Microcrystalline glass, preparation method therefor and use thereof

Abstract

NOT VISIBLE DUE TO STATUS OF PATENT

Description

A kind of microcrystalline glass and its preparation method and application

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application with application number 202410151202.X filed with the China Patent Office on February 2, 2024, entitled “A kind of microcrystalline glass, its preparation method and application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present application relates to the technical field of microcrystalline glass, and in particular to a microcrystalline glass having a lithium disilicate crystal phase as a main crystal phase and being easily chemically etched, as well as a preparation method and application thereof. Background Art

[0004] With the advent of the intelligent era, glass-ceramics are increasingly being used in the electronics industry, for example in mobile phones, e-book readers, tablets, in-car central control screens, and various wearable electronic devices. Market demand for increasingly thinner glass-ceramic cover plates for touch screens has made ultra-thin glass-ceramic cover plates a key development trend for the industry. Furthermore, with the growing demand for more diverse consumer electronics, glass-ceramic cover plates are becoming increasingly customized, with varying thicknesses and shapes, for example. Mobile phone back covers made of frosted glass-ceramic are increasingly popular among consumers. This suggests that increasing the chemical etching thinning rate of glass-ceramics can improve the production efficiency of ultra-thin or customized glass-ceramic products, thereby increasing their economic benefits.

[0005] In addition, the chemical thinning technology and AG (anti-reflection / anti-glare) etching technology commonly used in microcrystalline glass currently usually use etching liquid or frosting liquid, such as using a higher concentration of hydrofluoric acid or a mixture with other acids for etching. This process requires the use of high-concentration acidic liquid during the production process. The longer it is used, the greater the harm to the health of operators and the environment. Summary of the Invention

[0006] The purpose of the present application is to provide a glass-ceramic that is easy to chemically etch and thin with a lithium disilicate crystal phase as the main crystal phase, as well as a preparation method and application thereof. The glass-ceramic of the present application can achieve a relatively excellent chemical etching and thinning effect in a relatively low concentration of acidic liquid, which is not only conducive to improving the chemical etching and thinning rate of the glass-ceramic, but also conducive to improving the production efficiency of ultra-thin glass-ceramic products or customized glass-ceramic products, etc., and can avoid the use of high-concentration acidic liquid for etching and thinning, thereby better reducing the harm of the etching liquid to the health of operators and the environment.

[0007] The technical solutions provided in this application include:

[0008] In a first aspect, a glass-ceramic is provided, wherein the glass-ceramic contains a lithium disilicate crystalline phase, wherein the content of the lithium disilicate crystalline phase is greater than the content of other crystalline phases in the glass-ceramic; and the glass-ceramic comprises the following components, expressed in molar percentage based on oxides:

[0009] SiO2: 55.00~65.00mol%, P2O5: 1.00~3.00mol%, ZrO2: 2.00~5.00mol%, Li2O: 25.00~32.00mol%, Al2O3: 0~2.00mol%, MgO: 0~ 2.00mol%, Na2O: 0~3.00mol%, K2O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta2O5: 0~1.00mol%, La2O3: 0~1.00mol%;

[0010] The composition of the glass-ceramics, expressed as a molar percentage based on oxides, satisfies the following: 2×Li₂O+9×ZrO₂+1.2×CaO≥88.00mol%, or alternatively, 2×Li₂O+9×ZrO₂+1.2×CaO≥90.00mol%, where each oxide chemical formula represents the molar percentage content of the corresponding component in the glass-ceramics. For example, if the molar percentage of Li₂O is 28%, 28% is substituted into the formula for calculation.

[0011] In some embodiments of the present application, the SiO2 content and the Li2O content in the glass-ceramics are calculated as molar percentages based on oxides and meet the following conditions:

[0012] SiO2+Li2O=89.00~96.00mol%; optionally, SiO2+Li2O=90.00~95.00mol%.

[0013] In some embodiments of the present application, the SiO2 content and the Li2O content in the glass-ceramics are calculated as molar percentages based on oxides and meet the following conditions:

[0014] SiO2 / Li2O=2.00~2.50; optionally, SiO2 / Li2O=2.00~2.30.

[0015] In some embodiments of the present application, the component contents in the glass-ceramics, calculated as molar percentages based on oxides, further satisfy the following conditions:

[0016] (Li2O+ZrO2) / (SiO2+Al2O3+CaO)≥0.50; optionally, the value of (Li2O+ZrO2) / (SiO2+Al2O3+CaO) is 0.50~0.60, wherein the chemical formula of each oxide represents the molar percentage content of the corresponding component in the microcrystalline glass composition.

[0017] In some embodiments of the present application, the component contents in the glass-ceramics, calculated as molar percentages based on oxides, further satisfy the following conditions:

[0018] (2×Li2O-6×P2O5) / SiO2≥0.70, optionally, the value of (2×Li2O-6×P2O5) / SiO2 is 0.70~1.00, wherein the chemical formula of each oxide represents the molar percentage content of the corresponding component in the microcrystalline glass composition.

[0019] In some embodiments of the present application, expressed as a molar percentage based on oxides: the glass-ceramics contains 58.00 to 65.00 mol% SiO2, optionally 60.00 to 64.00 mol% SiO2; and / or the glass-ceramics contains 26.00 to 32.00 mol% Li2O, optionally 27.00 to 31.00 mol% Li2O;

[0020] And / or, the glass-ceramics contains 2.50-5.00 mol% ZrO2, optionally, contains 3.00-5.00 mol% ZrO2;

[0021] And / or, the glass-ceramics contains 1.50 to 3.00 mol% of P2O5, optionally, contains 1.50 to 2.50 mol% of P2O5.

[0022] In some embodiments of the present application, the glass-ceramics comprises the following components, expressed in terms of molar percentage based on oxides:

[0023] SiO2: 60.50~64.00mol%, P2O5: 1.50~2.50mol%, ZrO2: 4.00~5.00mol%, Li2O: 28.00~31.00mol%, Al2O3: 0~1.50mol%, MgO: 0~ 2.00mol%, Na2O: 0~3.00mol%, K2O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta2O5: 0~1.00mol%, La2O3: 0~1.00mol%.

[0024] In some embodiments of the present application, the crystallinity of the glass-ceramics is ≥60.00 wt %. Optionally, the crystallinity is 60.00 wt % to 90.00 wt %.

[0025] In some embodiments of the present application, in the glass-ceramics, the average crystal size is less than or equal to 100 nm, optionally, the average crystal size is less than or equal to 50 nm, and more optionally, the average crystal size is 10 to 40 nm.

[0026] In some embodiments of the present application, the density of the glass-ceramics is ≥2.50 g / cm 3 , optionally, a density of 2.50 g / cm 3 ~2.70g / cm 3 .

[0027] In some embodiments of the present application, the refractive index of the glass-ceramics is ≤1.60, optionally, the refractive index is 1.50-1.60.

[0028] In some embodiments of the present application, the Young's modulus of the glass-ceramics is ≥100 GPa, optionally, the Young's modulus is 108-130 GPa, and more optionally, the Young's modulus is 114-130 GPa.

[0029] In some embodiments of the present application, the microcrystalline glass is transparent in the visible light range; when the microcrystalline glass is 0.5 mm thick, for light with a wavelength of 550 nm, the transmittance of the microcrystalline glass is ≥85.00%, optionally, the transmittance of the microcrystalline glass is ≥90.00%.

[0030] In some embodiments of the present application, when the glass-ceramics is 0.5 mm thick, the optical b-value of the glass-ceramics is ≤1.0, optionally, the optical b-value is ≤0.8.

[0031] In some embodiments of the present application, when the glass-ceramics is placed in a 10% hydrofluoric acid aqueous solution at 20°C for 20 minutes, the change in mass per unit area of ​​the glass-ceramics is greater than or equal to 28.00 mg / cm 2 Optionally, the change in mass per unit area of ​​the glass-ceramics is 30.00 to 50.00 mg / cm 2 .

[0032] In some embodiments of the present application, a microcrystalline glass having a protective film on one of its two main surfaces is taken and placed in a mixed acid solution at 20°C for etching and thinning. The etching rate of the microcrystalline glass is ≥7.00μm / min. Optionally, the etching rate of the microcrystalline glass is ≥9.00μm / min. In the mixed acid solution, the mass concentration of hydrofluoric acid is 10wt%, the mass concentration of nitric acid is 10wt%, the mass concentration of phosphoric acid is 8wt%, the mass concentration of surfactant is 1wt%, the mass concentration of diethylenetriaminepentaacetic acid is 0.5wt%, and the remainder is water. Specifically, the etching rate is calculated using the following formula: Etching rate = (thickness of the microcrystalline glass sample before etching - thickness of the microcrystalline glass sample after etching) / etching time. In the present application, optionally, the surfactant includes sodium dodecylsulfonate. In the present application, optionally, etching and thinning are performed under chamfering conditions to ensure that the side without a protective film is uniformly etched.

[0033] In some embodiments of the present application, the aforementioned microcrystalline glass can be processed by chemical etching to obtain anti-glare microcrystalline glass or anti-reflective microcrystalline glass, and the composition of the anti-glare microcrystalline glass or anti-reflective microcrystalline glass at the center of the depth is the same as that of the microcrystalline glass.

[0034] In some embodiments of the present application, the aforementioned glass-ceramics can be processed into chemically strengthened glass-ceramics through chemical strengthening treatment, and the composition at the center of the chemically strengthened glass-ceramics is the same as that of the glass-ceramics.

[0035] In a second aspect, a method for preparing the aforementioned glass-ceramics is provided, comprising the following steps:

[0036] A substrate glass is provided. The substrate glass comprises the following components, expressed in molar percentage based on oxides: SiO2: 55.00-65.00 mol%, P2O5: 1.00-3.00 mol%, ZrO2: 2.00-5.00 mol%, Li2O: 25.00-32.00 mol%, Al2O3: 0-2.00 mol%, MgO: 0-2.00 mol%, Na2O: 0-3.00 mol%, K2O: 0-1.00 mol%, CaO: 0-2.00 mol%, SrO: 0-2.00 mol%, Ta2O5: 0-1.00 mol%, and La2O3: 0-1.00 mol%. The composition of the substrate glass, expressed in molar percentage based on oxides, satisfies the following: 2×Li2O+9×ZrO2+1.2×CaO≥88.00 mol%.

