Glass ceramic as well as preparation method and application thereof

Abstract

The invention discloses a glass ceramic, which comprises a lithium disilicate crystal phase as a main crystal phase, and is prepared from the following components in percentage by mole based on oxide: 55.00 to 65.00 mol percent of SiO2, 1.00 to 3.00 mol percent of P2O5, 2.00 to 5.00 mol percent of ZrO2, 25.00 to 32.00 mol percent of Li2O, 0 to 2.00 mol percent of Al2O3, 0 to 2.00 mol percent of MgO, 0 to 3.00 mol percent of Na2O, 0 to 1.00 mol percent of K2O, 0 to 2.00 mol percent of CaO, 0 to 2.00 mol percent of SrO, 0 to 1.00 mol percent of Ta2O5 and 0 to 1.00 mol percent of La2O3, and meanwhile, each component in the glass ceramic also meets a specific content relationship. The components of the glass ceramic are optimized and adjusted, so that the glass ceramic meets the specific composition and structure, it is guaranteed that the glass ceramic contains a large number of lithium disilicate crystalline phases, it is guaranteed that the glass ceramic has high intrinsic strength and excellent optical performance, the chemical etching thinning effect of the glass ceramic is obviously improved, and the glass ceramic has the good application prospect. The glass ceramic can achieve a relatively excellent chemical etching thinning effect in the acid liquid with relatively low concentration, and the chemical etching thinning rate of the glass ceramic is favorably improved.

Description

Technical Field

[0001] The present application relates to the field of microcrystalline glass technology, and in particular to a microcrystalline glass with lithium disilicate crystal phase as the main crystal phase, which is easy to be chemically etched, and its preparation method and application. This invention patent application is a divisional application of the invention patent application with the application date of February 2, 2024, the application number of 202410151202X, and the invention name of "a kind of microcrystalline glass and its preparation method and application". Background Art

[0002] With the advent of the smart era, microcrystalline glass is increasingly used in the electronics industry, such as mobile phones, e-book readers, tablets, car central control screens, and various wearable electronic devices. The market's requirements for the thickness of touch screen microcrystalline glass covers are getting thinner and thinner, which makes the ultra-thinness of microcrystalline glass covers gradually become one of the important development trends of microcrystalline glass. In addition, with people's demand for diversified consumer electronic products, microcrystalline glass covers are gradually becoming customized. For example, mobile phone back covers made of frosted microcrystalline glass are becoming more and more popular among consumers. It can be seen that improving the chemical etching thinning rate of microcrystalline glass is conducive to improving the production efficiency of ultra-thin microcrystalline glass products or customized microcrystalline glass products, thereby improving their economic benefits.

[0003] In addition, the chemical thinning technology and AG (anti-reflection / anti-glare) etching technology commonly used in microcrystalline glass currently usually adopt etching solution or frosting solution, such as using higher concentration of hydrofluoric acid or a mixture with other acids for etching. This process requires the use of high concentration of acidic liquid in the production process. The longer it is used, the greater the harm to the health of operators and the environment. Summary of the invention

[0004] The purpose of the present application is to provide a microcrystalline glass that is easy to chemically etch and thin with lithium disilicate crystal phase as the main crystal phase, and a preparation method and application thereof. The microcrystalline glass 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 microcrystalline glass, but also conducive to improving the production efficiency of ultra-thin microcrystalline glass products or customized microcrystalline glass products, etc., and can avoid the use of high-concentration acidic liquid for etching and thinning, thereby better reducing the harm of etching liquid to the health of operators and the environment.

[0005] The technical solutions provided in this application include:

[0006] 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 contains the following components, expressed in molar percentage based on an oxide:

[0007] SiO 2 :55.00~65.00mol%、P 2 O 5 :1.00~3.00mol%、ZrO 2 :2.00~5.00mol%、Li 2 O: 25.00~32.00mol%, Al 2 O 3 :0~2.00mol%, MgO: 0~2.00mol%, Na 2 O: 0-3.00 mol%, K 2 O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta 2 O 5 :0~1.00mol%、La 2 O 3 :0~1.00mol%;

[0008] The composition of the glass-ceramics satisfies the following conditions: 2×Li 2 O+9×ZrO 2 +1.2×CaO≥88.00mol%, preferably≥90.00mol%, wherein each oxide chemical formula represents the molar percentage content of the corresponding component in the microcrystalline glass composition. For example, Li 2 The molar content of O is 28%, so 28% is substituted into the formula for calculation.

