 50% ≤ SiO2 ≤ 80%; 5% ≤ Li2O ≤ 20%; 1% ≤ Na2O ≤ 10%; 0% < K2O ≤ 5%; 0% ≤ ZnO ≤ 5%; 0% ≤ B2O3 ≤ 3%; 0% ≤ P2O5 ≤ 5%; 0% ≤ Al2O3 ≤ 2%.

[0127] In some embodiments, after ion exchange, the surface compressive stress CS of the chemically strengthened glass satisfies: CS ≥ 800 MPa. For example, the surface compressive stress CS of the chemically strengthened glass can be 800 MPa, 1000 MPa, 1200 MPa, 1500 MPa, 2000 MPa, etc. It is understood that the surface compressive stress CS of the traditional Al2O3-SiO2 system chemically strengthened glass is less than 800 MPa. The MgO-ZrO2-SiO2 chemically strengthened glass provided in this application has a higher surface compressive stress, which enables the chemically strengthened glass to have higher hardness and fracture toughness, and thus excellent drop resistance.

[0128] In some embodiments, the compressive stress CS50 of the chemically strengthened glass at a depth of 50 μm in the strengthening layer can satisfy: 120 MPa ≤ CS50 ≤ 400 MPa. Here, 50 μm is the depth of the strengthening layer measured from its surface, specifically the compressive stress value at a distance of 50 μm from the surface of the strengthening layer within the chemically strengthened glass. Traditional Al2O3-SiO2 system chemically strengthened glass has a CS50 of less than 100 MPa. The MgO-ZrO2-SiO2 chemically strengthened glass provided in this application has a higher CS50 value, which can effectively suppress the initiation and propagation of surface defects in the chemically strengthened glass, thus ensuring higher strength and better drop resistance.

[0129] In some embodiments, the thickness T of the chemically strengthened glass is less than or equal to 2 mm. It is understood that a smaller thickness facilitates the use of chemically strengthened glass in the fabrication of the glass cover 10, resulting in a thinner and lighter glass cover. Chemically strengthened glass can maintain excellent mechanical properties while maintaining a relatively small thickness.

[0130] In some embodiments, the average tensile stress CT.av in the tensile stress zone of chemically strengthened glass can satisfy: 50MPa≤CT.av≤300MPa. It is understood that a higher average tensile stress CT.av in the tensile stress zone of chemically strengthened glass indicates better drop resistance and impact resistance.

[0131] In some embodiments, the relationship between the depth DOL of the strengthening layer and the thickness D of the chemically strengthened glass satisfies: DOL / D ≥ 10%. For example, DOL can be in the range of 50 μm to 180 μm. It is understood that the strengthening layer depth DOL refers to the depth of the strengthening layer on one side of the chemically strengthened glass, that is, the distance from the surface of the chemically strengthened glass to the location where the compressive stress value is 0. A larger strengthening layer depth DOL reflects better drop resistance of the chemically strengthened glass, thus improving the reliability of electronic devices.

[0132] In some implementations, the Young's modulus E of the chemically strengthened glass can satisfy: E≥85GPa. It is understood that a high Young's modulus results in better stiffness and strength in the chemically strengthened glass, giving it excellent drop resistance and impact resistance.

[0133] In some implementations, the shear modulus G of the chemically strengthened glass can satisfy: G≥30GPa. It is understood that a high shear modulus can help improve the structural stiffness of the chemically strengthened glass and ensure its dimensional accuracy.

[0134] In some embodiments, the composite fracture toughness of chemically strengthened glass It can satisfy: It is understandable that the composite fracture toughness of chemically strengthened glasses based on the traditional Al2O3-SiO2 system is limited. With a strength of 1.1 MPa·m0.5, the MgO-ZrO2-SiO2 chemically strengthened glass provided in this application clearly exhibits high composite fracture toughness. Chemically strengthened glass has better drop resistance and impact resistance.

[0135] In some embodiments, the composite fracture toughness of the chemically strengthened glass according to the embodiments of this application is utilized. It can effectively predict the drop failure height of chemically strengthened glass. Specifically, the drop failure height H of chemically strengthened glass is related to its composite fracture toughness. A linear positive correlation exists. The larger the drop failure height H, the better the drop resistance and impact resistance of chemically strengthened glass. For example, the drop failure height H of chemically strengthened glass can satisfy: 1.5m ≤ H ≤ 4.5m. Thus, a larger drop failure height H results in better drop resistance and impact resistance.