[0037] The substrate glass is subjected to heat treatment and crystallization to obtain microcrystalline glass, which contains a lithium disilicate crystal phase, wherein the content of the lithium disilicate crystal phase is greater than the content of other crystal phases in the microcrystalline glass.

[0038] In some embodiments of the present application, the heat treatment includes nucleation treatment and crystallization treatment, wherein the nucleation treatment temperature is 500-700°C, the nucleation treatment time is 10-1440 minutes, the crystallization treatment temperature is 600-750°C, and the crystallization treatment time is 5-1440 minutes.

[0039] In some embodiments of the present application, the heating rate of the heat treatment process is 3 to 15° C. / min, optionally, the heating rate is 3 to 10° C. / min.

[0040] In a third aspect, an electronic device is provided, comprising the glass-ceramics of any of the aforementioned embodiments, or chemically strengthened glass-ceramics obtained by chemically strengthening the glass-ceramics of any of the aforementioned embodiments, wherein the composition at the depth center of the chemically strengthened glass-ceramics is the same as the composition of the glass-ceramics of the present application. The electronic device includes, but is not limited to, a mobile phone, a tablet computer, a television, a computer display, or a smart wearable device.

[0041] Compared with the prior art, one or more technical solutions of this application include the following beneficial effects:

[0042] The present application optimizes and adjusts the components of the glass-ceramics. By ensuring that the glass-ceramics meet specific composition and structure and containing a large amount of lithium disilicate crystal phase, the glass-ceramics not only ensures that the glass-ceramics have high intrinsic strength and excellent optical properties, but also significantly improves the chemical etching and thinning effect of the glass-ceramics, enabling the glass-ceramics to achieve a relatively excellent chemical etching and thinning effect in a relatively low concentration of acidic liquid, which is beneficial to improving the chemical etching and thinning rate of the glass-ceramics, and further beneficial to improving the production efficiency of ultra-thin glass-ceramics products or customized glass-ceramics products. Using the glass-ceramics of the present application for chemical etching and thinning can avoid the use of high-concentration acidic liquids, thereby better reducing the harm of the etching solution to the health of operators and the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIG1 is a schematic diagram of the process of chemical etching and thinning of glass-ceramics in this application.

[0044] FIG2 is a comparison chart of the XRD patterns of the glass-ceramics of Example 3, Example 6, Example 8, Comparative Example 1 and Comparative Example 6.

[0045] FIG3 is a comparison diagram of the DSC curves of the substrate glasses of Example 8 and Comparative Example 6.

[0046] FIG4 is a transmittance curve diagram of the glass-ceramics of Example 8.

[0047] FIG5 is a transmittance curve diagram of the glass-ceramics of Comparative Example 6. DETAILED DESCRIPTION

[0048] This application will provide a clear and complete description of the technical solutions in the embodiments of this application in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of this application, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on this application are within the scope of protection of this application.

[0049] Unless otherwise indicated in specific circumstances in this application, the numerical ranges listed herein include upper and lower limits, as well as all integers and fractions within the range, and are not limited to the specific values ​​listed when defining the range. The term "and / or" herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0050] 1. The following are some explanations of the relevant terms involved in this application

[0051] 1. Base glass: refers to glass that has not been subjected to nucleation treatment, crystallization treatment and strengthening treatment, or is also called basic glass.

[0052] 2. Glass-ceramics: also known as glass ceramics, is a type of solid composite material that contains both glass phase and microcrystalline phase (also called crystal phase or crystalline phase) and is prepared by targeted and controlled heat treatment of the base glass.

[0053] 3. Nucleation: Through heat treatment, the nucleating material in the glass grows small crystal nuclei.

[0054] 4. Crystallization: Glass grows a certain crystal based on the crystal nucleus through heat treatment.

[0055] 5. Transmittance: When light of a certain wavelength hits the glass surface, the light will be reflected, absorbed and transmitted. The ratio of the intensity of the transmitted part to the intensity of the incident light is the transmittance.

[0056] 6. Crystallinity: refers to the percentage of the total mass of the crystalline phase or crystals in the microcrystalline glass to the mass of the microcrystalline glass, or also called the total crystalline phase content in the microcrystalline glass.

[0057] 7. Optical b-value: This value is used to characterize the yellow-blue value of a material. The optical b-value in this application refers to the b-value of transmitted light. A positive optical b-value indicates a blue tint.

[0058] 8. Refractive index: The refractive index refers to the ratio of the speed of light in a vacuum to the speed of light in the medium.

[0059] 9. Main surface: refers to the surface with the largest surface area in the glass brick or glass sheet, such as the upper or lower surface of the cover glass.

[0060] 10. The center of chemically strengthened glass-ceramics: including the center depth of chemically strengthened glass-ceramics and the position close to the center depth.

[0061] 11. Main crystalline phase: also known as the main crystalline phase, refers to a crystalline phase with a higher weight content than other crystalline phases present in the microcrystalline glass.

[0062] 2. Related detection methods involved in this application

[0063] 1. Synchronous thermal analysis test

[0064] The substrate glass was crushed, ground, and sieved through a 200-mesh sieve to obtain a sample. Approximately 20 mg of the sample was weighed and heated from room temperature to 1100°C at a heating rate of 10°C / min under a nitrogen atmosphere using a differential thermal analyzer to obtain a DSC curve for the sample. The differential thermal analyzer used in this application was a Mettler-Toledo TGA / DSC3+ thermogravimetric and simultaneous thermal analyzer. The standard used in the test was α-Al2O3 powder. The sample was placed in a platinum crucible. The instrument was placed in an ambient temperature of 24°C and an air humidity of ≤40%.

[0065] 2. XRD test

[0066] (1) Test steps

[0067] The glass-ceramics was crushed and ground into samples with a particle size of less than 75 μm. The ground samples were tested using an X-ray diffractometer to obtain an XRD diffraction peak curve and XRD diffraction data.

[0068] The X-ray diffractometer was Shimadzu XRD-6100, with 2θ=10-50°, a scanning speed of 6° / min, an operating voltage of 40 kV, and an operating current of 30 mA.

[0069] (2) Determination of crystal phase

[0070] The XRD diffraction data were analyzed using Jade software (JADE Standard 8.6) to determine the crystalline phase in the glass-ceramic sample.

[0071] (3) Determination of crystallinity

[0072] Importing the XRD test results (RAW format) into Jade, an X-ray diffraction data refinement software, for fitting and calculation can determine the crystallinity of the glass-ceramic sample. Specifically, the ratio of the fitted crystalline phase peak area to the fitted total peak area is recorded as the crystallinity of the glass-ceramic sample.

[0073] (4) Determination of average crystal size

[0074] The average crystal size of the sample can be calculated using the data obtained from the XRD test according to the Scherrer formula D = Kλ / (βcosθ). Here, λ is the X-ray wavelength, λ = 0.154056nm, β is the half-height width of the diffraction peak, K = 0.89, and θ is the Bragg diffraction angle. Specifically, the RAW format file output by the XRD instrument is curve fitted in Jade software. Jade outputs a fitting report. Based on the angle 2θ value and Peak FWHM value corresponding to each diffraction peak in the fitting report, the Peak FWHM value is converted to radians: β = (FWHM / 180×3.14). The crystal size of each diffraction peak is calculated using the Scherrer formula D = Kλ / (βcosθ) and then averaged to obtain the average crystal size in the sample.

[0075] 3. Thickness test

[0076] Use a micrometer to test the thickness of glass-ceramics.

[0077] 4. Optical performance test

[0078] With reference to the national standard "GB / T 7962.12-2010 Test Methods for Colorless Optical Glass - Part 12: Spectral Transmittance," a haze meter was used to test the transmittance and optical b-value of the glass-ceramics of this application. Specifically, the haze meter was used to test the transmittance and optical b-value of five glass-ceramics from the same batch for light of different wavelengths. The average transmittance of the five glass-ceramics at a wavelength of 550 nm was taken as the transmittance result of the glass-ceramics at a wavelength of 550 nm. The average optical b-value of the five glass-ceramics was taken as the optical b-value result of the glass-ceramics.

[0079] The haze meter used in the test of this application is a Konica Minolta spectrophotometer CM-3600A from Japan. The light receiving optical system is transmission, the spectroscopic method is a plane reflective grating, the wavelength range is 360nm to 740nm, the wavelength spacing is 10nm, the illumination light source is 4 pulsed xenon lamps, and the ambient temperature of the instrument is 24°C and the air humidity is 40%.

[0080] 5. Young's modulus test

[0081] The UMS-100 ultrasonic material characterization system was used to test the Young's modulus of glass-ceramics using acoustic waves.

[0082] 6. Chemical etching effect test

[0083] (1) Etching test with hydrofluoric acid (HF) aqueous solution, HCl aqueous solution or NaOH aqueous solution

[0084] In this application, according to GB / T 32644-2016 "Test method for chemical durability of flat panel display substrate glass", the etching effect of microcrystalline glass in HF aqueous solution, HCl aqueous solution or NaOH aqueous solution was tested, and the change in the unit area mass of microcrystalline glass under each test condition was calculated respectively.

[0085] The mass concentration of the HF aqueous solution used in the test of this application is 10wt% or 5wt%, and the test conditions are: test temperature is 20°C, and etching time or reaction time is 20min.

[0086] The mass concentration of the HCl aqueous solution used in the test of this application is 5 wt %, and the test conditions are: the test temperature is 95° C., and the etching time or reaction time is 24 h.

[0087] The mass concentration of the NaOH aqueous solution used in the test of this application is 5 wt %, and the test conditions are: the test temperature is 95° C., and the etching time or reaction time is 6 h.

