CN120817729A

CN120817729A - Chemically strengthened microcrystalline glass, cover glass, electronic equipment and glass device

Info

Publication number: CN120817729A
Application number: CN202410436177.XA
Authority: CN
Inventors: 周靖鹏; 黄昊; 罗峰; 刘志强; 朱广祥; 黄义宏; 陈杰杰
Original assignee: Huawei Technologies Co Ltd; Chongqing Aureavia Hi Tech Glass Co Ltd
Current assignee: Huawei Technologies Co Ltd; Chongqing Aureavia Hi Tech Glass Co Ltd
Priority date: 2024-04-11
Filing date: 2024-04-11
Publication date: 2025-10-21
Also published as: WO2025214396A1

Abstract

The present application provides a chemically strengthened glass-ceramic, cover glass, electronic device, and glass device, belonging to the field of glass-ceramic technology. By ensuring that ultra-thin chemically strengthened glass-ceramic with a thickness of 0.38 mm to 0.60 mm meets specific requirements for crystal phase structure and stress structure, the ultra-thin chemically strengthened glass-ceramic exhibits excellent resistance to penetration by sharp objects and excellent resistance to damage from falling onto rough surfaces. Furthermore, the chemically strengthened glass-ceramic maintains excellent optical properties, meeting the application requirements of cover glass for electronic device protection.

Description

Chemically strengthened glass ceramic, cover plate glass, electronic equipment and glass device

Technical Field

The application relates to the technical field of glass ceramics, in particular to chemically strengthened glass ceramics, cover plate glass, electronic equipment and glass devices.

Background

In recent years, with the continuous development of the electronic product industry, the performance requirements of the market on cover glass materials for electronic equipment are gradually improved, and for this purpose, the cover glass industry sequentially pushes out chemically strengthened glass ceramics with better mechanical strength performance so as to improve the problem that the cover glass is easy to damage, such as falling, chipping, puncturing, scratching, and the like.

Under the market demand of large-screen and light-weight electronic equipment, the thickness of the cover glass material is required to be thinner and thinner, so that the ultrathin cover glass has become an important development trend of the cover glass. However, with the thickness reduction, when the existing chemically strengthened glass ceramic is used as cover glass, the damage probability is generally increased greatly, so that the glass ceramic cannot meet the higher application requirements. Especially when electronic equipment (such as mobile phones, flat plates and the like) is carelessly dropped on gravel roads or stone roads with sharp protruding edges and corners or asphalt roads, thinner cover plate glass adopted by a screen of the electronic equipment is very easy to appear, collides with sharp protruding objects, and is in a condition of penetrating or even puncturing and crushing the sharp protruding objects, so that the appearance of the screen of the electronic equipment can be directly influenced, and the normal use of the electronic equipment can be influenced.

Therefore, under the condition of meeting the demand of light and thin market, it is required to develop a chemically strengthened glass ceramic with excellent anti-damage performance, especially to make it have excellent anti-penetration performance of sharp objects and excellent anti-drop damage performance, so as to reduce the probability of surface damage and breakage caused by impact or penetration of sharp objects on the screen cover glass of the electronic equipment, and further ensure safe and stable operation of the electronic equipment.

Disclosure of Invention

The application provides chemically strengthened glass ceramics, cover plate glass, electronic equipment and glass devices comprising the chemically strengthened glass ceramics, and the chemically strengthened glass ceramics can have excellent capability of resisting penetration of sharp objects and excellent drop damage resistance under ultrathin thickness.

Specifically, the technical scheme provided by the application comprises the following steps:

in a first aspect, a chemically strengthened glass-ceramic is provided, the chemically strengthened glass-ceramic comprising a petalite crystal phase and a lithium disilicate crystal phase, wherein the petalite crystal phase and the lithium disilicate crystal phase have a higher mass percentage than other crystal phases present in the chemically strengthened glass-ceramic;

the thickness t of the chemically strengthened microcrystalline glass is 0.38 mm-0.60 mm;

the chemically strengthened glass ceramics have a compressive stress layer on the surface and a tensile stress in the interior, and the chemically strengthened glass ceramics satisfy the following conditions:

0.18≤DOL_0/t≤0.25,

It is preferred that the composition is, More preferably, the method further comprises the steps of,

Wherein DOL_0 is the depth of the compressive stress layer, t is the thickness of the chemically strengthened glass ceramic, h is the depth from the main surface of the chemically strengthened glass ceramic, CS (h) is the compressive stress value when the depth is h,Is the compressive stress integral of any one of the main surfaces of the chemically strengthened glass ceramic to a compressive stress layer having a depth of 80 μm from the main surface.

According to the application, through the chemical strengthening microcrystalline glass with a thinner thickness, a specific crystal phase structure and a stress structure are met, the problems that the penetration resistance of sharp objects and the drop damage resistance of rough ground of the existing chemical strengthening microcrystalline glass are to be improved after the thickness is thinned are solved, the ultra-thin chemical strengthening microcrystalline glass is endowed with excellent penetration resistance of sharp objects and excellent drop damage resistance, and meanwhile, the chemical strengthening microcrystalline glass can be ensured to maintain excellent optical performance, so that the application requirements of cover plate glass for screen protection of electronic equipment can be met.

As an alternative embodiment, the chemically strengthened glass ceramic satisfies the following:

It is preferred that the composition is, More preferably, the method further comprises the steps of,Where, |CT_AV| is the absolute value of the average tensile stress in MPa. The chemical strengthening microcrystalline glass with smaller thickness meets a specific stress structure, so that the effect of improving the mechanical strength performance of the stress structure is exerted, and the chemical strengthening microcrystalline glass is further facilitated to obtain excellent damage resistance.

100MPa < CT_AV, preferably 110MPa < CT_AV, where CT_AV is the absolute value of the mean tensile stress, and/or,

90 Μm or less DOL_0, preferably 90 μm or less DOL_0.or less 120 μm, more preferably 105 μm or less DOL_0.or less 118 μm, wherein DOL_0 is the depth of layer of compressive stress, and/or,

55000 MPa/mm≤CT_LD, preferably 56400 MPa/mm≤CT_LD≤72000 MPa/mm, more preferably 62000 MPa/mm≤CT_LD≤65000 MPa/mm, where CT_LD is tensile stress linear density. The chemically strengthened glass ceramics can meet the proper stress structure, so that the chemically strengthened glass ceramics with higher stress level can be obtained, the improvement effect of the stress structure on the mechanical strength performance can be exerted, and the chemically strengthened glass ceramics can meet the excellent damage resistance performance.

has a value of ：17652.28MPa·μm、18648.12MPa·μm、18393.52MPa·μm、17182.91MPa·μm、16421.45MPa·μm、15951.66MPa·μm、16840.06MPa·μm、17087.83MPa·μm、20558.47MPa·μm or 16014.47MPa μm, and/or,

Is ：1979.4MPa²·mm、2169.7MPa²·mm、2072.2MPa²·mm、1831.0MPa²·mm、1667.1MPa²·mm、1604.1MPa²·mm、1777.7MPa²·mm、1935.2MPa²·mm、2224.4MPa²·mm or 2199.7MPa ² mm, and/or,

The value of CT_AV is 112.13MPa, 116.35MPa, 112.66MPa, 106.6MPa, 101.5MPa, 100.6MPa, 105.6MPa, 113.25MPa, 108.2MPa or 137.36MPa, and/or,

DOL_0 has a value of 111.62 μm, 112.28 μm, 109.58 μm, 107.24 μm, 108.86 μm, 109.68 μm, 110.16 μm, 106.69 μm, 117.52 μm or 98.86 μm, and/or,

The value of CT_LD is ：62066.20MPa/mm、64094.89MPa/mm、63278.87MPa/mm、60850.02MPa/mm、57316.32MPa/mm、56440.71MPa/mm、59046.32MPa/mm、62375.72MPa/mm、61537.01MPa/mm or 71118.98MPa/mm.

As an alternative embodiment, the composition at the center of the chemically strengthened glass-ceramic, in mole percent of oxides, comprises:

SiO₂：64％～70％、Al₂O₃：3.5％～5.0％、P₂O₅：0.7％～1.5％、ZrO₂：1.5％～3％、Na₂O：0～3％、K₂O：0～1％、Li₂O：20％～26％、CaO：0～1.5％、B₂O₃：0～2％. By meeting specific glass composition, the glass ceramics meeting specific crystal phase structure and the chemically strengthened glass ceramics meeting specific stress structure are obtained.

The molar percentage of SiO ₂ is 64% -69.5%, preferably the molar percentage of SiO ₂ is 67.5% -69.5%, and/or,

Al ₂O₃ to 4.8 mol%, preferably Al ₂O₃ to 4.5 mol%, and/or,

P ₂O₅ to 1.5 mol%, preferably P ₂O₅ to 0.8 to 1.2 mol%, and/or,

The mol percentage of ZrO ₂ is 2.5-3%, preferably the mol percentage of ZrO ₂ is 2.6-3%, and/or,

The mole percentage of Na ₂ O is 0-2%, preferably, the mole percentage of Na ₂ O is 0-1%, and/or,

K ₂ O is 0 to 0.5 mol%, preferably K ₂ O is 0 to 0.3 mol%, and/or,

The mole percentage of Li ₂ O is 20.5% -25%, preferably the mole percentage of Li ₂ O is 20.5% -23.5%, and/or,

The mol percent of CaO is 0% -1%, preferably, the mol percent of CaO is 0.5% -1%, and/or,

The mole percentage of B ₂O₃ is 0-1%, preferably, the mole percentage of B ₂O₃ is 0-0.8%.

The mole percent of SiO ₂ is 68.02%, 65.37%, 64.39%, 68.21%, 68.74%, 68.10% or 68.31%, and/or,

The mole percentage of Al ₂O₃ is 4.30%, 4.33%, 4.07%, 4.37%, 4.41%, 4.31% or 4.38%, and/or,

P ₂O₅ is 1.17%, 1.16%, 1.14%, 1.10%, 0.95%, 1.13% or 1.22% by mole, and/or,

The mol percent of ZrO ₂ is 2.88%, 2.93%, 2.98%, 2.77%, 2.89%, 2.90% or 2.92%, and/or,

The mole percent of Na ₂ O is 0.15%, 1.68%, 0.78%, 0.09% or 0%, and/or,

K ₂ O is 0.07%, 0.06%, 0% or 0.61% by mole, and/or,

The mole percent of Li ₂ O is 22.40%, 23.17%, 25.68%, 22.47%, 21.48%, 22.43% or 22.50%, and/or,

The mol percent of CaO is 1.29%, 0.89%, 0.93%, 0.73% or 0.52%, and/or,

The mole percent of B ₂O₃ is 0.08%, 0.8% or 0%.

As an alternative embodiment, in the composition at the center of the chemically strengthened glass-ceramic, the mole percent of ZrO ₂ [ ZrO ₂ ], the mole percent of CaO [ CaO ], the mole percent of P ₂O₅ [ P ₂O₅]、Na₂ O ], the mole percent of Na ₂O]、K₂ O [ K ₂O]、B₂O₃ ], the mole percent of B ₂O₃]、Al₂O₃ [ Al ₂O₃ ] and the mole percent of SiO ₂ [ SiO ₂ ], satisfy the following relationship:

3.5％≤([ZrO₂]+[CaO]+[P₂O₅])/EXP([Na₂O]+[K₂O]+[B₂O₃])≤5.5％, Preferably ,4.5％≤([ZrO₂]+[CaO]+[P₂O₅])/EXP([Na₂O]+[K₂O]+[B₂O₃])≤5.3％; and/or,

5% Or less of [ P ₂O₅]+[Al₂O₃ ] or less than 6%, preferably 5.0% or less of [ P ₂O₅]+[Al₂O₃ ] or less than 5.6%, and/or,

15.Ltoreq.17 ([ SiO ₂]+2×[B₂O₃])/[Al₂O₃ ]. Ltoreq.17, preferably 15.0≤16.5 ([ SiO ₂]+2×[B₂O₃])/[Al₂O₃ ]. Ltoreq.SiO).

([ZrO₂]+[CaO]+[P₂O₅])/EXP([Na₂O]+[K₂O]+[B₂O₃]) Is 4.97%, 5.29%, 4.79%, 4.53%, 4.52% or 4.65%, and/or,

[ P ₂O₅]+[Al₂O₃ ] is 5.49%, 5.21%, 5.47%, 5.36%, 5.44% or 5.60%, and/or

([ SiO ₂]+2×[B₂O₃])/[Al₂O₃ ] has a value of 15.86, 15.10, 15.82, 15.61, 15.95, 15.80 or 15.60).

As an alternative embodiment, the sum of the masses of the petalite crystalline phase and the lithium disilicate crystalline phase accounts for more than 80wt% of all the crystalline phases of the chemically strengthened glass ceramic,

Preferably, the sum of the masses of the petalite crystalline phase and the lithium disilicate crystalline phase accounts for 85-100 wt% of all crystalline phases of the chemically strengthened glass ceramic.

As an alternative embodiment, the chemically strengthened glass ceramic has an average grain size of not more than 100nm, preferably not more than 50nm, more preferably 15 to 30nm, and/or

The crystallinity of the chemically strengthened glass ceramic is not lower than 70%, preferably the crystallinity of the chemically strengthened glass ceramic is 80% -90%, more preferably the crystallinity of the chemically strengthened glass ceramic is 85% -90%.