[0009] In some embodiments of the present application, the SiO in the microcrystalline glass is calculated according to the content expressed as a molar percentage of the oxide basis. 2 The content and Li 2 The content of O meets the following conditions:

[0010] SiO 2 +Li 2 O = 89.00 to 96.00 mol%; preferably, SiO 2 +Li 2 O=90.00~95.00mol%.

[0011] In some embodiments of the present application, the SiO in the microcrystalline glass is calculated according to the content expressed as a molar percentage of the oxide basis. 2 The content and Li 2 The content of O meets the following conditions:

[0012] SiO 2 / Li2 O=2.00~2.50;Preferably, SiO 2 / Li 2 O=2.00~2.30.

[0013] In some embodiments of the present application, the content of the components in the microcrystalline glass also satisfies the following conditions, calculated according to the content expressed as a molar percentage based on the oxide:

[0014] (Li 2 O+ZrO 2 ) / (SiO 2 +Al 2 O 3 +CaO)≥0.50; preferably, (Li 2 O+ZrO 2 ) / (SiO 2 +Al 2 O 3 +CaO) is 0.50-0.60, wherein the chemical formulas of each oxide respectively represent the molar percentage content of the corresponding component in the microcrystalline glass composition.

[0015] In some embodiments of the present application, the content of the components in the microcrystalline glass also satisfies the following conditions, calculated according to the content expressed as a molar percentage based on the oxide:

[0016] (2×Li 2 O-6×P 2 O 5 ) / SiO 2 ≥0.70, preferably, (2×Li 2 O-6×P 2 O 5 ) / SiO 2 The value of is 0.70 to 1.00, wherein each oxide chemical formula represents the molar percentage content of the corresponding component in the microcrystalline glass composition.

[0017] In some embodiments of the present application, expressed in terms of molar percentage based on oxides: the microcrystalline glass contains 58.00 to 65.00 mol % SiO 2 , preferably containing 60.00 to 64.00 mol% SiO 2 ; and / or, the glass-ceramics contains 26.00 to 32.00 mol% Li 2 O, preferably containing 27.00 to 31.00 mol% of Li 2 O;

[0018] And / or, the glass-ceramics contains 2.50-5.00 mol% ZrO 2, preferably containing 3.00 to 5.00 mol% ZrO 2 ; and / or, the glass-ceramics contains 1.50 to 3.00 mol% of P 2 O 5 , preferably containing 1.50 to 2.50 mol% of P 2 O 5 .

[0019] In some embodiments of the present application, the microcrystalline glass comprises the following components, expressed in terms of molar percentage based on oxides:

[0020] SiO 2 :60.50~64.00mol%、P 2 O 5 :1.50~2.50mol%、ZrO 2 :4.00~5.00mol%、Li 2 O: 28.00-31.00 mol%, Al 2 O 3 :0~1.50mol%, MgO: 0~2.00mol%, Na 2 O: 0-3.00 mol%, K 2 O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta 2 O 5 :0~1.00mol%、La 2 O 3 :0~1.00mol%.

[0021] In some embodiments of the present application, the crystallinity of the glass-ceramics is ≥ 60.00 wt %, preferably 60.00 wt % to 90.00 wt %.

[0022] In some embodiments of the present application, in the glass-ceramics, the average crystal size is less than or equal to 100 nm, preferably the average crystal size is less than or equal to 50 nm, and more preferably the average crystal size is 10 to 40 nm.

[0023] In some embodiments of the present application, the density of the microcrystalline glass is ≥2.50 g / cm 3 , preferably with a density of 2.50 g / cm 3 ~2.70g / cm 3 .

[0024] In some embodiments of the present application, the refractive index of the microcrystalline glass is ≤1.60, preferably the refractive index is 1.50-1.60.

[0025] In some embodiments of the present application, the Young's modulus of the glass-ceramics is ≥100 GPa, preferably the Young's modulus is 108 to 130 GPa, and more preferably the Young's modulus is 114 to 130 GPa.