[0088] (2) Etching test of mixed acid solution

[0089] The mixed acid solution used in this application includes: hydrofluoric acid at a mass concentration of 10 wt %, nitric acid at a mass concentration of 10 wt %, phosphoric acid at a mass concentration of 8 wt %, a surfactant at a mass concentration of 1 wt %, diethylenetriaminepentaacetic acid at a mass concentration of 0.5 wt %, and the balance being water. The surfactant is sodium dodecylsulfonate.

[0090] The above reagents for preparing the mixed acid solution are from the following sources: surfactant: sodium dodecylsulfonate, purity ≥40%; diethylenetriaminepentaacetic acid, purity ≥13.0%; hydrofluoric acid, purity ≥40%; phosphoric acid, purity ≥85%; nitric acid, purity ≥65%.

[0091] The test conditions for etching treatment using a mixed acid solution adopted in this application are: the test temperature is 20°C, and the etching time or reaction time is 30 minutes. Specifically: first attach a protective film to one of the two main surfaces of the microcrystalline glass sample and test its thickness (T1), then place the coated microcrystalline glass sample into the spray equipment, set the spray flow of the spray equipment to 500L / min, and make the spray equipment continuously spray the above-mentioned mixed acid solution to the uncoated side of the microcrystalline glass sample. During this process, the sample is chamfered every 15 minutes and the sample is rotated 180° to ensure the uniformity of sample etching. Record the initial placement time, and after the spray equipment has sprayed the microcrystalline glass sample for 30 minutes, take out the microcrystalline glass sample and test its thickness (T2). Etching rate = (T1-T2) / 30.

[0092] 7. Density test

[0093] This application uses the electronic density balance SD-200L of Japan ALFA MIRAGE to test the density of microcrystalline glass.

[0094] 8. Refractive index test

[0095] This application uses the Abbe refractometer WYA-2WAJ produced by Shanghai Lichen Bangxi Instrument Technology Co., Ltd. in China to test the refractive index of microcrystalline glass.

[0096] 3. Glass-ceramics and its preparation method and application scheme

[0097] To improve the efficiency of chemical etching of glass-ceramics, conventional techniques typically employ a high-concentration etching solution in conjunction with high temperatures to increase the etching rate. However, high temperatures not only deteriorate the working environment but also cause the etching solution to boil and evaporate, further increasing the consumption of high-concentration etching solutions and posing risks to operator health and the environment.

[0098] In order to avoid the aforementioned problems, the present application provides a glass-ceramic that can achieve a relatively excellent chemical etching effect in an acidic liquid with a relatively low concentration. This not only reduces the amount of acidic liquid used in the etching solution, but also reduces the working temperature during chemical etching, avoids the deterioration of the working environment caused by the evaporation of the etching solution, and can further reduce the amount of acidic liquid used in the etching solution. The present application optimizes and adjusts the components of the glass-ceramic, and ensures that the glass-ceramic contains a large amount of lithium disilicate crystal phase by making the glass-ceramic meet specific composition and structure. It not only ensures that the glass-ceramic has high intrinsic strength and excellent optical properties, but also significantly improves the chemical etching thinning effect of the glass-ceramic, so that the glass-ceramic can achieve a relatively excellent chemical etching thinning effect in an acidic liquid with a relatively low concentration, which is beneficial to improving the chemical etching thinning rate of the glass-ceramic, and further helps to improve the production efficiency of ultra-thin glass-ceramic products or customized glass-ceramic products. The glass-ceramics can rapidly etch with low-concentration etching solutions at a relatively high etching rate, even at room temperature. This can effectively improve etching conditions while accelerating the etching rate and reducing etching solution consumption. Furthermore, chemical etching thinning using the glass-ceramics of this application avoids the use of highly concentrated acidic liquids, thereby further reducing the hazards of etching solutions to operator health and the environment.

[0099] In some embodiments of the present application, a glass-ceramic is provided, wherein the glass-ceramic contains a lithium disilicate crystalline phase, and the content of the lithium disilicate crystalline phase is greater than the content of other crystalline phases in the glass-ceramic. The glass-ceramic comprises the following components, expressed in molar percentage based on oxides:

[0100] SiO2: 55.00~65.00mol%, P2O5: 1.00~3.00mol%, ZrO2: 2.00~5.00mol%, Li2O: 25.00~32.00mol%, Al2O3: 0~2.00mol%, MgO: 0~ 2.00mol%, Na2O: 0~3.00mol%, K2O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta2O5: 0~1.00mol%, La2O3: 0~1.00mol%;

[0101] The composition of the glass-ceramics, expressed as a molar percentage of oxides, satisfies the following: 2×Li2O+9×ZrO2+1.2×CaO≥88.00mol%, optionally ≥90.00mol%, wherein the chemical formulas of the oxides represent the molar percentage content of the corresponding components in the glass-ceramics composition. By optimizing the composition of the glass-ceramics, the components in the glass-ceramics satisfy specific content and content relationships, and the synergistic effect between the components is exerted, thereby ensuring that a specific structure can be formed inside the glass-ceramics. While ensuring that the glass-ceramics contains a large amount of lithium disilicate crystal phase and that the glass-ceramics has high intrinsic strength and excellent optical properties, the chemical etching thinning effect of the glass-ceramics is also significantly improved, enabling the glass-ceramics to achieve a relatively excellent chemical etching thinning effect in acidic liquids of lower concentration and lower temperature, which is beneficial to improving the chemical etching thinning rate of the glass-ceramics, and thereby improving the production efficiency of ultra-thin glass-ceramics products or customized glass-ceramics products.

[0102] The lithium disilicate (Li2Si2O5) crystalline phase is an orthorhombic crystal based on an array of [Si2O5] tetrahedrons, and the shape of the crystals is flat or plate-like. Inside the glass-ceramics, the lithium disilicate crystals are randomly oriented interlocking microstructures, forcing the crack path to be distorted when passing through the crystal, thereby preventing the crack from expanding and improving the strength and fracture toughness of the glass-ceramics. At the same time, the refractive index of the lithium disilicate crystals is close to that of the glass matrix (e.g., the base glass for preparing glass-ceramics), and it is an ideal crystalline phase for preparing highly transparent glass-ceramics. In the present application, the glass-ceramics contains a structure with lithium disilicate as the main crystalline phase, which can ensure that it obtains high intrinsic strength (or also called inherent strength) and excellent optical properties. At the same time, the glass-ceramics of the present application is easier to chemically etch and thin compared to other glass-ceramics.

[0103] In this application, SiO2, as a glass network-forming oxide, is an indispensable component of the glass network structure. Furthermore, as a crucial component of the lithium disilicate crystalline phase, SiO2 is also essential. However, excessive SiO2 increases the viscosity of the glass melt, making it difficult to melt. Therefore, to meet the glass formability requirements and achieve the desired crystallization effect of this application, the SiO2 content is controlled within a range of 55.00 to 65.00 mol%.

[0104] In some embodiments of the present application, the content of SiO2 in the microcrystalline glass can be 55.00-65.00 mol%, 58.00-64.00 mol%, 60.00-65.00 mol%, 60.50-63.50 mol%, 58.00-65.00 mol% or 60.00-64.00 mol%. In some embodiments, in the glass-ceramics, the content of SiO2 can be 55.00mol%, 56.00mol%, 57.00mol%, 58.00mol%, 59.00mol%, 60.00mol%, 60.50mol%, 60.74mol%, 61.00mol%, 61.15mol%, 61.72mol%, 61.76mol%, 61.83mol%, 62.00mol%, 62.58mol%, 63.00mol%, 63.17mol%, 63.50mol%, 64.17mol%, 64.50mol% or 65.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the glass-ceramics with the desired performance of the present application can be obtained.

[0105] In this application, Al2O3 is an optional component and an intermediate oxide in glass formation. While an appropriate amount of Al2O3 can stabilize the network structure, an excessive amount of Al2O3 can increase the viscosity of the glass liquid, leading to the precipitation of other crystalline phases such as petalite, and reducing the content of the primary lithium disilicate phase. Therefore, in this application, to achieve the desired crystalline structure, the Al2O3 content is controlled to 0-2.00 mol%.

[0106] In some embodiments of the present application, the content of Al2O3 in the microcrystalline glass can be 0-2.00 mol%, 0.10-1.80 mol%, 0-1.50 mol%, 0.20-1.60 mol%, 0.00-0.50 mol% or 1.30-1.50 mol%. In some embodiments, the content of Al2O3 can be 0.00mol%, 0.10mol%, 0.30mol%, 0.50mol%, 0.70mol%, 0.80mol%, 0.90mol%, 1.00mol%, 1.10mol%, 1.20mol%, 1.30mol%, 1.36mol%, 1.37mol%, 1.38mol%, 1.39mol%, 1.40mol%, 1.42mol%, 1.45mol%, 1.50mol%, 1.60mol%, 1.70mol% or 2.0mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the desired performance of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the desired performance of the present application can be obtained.

[0107] In this application, P2O5 is an essential nucleating agent. Excessive or excessive amounts of P2O5 can result in poor crystallization, making it difficult to achieve the desired optical properties and intrinsic strength of the glass-ceramics. For example, the glass-ceramics may be less transparent. Therefore, to ensure the desired glass-ceramics that meet the specific structure of this application, the P2O5 content is controlled to 1.00 to 3.00 mol%.

[0108] In some embodiments of the present application, the content of P2O5 in the glass-ceramics may be 1.00-3.00 mol%, 1.50-2.50 mol%, 1.80-1.90 mol%, 1.60-2.00 mol% or 1.50-3.00 mol%. In some embodiments, the content of P2O5 may be 1.00 mol%, 1.20 mol%, 1.40 mol%, 1.50 mol%, 1.60 mol%, 1.70 mol%, 1.80 mol%, 1.87 mol%, 1.86 mol%. mol%, 1.85mol%, 1.83mol%, 1.89mol%, 1.82mol%, 1.90mol%, 2.00mol%, 2.10mol%, 2.20mol%, 2.30mol%, 2.40mol%, 2.50mol%, 2.60mol%, 2.70mol%, 2.80mol%, 2.90mol% or 3.00mol%, or it can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the required performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required performance of the present application can be obtained.