As an alternative embodiment, the Young's modulus of the chemically strengthened glass ceramic is greater than 100GPa, preferably greater than 105GPa, more preferably 110GPa to 120GPa.

As an alternative embodiment, the chemically strengthened glass-ceramic has a b value of <1.0, preferably a b value of <0.7, more preferably a b value of 0.6 or less, and/or is transparent in the visible wavelength range, preferably has a transmittance of 85% or more, preferably 90% or more, more preferably a transmittance of 90.29% or more for 550nm wavelength light.

As an alternative embodiment, a Mohs hardness pen having a Mohs hardness scale of 6 and a pen point at an angle of 35 DEG in a horizontal projection is used, such that the pen point of the Mohs hardness pen vertically penetrates into the chemically strengthened glass ceramic in a thickness direction, a load F _80μm of not less than 100N, preferably a load F _80μm of not less than 110N, is required to be applied when the penetration depth is 80 μm, and/or,

And (3) carrying out anti-sand paper drop test on the chemically strengthened microcrystalline glass, wherein the adopted sand paper is 80-mesh sand paper, the average anti-sand paper drop height of the chemically strengthened microcrystalline glass is more than or equal to 0.88m, and preferably, the average anti-sand paper drop height of the chemically strengthened microcrystalline glass is more than or equal to 1.1m.

As an alternative implementation, a Mohs hardness pen with a Mohs hardness grade of 6 and a pen point at an angle of 35 DEG on a horizontal projection is adopted, so that the pen point of the Mohs hardness pen vertically penetrates into chemically strengthened glass ceramics along the thickness direction, and the chemically strengthened glass ceramics meets the following conditions: Preferably is More preferably Wherein h' is the penetration depth of the Mohs hardness pen into the chemically strengthened glass ceramic, and the angle theta is the angle of the Mohs hardness pen represented by the pen point on the horizontal projection and is 35 degrees.

In a second aspect, there is provided a glass device comprising a chemically strengthened glass ceramic as described in any one of the embodiments of the first aspect.

In a third aspect, there is provided a cover glass made from the chemically strengthened glass ceramic of any one of the embodiments of the first aspect. The cover glass can be a display screen cover plate, a rear cover or a camera protection cover plate of the electronic equipment.

In a fourth aspect, there is provided an electronic device comprising a chemically strengthened glass ceramic as described in any one of the embodiments of the first aspect.

As an alternative embodiment, an electronic device comprises a housing assembled outside the electronic device, and a circuit board located inside the housing, the housing comprising the chemically strengthened glass-ceramic according to any one of the embodiments of the first aspect.

As an alternative embodiment, the housing comprises a display cover plate assembled on the front side of the electronic device, the display cover plate comprising the chemically strengthened glass ceramic according to any one of the embodiments of the first aspect.

As an alternative embodiment, the housing comprises a rear cover assembled on the rear side of the electronic device, the rear cover comprising the chemically strengthened glass ceramic according to any of the embodiments of the first aspect.

As an alternative embodiment, the electronic device further comprises a camera assembly located inside the housing, the housing comprising a camera protection cover plate, the camera protection cover plate being arranged over the camera assembly, the camera protection cover plate comprising the chemically strengthened glass ceramic according to any one of the embodiments of the first aspect.

As an alternative embodiment, the electronic device further comprises a middle frame between the display module and the housing, the middle frame comprising the chemically strengthened glass ceramic according to any one of the embodiments of the first aspect.

In some embodiments, the shell may be partially or entirely chemically strengthened glass ceramic. The electronic equipment in the application can be one or more of a display screen cover plate, a rear cover, a camera protection cover plate and a middle frame, and the chemically strengthened glass ceramic is adopted according to any embodiment of the first aspect.

One or more of the above technical solutions provided by the present application, compared with the prior art, comprises the following advantages:

According to the application, through the ultrathin chemically-strengthened glass ceramic with the thickness of 0.38-0.60 mm, the crystal phase structure and stress structure of specific requirements are met, the problem that the penetration resistance of sharp objects and the drop damage resistance of rough grounds are to be improved after the thickness of the existing chemically-strengthened glass ceramic is thinned is solved, the excellent penetration resistance of sharp objects and the excellent drop damage resistance of rough grounds are endowed to the ultrathin chemically-strengthened glass ceramic, and meanwhile, the excellent optical performance of the chemically-strengthened glass ceramic can be ensured, so that the application requirements of cover plate glass for screen protection of electronic equipment can be met. The chemically strengthened glass ceramic can greatly reduce the probability of surface damage and breakage caused by impact or sharp object penetration of the screen cover plate glass of the electronic equipment under the condition of meeting the market demand of lightening and thinning of the electronic equipment, thereby ensuring the safe and stable operation of the electronic equipment.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.

In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.

FIG. 1 is an XRD pattern of glass ceramic of example 1 of the present application;

FIG. 2 is a graph showing XRD patterns of glass ceramics and chemically strengthened glass ceramics according to example 1 of the present application;

FIG. 3 is a graph showing the XRD patterns of the glass ceramics according to example 1 and comparative example 1 of the present application;

FIG. 4 is a graph showing the transmittance of glass ceramics according to example 1 of the present application;

FIG. 5 is a graph showing the transmittance curve of glass ceramics and chemically strengthened glass ceramics according to example 1 of the present application;

FIG. 6 is a graph showing the change in compressive stress with depth of chemically strengthened glass ceramics according to example 1, comparative example 1 and comparative example 5 of the present application;

FIG. 7 is a schematic illustration of an anti-penetration test performed in accordance with the present application;

FIG. 8 is a schematic view of a part of a Mohs hardness pen for performing penetration resistance test according to the present application;

FIG. 9 is a graph showing the relationship between the load and penetration depth when the chemically strengthened glass ceramics of example 1 and comparative example 1 of the present application are subjected to penetration resistance test;

Fig. 10 is a schematic diagram of a front structure of an electronic device according to an embodiment of the present application;

Fig. 11 is a schematic view of a rear structure of an electronic device according to an embodiment of the present application;

fig. 12 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

The display device comprises a 1-shell, a 11-display screen cover plate, a 12-rear cover, a 13-camera protection cover plate, a 2-camera assembly, a 3-middle frame and a 4-display module.

Detailed Description

Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. Wherein the terms "optional" and "optionally" mean either comprising or not comprising (or may not be present). The term "and/or" as used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.

Term interpretation and test method:

In the present application, glass-ceramic is a type of solid composite material comprising both a glass phase and a crystalline phase (or also called microcrystalline phase, crystalline phase) prepared by targeted controlled heat treatment of a substrate glass. Glass ceramics are also known as glass ceramics or crystallized glass.

In the application, the chemically strengthened glass ceramic refers to a solid composite material obtained by chemically strengthening glass ceramic. It should be appreciated that when the chemical strengthening treatment is performed, alkali metal ions (e.g., potassium ions or sodium ions) with a large ionic radius in the molten salt bath (or molten salt bath) replace alkali metal ions (e.g., sodium ions or lithium ions) with a small ionic radius in the glass-ceramic, thereby generating a difference in exchanged ion volume and generating compressive stress (or compressive stress) on the glass-ceramic surface.

In the present application, the base glass means a glass which has not been subjected to nucleation treatment, crystallization treatment and strengthening treatment, or also referred to as base glass.

In the present application, the composition at the center of the chemically strengthened glass-ceramic means the composition at or near the center of the depth or thickness of the chemically strengthened glass-ceramic, that is, the composition of the region of the chemically strengthened glass-ceramic where ion exchange is not performed.

In the application, the visible light wavelength range is 360nm to 740nm.

In the present application, the main crystalline phase (or also referred to as the primary crystalline phase) refers to a crystalline phase having a higher mass content than other crystalline phases present in glass-ceramics or chemically strengthened glass-ceramics.

In the present application, the main surface means a surface having the largest surface area, for example, an upper surface or a lower surface of a glass ceramic sheet placed horizontally.

In the present application, the crystallinity refers to the percentage of the total mass of the crystalline phase in the glass-ceramic or the chemically strengthened glass-ceramic to the mass of the glass-ceramic or the chemically strengthened glass-ceramic, or also referred to as the total content of the crystalline phase in the glass-ceramic or the chemically strengthened glass-ceramic.

In the application, light with a certain wavelength irradiates the main surface of the microcrystalline glass or the chemically strengthened microcrystalline glass, and the light can be reflected, absorbed and transmitted, wherein the ratio of the intensity of the transmitted part to the intensity of the incident light is the transmittance.

In the application, the crystallized glass raw material refers to a glass raw material which is subjected to heat treatment for a period of time to enable the glass to reach a certain crystallinity but not reach a target crystallinity yet and can be continuously crystallized by heating to reach the target crystallinity.

In the application, CT_LD refers to tensile stress linear density in MPa/mm. It should be understood that after the glass-ceramic is placed in a molten salt bath for ion exchange, a compressive stress layer (or also called a compressive stress layer) is formed on the surface of the glass-ceramic, and a tensile stress layer (or also called a tensile stress layer) is formed inside the glass-ceramic. Illustratively, in the chemical strengthening treatment, alkali metal ions with large radius in a molten salt bath are ion-exchanged with alkali metal ions with small radius in the glass-ceramic, so that a compressive stress layer is formed on the surface of the glass-ceramic, and a tensile stress layer is formed inside the glass-ceramic, that is, the chemically strengthened glass-ceramic comprising the compressive stress layer and the tensile stress layer is prepared. In the application, CT_LD is obtained through calculation according to the following formula:

Wherein t is the thickness of the chemically strengthened glass ceramics, the unit is mm, DOL_0 is the depth of a compressive stress layer of the chemically strengthened glass ceramics, the unit is mu m, and CT_AV is the absolute value of the average tensile stress of the chemically strengthened glass ceramics, and the unit is MPa. It should be understood that, in the calculation formula of the tensile stress linear density, data is substituted into the calculation according to the unit requirement, and a calculation result is obtained, and the unit does not participate in the calculation.

In the application, CS_80 refers to a compressive stress value at a depth of 80 mu m from the main surface of the chemically strengthened glass ceramic, and the unit is MPa, and the compressive stress value is obtained by testing by an SLP-2000 stress meter.

In the application, |CT_AV| refers to the absolute value of the average tensile stress, the unit is MPa, and the absolute value of the average value of all tensile stresses in a tensile stress layer is obtained by testing by an SLP-2000 stress meter.

In the application, DOL_0 refers to the depth of a compressive stress layer or the depth of the compressive stress layer, and specifically refers to the distance from any main surface of chemically strengthened microcrystalline glass to a position close to the surface, wherein the compressive stress is zero, and the distance is obtained by testing by an SLP-2000 stress meter.

In the application, the stress performance test mode is specifically that an SLP-2000 stress meter is adopted for testing, the wavelength of a light source is 518nm, the SOC=25.5 (nm/cm)/MPa, the refractive index=1.54, and the exposure time is 300usec. When testing the stress performance of the chemically strengthened glass ceramics, a conducting liquid is firstly dripped on a stress meter, then a sample of the chemically strengthened glass ceramics to be tested is wiped clean and placed on a test passage, and the stress value of the sample is tested. Wherein the stress meter is SLP-2000 and the conducting liquid used by the stress meter is a conducting liquid with a refractive index of 1.51. Calculating the tensile stress linear density (CT_LD) value of the chemically strengthened glass ceramics by the calculation formula of the tensile stress linear density, and calculating the stress data of the chemically strengthened glass ceramics measured by SLP-2000Is a value of (2).

In the present application, the b value is used to characterize the yellow Lan Zhi of the material. The b value in the application is the b value of the transmitted light, and the b value is positive to indicate that the material is blue.

In the present application, the nucleation treatment means that small crystal nuclei are grown from a nucleation substance in the base glass by heat treatment, and the crystallization treatment means that a certain crystal is grown on the basis of the crystal nuclei by heat treatment.

In the application, the thickness is obtained by micrometer test. It should be understood that the ion exchange degree varies in gradient from surface to center in the thickness direction of the glass ceramic sample, and the total Na-K and/or Li-Na exchange amount is generally not more than 1.5% of the total mass of the sample, and the difference of ion radii is in pm level, so that the expansion effect in the thickness direction is extremely slight, and can be approximated as basically no variation in thickness. That is, the thickness of the glass-ceramic before and after chemical strengthening has very small variation, which is negligible.

In the application, the size and specification of the glass ceramic sheet are tested by adopting a two-dimensional measuring machine (the instrument model is Miyu MY-YXCL-4030).

In the present application, young's modulus is a property used to characterize the ability of glass to resist elastic deformation due to external forces. The application adopts UMS-100 ultrasonic material characterization system, and tests the Young modulus of microcrystalline glass by sound waves.

In the present application, the crystal phase, crystallinity and average crystal grain size of the glass ceramics or chemically strengthened glass ceramics were confirmed by XRD test. Specifically:

(1) XRD test, namely crushing the microcrystalline glass or the chemically strengthened microcrystalline glass, grinding the microcrystalline glass or the chemically strengthened microcrystalline glass into samples with the particle size smaller than 75 mu m, and testing the ground samples by using an X-ray diffractometer to obtain XRD diffraction peak curves and XRD diffraction data. The X-ray diffractometer adopted in the application is Shimadzu XRD-6100, the target material is copper, the incidence angle range used in the test is 2 theta=10 DEG-50 DEG, the scanning speed is 0.2 DEG/min, the working voltage is 40kV, and the working current is 30mA.