[0136] In some embodiments, the chemically strengthened glass of this application, while possessing the aforementioned excellent mechanical properties, also exhibits excellent optical properties. For example, the light transmittance of the chemically strengthened glass can be greater than or equal to 85%. It is understood that the chemically strengthened glass, while possessing good mechanical properties, can still remain transparent in the visible light band, which is beneficial for its application in the field of electronic devices.

[0137] The aforementioned chemically strengthened glass can be obtained by ion exchange of the raw glass or microcrystalline glass described in the embodiments of this application. This ion exchange can be a two-step ion exchange process. Under a two-step ion exchange process, ion diffusion can proceed sufficiently, while stress relaxation can be greatly suppressed, which is beneficial for obtaining chemically strengthened glass with high-pressure stress.

[0138] For example, the first ion exchange molten salt used in the first step of ion exchange can be pure NaNO3 molten salt, or a mixed molten salt of KNO3 and NaNO3, and this exchange step uses Na... + →Li + Exchange is the main factor, Na + The minimum content must be higher than the molar ratio of Na2O / (Li2O+Na2O+K2O) in the raw glass composition; the second ion exchange molten salt used in the second step of ion exchange can be KNO3 molten salt, or a mixed molten salt of KNO3 and NaNO3, and this exchange step uses K... + →Na + Exchange is the main method, K + The minimum content must be higher than the molar ratio of Na2O / (Li2O+Na2O+K2O) in the raw glass composition. The temperatures of the first and second ion exchange steps can be independently within a range greater than or equal to 360°, and the times of both the first and second ion exchange steps must be greater than 1 hour.

[0139] In other embodiments, ion exchange can also be a one-step ion exchange process.

[0140] The raw glass, microcrystalline glass, and chemically strengthened glass provided in this application embodiment have high transmittance and excellent mechanical properties, and can be used in various electronic devices 1000. Specifically, they can be used as glass cover plates 10 in electronic devices 1000 to meet the optical requirements of electronic devices 1000 such as display and shooting, while improving product reliability.

[0141] The embodiments of this application will be further described below through multiple examples.

[0142] Table 1 summarizes the composition and performance parameters of the raw glass used in Examples 1-10 of this application.

[0143] Accurately weigh the raw glass materials according to the proportions listed in Table 1, mix them thoroughly, and melt them completely at a high temperature of 1600℃-1680℃ to obtain a homogeneous glass melt. The formulations in the examples can be used to obtain glass sheets or glass bricks of the target thickness by methods such as casting, overflow drawing, or rolling. Subsequently, a long-term annealing treatment is performed near the glass transition temperature to obtain stress-free glass raw materials.

[0144] According to the desired shape and size requirements, the raw glass is cut, CNC machined, ground, and cleaned to obtain a raw glass substrate of the desired shape (such as a sheet). Then, the raw glass substrate is immersed in ion-exchange molten salt for ion exchange to obtain chemically strengthened glass.

[0145] The physical properties of the raw glass can be tested using the following methods: the density of the raw glass is measured using a density balance with the Archimedes method; the Young's modulus E and shear modulus G of the raw glass are tested using a pulse echo spectrometer based on the sound velocity method; the fracture toughness of the raw glass is tested using a universal testing machine based on standard ISO 15732:2003; and the volume expansion coefficient B(Na) of the raw glass is also tested. + →Li + The following formula was used to calculate the result through molecular dynamics simulation:

[0146] Where V is the molar volume and C is the Na content. + →Li + Na produced by ion exchange + The change in molar concentration.

[0147] Table 1. Composition of Raw Glass Materials

[0148] As shown in Table 1, many of the new glass formulations listed in Table 1 exhibit excellent mechanical properties.

[0149] For example, the Young's modulus of the raw glass materials in Table 1 is all greater than or equal to 82 GPa. In some embodiments, the Young's modulus is close to 100 GPa, or even close to 120 GPa. It is understood that a high Young's modulus in the raw glass material is beneficial in two ways: firstly, it helps to ensure the stiffness and strength of the raw glass material, which is beneficial for supporting the thinning of the cover plate when the raw glass material is used directly or after chemical strengthening; secondly, it also helps to obtain a high compressive stress value after the raw glass material is chemically strengthened.