[0109] In the present application, ZrO2 is an intermediate oxide in the formation of glass and an indispensable component. Increasing the content of a certain amount of ZrO2 can improve the alkali resistance of the microcrystalline glass, but the acid resistance will be reduced. An appropriate amount of ZrO2 is conducive to the efficient chemical etching and thinning of the microcrystalline glass in an acid solution, and can also play a role in reducing the crystal size and increasing the toughness of the microcrystalline glass. However, when its content is too high, it will increase the difficulty of melting the substrate glass and cause a large amount of white precipitate to appear in the glass. Therefore, in order to ensure the formability of the glass, make the microcrystalline glass have higher intrinsic strength and optical properties, and improve the chemical etching effect of the microcrystalline glass, the ZrO2 content is controlled to be 2.00~5.00mol%.

[0110] In some embodiments of the present application, the ZrO2 content in the glass-ceramics may be 2.00-5.00 mol%, 3.00-4.50 mol%, 2.50-5.00 mol%, 4.50-5.00 mol%, or 3.00-5.00 mol%. In some embodiments, the ZrO2 content may be 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.10 mol%, 3.31 mol%, 3.50 mol%, 3.72 mol%, 4.00 mol%, 4.21 mol%, 4.44 mol%, 4.50 mol%, 4.57 mol%, 4.61 mol%, 4.63 mol%, 4.66 mol%, 4.68 mol%, 4.72 mol%, or 5.00 mol%, or may be all ranges and subranges between any two of the above specific values, as long as the glass-ceramics having the desired properties of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0111] In this application, MgO is an optional component that can play a role in regulating the glass phase composition in microcrystalline glass. However, excessive MgO will affect the growth of crystals, thereby affecting the structure of microcrystalline glass, affecting the mechanical strength or optical properties of microcrystalline glass, etc. Therefore, in order to ensure that the microcrystalline glass meets the desired structure, the MgO content is controlled to 0-2.00 mol%.

[0112] In some embodiments of the present application, the content of MgO in the glass-ceramics may be 0-2.00 mol%, 0.10-1.80 mol%, 0-1.34 mol%, 0.50-1.60 mol%, 0.00-0.50 mol% or 1.60-1.80 mol%. In some embodiments, the content of MgO can be 0, 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.46 mol%, 0.50 mol%, 0.60 mol%, 0.70 mol%, 0.80 mol%, 0.87 mol%, 0.90 mol%, 1.00 mol%, 1.06 mol%, 1.10 mol%, 1.20 mol%, 1.30 mol%, 1.34 mol%, 1.40 mol%, 1.50 mol%, 1.57 mol%, 1.60 mol%, 1.70 mol%, 1.80 mol%, 1.89 mol% or 2.00 mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the desired properties of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the desired properties of the present application can be obtained.

[0113] In this application, Na2O is an optional component, a network-external oxide that provides free oxygen. A moderate amount of Na2O improves the viscosity of the glass and promotes melting and clarification of the molten glass. However, excessive Na2O can affect the glass's network structure and, in turn, the performance of the glass-ceramics. Therefore, to ensure the desired structure of the glass-ceramics, the Na2O content is controlled to 0-3.00 mol%.

[0114] In some embodiments of the present application, the content of Na2O in the glass-ceramics may be 0-3.00 mol%, 0.10-2.80 mol%, 0.50-2.50 mol%, 1.00-2.00 mol%, 0-0.50 mol%, or 0.50-2.59 mol%. In some embodiments, the content of Na2O may be 0, 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.56 mol%, 0.80 mol%, 1.00 mol%, 1.48 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 2.59 mol%, 2.80 mol%, or 3.00 mol%, or may be all ranges and subranges between any two of the above specific values, as long as the glass-ceramics having the desired properties of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0115] In this application, K2O is an optional component. A moderate amount of K2O can reduce the viscosity of the glass liquid and promote crystal formation. However, excessive K2O can easily lead to coarsening of the glass crystals, reducing the transmittance of the glass-ceramics and glass-ceramics products. Therefore, to ensure that the glass-ceramics achieves excellent optical properties and high intrinsic strength, this application controls the K2O content to 0-1.00 mol%.

[0116] In some embodiments of the present application, the content of K2O in the glass-ceramics may be 0-1.00 mol%, 0.10-0.90 mol%, 0-0.50 mol%, 0.50-1.00 mol%, or 0-0.92 mol%. In some embodiments, the content of K2O may be 0, 0.10 mol%, 0.20 mol%, 0.21 mol%, 0.36 mol%, 0.40 mol%, 0.50 mol%, 0.60 mol%, 0.69 mol%, 0.72 mol%, 0.80 mol%, 0.92 mol%, or 1.00 mol%, or may be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges may be combined with any other ranges, as long as the glass-ceramics with the desired properties of the present application can be obtained.

[0117] In the present application, Li2O is an essential component of the lithium disilicate crystalline phase (Li2Si2O5), which will directly affect the content of the lithium disilicate crystalline phase contained in the microcrystalline glass. As a network exometallic oxide formed by the glass, it can provide free oxygen, improve the viscosity of the glass liquid, and promote the melting and clarification of the glass liquid. At the same time, it can also provide lithium ions for ion exchange with the molten salt bath, which is an important factor affecting the stress level that can be obtained by the microcrystalline glass. However, the addition of excessive Li2O may lead to poor stability of the glass crystallization process, and even cause the precipitation of other crystalline phases, affecting the structure of the microcrystalline glass. Therefore, in order to ensure that the microcrystalline glass meets the desired structure, has excellent optical properties and high intrinsic strength, and at the same time improve the chemical etching thinning effect of the microcrystalline glass, the Li2O content is controlled at 25.00~32.00mol%.

[0118] In some embodiments of the present application, the content of Li2O in the microcrystalline glass can be 25.00-32.00 mol%, 27.00-30.00 mol%, 26.00-32.00 mol%, 28.00-30.00 mol%, 27.00-31.00 mol%, 29.00-32.00 mol% or 25.00-30.00 mol%. In some embodiments, the content of Li2O can be 25.00mol%, 26.00mol%, 27.00mol%, 28.00mol%, 28.59mol%, 29.00mol%, 29.80mol%, 29.52mol%, 29.93mol%, 29.25mol%, 29.30mol%, 29.66mol%, 29.52mol%, 29.05mol%, 30.00mol%, 30.22mol%, 31.00mol%, 31.07mol% or 32.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the desired performance of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the desired performance of the present application can be obtained.

[0119] In the present application, CaO is an optional component. An appropriate amount of CaO can reduce the high-temperature viscosity of the glass liquid, which is beneficial to glass molding and can enhance the network structure and density of the glass. However, excessive CaO will cause the crystallinity of the glass to drop sharply, affecting the intrinsic strength of the microcrystalline glass and the chemical etching thinning effect of the microcrystalline glass. Therefore, in order to ensure that the microcrystalline glass obtains the desired intrinsic strength and achieves the desired chemical etching thinning effect, the CaO content is controlled to 0-2.00 mol%.

[0120] In some embodiments of the present application, the CaO content in the glass-ceramics may be 0-2.00 mol%, 0.10-1.90 mol%, 0-1.83 mol%, 0.5-1.50 mol%, 0.60-1.00 mol%, 0.80-2.00 mol%, or 0-0.80 mol%. In some embodiments, the CaO content may be 0, 0.10 mol%, 0.30 mol%, 0.50 mol%, 0.60 mol%, 0.80 mol%, 0.90 mol%, 0.92 mol%, 0.93 mol%, 0.94 mol%, 1.00 mol%, 1.50 mol%, 1.80 mol%, 1.83 mol%, 1.90 mol%, or 2.00 mol%, or may be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics having the desired properties of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0121] In this application, SrO is an optional component and an alkaline earth metal oxide. An appropriate amount of SrO can regulate the glass phase composition in the glass-ceramic, increasing its density and lowering its expansion softening point, thereby facilitating hot bending. However, the introduction of excessive SrO can deteriorate the optical properties of the glass-ceramic. Therefore, in order to ensure that the glass-ceramic meets excellent optical properties and high intrinsic strength while also improving the hot bending performance of the glass-ceramic, the SrO content is controlled to 0-2.00 mol%.

[0122] In some embodiments of the present application, the content of SrO in the glass-ceramics may be 0-2.00 mol%, 0.10-1.90 mol%, 0-0.40 mol%, 0.40-2.00 mol%, 0-0.46 mol%, 0.46-1.83 mol% or 0.40-1.90 mol%. In some embodiments, the content of SrO may be 0, 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.46 mol%, 0.50 mol%, 0.60 mol%, 0.70mol%, 0.80mol%, 0.90mol%, 0.92mol%, 1.00mol%, 1.10mol%, 1.20mol%, 1.30mol%, 1.40mol%, 1.50mol%, 1.60mol%, 1.70mol%, 1.80mol%, 1.83mol%, 1.90mol% or 2.00mol%, or it can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the required performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required performance of the present application can be obtained.

[0123] In the present application, Ta2O5 is an optional component that can improve the mechanical strength of glass. However, excessive Ta2O5 can easily lead to a decrease in the glass's resistance to devitrification. Therefore, in order to ensure that the microcrystalline glass has excellent optical properties and high intrinsic strength, the Ta2O5 content is controlled to be 0-1.00 mol%. In some embodiments of the present application, the Ta2O5 content in the microcrystalline glass can be 0-1.00 mol%, 0.5-0.9 mol%, 0-0.50 mol%, 0.3-0.80 mol%, or 0-0.46 mol%. In some embodiments, the content of Ta2O5 can be 0, 0.10mol%, 0.20mol%, 0.30mol%, 0.40mol%, 0.46mol%, 0.50mol%, 0.60mol%, 0.70mol%, 0.80mol%, 0.90mol%, 0.98mol% or 1.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the micro-ceramics with the desired properties of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the micro-ceramics with the desired properties of the present application can be obtained.

[0124] In this application, La2O3 is an optional component that can increase the density and Young's modulus of glass. However, excessive La2O3 can easily reduce the transmittance of the glass. Therefore, to ensure that the micro-ceramic glass has excellent optical properties and high intrinsic strength, the La2O3 content is controlled to 0-1.00 mol%.