(2) Determination of crystalline phases XRD diffraction data was analyzed using the jace software (jace Standard 8.6) to determine crystalline phases in the samples.

(3) And determining the crystallinity, namely introducing the XRD test result (RAW format) into X-ray diffraction data Rietveld finishing software Jade to perform fitting and calculation, and determining the crystallinity of the sample. Specifically, the ratio of the fitted peak areas of the crystalline phases to the fitted total peak areas was recorded as the crystallinity of the sample.

(4) Determination of the average grain size (or average crystal size) of the sample can be calculated from the data obtained by XRD testing according to Scherrer formula d=kλ/(βcosθ). Where λ is the X-ray wavelength, λ= 0.154056nm, β is the diffraction peak half-width, k=0.89, θ is the bragg diffraction angle. Specifically, curve fitting is performed on a RAW format file output by an XRD instrument in Jade software, jade outputs a fitting report, the Peak FWHM value is converted into a radian system β= (FWHM/180×3.14) according to an angle 2θ value and a Peak FWHM value corresponding to each diffraction Peak in the fitting report, and the average grain size of each diffraction Peak is obtained by calculating the grain size of each diffraction Peak through a Scherrer formula d=kλ/(βcos θ) and then averaging.

In the application, the transmittance and the b value of the glass ceramics are tested by adopting a haze meter by referring to the transmission ratio in the spectrum of the part 12 of the test method of the national standard GB/T7962.12-2010 colorless optical glass. Specifically, the transmittance and b value of the same batch of 5 glass ceramics to light with different wavelengths are tested by using a haze meter. Taking the average value of the b values measured by 5 pieces of glass ceramics, and recording the average value as the b value result of the glass ceramics. The average value of the transmittance of 5 glass ceramics at 550nm is taken and recorded as the transmittance result of the glass ceramics at 550 nm. The haze meter adopted in the test of the application is a Konikoku Meida spectrocolorimeter CM-3600A, the light receiving optical system is transmission, the light splitting mode is a plane back-folded grating, the wavelength range is 360nm-740nm, the wavelength interval is 10nm, the illumination light source is a pulse xenon lamp X4, the ambient temperature of the instrument is 24 ℃, and the air humidity is 40%.

In the application, an ultraviolet-visible spectrophotometer UV-2600 of Shimadzu is also used for testing the transmittance curve of the glass ceramics under the wavelength light in the range of 200 nm-1000 nm.

Refractive index refers to the ratio of the propagation speed of light in vacuum to the propagation speed of light in the medium.

Penetration resistance test in the application, the nib of the Mohs hardness pen is penetrated into the chemically strengthened glass ceramics along the thickness direction, so as to simulate the penetration of sharp protruding objects into the chemically strengthened glass ceramics. The penetration resistance of the sharp object is obtained through the penetration test of a single sharp object, and the application scene that the chemically strengthened glass ceramics falls to the ground with the sharp protrusion object can be simulated. Test when the penetration depth of the nib of the mohs hardness pen was 80 μm, the load F _80μm applied to the mohs hardness pen was required. In the application, a pen with the Mohs hardness grade of 6 in the United states Mineralab is adopted as a test pen. The test is performed by using a pen with the Mohs hardness level of 6, mainly because in daily life, the cover glass of the electronic equipment can be contacted with the environment, such as cement ground, fine sand ground and the like, and the hardness is approximately equal to the Mohs hardness level of 6. The penetration resistance of the sample was characterized by the applied load F _80μm required to penetrate into the chemically strengthened glass ceramic to a depth of 80. Mu.m. When the F _80μm value is larger, the load or force required by the pen point of the pen with the Mohs hardness grade of 6 to penetrate into the chemically strengthened microcrystalline glass at the depth of 80 mu m is larger, and the penetration resistance is better when the penetration difficulty of the chemically strengthened microcrystalline glass is larger.

The specific operation steps of the puncture resistance test comprise that firstly, a stainless steel plate is placed on a bottom ring of a tensile testing machine (LT-850A), then a chemically strengthened microcrystalline glass sample to be tested is placed on the stainless steel plate, an extrusion pen with the Mohs hardness of U.S. Mineralab of 6 grade (M6) is equipped, the acute angle of the pen point of the extrusion pen is 35 degrees as shown in figure 8, test software is started, the moving speed is set to be 1mm/min, the test is started by clicking, and the extrusion pen of M6 applies force to the center of the chemically strengthened microcrystalline glass sample to be tested according to the set moving speed until the chemically strengthened microcrystalline glass sample is cracked and broken, as shown in figure 7. The test software was used to output raw data of the penetration depth and the load applied to the M6 nib, and the load F _80μm applied to the M6 nib when the penetration depth was 80 μm was read as a characterization value of the penetration resistance of the chemically strengthened glass ceramic sample. And taking 10 chemically strengthened microcrystalline glass sample wafers in the same state for testing, and taking the average value of the test results as F _80μm of the chemically strengthened microcrystalline glass sample wafers to be tested.

The fracture generated by local penetration means that when the surface of the glass collides with a sharp object with higher hardness (such as small stones and cement), the surface of the glass is locally destroyed, a crack propagation source is formed at the destruction point, when the compressive stress level of the surface of the glass is insufficient to counteract the energy caused by the impact during the collision, the crack propagation can pass through the surface area of the glass, and when the crack in the thickness direction passes through the depth of the compressive stress layer to reach the tensile stress layer area, the crack can rapidly propagate in the tensile stress area, so that the crack penetrates the whole glass, and the glass is broken.

Density test the application adopts an electronic density balance SD-200L of Japanese ALFA MIRAGE to test the density of microcrystalline glass.

Refractive index test the refractive index of the glass ceramics is tested by adopting an Abbe refractometer WYA-2WAJ of the Shanghai Libang West instrument technology in China.

Thermal expansion softening point test the sample was made into a cylinder with a diameter of 5.5mm and a length of 20mm, and the sample was tested using a thermal expansion instrument LINSEIS L VD1000 to test and output a thermal expansion test curve. The temperature corresponding to the peak position of the curve is the thermal expansion softening point temperature of the sample.

Average anti-sand paper drop height test in the application, in a plurality of chemically strengthened microcrystalline glass samples in the same embodiment or the same comparative example, the measured anti-sand paper drop height of each sample is added, and the value obtained by dividing the sum of the measured anti-sand paper drop heights by the number of the measured samples is recorded as the average anti-sand paper drop height of the tested chemically strengthened microcrystalline glass and is used for representing the anti-drop damage performance of the chemically strengthened microcrystalline glass. The drop damage resistance is obtained by testing with uniform sand paper, and can simulate the application scene that the chemically strengthened glass ceramics drop to the ground with uniform roughness.

Specifically, at least 10 samples per batch were taken for testing, average sandpaper drop height

Where n is the number of glass samples tested per batch and hi is the height of sandpaper drop resistance for a single sample test.

The test method of the single sample anti-sand paper falling height comprises the following steps:

Step 1, sticking 80-mesh sand paper on the lower surface of a 181g model machine, and placing the model machine on a green map LT-SKDL-CD type drop machine;

and 2, placing a chemical strengthening microcrystalline glass sample to be tested under the model machine, so that the chemical strengthening microcrystalline glass sample faces the sand paper. The model machine is impacted to fall at a certain falling height, and the chemically strengthened glass ceramic sample positioned right below the model machine is impacted. If the chemically strengthened glass ceramic sample is not broken, the falling height of the model machine is increased according to a certain rule, so that the model machine continuously impacts and falls, and the chemically strengthened glass ceramic sample positioned right below the model machine is impacted until the chemically strengthened glass ceramic sample is broken. For example, the falling height of the model machine starts from 0.4m, the sample is subjected to one-time falling impact, if the sample is not broken, the falling height of the model machine is increased by 0.1m, the model machine falls again, and the process is repeated until the chemically strengthened glass ceramic sample is broken;

And 3, marking the last falling height of the chemically strengthened microcrystalline glass sample before breaking as the anti-sand paper falling height of the chemically strengthened microcrystalline glass sample, for example, if the falling height of the chemically strengthened microcrystalline glass sample is 0.5m when the falling height of the chemically strengthened microcrystalline glass sample is increased by 0.1m each time, the anti-sand paper falling height of the chemically strengthened microcrystalline glass sample is 0.4m.

Without being bound by any theory, chemically strengthened glass ceramics having a relatively thin thickness have a stress structure, a crystalline phase structure, and a composition that are closely related to their resistance to damage, particularly their resistance to penetration by sharp objects and their resistance to drop damage. The chemically strengthened glass ceramics with a thinner thickness can meet specific crystal phase structures and stress structures, so that the damage resistance of the chemically strengthened glass ceramics is further improved under the condition of ensuring the excellent optical performance of the chemically strengthened glass ceramics, and particularly the chemically strengthened glass ceramics is favorable for ensuring the excellent penetration resistance of sharp objects and the excellent drop damage resistance of the chemically strengthened glass ceramics.

Without being limited by any theory, the application discovers that the larger the area enclosed by the compressive stress curve and the straight line y=0, the straight line x=0 and the straight line x=80 μm is, the larger the stress intensity value in the interval range of 0 μm of the depth of the compressive stress layer and 80 μm of the depth of the compressive stress layer is, and the better the anti-penetration effect of a sharp object and the anti-falling effect of a rough surface of the chemically strengthened microcrystalline glass are. Therefore, in the application, the integral area of the compressive stress curve of the chemically strengthened glass ceramics in the range of h epsilon [0 mu m,80 mu m ] interval is more than or equal to 15500MPa & mu m, so that the penetration resistance of sharp objects and the drop damage resistance of rough surfaces of the chemically strengthened glass ceramics can be improved, and further the surface penetration damage resistance and drop damage resistance of cover glass and electronic equipment comprising the cover glass can be improved.

In order to solve the problem that the penetration resistance of sharp objects and the drop damage resistance of rough ground are required to be improved after the thickness of the chemically strengthened glass ceramics is thinned, the chemically strengthened glass ceramics, cover plate glass, electronic equipment and glass devices which meet the specific crystal phase structure and stress structure are provided. When the thickness is 0.38-0.60 mm, the chemically strengthened glass ceramic has excellent capability of resisting penetration of sharp objects and excellent performance of resisting drop damage of rough ground, and meanwhile, the chemically strengthened glass ceramic maintains excellent optical performance, and can meet application requirements of cover plate glass.

As described above, in some embodiments of the present application, a chemically strengthened glass-ceramic is provided, wherein the chemically strengthened glass-ceramic comprises a petalite crystal phase and a lithium disilicate crystal phase, wherein the petalite crystal phase and the lithium disilicate crystal phase have a higher mass percentage than other crystal phases present in the chemically strengthened glass-ceramic;

0.18≤DOL_0/t≤0.25,

The lithium disilicate (Li ₂Si₂O₅) crystalline phase is an orthorhombic crystal based on an array of [ Si ₂O₅ ] tetrahedra, the shape of the crystal being flat or plate-like. Petalite liaalsi ₄O₁₀ is a monoclinic crystal having a three-dimensional framework structure including a layered structure with folded Si ₂O₅ layers connected by Li and Al tetrahedra. The crystallinity of the microcrystalline glass taking petalite and lithium disilicate as main crystalline phases can reach more than 70wt%, and the existence of a large number of microcrystalline phases in the microcrystalline glass is beneficial to better preventing crack growth, and can consume more impact energy in the breaking and crushing process, thereby being beneficial to improving the strength and the fracture toughness of the microcrystalline glass. Meanwhile, the light refraction coefficient of the lithium disilicate crystal is close to that of a glass matrix (such as the base glass for preparing the microcrystalline glass), so that the crystal phase for preparing the high-transparency microcrystalline glass is ideal, and petalite and lithium disilicate are used as main crystal phases, so that the microcrystalline glass can maintain excellent optical performance. In addition, the lithium disilicate crystalline phase and the petalite crystalline phase both contain lithium ions which can participate in ion exchange, chemical strengthening can be performed in a molten salt bath, na ⁺ and/or K ⁺ in the salt bath replace Li ⁺ in the crystalline phase structure, a surface stress structure can be formed, and the mechanical strength performance of the microcrystalline glass can be further improved.

In the application, the chemically strengthened glass ceramics comprises petalite crystal phase and lithium disilicate crystal phase as main crystal phases, which is beneficial to obtaining a desired stress structure under the condition of ensuring that the glass ceramics has high intrinsic strength (or also called intrinsic strength), thereby ensuring that the chemically strengthened glass ceramics realizes excellent damage resistance under ultra-thin thickness.

According to the application, through the chemical strengthening microcrystalline glass with a thinner thickness, a specific crystal phase structure and a stress structure are met, the problems that the penetration resistance of sharp objects and the drop damage resistance of rough ground of the existing chemical strengthening microcrystalline glass are to be improved after the thickness is thinned are solved, the excellent penetration resistance of the ultrathin chemical strengthening microcrystalline glass and the excellent drop damage resistance of the rough ground are endowed, and meanwhile, the excellent optical performance of the chemical strengthening microcrystalline glass can be ensured to be kept, so that the application requirements of cover plate glass for screen protection of electronic equipment can be met.