[0150] For example, the coefficient of volume expansion B (Na) of the raw glass in Table 1 + →Li + The B(Na) content is generally higher than 0.06, reaching 0.08, and some even reach 0.1. This is typical for traditional Al-Si glass systems. + →Li+ The coefficient of volume expansion (B(Na)) is generally about 0.05-0.06. The coefficient of volume expansion of the raw glass in the MgO-ZrO2-SiO2 system of this application is approximately 0.05-0.06. + →Li + It is significantly higher than that of traditional Al-Si system glass.

[0151] For example, the coefficient of volume expansion B(K) of the raw glass in Table 1 + →Na + The α value is generally higher than 0.09, with some examples reaching 0.12, 0.15, and even 0.18. Traditional Al-Si system glass B(K) + →Na + The coefficient of volume expansion B(K) of the MgO-ZrO2-SiO2 system of this application is approximately 0.08. + →Na + It is significantly higher than that of traditional Al-Si system glass.

[0152] For example, the fracture toughness of the raw glass materials in Table 1 is generally higher than 0.75 MPa·m. 0.5 Some embodiments have a strength higher than 0.8 MPa·m 0.5 0.9 MPa·m 0.5 Even higher than 1.1 MPa·m 0.5 It is understandable that the high fracture toughness of the raw glass can improve its intrinsic damage resistance on the one hand, and enhance its resistance to crack propagation and bifurcation on the other, thereby increasing the tensile stress limit of the chemically strengthened raw glass.

[0153] Table 2 summarizes the process parameters of the raw glass materials from some of the embodiments in Table 1 after two-step ion exchange, the performance parameters of the chemically strengthened glass formed after strengthening, and the parameters of existing products. In Table 2, the serial numbers of the embodiments correspond to the serial numbers of the embodiments in Table 1. Comparative Example 1 is a two-strength glass of the Al2O3-SiO2 system, and Comparative Example 2 is a one-strength glass of the Al2O3-SiO2 system.

[0154] Among these tests, stress performance can be measured using a stress meter. For example, the FSM6000 instrument can be used to test the CS of chemically strengthened glass; the SLP2000 instrument can be used to test the CS50, DOL, and CT.AV of chemically strengthened glass.

[0155] The composite fracture toughness of chemically strengthened glass can be tested using the method described in CN116143422A of the published literature. The drop resistance and impact resistance of chemically strengthened glass on rough surfaces.

[0156] Exemplarily, a method for testing the drop resistance of chemically strengthened glass on a rough surface may include: assembling the obtained chemically strengthened glass in a commercial mobile phone, and using a drop tester to test the failure height of the commercial mobile phone in a controlled drop on a surface of 180-grit SiC sandpaper. The initial drop height is 0.6m, gradually increased in increments of 0.1m, and the failure height is the height H at which the glass screen breaks. To obtain the average failure height of the cover glass in the embodiments and comparative examples, at least 5 cover glass pieces are selected for 5 drop tests.

[0157] Table 2 Chemical strengthening process and stress performance

[0158] As shown in Table 2, the raw glass in the examples in Table 2 exhibits very high compressive stress characteristics after chemical strengthening.

[0159] For example, the CS of the chemically strengthened glasses in Table 2 all exceed 0.8 GPa, and some embodiments reach 1.0 GPa. The CS50 of the chemically strengthened glasses in Table 2 generally exceeds 160 MPa, and in some embodiments even exceeds 260 MPa, reaching a maximum of 400 MPa, the highest in known literature. The CT.av of the chemically strengthened glasses in Table 2 generally exceeds 100 MPa, even exceeding 200 MPa, with a maximum reaching 350 MPa. The DOL of the chemically strengthened glasses in Table 2 is also generally higher than 13% of the thickness of the chemically strengthened glass.

[0160] It is understandable that, based on the analysis of the ratios of DOL to glass thickness in the various embodiments and Comparative Example 1, the DOL in Example 1 accounts for 20.2% of the glass thickness, the DOL in Example 2 accounts for 17.5% of the glass thickness, the DOL in Example 3 accounts for 20.0% of the glass thickness, the DOL in Example 6 accounts for 24.8% of the glass thickness, the DOL in Example 7 accounts for 19.0% of the glass thickness, the DOL in Example 8 accounts for 21.0% of the glass thickness, and the DOL in Comparative Example 1 accounts for 19.6% of the glass thickness. While the ratios of DOL to glass thickness in the various embodiments and Comparative Example 1 are similar, the stress parameters of the chemically strengthened glass provided in this application far exceed those of Comparative Example 1, being twice or more.