[0125] In some embodiments, the content of La2O3 may be 0-1.00 mol%, 0.10-0.90 mol%, 0-0.60 mol%, 0.20-0.80 mol%, 0.30-0.70 mol%, 0-0.53 mol%, or 0.60-1.00 mol%. In some embodiments, the content of La2O3 may be 0, 0.10 mol%, 0.20 mol%, 0.27 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.53 mol%, 0.60 mol%, 0.70 mol%, 0.80 mol%, 0.89 mol%, 0.90 mol%, or 1.00 mol%, or may be all ranges and subranges between any two of the above specific values, as long as the microcrystalline glass having the desired properties of the present application is obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0126] In the present application, the composition of the glass-ceramics is also optimized and adjusted so that the composition of the glass-ceramics satisfies the following conditions: 2×Li2O+9×ZrO2+1.2×CaO≥88.00mol%, or alternatively, 2×Li2O+9×ZrO2+1.2×CaO≥90.00mol%, where the chemical formulas of the oxides represent the molar percentage content of the corresponding components in the glass-ceramics. By ensuring that the composition of the glass-ceramics satisfies this relationship, the chemical etching thinning effect of the glass-ceramics can be significantly improved while ensuring that the glass-ceramics obtains high intrinsic strength and excellent optical properties, enabling the glass-ceramics to achieve a relatively excellent chemical etching thinning effect in a relatively low concentration of acidic liquid.

[0127] In some embodiments of the present application, in the microcrystalline glass, calculated as the molar percentage of oxides, the value of 2×Li2O+9×ZrO2+1.2×CaO can be 88.00mol% to 105.00mol%, 90.00mol% to 99.00mol%, 89.00mol% to 104.00mol%, 90.00mol% to 103.00mol%, 99.00 to 105.00mol%, 88.00mol% to 105.00mol%, 92.00mol% to 105.00mol%, 94.00mol% to 104.00mol%, 98.00mol% to 103.00mol% or 88.00mol% to 98.00mol%. In some embodiments, the value of 2×Li2O+9×ZrO2+1.2×CaO may be 88.00 mol%, 89.00 mol%, 90.00 mol%, 90.18 mol%, 91.00 mol%, 92.00 mol%, 93.00 mol%, 94.00 mol%, 94.23 mol%, 95.00 mol%, 96.00 mol%, 97.00 mol%, 97.75 mol%, 98.00 mol%, 98.08 mol%, 99.00 mol%, 91.00 mol%, 92.00 mol%, 93.00 mol%, 94.23 mol%, 95.00 mol%, 96.00 mol%, 97.00 mol%, 97.75 mol%, 98.00 mol%, 98.08 mol%, 99.0 ... 1%, 99.63 mol%, 100.00 mol%, 100.41 mol%, 100.55 mol%, 101.00 mol%, 101.02 mol%, 101.09 mol%, 101.49 mol%, 101.66 mol%, 101.83 mol%, 102.00 mol%, 103.00 mol% or 105.00 mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the desired performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the desired performance of the present application can be obtained.

[0128] In some embodiments of the present application, the SiO2 content and the Li2O content in the glass-ceramics, calculated as molar percentages based on oxides, satisfy the following condition: SiO2 + Li2O = 89.00 to 96.00 mol%. By ensuring that the glass-ceramics satisfy this relationship, a desired amount of lithium disilicate crystals is precipitated in the glass-ceramics, and the precipitation of other crystals, such as petalite crystals, can be effectively reduced. This helps ensure that the glass-ceramics obtains higher intrinsic strength and excellent optical properties, and also helps the glass-ceramics obtain a higher stress level after chemical strengthening. Furthermore, it helps ensure that the substrate glass does not lose clarity during heat treatment to prepare the glass-ceramics, or that the substrate glass does not lose clarity during the melting process.

[0129] In some embodiments, in the microcrystalline glass, the value of SiO2+Li2O, calculated as the molar percentage of oxides, can be 89.00-96.00 mol%, 90.00-95.00 mol%, 91.00-93.00 mol%, 90.50-93.50 mol%, 90.00-92.00 mol% or 91.00-95.00 mol%. In some embodiments, the value of SiO2+Li2O can be 89.00mol%, 89.79mol%, 90.00mol%, 90.40mol%, 90.50mol%, 91.00mol%, 91.18mol%, 91.24mol%, 91.56mol%, 91.63mol%, 91.66mol%, 92.00mol%, 92.52mol%, 92.47mol%, 93.00mol%, 93.39mol%, 94.00mol%, 95.00mol% or 96.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the desired performance of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the desired performance of the present application can be obtained.

[0130] In some embodiments of the present application, the SiO2 content and Li2O content in the glass-ceramics, calculated as molar percentages based on oxides, satisfy the following condition: SiO2 / Li2O = 2.00-2.50. Ensuring that the glass-ceramics satisfy this relationship reduces the crystal size of the glass-ceramics, improving their optical properties. This also helps ensure the precipitation of lithium disilicate crystals, the primary crystalline phase, while effectively reducing the precipitation of other crystalline phases, such as petalite crystals. This helps ensure the glass-ceramics achieve high intrinsic strength and achieves a high stress level after chemical strengthening.

[0131] In some embodiments, in the glass-ceramics, the value of SiO2 / Li2O, calculated as the molar percentage of oxides, can be 2.00-2.50, 2.05-2.25, 2.00-2.30, or 2.10-2.35. In some embodiments, the value of SiO2 / Li2O can be 2.00, 2.05, 2.07, 2.08, 2.09, 2.10, 2.16, 2.19, 2.20, 2.25, 2.30, 2.35, 2.40, 2.45, or 2.50, or can be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the glass-ceramics with the desired properties of the present application can be obtained.

[0132] In some embodiments of the present application, the component content in the microcrystalline glass, calculated according to the content expressed as a molar percentage of the oxide, also satisfies the following conditions: (Li2O+ZrO2) / (SiO2+Al2O3+CaO)≥0.50; by making the microcrystalline glass satisfy the composition of this relationship, it is beneficial to further improve its chemical etching thinning effect while ensuring that the microcrystalline glass forms a specific network structure and has a higher intrinsic strength.

[0133] In some embodiments, in the glass-ceramics, the value of (Li2O+ZrO2) / (SiO2+Al2O3+CaO) calculated as the molar percentage of the oxides may be 0.50-0.60, 0.51-0.59, 0.55-0.60, 0.50-0.55, 0.52-0.58, 0.53-0.57, 0.54-0.56, or 0.51-0.55. In some embodiments, the value of (Li2O+ZrO2) / (SiO2+Al2O3+CaO) may be 0.50, 0.51, 0.52, 0.54, 0.53, 0.55, 0.56, 0.57, 0.58, 0.59, or 0.60, or may be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics having the desired properties of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0134] In some embodiments of the present application, the component contents in the glass-ceramics, calculated as molar percentages of the oxides, further satisfy the following condition: (2×Li₂O - 6×P₂O₅) / SiO₂ ≥ 0.70. Ensuring that the glass-ceramics satisfy this relationship helps ensure the desired amount of lithium disilicate crystalline phase precipitates in the glass-ceramics, thereby ensuring high intrinsic strength of the glass-ceramics.

[0135] In some embodiments, in the glass-ceramics, calculated as a molar percentage of oxides, the value of (2×Li2O-6×P2O5) / SiO2 can be 0.70-1.00, 0.80-0.90, 0.70-0.80, or 0.90-1.00. In some embodiments, the value of (2×Li2O-6×P2O5) / SiO2 can be 0.70, 0.73, 0.75, 0.78, 0.80, 0.90, or 1.00, or can be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the glass-ceramics with the desired properties of the present application can be obtained.

[0136] In some embodiments of the present application, expressed in molar percentage based on oxides, the microcrystalline glass contains the following components: SiO2: 60.50~64.00mol%, P2O5: 1.50~2.50mol%, ZrO2: 4.00~5.00mol%, Li2O: 28.00~31.00mol%, Al2O3: 0~1.50mol%, MgO: 0~2.00mol%, Na2O: 0~3.00mol%, K2O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta2O5: 0~1.00mol%, La2O3: 0~1.00mol%.

[0137] In some embodiments of the present application, the crystallinity of the glass-ceramics is ≥60.00wt%, optionally, 60.00~90.00wt%. The "crystallinity of the glass-ceramics" here refers to the percentage of the content of all crystalline phases / or crystals in the glass-ceramics to the mass of the glass-ceramics. A higher content of microcrystalline phase is more conducive to improving the mechanical strength properties of the glass-ceramics, thereby ensuring that the glass-ceramics has better intrinsic strength. In some embodiments, the crystallinity of the glass-ceramics can be 70.00~90.00wt%, 65.00~85.00wt%, 60.00~90.00wt% or 70.00~80.00wt%. In some embodiments, the crystallinity of the glass-ceramics can be 60.00wt%, 65.00wt%, 65.40wt%, 70.00wt%, 70.10wt%, 70.40wt%, 79.50wt%, 75.00wt%, 76.70wt%, 76.60wt%, 79.50wt%, 79.10wt%, 74.30wt%, 70.50wt%, 73.50wt%, 72.10wt%, 73.30wt%, 78.30wt%, 80.00wt%, 85.00wt% or 90.00wt%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. It should be understood that in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the glass-ceramics with the desired properties of the present application can be obtained.

[0138] In some embodiments of the present application, "lithium disilicate crystalline phase as the main crystalline phase" or "the content of lithium disilicate crystalline phase is greater than the content of other crystalline phases in the microcrystalline glass" and similar expressions mean that the lithium disilicate crystalline phase accounts for more than about 70 weight percent (wt %) of all crystalline phases of the microcrystalline glass according to the embodiments of the present application.