In some embodiments, the thickness t of the chemically strengthened glass-ceramic may be 0.38mm、0.39mm、0.40mm、0.41mm 、0.42mm、0.43mm、0.44mm、0.45mm、0.46mm、0.47mm、0.48mm、0.49mm、0.50mm、0.51mm、0.52mm、0.53mm、0.54mm、0.55mm、0.56mm、0.57mm、0.58mm、0.59mm or 0.60mm, or a value within a range of values defined by any of the 2 specific values described above as endpoints, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained. At present, electronic devices are often required to be light and thin, and it is considered that the smaller the thickness is, the lighter the weight is, and the more excellent the optical effect is. The application can make the chemically strengthened microcrystalline glass product as thin as possible under the condition of ensuring the strength so as to meet the requirement of lightening and thinning of electronic equipment.

In some embodiments, the DOL_0/t in the chemically strengthened glass ceramic may have a value of 0.18 to 0.25, 0.19 to 0.24, 0.20 to 0.23, or 0.21 to 0.22. In some embodiments, the value of DOL_0/t in the chemically strengthened glass-ceramic may be 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, or 0.25, or a value within a range of values defined by any 2 of the specific values recited above as endpoints, so long as the desired properties of the chemically strengthened glass-ceramic of the present application are achieved. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained. The depth of the compressive stress layer and the thickness of the chemically strengthened glass ceramics meet a proper proportion relation, so that the chemically strengthened glass ceramics are in a better stress distribution state, and the improvement effect of the stress structure on the mechanical strength performance is exerted.

In some embodiments of the present invention, in some embodiments,The values of (2) may be 15500 MPa.mu.m to 21000 MPa.mu.m, 16000 MPa.mu.m to 20000 MPa.mu.m, 16500 MPa.mu.m to 19500 MPa.mu.m,

17000 MPa-19000 MPa-mum or 17500 MPa-mum-18500 MPa-mum. In some embodiments of the present invention, in some embodiments,The value of (2) may be 15500MPa·μm、15900MPa·μm、17500MPa·μm、17652.28MPa·μm、18648.12MPa·μm、18393.52MPa·μm、17182.91MPa·μm、16421.45MPa·μm、15951.66MPa·μm、16840.06MPa·μm、17087.83MPa·μm、19000MPa·μm、19500MPa·μm、20558.47MPa·μm、16014.47MPa·μm or 21000 MPa. Mu.m, or a value within a range of values defined by any of the above 2 specific values as the end points, as long as the chemically strengthened glass ceramic of the present application can be obtained with the desired properties. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass ceramic satisfies:

In some embodiments of the present invention, in some embodiments,The value of (2) may be 1400MPa²·mm～2300MPa²·mm、1500MPa²·mm～2250MPa²·mm、1600MPa²·mm～2200MPa²·mm、1700MPa²·mm～2150MPa²·mm、1800MPa²·mm～2000MPa²·mm、1900MPa²·mm～2050MPa²·mm or 1950MPa ²·mm～2000MPa² mm. In some embodiments of the present invention, in some embodiments,The value of (2) may be 1400MPa²·mm、1500MPa²·mm、1600MPa²·mm、1700MPa²·mm、1800MPa²·mm、1900MPa²·mm、2000MPa²·mm、2100MPa²·mm、2200MPa²·mm、2300MPa²·mm、1979.4MPa²·mm、2169.7MPa²·mm、2072.2MPa²·mm、1831.0MPa²·mm、1667.1MPa²·mm、1604.1MPa²·mm、1777.7MPa²·mm、1935.2MPa²·mm、2224.4MPa²·mm or 2199.7MPa ² mm, or a value within a range of values defined by any of the above 2 specific values as the end points, as long as the chemically strengthened glass ceramic of the present application can be obtained with the desired properties. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass ceramic satisfies 30 MPa≤CS_80, where CS_80 refers to the compressive stress value at a depth of 80 μm from the major surface of the chemically strengthened glass ceramic. In some embodiments, CS_80 of the chemically strengthened glass-ceramic may be 30MPa、35MPa、40MPa、45MPa、50MPa、55MPa、60MPa、69MPa、85MPa、87.1MPa、94.79MPa、91.26MPa、79.59MPa、73.26MPa、69.37MPa、77.26MPa、79.63MPa、97.75MPa、100MPa、110MPa、120MPa、130MPa、140MPa or 150MPa, or a value within a range of values defined by any of the 2 specific values described above as endpoints, provided that the desired properties of the chemically strengthened glass-ceramic of the present application are achieved. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass ceramic meets 100MPa +.CT_AV, preferably 110MPa +.CT_AV, where CT_AV is the absolute value of the average tensile stress. By enabling the absolute value of CT_AV of the chemically strengthened glass ceramics to be more than 100MPa, the chemically strengthened glass ceramics is beneficial to ensuring that the chemically strengthened glass ceramics has a desired tensile stress layer distribution structure, ensuring that the chemically strengthened glass ceramics has higher surface stress level, and ensuring that the more the residual energy of drop, extrusion, penetration, impact or collision can be counteracted by the higher surface compressive stress level, further ensuring that the chemically strengthened glass ceramics has excellent damage resistance, such as excellent sharp object penetration resistance and excellent rough ground drop damage resistance.

In some embodiments, the |CT_AV| of the chemically strengthened glass-ceramic may be 100MPa to 160MPa, 100MPa to 125MPa, 105MPa to 120MPa, 100MPa to 150MPa, or 110MPa to 115MPa. In some embodiments, the |CT_AV| of the chemically strengthened glass-ceramic may be 100MPa、110MPa、112.13MPa、116.35MPa、112.66MPa、106.6MPa、101.5MPa、100.6MPa、105.6MPa、113.25MPa、108.2MPa、137.36MPa、125MPa、130MPa、135MPa、140MPa、150MPa or 160MPa, or a value within a range of values defined by any 2 of the specific values noted above as endpoints, provided that the desired properties of the chemically strengthened glass-ceramic of the present application are achieved. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass ceramic satisfies 90 μm and/or DOL_0, and illustratively, DOL_0 may be 90 μm to 135 μm, preferably 90 μm and/or DOL_0 and/or 120 μm, and more preferably 105 μm and/or DOL_0 and/or 118 μm, where DOL_0 is the depth of layer of compressive stress. Through the chemical strengthening microcrystalline glass with proper DOL_0, when a blunt object or a sharp object is impacted and penetrated, a sudden crack directly penetrates through a compressive stress area to reach a tensile stress area, so that the chemical strengthening microcrystalline glass is broken, the chemical strengthening microcrystalline glass is more beneficial to improving the energy of counteracting and driving crack expansion, and the chemical strengthening microcrystalline glass is further ensured to have excellent damage resistance, such as excellent penetration resistance of the sharp object and excellent drop damage resistance.

In some embodiments, dol—0 of the chemically strengthened glass-ceramic may be 90μm、92μm、95μm、98μm、100μm、105μm、113μm、115μm、111.62μm、112.28μm、109.58μm、107.24μm、108.86μm、109.68μm、110.16μm、106.69μm、117.52μm、98.86μm、118μm、120μm、125μm、130μm or 135 μm, or a value within a range of values defined by any 2 of the specific values described above as endpoints, as long as the desired properties of the chemically strengthened glass-ceramic of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the present application, the chemically strengthened glass ceramic satisfies 55000MPa/mm < CT_LD, illustratively, CT_LD may be 55000MPa/mm to 80000MPa/mm, preferably 56400MPa/mm < CT_LD < 72000MPa/mm, more preferably 62000MPa/mm < CT_LD < 65000MPa/mm, where CT_LD is tensile stress linear density. The CT_LD of the chemically strengthened glass ceramics is controlled to be not lower than 55000MPa/mm, which is beneficial to ensuring that the tensile stress stored in the chemically strengthened glass ceramics is sufficiently dense, further ensuring that the chemically strengthened glass ceramics has higher surface stress level, and ensuring that the chemically strengthened glass ceramics has excellent damage resistance, such as excellent drop damage resistance, so as to meet market demands.

In some embodiments, the CT_LD of the chemically strengthened glass ceramic may be 55000 to 72000MPa/mm, 58000 to 70000MPa/mm, 56000 to 64000MPa/mm, or 57000 to 63000MPa/mm. In some embodiments, the CT_LD of the chemically strengthened glass-ceramic may be 55000MPa/mm、56400MPa/mm、62000MPa/mm、64500MPa/mm、62066.20MPa/mm、64094.89MPa/mm、63278.87MPa/mm、60850.02MPa/mm、57316.32MPa/mm、56440.71MPa/mm、59046.32MPa/mm、62375.72MPa/mm、61537.01MPa/mm、71118.98MPa/mm、65000MPa/mm、66000MPa/mm、67000MPa/mm、68000MPa/mm、69000MPa/mm、70000MPa/mm、72000MPa/mm、74000MPa/mm、76000MPa/mm、78000MPa/mm or 80000MPa/mm, or a value within a range of values defined by any of the 2 specific values mentioned above as endpoints, as long as the desired properties of the chemically strengthened glass-ceramic of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

It should be understood that the chemically strengthened glass-ceramic of the present application may be made from glass-ceramic that has been chemically strengthened, with the composition at the center of the chemically strengthened glass-ceramic being the same or substantially the same as the composition of the glass-ceramic. The composition at the surface of the glass-ceramic article may be different from the composition of the glass-ceramic prior to its ion exchange process after the chemical strengthening treatment, as compared to the glass-ceramic prior to the chemical strengthening treatment. This is because, in the glass-ceramic just formed, one type of alkali metal ion (e.g., li ⁺ or Na ⁺) at the glass-ceramic surface is replaced by a larger alkali metal ion (e.g., na ⁺ or K ⁺), respectively, when ion exchange is performed. In embodiments, however, the glass composition and phase set at or near the depth or thickness center of the glass-ceramic article will still have the composition and phase set of the freshly formed glass-ceramic. That is, in the present application, the composition (e.g., the composition of the tensile stress layer) and the phase set at the center of the chemically strengthened glass-ceramic subjected to the chemical strengthening treatment are the same or substantially the same as those of the glass-ceramic not subjected to the chemical strengthening treatment.

The glass ceramics of the application can be prepared from base material glass through heat treatment, and the composition of the base material glass is the same or basically the same as that of the glass ceramics according to the mole percentage of oxides.

In some embodiments of the application, the composition of the substrate glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic, in mole percent of oxides, comprises ：SiO₂：64％～70％、Al₂O₃：3.5％～5.0％、P₂O₅：0.7％～1.5％、ZrO₂：1.5％～3％、Na₂O：0～3％、K₂O：0～1％、Li₂O：20％～26％、CaO：0～1.5％、B₂O₃：0～2％. to facilitate obtaining glass-ceramic that meets a specific crystalline phase structure by meeting a specific glass composition, and to facilitate obtaining chemically strengthened glass-ceramic that meets a specific stress structure.

In the application, siO ₂ is an oxide forming a glass network skeleton, is used for stabilizing the network structure of the base material glass, and is also an important component for forming a lithium disilicate crystal phase and a petalite crystal phase. When SiO ₂ is contained in the glass composition in a sufficiently high content, the formation of petalite crystals and lithium disilicate crystals in a sufficient amount is facilitated. However, when the SiO ₂ content is too high, not only the melting property of the glass becomes poor, the viscosity of the molten glass becomes high, the glass becomes difficult to clarify, the molding difficulty of the base material glass is increased, but also the heat treatment time becomes long when the base material glass is used for preparing glass ceramics. Therefore, in order to meet the glass formability requirement and realize the desired crystallization effect of the application, the content of SiO ₂ is made to be 64% -70%, preferably 64% -69.5%, more preferably 67.5% -69.5%.

In some embodiments, the mole percent of SiO ₂ in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic may be 64%, 65%, 66%, 67%, 68%, 69%, 69.5%, 70%, 68.02%, 65.37%, 64.39%, 68.21%, 68.74%, 68.10% or 68.31% in terms of mole percent of oxide, or a value within a range of values defined by any 2 of the specific values described above as endpoints, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the present application, al ₂O₃ can be used to construct a glass skeleton and is an indispensable component for forming petalite. The proper amount of Al ₂O₃ can stabilize the network structure of glass, is favorable for improving mechanical property, chemical durability and chemical strengthening effect, inhibits the phase separation of glass, reduces the thermal expansion coefficient and improves the strain point. When the content of Al ₂O₃ is too small, the glass tends to have a high thermal expansion coefficient, the chemical durability is lowered, crystal nuclei are enlarged, cloudiness is likely to occur in the glass, and when the content of Al ₂O₃ is too large, the glass becomes poor in meltability, production becomes difficult, and crystals such as mullite are likely to precipitate to devitrify the glass. Therefore, in order to meet the expected crystal phase structure, the microcrystalline glass or the chemically strengthened microcrystalline glass is enabled to obtain the expected performance, and the content of Al ₂O₃ is 3.5% -5.0%, preferably 4% -4.8%, and more preferably 4% -4.5%.