[0161] Combining the excellent intrinsic properties E of the raw glass in Table 1, the examples in Table 2 demonstrate extremely high composite fracture toughness. In Examples 1, 2, 3, 6, 7, and 8, the composite fracture toughness All of them exceed 80% of Comparative Example 1. The chemically strengthened glass of the MgO-ZrO2-SiO2 system provided in this application has superior composite fracture toughness, drop resistance, and impact resistance compared to traditional Al2O3-SiO2 system glass.

[0162] For example, in Embodiments 1, 2, 3, 6, 7, and 8, the minimum drop height H of the sandpaper is 3.2m, and the maximum can reach 4.5m. Compared to the drop height H of 1.1m in Comparative Example 1, the drop height H data in Table 2 clearly demonstrates that the chemically strengthened glass of the MgO-ZrO2-SiO2 system provided in this application has superior drop resistance and impact resistance compared to the traditional Al2O3-SiO2 system glass.

[0163] Figure 5 shows the stress versus depth curves for the embodiments illustrated in the table. In Figure 5, the horizontal axis represents the depth from the surface of the chemically strengthened glass, and the vertical axis represents the stress value. Except for the curves in the comparative examples indicated by the arrows, all other curves in Figure 5 represent the embodiments.

[0164] As shown in Figure 5, the stress value on the surface of the chemically strengthened glass is significantly greater than that of the comparative example (indicated by arrows in the figure). It is understood that the embodiments of this application, by controlling the appropriate component ratio of the raw glass, formed a high-performance MgO-ZrO2-SiO2 raw glass. After two rounds of chemical strengthening, the raw glass exhibits very high compressive stress characteristics, far exceeding those of traditional Al2O3-SiO2 system chemically strengthened glass.

[0165] In other embodiments, the present application also provides a structural component. The structural component includes a frame and a glass cover plate, with the glass cover plate fixed to the frame. It is understood that the glass cover plate can be used not only in devices with display functions but also in other non-electrical devices or electronic devices without display functions. For example, the structural component can be a pair of eyeglasses, a telescope, a magnifying glass, a microscope, or an automobile. The glass cover plate can serve as a lens for a telescope, a magnifying glass, a microscope, eyeglasses, or an automobile windshield. The glass cover plate can be made from the raw glass, microcrystalline glass, or chemically strengthened glass described in the above embodiments.

[0166] It is understood that, without conflict, the embodiments and features in the embodiments of this application can be combined with each other, and any combination of features in different embodiments is also within the protection scope of this application. That is to say, the multiple embodiments described above can also be arbitrarily combined according to actual needs.

[0167] It is understood that all the above figures are exemplary illustrations of this application and do not represent the actual size of the product. Furthermore, the dimensional proportions between the components in the figures are not intended to limit the actual product of this application.

[0168] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A raw material glass characterized by comprising: The raw material glass comprises the following components in terms of mole percentage: 4%≤ZrO2≤15%; 5%≤MgO≤15%; 50%≤SiO2≤80%; 5%≤Li2O≤20%; 1%≤Na2O≤10%; 0%≤K2O≤5%; 0%≤ZnO≤5%; 0%≤B2O3≤3%; 0%≤P2O5≤5%; 0%≤Al2O3≤2%.

2. The raw material glass according to claim 1, wherein The Young's modulus of the raw material glass is in the range of 85 GPa to 110 GPa.

3. The raw material glass according to claim 1 or 2, wherein The bulk expansion coefficient B (Na + → Li + ) of the raw material glass is in the range of 0.06 to 0.1; and / or The bulk expansion coefficient B (K + → Na + ) of the raw material glass is in the range of 0.09 to 0.

17.

4. The raw material glass according to any one of claims 1 to 3, wherein The raw material glass has a fracture toughness in the range of 0.8 MPam 0.5 to 1.1 MPam 0.5 .