[0139] In some embodiments of the present application, non-limiting examples of other possible crystalline phases in the glass-ceramics include, but are not limited to, a petalite crystalline phase and / or a lithium phosphate crystalline phase. In some embodiments, the glass-ceramics further comprises a petalite crystalline phase, and optionally, the petalite crystalline phase accounts for less than or equal to 20% by weight of the glass-ceramics. More optionally, the petalite crystalline phase may account for less than or equal to 15%, less than or equal to 10%, or less than or equal to 5% by weight of the glass-ceramics.

[0140] In some embodiments of the present application, the average crystal size of the glass-ceramics is ≤100.00 nm, and optionally, the average crystal size is less than or equal to 50 nm. A smaller average crystal size is beneficial to ensuring the excellent optical properties of the glass-ceramics. In some embodiments, the average crystal size of the glass-ceramics can be 5-100 nm, 10-90 nm, 5-30 nm, 10-40 nm, 5-50 nm, 18.70-26.80 nm, 20.10-25.60 nm, 22.80-23.00 nm, or 10-30 nm. In some embodiments, in the microcrystalline glass, the average crystal size can be 5.00nm, 10.00nm, 15.00nm, 18.00nm, 18.70nm, 19.00nm, 20.00nm, 20.10nm, 21.00nm, 22.20nm, 22.80nm, 23.00nm, 23.30nm, 25.00nm, 25.60nm, 26.80nm, 30.00nm, 35.00nm, 40.00nm, 45.00nm, 50.00nm, 60.00nm, 70.00nm, 80.00nm, 90.00nm or 100.00nm, or it can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the required performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0141] In some embodiments of the present application, the density of the glass-ceramics is ≥2.50 g / cm 3 In some embodiments, the density of the glass-ceramics can be 2.50 to 2.70 g / cm 3 , 2.51~2.65g / cm 3 or 2.50~3.00g / cm 3 In some embodiments, the density of the glass-ceramics can be 2.50 g / cm 3 , 2.51g / cm 3 , 2.52g / cm 3 , 2.53g / cm3 , 2.56g / cm 3 , 2.57g / cm 3 , 2.58g / cm 3 , 2.59g / cm 3 , 2.61g / cm 3 , 2.64g / cm 3 , 2.65g / cm 3 , 2.68g / cm 3 , 2.70g / cm 3 or 2.75g / cm 3 , or may be any range and sub-range between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the glass-ceramics with the desired properties of the present application can be obtained.

[0142] In some embodiments of the present application, the Young's modulus of the glass-ceramics is ≥100.00 GPa. A higher Young's modulus indicates that the glass-ceramics has higher intrinsic strength, which is conducive to achieving higher mechanical strength properties. In some embodiments, the Young's modulus of the glass-ceramics can be 100.00-130.00 GPa, 105.00-125.00 GPa, 108-130 GPa, 110.00-125.00 GPa, 114-130 GPa, or 110.00-120.00 GPa. In some embodiments, the Young's modulus of the glass-ceramics can be 100.00 GPa, 102.00 GPa, 105.00 GPa, 108.00 GPa, 110.00 GPa, 112.73 GPa, 113.92 GPa, 114.27 GPa, 114.62 GPa, 115.00 GPa, 115.87 GPa, 115.95 GPa, 116.05 GPa, 116.71 GPa, 117.07 GPa, 117.45 GPa, 118.95 GPa, 119.04 GPa, 120.00 GPa, 125.00 GPa or 130.00 GPa, or it can be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the required performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0143] In some embodiments of the present application, the refractive index of the glass-ceramics is ≤1.60, and optionally, the refractive index is 1.50-1.60.

[0144] In some embodiments of the present application, the glass-ceramic is transparent in the visible light range; at a thickness of 0.5 mm, the transmittance of the glass-ceramic for light with a wavelength of 550 nm is ≥ 85.00%; at a thickness of 0.5 mm, the transmittance of the glass-ceramic for light with a wavelength of 550 nm is ≥ 90.00%; further optionally, at a thickness of 0.5 mm, the transmittance of the glass-ceramic for light with a wavelength of 550 nm is 90.00-93.00%. Glass-ceramic with a higher transmittance can ensure good light transmittance and transparency, making it suitable for use in display cover glass with high display requirements. In some embodiments, at a thickness of 0.5 mm, for light of 550 nm wavelength, the transmittance of the microcrystalline glass can be 85.00%, 86.00%, 87.00%, 88.00%, 89.00%, 90.00%, 90.22%, 90.33%, 90.35%, 90.37%, 90.40%, 90.44%, 90.46%, 90.47%, 90.50%, 90.57%, 90.61%, 90.74%, 91.00%, 91.50%, 92.00%, 92.50% or 93.00%, or it can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the required performance of the present application can be obtained. It should be understood that, in a specific embodiment, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the required properties of the present application can be obtained.

[0145] In some embodiments of the present application, when the glass-ceramic is 0.5 mm thick, the optical b-value of the glass-ceramic is less than or equal to 1.00; optionally, when the glass-ceramic is 0.5 mm thick, the optical b-value of the glass-ceramic is less than 0.80. In some embodiments, the optical b-value of the 0.5 mm thick glass-ceramic can be 0.10, 0.20, 0.30, 0.31, 0.32, 0.35, 0.40, 0.41, 0.44, 0.48, 0.50, 0.56, 0.59, 0.60, 0.69, 0.70, 0.76, 0.80, 0.90 or 1.00, or can be all ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramic with the desired performance of the present application can be obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the glass-ceramic with the desired performance of the present application can be obtained.

[0146] In some embodiments of the present application, a microcrystalline glass having one side provided with a protective film on its two main surfaces is taken and placed in a mixed acid solution at 20°C to contact the same, thereby achieving etching and thinning, and the etching rate of the microcrystalline glass is ≥7.00μm / min, optionally, the etching rate of the microcrystalline glass is ≥9.00μm / min, and in the mixed acid solution: the mass concentration of hydrofluoric acid is 10wt%, the mass concentration of nitric acid is 10wt%, the mass concentration of phosphoric acid is 8wt%, the mass concentration of surfactant is 1wt%, the mass concentration of diethylenetriaminepentaacetic acid is 0.5wt%, and the remainder is water. Specifically, the etching rate is calculated using the following formula: etching rate = (thickness of the microcrystalline glass sample before etching - thickness of the microcrystalline glass sample after etching) / etching time. "Contact" refers to close physical contact that can cause at least one touched entity to undergo physical changes, chemical changes, or both. One or more main surfaces of the microcrystalline glass, for example, may involve selective partial or complete immersion, spraying, immersion, and similar treatments, or a combination of multiple treatments using an etching solution. In some embodiments, the etching solution is contacted with one or more main surfaces by spraying the solution onto one or more main surfaces. In some embodiments, the etching solution is contacted with one or more main surfaces by immersing the glass-ceramic in a container containing an etching solution (e.g., a bath). If one or more of the one or more main surfaces is required not to be in contact with the solution, a protective film can be placed on the surface before the glass-ceramic is in contact with the etching solution to isolate the contact of the etching solution with the glass-ceramic. At the same time, the protective film still exists after contact with the etching solution and can be easily removed. Any applicable method can be used, such as contacting the protective film with a soluble liquid, heating the protective film to liquefy it and discharge it, and similar methods and materials, or a combination thereof, to achieve the removal of the protective film. In the present application, optionally, the surfactant includes sodium dodecyl sulfate. In the present application, optionally, etching and thinning are performed under chamfering conditions to ensure that the side where the protective film is not provided is uniformly etched, but is not limited to such etching processes. The chemical etching and thinning processes commonly used in the art can be used for the glass-ceramic of the present application. Even at a relatively low temperature (20°C), the etching rate of the microcrystalline glass of the present application can reach above 7.00 μm / min, above 8.00 μm / min, above 9.00 μm / min, above 10.00 μm / min or above 11.00 μm / min, etc., which indicates that the microcrystalline glass of the present application can achieve a more efficient chemical etching thinning effect.

[0147] In some embodiments of the present application, when the glass-ceramics is placed in a 10% hydrofluoric acid aqueous solution at 20°C for 20 minutes, the change in mass per unit area of ​​the glass-ceramics is greater than or equal to 28.00 mg / cm 2 Optionally, the change in mass per unit area of ​​the glass-ceramics is 30.00 to 50.00 mg / cm2 In some embodiments, under the aforementioned conditions, the change in mass per unit area of ​​the glass-ceramics can be 28.00 mg / cm 2 、29.00mg / cm 2 、30.00mg / cm 2 、32.00mg / cm 2 、35.00mg / cm 2 、38.00mg / cm 2 、40.00mg / cm 2 、42.00mg / cm 2 、45.00mg / cm 2 、48.00mg / cm 2 or 50.00 mg / cm 2 , or all ranges and sub-ranges between any two of the above specific values. This indicates that when the acid content in the chemical etching solution is low, the micro-ceramic glass still has a relatively efficient chemical etching thinning effect, which is conducive to improving the etching thinning efficiency.

[0148] The present application also provides a method for preparing the aforementioned glass-ceramics, which comprises the following steps:

[0149] A substrate glass is provided. The substrate glass comprises the following components, expressed in molar percentage based on oxides: SiO2: 55.00-65.00 mol%, P2O5: 1.00-3.00 mol%, ZrO2: 2.00-5.00 mol%, Li2O: 25.00-32.00 mol%, Al2O3: 0-2.00 mol%, MgO: 0-2.00 mol%, Na2O: 0-3.00 mol%, K2O: 0-1.00 mol%, CaO: 0-2.00 mol%, SrO: 0-2.00 mol%, Ta2O5: 0-1.00 mol%, and La2O3: 0-1.00 mol%. The composition of the substrate glass, expressed in molar percentage based on oxides, satisfies the following: 2×Li2O+9×ZrO2+1.2×CaO≥88.00 mol%.

[0150] The substrate glass is heat-treated and crystallized to obtain glass-ceramics, wherein the glass-ceramics contain a lithium disilicate crystalline phase, wherein the content of the lithium disilicate crystalline phase is greater than the content of other crystalline phases in the glass-ceramics. It should be understood that the glass-ceramics is prepared by heat-treating the substrate glass, and therefore, the composition of the substrate glass used, in terms of mole percentage of oxides, is the same as or substantially the same as the composition of the glass-ceramics.