In some embodiments, the mole percent of Al ₂O₃ in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic may be 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.4%, 4.5%, 4.8%, 5.0%, 4.51%, 4.30%, 4.33%, 4.07%, 4.37%, 4.41%, 4.31%, or 4.38% in terms of mole percent of oxides, or a value within a range of values ending in any of the 2 specific values recited above, so long as the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the present application, P ₂O₅ is a glass former oxide which exists in the network structure as a phosphorus oxygen tetrahedron [ PO ₄ ]. P ₂O₅ preferentially appears in the heat treatment process, firstly, the glass is subjected to phase separation and segregation to form an amorphous precursor phase Li ₃PO₄, then Li ₃PO₄ is used as a non-uniform nucleation point, and crystalline phases such as lithium silicate and the like are attached to the amorphous Li ₃PO₄ for growth. With the increase of the content of P ₂O₅, the non-uniform nucleation points are increased, and the crystal grains taking Li ₃PO₄ as the nucleation points are effectively refined, so that the overall transmittance of the glass ceramics, the uniformity of the glass and the b value are improved. However, when the content of P ₂O₅ is too high, more Li ₃PO₄ crystals are easy to generate, so that the content of Li ₂ O for forming lithium silicate and petalite is insufficient, and further, quartz crystals are easy to precipitate in the base material glass, so that the transmittance of the microcrystalline glass is reduced, and the optical uniformity of the whole microcrystalline glass is reduced. When the content of P ₂O₅ is too small, the size of the precipitated crystals is larger, and the glass is easy to devitrify. Therefore, in order to achieve the expected crystallization effect of the application, the microcrystalline glass or the chemically strengthened microcrystalline glass is made to have the expected performance, and the content of P ₂O₅ is made to be 0.7% -1.5%, preferably 0.8% -1.5%, more preferably 0.8% -1.2%.

In some embodiments, the mole percent of P ₂O₅ in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic may be 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.17%, 1.16%, 1.14%, 1.10%, 0.95%, 1.13% or 1.22% in terms of mole percent of oxides, or a value within a range of values ending in any of the 2 specific values recited above, so long as the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the application, proper amount of ZrO ₂ can improve the viscosity, elastic modulus, refractive index and chemical stability of the glass and reduce the thermal expansion coefficient of the glass. ZrO ₂ exists in the residual glass phase after heat treatment, which is beneficial to improving the mechanical strength performance of the residual glass phase, but excessive ZrO ₂ can increase the melting difficulty of the base material glass, so that the crystallization phenomenon occurs in the melting process of the base material glass. Therefore, in order to meet the glass formability requirement and achieve the desired strength effect of the application, zrO ₂ is 1.5% -3%, preferably 2.5% -3%, more preferably 2.6% -3%.

In some embodiments, the mole percent of ZrO ₂ in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic, in terms of mole percent of oxides, may be 1.5％、1.6％、1.7％、1.8％、1.9％、2％、2.1％、2.2％、2.3％、2.4％、2.5％、2.6％、2.7％、2.8％、2.9％、3％、2.88％、2.93％、2.98％、2.77％、2.89％ or 2.92%, or a number within the range of values defined by any of the 2 specific numbers recited above as endpoints, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the application, na ₂ O belongs to network exosome oxide, can provide free oxygen, and proper amount of Na ₂ O is beneficial to improving the viscosity of glass, promoting the melting and clarification of glass liquid, promoting the precipitation of lithium disilicate crystal phase, reducing the crystallization tendency of glass and increasing the transmittance of glass. However, excessive Na ₂ O affects the network structure of the glass, and further affects the strength performance of the glass ceramics. Therefore, in order to ensure that the glass ceramic or chemically strengthened glass ceramic satisfies a desired structure and obtain a desired performance, the Na ₂ O content is set to 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%.

In some embodiments, the mole percent of Na ₂ O in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic, in terms of mole percent of oxides, may be 0％、0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、1.1％、1.2％、1.3％、1.4％、1.5％、1.6％、1.7％、1.8％、1.9％、2％、2.1％、2.2％、2.3％、2.4％、2.5％、2.6％、2.7％、2.8％、2.9％、3％、0.15％、1.68％、0.78％ or 0.09%, or a number within the range of values defined by any of the 2 specific numbers recited above as endpoints, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the application, K ₂ O is an external oxide of a glass network, and a proper amount of K ₂ O can reduce the crystallization tendency of the glass and increase the transparency and the luster of the glass. However, when the K ₂ O content is too high, the crystallization ability of the glass becomes strong, the glass is liable to devitrify, and the glass ceramics is liable to be broken. Therefore, in order to ensure that the glass ceramic or chemically strengthened glass ceramic satisfies a desired structure and obtain a desired performance, the K ₂ O content is set to 0 to 1%, preferably 0 to 0.5%, more preferably 0 to 0.3%.

In some embodiments, the mole percent of K ₂ O in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic may be 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 0.07%, 0.06% or 0.61% in terms of mole percent of oxides, or a value within a range of values ending in any of the 2 specific values described above, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the present application, li ₂ O is a main constituent of the petalite crystal phase and the lithium disilicate crystal phase, and is also an essential component for achieving chemical strengthening. The proper amount of Li ₂ O is favorable for ensuring that the transparency, the fusion forming effect, the crystallization capability, the chemical strengthening performance and the like of the microcrystalline glass meet the requirements. When the Li ₂ O content is too small, not only impurity crystal phases such as mullite and the like are easy to be separated out from the glass, but also the glass meltability is easy to be reduced or the viscosity is easy to be increased, so that the forming of the base material glass is difficult, and when the Li ₂ O content is too large, the network structure of the glass is easy to be influenced, the crystallization capacity of the glass is easy to be too strong, and the devitrification tendency of the glass is increased. Therefore, in order to obtain a glass ceramic or chemically strengthened glass ceramic satisfying desired crystal phase structure, optical properties, and mechanical strength properties, the content of Li ₂ O is 20% to 26%, preferably 20.5% to 25%, more preferably 20.5% to 23.5%.

In some embodiments, the mole percent of Li ₂ O in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic, in terms of mole percent of oxides, may be 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 22.40%, 23.17%, 25.68%, 22.47%, 21.48%, or 22.43%, or a value within a range of values ending in any of the 2 specific values described above, so long as the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the application, caO can reduce high-temperature viscosity, is beneficial to glass molding, and can enhance the network structure, so that the stress benefit of the glass ceramics in the strengthening process is enhanced. If the CaO content is too large, excessive CaO remains in the glass phase and a refractive index difference is generated between the glass phase and the main crystal phase, which results in a decrease in the transmittance and an increase in the haze of the glass ceramic. Therefore, in order to obtain a glass ceramic or a chemically strengthened glass ceramic satisfying desired optical properties and mechanical strength properties, the CaO content is set to 0 to 1.5%, preferably 0 to 1%, more preferably 0.5 to 1%.

In some embodiments, the mole percent of CaO in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic may be 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.29%, 0.89%, 0.93%, 0.73% or 0.52% in terms of mole percent of oxides, or a value within a range of values ending in any of the 2 specific values recited above, so long as the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the application, B ₂O₃ is beneficial to reducing the melting temperature of the base material glass and improving the performances of the microcrystalline glass or the chemically strengthened glass, such as transmittance, overall uniformity and the like. However, when the amount of B ₂O₃ is too large, the stress of the glass ceramics or the chemically strengthened glass ceramics is reduced, and at the same time, the increase of the content of B ₂O₃ in the residual glass phase reduces the viscosity of the residual glass phase, promotes the growth of crystals such as lithium silicate and the like, and influences the optical transmittance of the glass ceramics or the chemically strengthened glass. Therefore, in order to obtain a glass ceramic or a chemically strengthened glass ceramic satisfying desired optical properties and mechanical strength properties, the content of B ₂O₃ is set to 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.8%.

In some embodiments, the mole percent of B ₂O₃ in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic may be 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% or 0.08% in terms of mole percent of oxides, or a value within a range of values ending in any of the 2 specific values recited above, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the mole percent of ZrO ₂ [ ZrO ₂ ], the mole percent of CaO [ CaO ], the mole percent of P ₂O₅ [ P ₂O₅]、Na₂ O [ Na ₂O]、K₂ O [ K ₂ O ] and the mole percent of B ₂O₃ [ B ₂O₃ ] in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic satisfy the following relationship:

3.5％≤([ZrO₂]+[CaO]+[P₂O₅])/EXP([Na₂O]+[K₂O]+[B₂O₃])≤5.5％, Preferably ,4.5％≤([ZrO₂]+[CaO]+[P₂O₅])/EXP([Na₂O]+[K₂O]+[B₂O₃])≤5.3％. in the present application, the content relation of each oxide is obtained by substituting the content percentage calculated by mole of the oxide into each formula, and the mole unit does not participate in the calculation of the formula. The contents of the oxides are adjusted to meet a specific content relation, so that the microcrystalline glass or the chemically strengthened microcrystalline glass meeting the expected mechanical strength performance can be obtained.

In some embodiments ,([ZrO₂]+[CaO]+[P₂O₅])/EXP([Na₂O]+[K₂O]+[B₂O₃]) may have a value of 3.5%, 4.0%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 4.97%, 5.29%, 4.79%, 4.53%, 4.52% or 4.65%, or a value within a range of values defined by any 2 of the specific values recited above as endpoints, provided that the glass-ceramic or chemically strengthened glass-ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the mole percent of P ₂O₅ [ P ₂O₅ ] and the mole percent of Al ₂O₃ [ Al ₂O₃ ] in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic satisfy the following relationship:

p ₂O₅]+[Al₂O₃ is less than or equal to 5% and less than or equal to 6%, preferably P ₂O₅]+[Al₂O₃ is less than or equal to 5.0% and less than or equal to 5.6%. The contents of P ₂O₅ and Al ₂O₃ are adjusted to meet a specific range, so that the microcrystalline glass or the chemically strengthened microcrystalline glass meeting the expected crystal phase structure and stress structure can be obtained.

In some embodiments, the value of [ P ₂O₅]+[Al₂O₃ ] may be 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 5.49%, 5.21%, 5.47%, 5.36% or 5.44%, or a value within a range of values defined by any 2 of the specific values recited above as endpoints, so long as the desired properties of the present application are achieved. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, as long as the desired properties of the present application are achieved.

In some embodiments of the application, the mole percent of B ₂O₃ [ mole percent of B ₂O₃]、Al₂O₃ [ Al ₂O₃ ] and mole percent of SiO ₂ [ SiO ₂ ] in the composition of the base glass or the composition of the glass-ceramic or the composition at the center of the chemically strengthened glass-ceramic satisfy the following relationship:

15≤SiO ₂]+2×[B₂O₃])/[Al₂O₃≤17, preferably 15.0≤SiO ₂]+2×[B₂O₃])/[Al₂O₃≤16.5 by adjusting the contents of SiO ₂、B₂O₃ and Al ₂O₃ to meet the specified ranges, it is advantageous to obtain a glass-ceramic or chemically strengthened glass-ceramic satisfying the desired inherent strength and stress structure.

In some embodiments, ([ SiO ₂]+2×[B₂O₃])/[Al₂O₃ ] may have a value of 15, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6, 15.7, 15.8, 15.9, 16, 16.5, 17, 15.86, 15.82, 15.61, or 15.95, or a value within a range of values defined by any of the above 2 specified values as endpoints, as long as a glass ceramic or chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In the present application, "petalite crystal phase and lithium disilicate crystal phase have a higher mass percentage than other crystal phases present in the chemically strengthened glass-ceramic" or "petalite and lithium disilicate as main crystal phases" or the like means that the sum of the masses of the petalite crystal phase and the lithium disilicate crystal phase together accounts for more than 80 mass percent (mass%) of all crystal phases of the chemically strengthened glass-ceramic according to the embodiment of the present application. In some embodiments of the present application, the sum of the masses of the petalite crystal phase and the lithium disilicate crystal phase in the chemically strengthened glass ceramic accounts for 80wt% to 100wt% of all the crystal phases of the chemically strengthened glass ceramic, preferably, the sum of the masses of the petalite crystal phase and the lithium disilicate crystal phase accounts for 85wt% to 100wt% in all the crystal phases of the chemically strengthened glass ceramic. In some embodiments, the sum of the mass percentages of the petalite crystal phase and the lithium disilicate crystal phase in all crystal phases of the chemically strengthened glass ceramic may be 80wt％、80.5wt％、81wt％、81.5wt％、82wt％、82.5wt％、83wt％、83.5wt％、84wt％、84.5wt％、85wt％、85.5wt％、86wt％、86.5wt％、87wt％、87.5wt％、88wt％、88.5wt％、89wt％、89.5wt％、90wt％、95wt％ or 100wt%, or a value within a range of values defined by any of the above 2 specific values as endpoints, as long as the chemically strengthened glass ceramic of the desired properties of the present application can be obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the present application, the chemically strengthened glass ceramic has an average grain size of not more than 100nm, preferably not more than 50nm, more preferably 15 to 30nm. The proper average grain size is favorable for the glass-ceramics to have both excellent optical properties and high intrinsic strength, while if the average grain size is too high, the glass-ceramics is liable to devitrify and the chemical strengthening effect is also affected. In the application, the chemically strengthened glass ceramics are favorable for ensuring that the chemically strengthened glass ceramics realize excellent mechanical strength performance and excellent optical performance by enabling the chemically strengthened glass ceramics to meet proper average grain size.