5. A glass-ceramic, characterized in that, The glass-ceramic comprises the following components in terms of mole percentage: 4%≤ZrO2≤15%; 5%≤MgO≤15%; 50%≤SiO2≤80%; 5%≤Li2O≤20%; 1%≤Na2O≤10%; 0%≤K2O≤5%; 0%≤ZnO≤5%; 0%≤B2O3≤3%; 0%≤P2O5≤5%; 0%≤Al2O3≤2%.

6. The microcrystalline glass of claim 5, wherein, The crystals in the glass-ceramics include Zr 4+ solid-solution beta-quartz, Mg 2+ one or more of solid-solution beta-quartz, magnesium silicate, zircon silicate, lithium zirconate.

7. The glass-ceramic according to either of Claims 5 and 6, characterized in that, The grain size of the crystal in the glass-ceramic is in the range of 1 nm to 100 nm.

8. The microcrystalline glass of any one of claims 5-7, wherein, The crystallinity of the glass-ceramic is between 1% and 90%.

9. A chemically strengthened glass characterized in that, The chemically strengthened glass comprises the following components in terms of mole percentage: 4%≤ZrO2≤15%; 5%≤MgO≤15%; 50%≤SiO2≤80%; 5%≤Li2O≤20%; 1%≤Na2O≤10%; 0%<K2O≤5%; 0%≤ZnO≤5%; 0%≤B2O3≤3%; 0%≤P2O5≤5%; 0%≤Al2O3≤2%.

10. The chemically strengthened glass of claim 9, wherein, The surface compressive stress CS of the chemically strengthened glass satisfies: CS≥800 MPa.

11. The chemically strengthened glass according to claim 9 or 10, wherein The Young's modulus E of the chemically strengthened glass satisfies: E≥85 GPa; and / or, The shear modulus G of the chemically strengthened glass satisfies: G≥30 GPa.

12. The chemically strengthened glass of any of claims 9-11, wherein, The CS50 of the chemically strengthened glass satisfies: 120 MPa≤CS50≤400 MPa.

13. The chemically strengthened glass of any of claims 9-12, wherein, The relationship between the depth DOL of the strengthened layer of the chemically strengthened glass and the thickness D of the chemically strengthened glass satisfies: DOL / D≥10%.

14. The chemically strengthened glass of any of claims 9-13, wherein, The average tensile stress CT.av of the tensile stress zone of the chemically strengthened glass satisfies: 50 MPa≤CT.av≤250 MPa.

15. The chemically strengthened glass of any one of claims 9-14, wherein, Composite fracture toughness of the chemically strengthened glass satisfies:

16. The chemically strengthened glass of any of claims 9 to 15, wherein, The drop height H of the chemically strengthened glass satisfies: 1.5 m≤H≤4.5 m.

17. The chemically strengthened glass of any of claims 9 to 16, wherein, The thickness T of the chemically strengthened glass is ≤2 mm.

18. A chemically strengthened glass characterized in that, The chemically strengthened glass is obtained by ion exchange of the raw material glass according to any one of claims 1 to 4; or the chemically strengthened glass is obtained by ion exchange of the glass-ceramic according to any one of claims 5 to 8; The chemically strengthened glass comprises the following components in terms of mole percentage: 4%≤ZrO2≤15%; 5%≤MgO≤15%; 50%≤SiO2≤80%; 5%≤Li2O≤20%; 1%≤Na2O≤10%; 0%<K2O≤5%; 0%≤ZnO≤5%; 0%≤B2O3≤3%; 0%≤P2O5≤5%; 0%≤Al2O3≤2%.

19. The production method according to claim 18, wherein The ion exchange treatment is a two-step ion exchange process.

20. A glass cover plate characterized by, The glass cover plate is made of the raw material glass according to any one of claims 1 to 4, or made of the microcrystalline glass according to any one of claims 5 to 8, or made of the chemically strengthened glass according to any one of claims 6 to 14, or made of the chemically strengthened glass according to claim 18 or 19.

21. A display screen, characterized by A display panel comprising a glass cover plate as claimed in claim 20 fixed to a display surface of the display panel.

22. An electronic device, comprising: A display screen as claimed in claim 21 mounted to a housing.

23. A structural member, characterized by A frame comprising a glass cover plate as claimed in claim 20 fixed to the frame. A frame comprising a glass cover plate as claimed in claim 20 fixed to the frame.

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