[0151] In some embodiments of the present application, the composition of the substrate glass further satisfies, calculated as a molar percentage of oxides: SiO2+Li2O=89.00-96.00 mol%, optionally, SiO2+Li2O=90.00-95.00 mol%; and / or,

[0152] SiO2 / Li2O=2.00-2.50, optionally, SiO2 / Li2O=2.00-2.30; and / or,

[0153] (Li2O+ZrO2) / (SiO2+Al2O3+CaO)≥0.50, optionally, (Li2O+ZrO2) / (SiO2+Al2O3+CaO) is 0.50-0.60; and / or,

[0154] (2×Li2O-6×P2O5) / SiO2≥0.70, optionally, the value of (2×Li2O-6×P2O5) / SiO2 is 0.70-1.00;

[0155] In the above relationship, each oxide chemical formula represents the molar percentage content of the corresponding component in the base glass composition.

[0156] In the present application, the substrate glass can be prepared by conventional preparation methods. For example, the molding method of the substrate glass can include but is not limited to: float, overflow, rolling or casting. For example, in the substrate glass preparation method of the present application, the raw material components and the clarifier are first mixed, and then melted at 1550℃~1680℃ for 5 hours or more. The molten glass obtained after the melt is then cast into a forming mold and cooled to 850℃~950℃. The resulting formed and cooled glass sample is then placed in an annealing furnace at 450℃~500℃ for annealing for 12~48 hours, and then cooled to room temperature to obtain the substrate glass sample. Optionally, the clarifier can include but is not limited to one or more of sodium chloride, tin oxide or antimony oxide, and the amount of the clarifier added can be 0-1wt% of the total amount of the raw materials.

[0157] In some embodiments of the present application, the heat treatment includes a nucleation treatment and a crystallization treatment, wherein the nucleation treatment temperature is 500-700° C., the nucleation treatment time is 10-1440 minutes, and the crystallization treatment temperature is 600-750° C., and the crystallization treatment time is 5-1440 minutes.

[0158] In some embodiments, the nucleation temperature may be 500°C, 520°C, 545°C, 550°C, 560°C, 565°C, 570°C, 590°C, 600°C, 650°C, or 700°C, or any ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. In some embodiments, the crystallization temperature may be 600°C, 655°C, 670°C, 680°C, 685°C, 700°C, 705°C, or 750°C, or any ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. In some embodiments, the nucleation time may be 10 min, 180 min, 240 min, 300 min, 1200 min, or 1440 min, or any ranges and sub-ranges between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. In some embodiments, the crystallization treatment time may be 5 min, 10 min, 180 min, 240 min, 300 min, 1200 min, or 1440 min, or may be any range and sub-range between any two of the above specific values, as long as the glass-ceramics with the desired properties of the present application can be obtained. It should be understood that in the embodiments, any of the above ranges may be combined with any other ranges, as long as the glass-ceramics with the desired properties of the present application can be obtained.

[0159] In some embodiments of the present application, the heating rate of the heat treatment process is 3 to 15°C / min, optionally, the heating rate is 3 to 10°C / min. For example, the temperature is raised from room temperature to the nucleation treatment temperature at a heating rate of 3 to 15°C / min, and / or, the temperature is raised from the nucleation treatment temperature to the crystallization treatment temperature at a heating rate of 3 to 15°C / min. In some embodiments, the heating rate of the heat treatment process can be 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min or 15°C / min, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the required performance of the present application can be obtained.

[0160] In some embodiments of the present application, the aforementioned microcrystalline glass can be processed by chemical etching to obtain anti-glare microcrystalline glass or anti-reflective microcrystalline glass, and the composition of the anti-glare microcrystalline glass or anti-reflective microcrystalline glass at the center of the depth is the same as that of the microcrystalline glass.

[0161] In some embodiments of the present application, the aforementioned glass-ceramics can be obtained by chemically strengthening the glass-ceramics, and the composition at the center of the depth of the chemically strengthened glass-ceramics is the same as that of the glass-ceramics. It should be understood that, compared with the glass-ceramics before chemical strengthening, the composition at the surface of the glass-ceramics product after chemical strengthening may be different from the composition of the glass-ceramics before chemical strengthening (without ion exchange process). This is because, when chemical strengthening is performed, a type of alkali metal ion (for example, Li ion) at the surface of the glass-ceramics in the newly formed glass-ceramics (glass-ceramics before chemical strengthening) is + Or Na + ) are replaced by larger alkali metal ions (e.g., Na + or K + ) is replaced. However, in the embodiments, the glass composition and phase assembly at or near the depth center of the glass-ceramic product will still have the composition and phase assembly of the newly formed glass-ceramic. That is, in the present application, the composition (e.g., the composition of the tensile stress layer) and phase assembly at the center of the chemically strengthened glass-ceramic that has been chemically strengthened are the same or substantially the same as those of the newly formed glass-ceramic.

[0162] In this application, microcrystalline glass has high intrinsic strength and excellent optical properties. Chemically strengthened microcrystalline glass or anti-glare microcrystalline glass obtained by using microcrystalline glass also has excellent performance and can be used in electronic equipment or electronic products, mainly electronic equipment and electronic products that need to install glass products. Electronic equipment or electronic products include but are not limited to mobile phones, tablets, televisions, computer displays and smart wearable devices.

[0163] The glass-ceramics with excellent performance provided by the present application or the chemically strengthened glass-ceramics made therefrom can be used in electronic devices, including but not limited to mobile phones, tablet computers, handheld game consoles, portable digital devices (such as digital cameras), vehicle-mounted central control, electronic whiteboard glass, smart home, television, computer display and smart wearable devices (such as smart bracelets, smart watches, etc.), and can also be used in vehicles, aircraft or aircraft, and can also be used in any glass device of desired glass-ceramics. For example, it can be used for display screens, cover glass, touch screens, glass inner screens or inner frames of electronic devices; for example, it can be used for windshields of vehicles, aircraft or aircraft, such as front windshields or side windshields. For example, it can be used for worktops, other surfaces, appliance doors, floor tiles, wall panels or storage containers, etc. Other surfaces can include but are not limited to exterior wall surfaces, stair tread surfaces, column veneers or counter surfaces, etc. Storage containers can include but are not limited to cups, plates, medicine bottles or beverage bottles, etc.

[0164] 4. The technical solution of this application is described below through specific embodiments.

[0165] Example 1

[0166] Step 1: Substrate Glass Preparation

[0167] According to the raw material ratio, 1000g of raw materials were prepared (the raw materials were prepared according to the formula of Example 1 in Table 1), and 5g of sodium chloride was added to the prepared raw materials. The raw materials were then mixed with a V-type mixer for 30 minutes. After mixing, the raw materials were transferred to a platinum crucible, and then melted in a 1650°C lifting furnace for 5 hours. After that, they were poured into a forming mold and cooled to form glass bricks. After cooling to about 900°C, they were placed in a 460°C annealing furnace for annealing for 12 hours. After that, they were cooled to room temperature with the furnace to obtain base material glass bricks.

[0168] Step 2: Glass-ceramic preparation

[0169] The base glass brick obtained in step 1 was subjected to nucleation and crystallization treatments, respectively. The process conditions for the nucleation and crystallization treatments are shown in Table 3, thereby producing a transparent glass-ceramic brick. The composition of the resulting glass-ceramic, measured in molar percentage of oxides, was identical to that of the base glass, as shown in Table 1.

[0170] Specifically, the base glass brick is placed in a crystallization furnace and first heated from room temperature to the nucleation treatment temperature at a heating rate of 10°C / min. The nucleation treatment temperature is 520°C and the nucleation treatment time is 4 hours. Then, the temperature is raised to the crystallization treatment temperature at a heating rate of 10°C / min. The crystallization temperature is 720°C and the crystallization treatment time is 1.5 hours. Here, the nucleation treatment time refers to the time the crystallization furnace is kept warm after being heated to the set nucleation treatment temperature at a set heating rate. The crystallization treatment time refers to the time the crystallization furnace is kept warm after being heated to the set crystallization treatment temperature at a set heating rate.

[0171] Step 3: Glass-ceramic sample processing

[0172] After shaping, cutting and polishing the glass-ceramic brick obtained in step 2, a glass-ceramic sample of the desired size can be obtained. The glass-ceramic sample prepared in this application is a polished glass-ceramic sheet of 50 mm × 50 mm × 0.5 mm.

[0173] Referring to Example 1, Examples 2-12 and Comparative Examples 1-6 were prepared using the components listed in Tables 1-2 to produce the corresponding substrate glasses. Nucleation and crystallization treatments were then performed according to Tables 3-4 to produce the corresponding glass-ceramics. Chemical etching thinning tests were then performed, and the test results are shown in Tables 5-6.

[0174] Table 1 Note: In Table 1, an oxide content of "0.00%" indicates that the component was not actively or intentionally added to the glass composition during the initial batching process, but the component may be present as an impurity; in Table 1, the relationship between the oxide contents is calculated by substituting the content percentage in terms of the oxide mole percentage into each formula.

[0175] Table 2 Note: In Table 2, an oxide content of "0.00%" indicates that the component was not actively or intentionally added to the glass composition during the initial batching process, but the component may be present as an impurity; in Table 2, the relationship between the oxide contents is calculated by substituting the content percentage in terms of the oxide mole percentage into each formula.

[0176] Table 3

[0177] Table 4

[0178] Table 5

[0179] Table 6

[0180] From the above table and attached figures we can see that:

[0181] Examples 1-12 adjust the components of the microcrystalline glass, which not only ensures the preparation of microcrystalline glass with higher crystallinity and greater density, but also ensures that the prepared microcrystalline glass has both high Young's modulus and high intrinsic strength, so that the microcrystalline glass can effectively control the expansion of cracks when it is broken, but also ensures that the microcrystalline glass has excellent optical transmittance and low b value, which is conducive to improving the commercial application of microcrystalline glass.