In some embodiments, the average grain size of the chemically strengthened glass-ceramic may be 100nm, 50nm, 40nm, 35nm, 30nm, 25nm, 20nm, 15nm, 19.7nm, 18.6nm, 20.8nm, 20.3nm, 25.2nm, 23.2nm, 22.6nm, or 10nm, or a value within a range of values defined by any 2 of the specific values recited above as endpoints, so long as the desired properties of the chemically strengthened glass-ceramic of the application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the present application, the crystallinity of the chemically strengthened glass ceramic is not less than 70%, preferably the crystallinity of the chemically strengthened glass ceramic is 80% -90%, more preferably the crystallinity of the chemically strengthened glass ceramic is 85% -90%. It should be understood that in the present application, after the glass-ceramic is chemically strengthened to obtain the chemically strengthened glass-ceramic, the crystallinity of the glass-ceramic does not significantly change, i.e., the crystallinity of the glass-ceramic is the same or substantially the same as the crystallinity of the chemically strengthened glass-ceramic. The higher the crystallinity of the glass ceramics is, the more favorable the glass ceramics can obtain high mechanical strength performance and high damage resistance performance. However, the crystallinity is too high, so that the chemical strengthening effect of the glass ceramics is easily affected, the chemical strengthening time for preparing the chemically strengthened glass ceramics with high stress level is prolonged, and the optical performance of the glass ceramics is also easily affected. According to the application, the microcrystalline glass meets the expected crystallinity, so that the prepared chemically strengthened microcrystalline glass also meets the expected crystallinity, and the chemically strengthened microcrystalline glass meeting the expected high mechanical strength performance, high damage resistance performance and excellent optical performance is more facilitated to be obtained.

In some embodiments, the crystallinity of the chemically strengthened glass ceramic may be 70%, 72%, 74%, 76%, 78%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 86.2%, 88.6%, 87.5%, 87.2%, 86.5% or 90%, or a value within a range of values defined by any 2 of the specific values recited above as endpoints, provided that the desired properties of the chemically strengthened glass ceramic of the application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass-ceramic has a Young's modulus of greater than 100GPa, preferably greater than 105GPa, more preferably from 110GPa to 120GPa. It should be understood that, in the present application, after the glass-ceramic is chemically strengthened to obtain the chemically strengthened glass-ceramic, the young's modulus of the glass-ceramic is not reduced, that is, when the young's modulus of the glass-ceramic is greater than 100GPa, the young's modulus of the chemically strengthened glass-ceramic is also greater than 100GPa. The higher Young modulus is beneficial to ensuring that the chemically strengthened glass ceramics has high mechanical strength performance and high damage resistance performance.

In some embodiments, the Young's modulus of the chemically strengthened glass-ceramic may be 101GPa、102GPa、103GPa、104GPa、105GPa、106GPa、107GPa、108GPa、109GPa、110GPa、111GPa、112GPa、113GPa、114GPa、115GPa、116GPa、117GPa、118GPa、112.04GPa、113.41GPa、112.25GPa、113.64GPa、115.25GPa、116.621GPa、115.07GPa、119GPa or 120GPa, or a value within a range of values defined by any of the 2 specific values mentioned above as endpoints, as long as the desired properties of the chemically strengthened glass-ceramic of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass ceramic has a b value of <1.0, preferably a b value of <0.70, more preferably a b value of 0.60 or less. It should be understood that, in the present application, after the glass-ceramic is subjected to the chemical strengthening treatment to obtain the chemically strengthened glass-ceramic, the optical properties of the glass-ceramic are not significantly changed, that is, the b value, the transmittance, etc. of the glass-ceramic are the same or substantially the same as those of the chemically strengthened glass-ceramic. In the present application, the b value refers to the optical b value measured under the D65 light source, and b (D65) is shown in the result of testing the b value in the transmittance mode by adopting Kenicamantadine CM-3600A. The smaller the value of b is, the better display effect of the glass ceramics can be ensured, and when the value of b is larger, the glass ceramics can have unexpected color, so that the display effect of the glass ceramics cannot meet the application requirement of the cover plate glass of the display screen.

In some embodiments, the b value of the chemically strengthened glass ceramic may be 0.70, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35, 0.30, 0.25, 0.39, 0.49, 0.47, 0.59, 0.48, 0.52, 0.32, 0.37, 0.26, or 0.20, or a value within a range of values defined by any 2 of the specific values recited above, provided that the desired properties of the chemically strengthened glass ceramic of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the application, the chemically strengthened glass-ceramic is transparent in the visible wavelength range, preferably having a transmittance of greater than or equal to 85%, preferably greater than or equal to 90%, more preferably greater than or equal to 90.29% for 550nm wavelength light. The chemically strengthened glass ceramic meeting the transmittance can ensure better light transmittance and better transparent effect, and is suitable for being used in a display screen with requirements on display effect. The "visible wavelength range" herein refers to light having a wavelength of 360nm to 740 nm.

In some embodiments, the transmittance of the chemically strengthened glass ceramic for 550nm wavelength light may be 85％、90％、90.10％、90.20％、90.30％、90.40％、90.50％、91.00％、91.05％、91.14％、90.69％、90.81％、90.29％、90.77％、90.42％、91.08％、91.14％ or 92.00%, or a value within a range of values defined by any 2 of the specific values as the endpoints, as long as the chemically strengthened glass ceramic of the desired properties of the present application can be obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the present application, a Mohs hardness pen having a Mohs hardness scale of 6 and a pen tip at an angle of 35 DEG in a horizontal projection is used, such that the pen tip of the Mohs hardness pen penetrates vertically into the chemically strengthened glass ceramic in a thickness direction, and when the penetration depth is 80 μm, the required applied load F _80μm is not less than 100N, preferably the required applied load F _80μm is not less than 110N. In some embodiments, when the penetration depth is 80 μm, the required applied load F _80μm may be 100N、105N、110N、115N、120N、125N、130N、140N、145N、150N、117.1N、128.6N、121.5N、110.6N、103.3N、100.12N、106.7N、108.3N、132.5N or 103.2N, or a value within a range of values defined by any of the above 2 specific values as endpoints, so long as the chemically strengthened glass ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

In some embodiments of the present application, a mohs hardness pen with a mohs hardness level of 6 and a pen point at an angle of 35 ° on a horizontal projection is used, so that the pen point of the mohs hardness pen vertically penetrates into chemically strengthened glass ceramics along the thickness direction, and the chemically strengthened glass ceramics satisfies: Preferably is More preferably Wherein h' is the penetration depth of the Mohs hardness pen into the chemically strengthened glass ceramic, and the angle theta is the angle of the Mohs hardness pen represented by the pen point on the horizontal projection and is 35 degrees.

In some embodiments, a mohs hardness pen with a mohs hardness level of 6 and a pen point at an angle of 35 degrees on a horizontal projection is adopted, so that when the pen point of the mohs hardness pen vertically penetrates into the chemically strengthened glass ceramic along the thickness direction, h' is the penetration depth of the mohs hardness pen into the chemically strengthened glass ceramic, θ=35 degrees,May have a value of 8.3×10⁸MPa·μm⁴、8.5×10⁸MPa·μm⁴、9.0×10⁸MPa·μm⁴、9.4×10⁸MPa·μm⁴、9.9×10⁸MPa·μm⁴、9.8×10⁸MPa·μm⁴、9.2×10⁸MPa·μm⁴、8.8×10⁸MPa·μm⁴、9.1×10⁸MPa·μm⁴、9.5×10⁸MPa·μm⁴、1.0×10⁹MPa·μm⁴、1.1×10⁹MPa·μm⁴ or 1.2x10 ⁹MPa·μm⁴.

In some embodiments of the application, the chemically strengthened glass-ceramic is subjected to a sand paper drop test, wherein the sand paper is 80-mesh sand paper, and the average sand paper drop height of the chemically strengthened glass-ceramic is not less than 0.88m, preferably not less than 1.1m. In some embodiments, the average anti-sand paper drop height may be 0.88m、1.1m、1.11m、1.12m、1.13m、1.14m、1.15m、1.16m、1.17m、1.18m、1.19m、1.2m、1.25m、1.28m、1.3m、1.35m、1.4m、1.45m、1.5m、1.55m、1.6m、1.65m、1.7m、1.75m、1.8m、1.85m、1.9m、1.95m or 2m when the chemically strengthened glass ceramic is drop tested on 80 mesh sand paper, or a value within a range of values defined by any 2 of the specific values as endpoints, provided that the chemically strengthened glass ceramic of the desired properties of the present application are obtained. It should be understood that any of the above ranges may be combined with any other ranges in the specific embodiments, so long as the chemically strengthened glass ceramic of the desired properties of the present application is obtained.

After the foregoing description of the components, crystal phase structure, stress structure and the like of the chemically strengthened glass ceramic, the following specifically describes a method for preparing the chemically strengthened glass ceramic.

In the application, the preparation process of the chemically strengthened glass ceramics mainly comprises the preparation process of the glass ceramics and the chemical strengthening treatment process, and the preparation process of the glass ceramics mainly comprises the preparation process of the base material glass and the heat treatment process of the base material glass (the process of preparing the glass ceramics by forming crystalline phases in the base material glass through heat treatment).

In the present application, the substrate glass may be prepared by a molding method in the prior art, and the present application is not limited thereto, and for example, the molding method of the substrate glass may include, but is not limited to, a float, overflow, calendaring, or casting process. Illustratively, the substrate glass can be obtained by uniformly mixing the components according to the formula, performing cooling and annealing treatment after melt molding.

Illustratively, raw materials (industrial conventional raw materials) are prepared according to a formula proportion, a clarifying agent is added, and then the raw materials are mixed for a period of time to obtain a uniformly mixed raw material mixture. And (3) placing the raw material mixture into a platinum crucible or a melting furnace, heating to 1550-1650 ℃, preferably preserving heat for 5h or more under the condition of melting temperature, pouring into a forming die for cooling forming, preferably cooling to about 900 ℃, then placing into an annealing furnace for annealing treatment, preferably at 450-500 ℃, preferably for 12-48 h, and then cooling to room temperature along with the furnace to obtain the substrate glass. The type and amount of clarifying agent can be selected by those skilled in the art as desired without the need for inventive effort. Further, the clarifying agent can include, but is not limited to, one or more of sodium chloride, tin oxide, antimony oxide, arsenic oxide and the like, and the adding amount of the clarifying agent can be 0-1wt% of the total amount of the raw materials.

In some embodiments of the present application, the heat treatment process of the substrate glass may include a nucleation treatment and/or a crystallization treatment, preferably a nucleation treatment and a crystallization treatment. In some embodiments, the crystallization process comprises a one-step crystallization process or a two-step crystallization process. In some embodiments, in order to prepare curved glass ceramics, a two-step crystallization process may be used, and when a two-step crystallization process is used, the second crystallization process is to heat the crystallized glass raw material obtained by the first crystallization process to a crystallization temperature and perform a 3D hot-bending molding process.

In some embodiments of the present application, when the base glass is heat treated in order to obtain desired physicochemical properties, the heat treatment may be performed in one step or two or more steps. If the one-step heat treatment is performed, it means that the nucleation treatment (i.e., the nucleation treatment) is not performed alone, but the one-step temperature is directly increased, and the nucleation and the target crystal growth are performed at a temperature reached in the one-step temperature increasing process, which is understood as the crystallization treatment. If the two-step heat treatment is performed, the two-step heating process is performed, the nucleation treatment is performed first, that is, the nucleation treatment is performed, and then the target crystal growth treatment is performed, that is, the crystallization treatment is performed.

In some embodiments of the present application, the base glass is subjected to a nucleation treatment and a crystallization treatment in this order in order to precipitate a desired target crystal phase in the glass-ceramic and to obtain desired physical and chemical properties. Further, the nucleation temperature may be 500 to 700 ℃ and the nucleation time may be 10 to 1440min when the nucleation treatment is performed, and the crystallization temperature may be 600 to 750 ℃ and the crystallization time may be 5 to 1440min when the crystallization treatment is performed. In the heat treatment process for the nucleation treatment and the crystallization treatment, the temperature rising rate is preferably controlled to be 5-15 ℃ per minute, and more preferably the temperature rising rate is controlled to be 10 ℃ per minute.

In the present application, after the heat treatment, those skilled in the art may perform other conventional steps to obtain a glass ceramic sample meeting the required specification or requirement, for example, shaping treatment, cutting treatment (e.g., cutting using a multi-wire saw), CNC processing treatment (computer numerical control, i.e., a numerical control machine), thinning treatment, or polishing treatment.

In the application, the chemical strengthening treatment, namely the ion exchange method, is to impregnate the glass ceramics in a molten salt bath to enable alkali metal ions with smaller ionic radius in the glass ceramics to exchange with alkali metal ions with larger ionic radius in the molten salt bath, thereby forming a compressive stress layer on the surface of the glass ceramics and obtaining the chemical strengthening glass ceramics with better mechanical property.

In some embodiments of the application, the chemical strengthening treatment may be a single-stage strengthening process or a multi-stage strengthening process. The molten salt bath for chemical strengthening treatment is a molten salt bath containing sodium salt and/or potassium salt. Preferably, the molten salt bath is a mixed molten salt bath containing sodium salt and potassium salt, and the temperature of the molten salt bath is preferably 380-550 ℃. In some embodiments of the present application, it is preferred that the concentration of potassium salt in the salt bath is 0wt% to 80wt%, the concentration of sodium salt is 20wt% to 100wt%, and it is more preferred that a certain amount (e.g., 0.01wt% to 0.3 wt%) of lithium salt is added to the salt bath. In some embodiments of the present application, the chemical strengthening treatment is preferably performed for a period of 0.1 to 24 hours. Wherein, the sodium salt can be at least one selected from sodium nitrate, sodium sulfate and sodium carbonate, preferably sodium nitrate, the potassium salt can be at least one selected from potassium nitrate, potassium sulfate and potassium carbonate, preferably potassium nitrate, and the lithium salt can be at least one selected from lithium nitrate, lithium sulfate and lithium carbonate, preferably lithium nitrate.

The chemically strengthened glass ceramics with excellent performance provided by the application can be used for electronic equipment, including but not limited to mobile phones, tablet computers, palm game machines, portable digital devices (such as digital cameras), vehicle-mounted central control, electronic whiteboard glass, intelligent home, intelligent wearing (such as intelligent wrist rings, intelligent watches and intelligent glasses), vehicles, aircrafts or aircrafts, and glass devices of any required chemically strengthened glass ceramics. For example, it can be used for a display screen, a cover glass, a touch screen, an inner glass screen or an inner frame of an electronic device, for example, it can be used for a windshield of a vehicle, an aircraft or an aircraft, such as a front windshield or a side windshield. For example, it can be used on countertops, other surfaces, electrical doors, floor tiles, wall panels, storage containers, etc. Other surfaces may include, but are not limited to, exterior wall surfaces, stair tread surfaces, stud veneers or counter surfaces, etc., and storage containers may include, but are not limited to, cups, plates, bottles or beverage bottles, etc.

The chemically strengthened glass ceramics with excellent performance provided by the application can be used for manufacturing glass devices. The glass devices referred to herein may be either regular or irregular and may be manufactured as desired by one skilled in the art.

The chemically strengthened glass ceramic with excellent performance provided by the application can be used for manufacturing cover plate glass, and the cover plate glass can be a display screen cover plate, a rear cover or a camera protection cover plate of electronic equipment. The chemically strengthened glass ceramic with excellent performance provided by the application can be used in electronic equipment. Referring to fig. 10, 11 and 12, an embodiment of the present application provides an electronic device, which may be an electronic product such as a mobile phone, a tablet pc, an intelligent wearable device, etc., where the electronic device includes a housing 1 assembled on an outer side of the electronic device, and components such as a circuit board and a battery located inside the housing 1, the housing 1 includes a display screen cover plate 11 assembled on a front side and a rear cover 12 assembled on a rear side, and the display screen cover plate 11 is covered on the display module 4, where the display screen cover plate 11 and/or the rear cover 12 is made of the foregoing chemically strengthened glass ceramic. In the embodiment of the present application, the display screen cover plate 11 and the rear cover 12 may be all made of the aforementioned chemically strengthened glass ceramics, or may be partially made of the aforementioned chemically strengthened glass ceramics. In the embodiment of the present application, the display screen may be a touch display screen, and the display screen cover 11 may be a protective cover disposed on the touch display screen. In the embodiment of the present application, the rear cover 12 may cover only the rear side (and the side facing away from the display screen) of the electronic device, or may cover both the rear side and the side frame of the electronic device, or alternatively, the rear cover 12 may cover all side frames around the electronic device, or may cover part of the side frames.

In some embodiments of the present application, as shown in fig. 11, the electronic device further includes a camera module 2 located inside the housing 1, where the housing 1 may include a camera protection cover 13, and the camera protection cover 13 is disposed on the camera module 2 to protect the camera module 2, where the camera protection cover 13 uses the chemically strengthened glass ceramic as described above. In the embodiment of the present application, the camera protective cover 13 may be partially or entirely made of the aforementioned chemically strengthened glass ceramics. In the embodiment of the present application, the installation position of the camera protection cover 13 is determined according to the installation position of the camera module 2, and may be located on the front side of the electronic device or may be located on the rear side of the electronic device. In some embodiments of the present application, the camera protection cover 13 may be a separate structure from the display cover 11 or the rear cover 12. In other embodiments of the present application, the camera protection cover 13 may also be integrally formed with the display cover 11 or the rear cover 12.

In some embodiments of the present application, as shown in fig. 12, the electronic device further includes a middle frame 3 between the display module 4 and the housing 1, where the middle frame 3 may include the aforementioned chemically strengthened glass ceramic.

In the embodiment of the application, the display screen cover plate, the rear cover, the camera protection cover plate and the middle frame in the electronic equipment can be any one of the four types of chemically strengthened microcrystalline glass, any two types of the four types of the chemically strengthened microcrystalline glass, all the three types of the chemically strengthened microcrystalline glass and all the four types of the chemically strengthened microcrystalline glass.

The technical scheme of the present application is described in further detail below with reference to examples. The embodiments of the present application described in detail below are exemplary only for the purpose of illustrating the application and are not to be construed as limiting the application.

Example 1

1. Preparation of substrate glass

The raw materials were prepared in the proportions of the oxides shown in Table 1, the total mass of the prepared raw materials was 1000g, 5g of clarifier sodium chloride (NaCl) was added to the prepared raw materials, and the mixture was mixed with a V-type mixer for 30 minutes or longer to obtain a raw material mixture having a uniform mixture.

Transferring the uniformly mixed raw material mixture into a platinum crucible, melting for more than 5 hours in a 1600 ℃ lifting furnace, pouring into a forming die for forming and cooling, cooling to about 900 ℃, putting into a 470 ℃ annealing furnace for annealing for 12 hours, and cooling to room temperature along with the furnace to obtain the substrate glass brick.

2. Preparation of microcrystalline glass

And (3) sequentially carrying out nucleation treatment and crystallization treatment on the substrate glass brick to obtain the transparent glass ceramic-like brick. The composition of the glass ceramics prepared in terms of mole percent of oxides is the same as that of the base glass, and is shown in Table 1.

In order to obtain the microcrystalline glass product of example 1 of the present application, the temperature was raised to the nucleation temperature at a temperature-raising rate of 10℃per minute during the nucleation treatment, the nucleation temperature was 570℃and the nucleation time was 240 minutes, and the temperature was raised from the nucleation temperature to the crystallization temperature at a temperature-raising rate of 10℃per minute during the crystallization treatment, the crystallization temperature was 715℃and the crystallization time was 90 minutes. The nucleation treatment time refers to the time of heating the crystallization furnace to the set nucleation temperature at the set heating rate and then maintaining the temperature. The crystallization treatment time refers to the time of heating the crystallization furnace to a set crystallization temperature at a set heating rate and then maintaining the temperature.

Cutting, CNC processing (CNC instrument and equipment model adopted by the application is RCG 500S) and polishing cold processing are sequentially carried out on the obtained glass ceramic sample, so that the glass ceramic sample meeting the required specification and the required requirement can be obtained. In the application, the glass ceramic-like brick is subjected to the cold working treatment to prepare a glass ceramic polished wafer sample with the length and width specification of 50mm multiplied by 50mm and the thickness of 0.4 mm-0.55 mm.

3. Preparation of chemically strengthened glass ceramics

And (3) carrying out one-step chemical strengthening treatment on the glass ceramic polished wafer in mixed salt at 500 ℃ for 5.0h, wherein the mixed salt comprises 29.99wt% NaNO ₃+69.98wt％KNO₃+0.03wt％LiNO₃.

And after the chemical strengthening treatment, taking out the microcrystalline glass sample, slowly cooling the microcrystalline glass sample on a strengthening furnace body to room temperature, washing off salt wrapped on the surface of the microcrystalline glass by using clear water, and drying the microcrystalline glass sample to obtain the chemical strengthening microcrystalline glass.

Test of the glass ceramics or chemically strengthened glass ceramics obtained in example 1:

The crystalline phase composition, crystallinity, average grain size, optical b-value, transmittance (at 550nm wavelength), thermal expansion softening point, density, refractive index and Young's modulus of the glass-ceramic samples were each measured, and the results are shown in Table 2.

DOL_0, CS_80, |CT_AV|, F _80μm and average anti-sand paper drop height of the chemically strengthened glass ceramic sample are respectively tested, the value of CT_LD is calculated according to the calculation formula of CT_LD, and meanwhile, the value of CT_LD is calculated according to the stress data of the chemically strengthened glass ceramic measured by SLP-2000AndIs combined with the puncture resistance test condition to calculateThe results are shown in Table 3.

The XRD pattern of the glass ceramics of example 1 is shown in fig. 1, and the XRD pattern of the glass ceramics of example 1 is shown in fig. 2 in comparison with that of the chemically strengthened glass ceramics. As can be seen from fig. 1 and 2, in the present application, the main crystal phases in the glass ceramic and the chemically strengthened glass ceramic are lithium disilicate crystal phase and petalite crystal phase, and the crystal phase structure of the glass ceramic is not significantly changed before and after the chemical strengthening treatment.

The transmittance graph of the glass-ceramic of example 1 is shown in fig. 4, and the transmittance graph of the glass-ceramic and the chemically strengthened glass-ceramic of example 1 is shown in fig. 5. As can be seen from fig. 4 and 5, in the present application, both the glass ceramics and the chemically strengthened glass ceramics are transparent in the visible light range, and have high transmittance, and the transmittance of the glass ceramics is not significantly changed before and after the chemical strengthening treatment.

Example 2-example 10

It was conducted with reference to example 1, respectively, except that the raw material composition, the different process parameters and the corresponding test results of each example are shown in tables 1 to 3, respectively.

Comparative example 1-comparative example 8

Which were carried out with reference to example 1, respectively, except that the raw material composition, the different process parameters and the corresponding test results of each comparative example are shown in tables 1 to 3, respectively.

As shown in fig. 3, the XRD patterns of the glass ceramics provided in example 1 and comparative example 1 show that in the present application, the main crystal phases in the glass ceramics provided in example 1 and comparative example 1 are lithium disilicate crystal phase and petalite crystal phase. As shown in fig. 6, the curves of the compressive stress of the chemically strengthened glass ceramics provided in example 1, comparative example 1 and comparative example 5 with respect to depth show that the areas enclosed by the compressive stress curves of the chemically strengthened glass ceramics provided in example 1 and the straight lines y=0, x=0 and x=80 μm are larger than those of the chemically strengthened glass ceramics provided in comparative example 1 and comparative example 5, and the integral areas of the compressive stress curves of the chemically strengthened glass ceramics provided in example 1 within the interval h e [0 μm,80 μm ] are also larger than those of the chemically strengthened glass ceramics provided in comparative example 1 and comparative example 5.

The relationship between the load and penetration depth of the chemically strengthened glass ceramics of example 1 and comparative example 1 is shown in FIG. 9, and it is understood that the force required to penetrate the chemically strengthened glass ceramics of example 1 to a depth of 80 μm is significantly greater than that of comparative example 1.

As can be obtained from the examples and comparative examples described in tables 1 to 3, compared with the comparative examples, by adopting the embodiment of the present application, the chemically strengthened glass-ceramic is made to have a microstructure in which lithium disilicate and petalite are the main crystal phases by satisfying the specific crystal phase structure and stress structure, not only is the chemically strengthened glass-ceramic endowed with excellent optical properties (e.g., high transmittance and low b-value) and high intrinsic strength (e.g., high young's modulus), but also the ultra-thin chemically strengthened glass-ceramic having a thickness of 0.38mm to 0.60mm is made to have both excellent resistance to penetration by sharp objects and excellent resistance to drop damage by rough surfaces, and can satisfy the application requirements of cover glass. The chemically strengthened glass ceramic can greatly reduce the probability of surface damage and breakage caused by impact or sharp object penetration of the screen cover plate glass of the electronic equipment under the condition of meeting the market demand of lightening and thinning of the electronic equipment, thereby ensuring the safe and stable operation of the electronic equipment.

In the schemes of comparative examples 1 to 8, the stress structure of the chemically strengthened glass ceramics does not meet the specific requirements of the present application, and finally, the chemically strengthened glass ceramics prepared in the schemes of each comparative example cannot meet both excellent resistance to penetration of sharp objects and excellent resistance to drop damage of rough surfaces.

The above is only a specific embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A chemically strengthened glass-ceramics, characterized in that the chemically strengthened glass-ceramics contains a petalite crystalline phase and a lithium disilicate crystalline phase, wherein the petalite crystalline phase and the lithium disilicate crystalline phase have a higher mass percentage than other crystalline phases present in the chemically strengthened glass-ceramics;

The thickness t of the chemically strengthened glass-ceramics is 0.38 mm to 0.60 mm;

The chemically strengthened glass-ceramics has a compressive stress layer on the surface and tensile stress inside; the chemically strengthened glass-ceramics satisfies:

0.18≤DOL_0/t≤0.25,

Preferably, More preferably,

Where DOL_0 is the depth of the compressive stress layer, t is the thickness of the chemically strengthened glass-ceramics, h is the depth from the main surface of the chemically strengthened glass-ceramics, and CS(h) is the compressive stress value at the depth h. It is the integral of the compressive stress from any main surface of the chemically strengthened glass-ceramics to the compressive stress layer with a depth of 80 μm from the main surface.

2. The chemically strengthened glass-ceramics according to claim 1, wherein the chemically strengthened glass-ceramics satisfies:

Preferably, More preferably, Where |CT_AV| is the absolute value of the average tensile stress, in MPa.