[0182] As can be seen from Figure 2, the main crystalline phase in the microcrystalline glass obtained in the embodiment and the comparative example is lithium disilicate. As can be seen from the comparison of Figures 4 and 5, the optical transmittance of the microcrystalline glass obtained by the glass formula scheme of Example 8 is better than that of Comparative Example 6. As can be seen from the comparison of Table 5 and Table 6, the chemical etching thinning effect of the microcrystalline glass of Examples 1-12 in 10% or 5% HF solution is better than that of Comparative Examples 1-6. This shows that compared with Comparative Examples 1-6 that do not meet the formula scheme of the present application, the chemical etching thinning effect of the microcrystalline glass of Examples 1-12 has been significantly improved. In addition, through tests in HCl solution and NaOH solution, the change in the unit area mass of the microcrystalline glass of Examples 1-12 is similar to that of the microcrystalline glass of Comparative Examples 1-6, both of which are lower. This shows that the microcrystalline glass of the embodiment maintains good acid and alkali resistance even at higher temperatures while improving the chemical etching thinning effect.

[0183] From the above tests, it can be seen that the microcrystalline glass of the present application can achieve efficient chemical etching and thinning in a lower concentration HF solution, which is not only beneficial to improving the chemical etching and thinning rate of the microcrystalline glass, and thus beneficial to improving the production efficiency of ultra-thin microcrystalline glass products or customized microcrystalline glass products, but also can avoid the use of high-concentration acidic liquids, thereby better reducing the harm of etching liquids to the health of operators and the environment.

[0184] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and not to limit the technical solutions. Those skilled in the art should understand that modifications or equivalent replacements of the technical solutions of the present application that do not depart from the purpose and scope of the technical solutions of the present application should be included in the scope of the claims of the present application. Industrial Applicability

[0185] The present application optimizes and adjusts the components of the glass-ceramics. By ensuring that the glass-ceramics meet specific composition and structure and containing a large amount of lithium disilicate crystal phase, the glass-ceramics not only ensures that the glass-ceramics have high intrinsic strength and excellent optical properties, but also significantly improves the chemical etching and thinning effect of the glass-ceramics, enabling the glass-ceramics to achieve a relatively excellent chemical etching and thinning effect in a relatively low concentration of acidic liquid, which is beneficial to improving the chemical etching and thinning rate of the glass-ceramics, and further beneficial to improving the production efficiency of ultra-thin glass-ceramics products or customized glass-ceramics products. Moreover, the use of the glass-ceramics of the present application for chemical etching and thinning can avoid the use of high-concentration acidic liquids, thereby better reducing the harm of the etching liquid to the health of operators and the environment.

Claims

1. A glass-ceramic, characterized in that: The glass-ceramics contains a lithium disilicate crystalline phase, wherein the content of the lithium disilicate crystalline phase is greater than the content of other crystalline phases in the glass-ceramics; the glass-ceramics contains the following components, expressed in molar percentage based on oxides: SiO2: 55.00-65.00 mol%, P2O5: 1.00-3.00 mol%, ZrO2: 2.00-5.00 mol%, Li2O: 25.00-32.00 mol%, Al2O3: 0-2.00 mol%, MgO: 0-2.00 mol%, Na2O: 0-3.00 mol%, K2O: 0-1.00 mol%, CaO: 0-2.00 mol%, SrO: 0-2.00 mol%, Ta2O5: 0-1.00 mol%, and La2O3: 0-1.00 mol%. The composition of the microcrystalline glass satisfies the following requirements, expressed as a molar percentage based on oxides: 2×Li2O+9×ZrO2+1.2×CaO≥88.00mol%, optionally, 2×Li2O+9×ZrO2+1.2×CaO≥90.00mol%; wherein the chemical formulas of each oxide respectively represent the molar percentage content of the corresponding component in the composition of the microcrystalline glass.

2. The glass-ceramic according to claim 1, characterized in that: Calculated according to the content expressed as molar percentage based on oxides, the content of SiO2 and the content of Li2O in the microcrystalline glass meet the following conditions: SiO2+Li2O=89.00~96.00mol%, optionally, SiO2+Li2O=90.00~95.00mol%.

3. The glass-ceramics according to claim 1 or 2, characterized in that: Calculated according to the content expressed as molar percentage based on oxides, the content of SiO2 and the content of Li2O in the microcrystalline glass meet the following conditions: SiO2 / Li2O=2.00~2.50, optionally, SiO2 / Li2O=2.00~2.

30.

4. The glass-ceramic according to any one of claims 1 to 3, characterized in that: Calculated according to the content expressed as molar percentage based on the oxide basis, the component content in the microcrystalline glass also meets the following conditions: (Li2O+ZrO2) / (SiO2+Al2O3+CaO)≥0.

50. Optionally, the value of (Li2O+ZrO2) / (SiO2+Al2O3+CaO) is 0.50~0.60, where the chemical formula of each oxide represents the molar percentage content of the corresponding component in the microcrystalline glass composition.

5. The glass-ceramic according to any one of claims 1 to 4, characterized in that: Calculated according to the content expressed as molar percentage based on the oxide basis, the component content in the microcrystalline glass also meets the following conditions: (2×Li2O-6×P2O5) / SiO2≥0.

70. Optionally, the value of (2×Li2O-6×P2O5) / SiO2 is 0.70~1.00, where the chemical formula of each oxide represents the molar percentage content of the corresponding component in the microcrystalline glass composition.

6. The glass-ceramic according to any one of claims 1 to 5, characterized in that: Expressed as a molar percentage based on oxides: the glass-ceramics contains 58.00 to 65.00 mol% SiO2, and optionally, contains 60.00 to 64.00 mol% SiO2; And / or, the glass-ceramics contains 26.00-32.00 mol% of Li2O, optionally, contains 27.00-31.00 mol% of Li2O; And / or, the glass-ceramics contains 2.50-5.00 mol% ZrO2, optionally, contains 3.00-5.00 mol% ZrO2; And / or, the glass-ceramics contains 1.50 to 3.00 mol% of P2O5, optionally, contains 1.50 to 2.50 mol% of P2O5.

7. The glass-ceramic according to any one of claims 1 to 6, characterized in that: Expressed in molar percentage based on oxides, the microcrystalline glass contains the following components: SiO2: 60.50~64.00mol%, P2O5: 1.50~2.50mol%, ZrO2: 4.00~5.00mol%, Li2O: 28.00~31.00mol%, Al2O3: 0~1.50mol%, MgO: 0~2.00mol%, Na2O: 0~3.00mol%, K2O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta2O5: 0~1.00mol%, La2O3: 0~1.00mol%.

8. The glass-ceramic according to any one of claims 1 to 7, characterized in that: The crystallinity of the glass-ceramics is ≥60.00 wt %, and optionally, the crystallinity is 60.00 wt % to 90.00 wt %; And / or, in the glass-ceramics, the average crystal size is less than or equal to 100 nm, optionally, the average crystal size is less than or equal to 50 nm, further optionally, the average crystal size is 10 to 40 nm.

9. The glass-ceramic according to any one of claims 1 to 8, characterized in that: The density of the glass-ceramic is ≥2.50 g / cm 3 , optionally, a density of 2.50 g / cm 3 ~2.70g / cm 3 and / or, The refractive index of the microcrystalline glass is ≤1.60, and optionally, the refractive index is 1.50-1.

60.

10. The glass-ceramic according to any one of claims 1 to 9, characterized in that: The Young's modulus of the glass-ceramics is ≥100 GPa. Optionally, the Young's modulus is 108 to 130 GPa. Further optionally, the Young's modulus is 114 to 130 GPa.

11. The glass-ceramic according to any one of claims 1 to 10, characterized in that: The microcrystalline glass is transparent in the visible light range; at a thickness of 0.5 mm, for light of 550 nm wavelength, the transmittance of the microcrystalline glass is ≥85.00%, optionally, the transmittance of the microcrystalline glass is ≥90.00%; and / or, at a thickness of 0.5 mm, the optical b value of the microcrystalline glass is ≤1.0, optionally, the optical b value is ≤0.

8.

12. The glass-ceramic according to any one of claims 1 to 11, characterized in that: When placed in a 10% hydrofluoric acid aqueous solution at 20°C for 20 minutes, the change in mass per unit area of the glass-ceramics is greater than or equal to 28.00 mg / cm 2 Optionally, the change in mass per unit area of the glass-ceramics is 30.00-50.00 mg / cm 2 .

13. A method for preparing glass-ceramics according to any one of claims 1 to 11, characterized in that: The steps include: A substrate glass is provided, wherein the substrate glass comprises the following components, expressed in molar percentage based on oxides: SiO2: 55.00-65.00 mol%, P2O5: 1.00-3.00 mol%, ZrO2: 2.00-5.00 mol%, Li2O: 25.00-32.00 mol%, Al2O3: 0-2.00 mol%, MgO: 0-2.00 mol%, Na2O: 0-3.00 mol%, K2O: 0-1.00 mol%, CaO: 0-2.00 mol%, SrO: 0-2.00 mol%, Ta2O5: 0-1.00 mol%, and La2O3: 0-1.00 mol%, wherein, in terms of content expressed in molar percentage based on oxides, the composition of the substrate glass satisfies the following: 2×Li2O+9×ZrO2+1.2×CaO≥88.00 mol%. The substrate glass is subjected to heat treatment and crystallization to obtain a microcrystalline glass, wherein the microcrystalline glass contains a lithium disilicate crystal phase, wherein the content of the lithium disilicate crystal phase is greater than the content of other crystal phases in the microcrystalline glass.

14. The method for preparing glass-ceramics according to claim 13, characterized in that: The heat treatment includes nucleation treatment and crystallization treatment, wherein the nucleation treatment temperature is 500-700° C., the nucleation treatment time is 10-1440 minutes, the crystallization treatment temperature is 600-750° C., and the crystallization treatment time is 5-1440 minutes.

15. An electronic device, characterized in that: The electronic device comprises the glass-ceramics according to any one of claims 1 to 12, or comprises chemically strengthened glass-ceramics obtained by chemically strengthening the glass-ceramics according to any one of claims 1 to 12.