3. The chemically strengthened glass-ceramics according to claim 1 or 2, wherein the chemically strengthened glass-ceramics satisfies:

90 μm≤DOL_0, preferably, 90 μm≤DOL_0≤120 μm, more preferably, 105 μm≤DOL_0≤118 μm, wherein DOL_0 is the depth of the compressive stress layer; and/or,

55000 MPa/mm≤CT_LD, preferably, 56400 MPa/mm≤CT_LD≤72000 MPa/mm, more preferably, 62000 MPa/mm≤CT_LD≤65000 MPa/mm, wherein CT_LD is the tensile stress linear density.

4. The chemically strengthened glass-ceramics according to any one of claims 1 to 3, wherein the chemically strengthened glass-ceramics satisfies:

The value of is: 17652.28 MPa·μm, 18648.12 MPa·μm, 18393.52 MPa·μm, 17182.91 MPa·μm, 16421.45 MPa·μm, 15951.66 MPa·μm, 16840.06 MPa·μm, 17087.83 MPa·μm, 20558.47 MPa·μm or 16014.47 MPa·μm; and/or,

the value of |CT_AV ^| is: 1979.4 MPa ² ·mm, 2169.7 MPa ² ·mm, 2072.2 MPa ² ·mm, 1831.0 MPa ² ·mm, 1667.1 MPa ² ·mm, 1604.1 MPa ² ·mm, 1777.7 MPa 2 ·mm, 1935.2 MPa ² ·mm, 2224.4 MPa ² ·mm or 2199.7 MPa ² ·mm; and/or the value of |CT_AV| is: 112.13 MPa, 116.35 MPa, 112.66 MPa, 106.6 MPa, 101.5 MPa, 100.6 MPa, 105.6 MPa, 113.25 MPa, 108.2 MPa or 137.36 MPa; and/or,

The value of DOL_0 is: 111.62 μm, 112.28 μm, 109.58 μm, 107.24 μm, 108.86 μm, 109.68 μm, 110.16 μm, 106.69 μm, 117.52 μm or 98.86 μm; and/or,

The values of CT_LD are: 62066.20 MPa/mm, 64094.89 MPa/mm, 63278.87 MPa/mm, 60850.02 MPa/mm, 57316.32 MPa/mm, 56440.71 MPa/mm, 59046.32 MPa/mm, 62375.72 MPa/mm, 61537.01 MPa/mm or 71118.98 MPa/mm.

5. The chemically strengthened glass-ceramics according to any one of claims 1 to 4, wherein the composition at the center of the chemically strengthened glass-ceramics, expressed in terms of molar percentage of oxides, comprises:

SiO ₂ : 64% to 70%, Al ₂ O ₃ : 3.5% to 5.0%, P ₂ O ₅ : 0.7% to 1.5%, ZrO ₂ : 1.5% to 3%, Na ₂ O: 0 to 3%, K ₂ O: 0 to 1%, Li ₂ O: 20% to 26%, CaO: 0 to 1.5%, B ₂ O ₃ :0~2%.

6. The chemically strengthened glass-ceramics according to any one of claims 1 to 5, wherein the composition at the center of the chemically strengthened glass-ceramics comprises, in terms of molar percentage of oxides:

The molar percentage of _SiO2 is 64% to 69.5%, preferably, the molar percentage of _SiO2 is 67.5% to 69.5%; and/or,

The molar percentage of Al ₂ O ₃ is 4% to 4.8%, preferably, the molar percentage of Al ₂ O ₃ is 4% to 4.5%; and/or,

The molar percentage of P ₂ O ₅ is 0.8% to 1.5%, preferably, the molar percentage of P ₂ O ₅ is 0.8% to 1.2%; and/or,

The molar percentage of _ZrO2 is 2.5% to 3%, preferably, the molar percentage of _ZrO2 is 2.6% to 3%; and/or,

The molar percentage of Na ₂ O is 0-2%, preferably, the molar percentage of Na ₂ O is 0-1%; and/or,

The molar percentage of K ₂ O is 0 to 0.5%, preferably, the molar percentage of K ₂ O is 0 to 0.3%; and/or,

The molar percentage of Li ₂ O is 20.5% to 25%, preferably, the molar percentage of Li ₂ O is 20.5% to 23.5%; and/or,

The molar percentage of CaO is 0% to 1%, preferably, the molar percentage of CaO is 0.5% to 1%; and/or,

The molar percentage of B ₂ O ₃ is 0 to 1%, and preferably, the molar percentage of B ₂ O ₃ is 0 to 0.8%.

7. The chemically strengthened glass-ceramics according to any one of claims 1 to 6, wherein the composition at the center of the chemically strengthened glass-ceramics comprises, in terms of molar percentage of oxides:

The molar percentage of _SiO2 is 68.02%, 65.37%, 64.39%, 68.21%, 68.74%, 68.10% or 68.31%; and/or,

The molar _percentage of _Al2O3 is 4.30%, 4.33%, 4.07%, 4.37%, 4.41%, 4.31% or 4.38%; and/or,

The mole _percentage of _P2O5 is 1.17%, 1.16%, 1.14%, 1.10%, 0.95%, 1.13% or 1.22%; and/or,

The mole percentage of _ZrO2 is 2.88%, 2.93%, 2.98%, 2.77%, 2.89%, 2.90% or 2.92%; and/or,

The molar percentage of Na ₂ O is 0.15%, 1.68%, 0.78%, 0.09% or 0%; and/or,

The molar percentage of K ₂ O is 0.07%, 0.06%, 0% or 0.61%; and/or,

The molar percentage of Li ₂ O is 22.40%, 23.17%, 25.68%, 22.47%, 21.48%, 22.43% or 22.50%; and/or,

The molar percentage of CaO is 1.29%, 0.89%, 0.93%, 0.73% or 0.52%; and/or,

The mole percentage of B ₂ O ₃ is 0.08%, 0.8% or 0%.

8. The chemically strengthened glass-ceramics according to any one of claims 1 to 7, characterized in that, in the composition at the center of the chemically strengthened glass-ceramics, the molar percentage of ZrO ₂ [ZrO ₂ ], the molar percentage of CaO [CaO], the molar percentage of P ₂ O ₅ [P ₂ O ₅ ], the molar percentage of Na ₂ O [Na ₂ O], the molar percentage of K ₂ O [K ₂ O], the molar percentage of B ₂ O ₃ [B ₂ O ₃ ], the molar percentage of Al ₂ O ₃ [Al ₂ O ₃ ], and the molar percentage of SiO ₂ [SiO ₂ ] satisfy the following relationship:

3.5%≤([ _ZrO2 ]+[CaO]+ _[ _P2O5 ])/EXP([ _Na2O ]+[ _K2O ]+[ _B2O3 ])≤5.5%, preferably, 4.5%≤([ _ZrO2 ]+[CaO]+[ _P2O5 ])/EXP ₍ _[ _Na2O ]+[ _K2O ]+ _[B2O3 _] )≤5.3%; and/or,

5%≤[P ₂ O ₅ ]+[Al ₂ O ₃ ]≤6%, preferably, 5.0%≤[P ₂ O ₅ ]+[Al ₂ O ₃ ]≤5.6%, and/or,

15≤([SiO ₂ ]+2×[B ₂ O ₃ ])/[Al ₂ O ₃ ]≤17, preferably, 15.0≤([SiO ₂ ]+2×[B ₂ O ₃ ])/[Al ₂ O ₃ ]≤16.5.

9. The chemically strengthened glass-ceramics according to any one of claims 1 to 8, characterized in that, in the composition at the center of the chemically strengthened glass-ceramics, the molar percentage of ZrO ₂ [ZrO ₂ ], the molar percentage of CaO [CaO], the molar percentage of P ₂ O ₅ [P ₂ O ₅ ], the molar percentage of Na ₂ O [Na ₂ O], the molar percentage of K ₂ O [K ₂ O], the molar percentage of B ₂ O ₃ [B ₂ O ₃ ], the molar percentage of Al ₂ O ₃ [Al ₂ O ₃ ], and the molar percentage of SiO ₂ [SiO ₂ ] satisfy the following relationship:

the value of ([ZrO ₂ ]+[CaO]+[P ₂ O ₅ ])/EXP([Na ₂ O]+[K ₂ O]+[B ₂ O ₃ ]) is 4.97%, 5.29%, 4.79%, 4.53%, 4.52% or 4.65%; and/or,

The value of [P ₂ O ₅ ]+[Al ₂ O ₃ ] is 5.49%, 5.21%, 5.47%, 5.36%, 5.44% or 5.60%; and/or

The value of ([SiO ₂ ]+2×[B ₂ O ₃ ])/[Al ₂ O ₃ ] is 15.86, 15.10, 15.82, 15.61, 15.95, 15.80, or 15.60.

10. The chemically strengthened glass-ceramics according to any one of claims 1 to 9, wherein the sum of the weights of the petalite crystalline phase and the lithium disilicate crystalline phase accounts for more than 80 wt % of all crystalline phases of the chemically strengthened glass-ceramics.

Preferably, the total mass of the petalite crystal phase and the lithium disilicate crystal phase accounts for 85 wt % to 100 wt % of all crystal phases of the chemically strengthened glass-ceramics.

11. The chemically strengthened glass-ceramics according to any one of claims 1 to 10, wherein the chemically strengthened glass-ceramics has an average grain size of no more than 100 nm, preferably no more than 50 nm, more preferably 15 to 30 nm; and/or

The chemically strengthened glass-ceramics has a crystallinity of not less than 70%. Preferably, the chemically strengthened glass-ceramics has a crystallinity of 80% to 90%. More preferably, the chemically strengthened glass-ceramics has a crystallinity of 85% to 90%.

12. The chemically strengthened glass-ceramics according to any one of claims 1 to 11, characterized in that the Young's modulus of the chemically strengthened glass-ceramics is greater than 100 GPa, preferably, the Young's modulus is greater than 105 GPa, and more preferably, the Young's modulus is 110 GPa to 120 GPa.

13. The chemically strengthened glass-ceramics according to any one of claims 1 to 12, wherein the b value of the chemically strengthened glass-ceramics is less than 1.0, preferably, less than 0.7, and more preferably, less than 0.6; and/or

The chemically strengthened glass-ceramics is transparent in the visible light wavelength range. Preferably, for light with a wavelength of 550 nm, the transmittance of the chemically strengthened glass-ceramics is ≥85%, preferably ≥90%, and more preferably ≥90.29%.

14. The chemically strengthened glass-ceramics according to any one of claims 1 to 13, characterized in that, when a Mohs hardness pen with a Mohs hardness rating of 6 and a tip angle of 35° in horizontal projection is used and the tip of the Mohs hardness pen is vertically inserted into the chemically strengthened glass-ceramics along the thickness direction, when the penetration depth is 80 μm, the load required to be applied is F _{80 μm} ≥ 100 N, preferably, the load required to be applied is F _{80 μm} ≥ 110 N; and/or

The chemically strengthened glass-ceramics is subjected to a sandpaper drop resistance test, using 80-mesh sandpaper. The average sandpaper drop resistance height of the chemically strengthened glass-ceramics is ≥0.88 m, preferably, the average sandpaper drop resistance height of the chemically strengthened glass-ceramics is ≥1.1 m.

15. The chemically strengthened glass-ceramics according to any one of claims 1 to 14, wherein a Mohs hardness pen with a Mohs hardness rating of 6 and a tip angle of 35° in horizontal projection is used, and the tip of the Mohs hardness pen is vertically inserted into the chemically strengthened glass-ceramics along the thickness direction, and the chemically strengthened glass-ceramics meets the following requirements: Preferably, More preferably, Where h' is the depth of the Mohs hardness pen penetrating into the chemically strengthened micro-ceramic glass, and the angle θ is the angle of the Mohs hardness pen tip in horizontal projection, which is 35°.

16 . A cover glass, characterized in that the cover glass is made of the chemically strengthened glass-ceramics according to claim 1 .

17. An electronic device, characterized in that the electronic device comprises the chemically strengthened glass-ceramics according to any one of claims 1 to 15.

18. The electronic device according to claim 17, characterized in that the electronic device comprises a housing assembled on the outside of the electronic device, and a circuit board located inside the housing, and the housing comprises the chemically strengthened microcrystalline glass according to any one of claims 1 to 15.

19 . The electronic device according to claim 18 , wherein the housing comprises a display screen cover assembled on the front side of the electronic device, and the display screen cover comprises the chemically strengthened glass-ceramic according to claim 1 .

20 . The electronic device according to claim 18 , wherein the housing comprises a back cover assembled on the back side of the electronic device, and the back cover comprises the chemically strengthened glass-ceramic according to claim 1 .

21. An electronic device according to any one of claims 18 to 20, characterized in that the electronic device also includes a camera assembly located inside the housing, the housing includes a camera protection cover, the camera protection cover is covered on the camera assembly, and the camera protection cover includes the chemically strengthened microcrystalline glass according to any one of claims 1-15.

22. The electronic device according to any one of claims 18 to 21, further comprising a middle frame, wherein the middle frame comprises the chemically strengthened glass-ceramics according to any one of claims 1 to 15.

23. A glass device, characterized in that the glass device comprises the chemically strengthened glass-ceramics according to any one of claims 1 to 15.