[0026] In some embodiments of the present application, 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%, preferably the transmittance of the microcrystalline glass is ≥ 90.00%.

[0027] In some embodiments of the present application, at a thickness of 0.5 mm, the optical b value of the glass-ceramics is ≤1.0, preferably the optical b value is ≤0.8.

[0028] In some embodiments of the present application, when the microcrystalline glass is placed in a hydrofluoric acid aqueous solution with a mass concentration of 10% at 20°C for 20 minutes, the change in the mass per unit area of ​​the microcrystalline glass is greater than or equal to 28.00 mg / cm 2 Preferably, the change in mass per unit area of ​​the microcrystalline glass is 30.00 to 50.00 mg / cm 2 .

[0029] In some embodiments of the present application, a microcrystalline glass having one of its two main surfaces provided with a protective film is taken and placed in a mixed acid solution at 20°C for etching and thinning, wherein the etching rate of the microcrystalline glass is ≥7.00μm / min, and preferably 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. In the present application, it is preferred that the surfactant includes sodium dodecyl sulfate. In the present application, it is preferred to perform etching and thinning under chamfering conditions to ensure uniform etching of the side without a protective film.

[0030] In some embodiments of the present application, the microcrystalline glass can be processed by chemical etching to produce 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.

[0031] In some embodiments of the present application, the glass-ceramics can be processed into chemically strengthened glass-ceramics by chemical strengthening, and the composition at the center of the chemically strengthened glass-ceramics is the same as that of the glass-ceramics.

[0032] In a second aspect, a method for preparing the aforementioned microcrystalline glass is provided, wherein the method comprises the following steps:

[0033] A substrate glass is provided, wherein the substrate glass comprises the following components expressed in terms of molar percentage on an oxide basis: SiO 2 :55.00~65.00mol%、P 2 O 5 :1.00~3.00mol%、ZrO 2 :2.00~5.00mol%、Li 2 O: 25.00~32.00mol%, Al 2 O 3 :0~2.00mol%, MgO: 0~2.00mol%, Na 2 O: 0-3.00 mol%, K 2 O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta 2 O 5 :0~1.00mol%、La 2 O 3 :0~1.00mol%, wherein, in terms of the content expressed as a molar percentage based on the oxide, the composition of the substrate glass satisfies: 2×Li 2 O+9×ZrO 2 +1.2×CaO≥88.00mol%;

[0034] The substrate glass is subjected to heat treatment and crystallization to obtain 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.

[0035] 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 min, the crystallization treatment temperature is 600-750°C, and the crystallization treatment time is 5-1440 min.

[0036] In some embodiments of the present application, the heating rate of the heat treatment process is 3 to 15° C. / min, preferably 3 to 10° C. / min.

[0037] In a third aspect, an electronic device is provided, the electronic device comprising the glass-ceramic in any of the foregoing embodiments, or comprising a chemically strengthened glass-ceramic obtained by chemically strengthening the glass-ceramic in any of the foregoing embodiments, wherein the composition at the depth center of the chemically strengthened glass-ceramic is the same as the composition of the glass-ceramic described in 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.

[0038] Compared with the prior art, one or more technical solutions of the present application include the following beneficial effects:

[0039] The present application optimizes and adjusts the components of glass-ceramics, and ensures that the glass-ceramics contain a large amount of lithium disilicate crystal phase by making the glass-ceramics meet specific composition and structure, which not only ensures that the glass-ceramics have high intrinsic strength and excellent optical properties, but also significantly improves the chemical etching thinning effect of the glass-ceramics, so that the glass-ceramics can achieve a relatively excellent chemical etching thinning effect in a relatively low concentration of acidic liquid, which is conducive to improving the chemical etching thinning rate of the glass-ceramics, and then helps to improve the production efficiency of ultra-thin glass-ceramics products or customized glass-ceramics products. Chemical etching and thinning using the glass-ceramics of the present application 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 Schematic diagram of the process of chemical etching and thinning of glass-ceramics in this application.

[0041] Figure 2 It is a comparison chart of the XRD spectra of the microcrystalline glass of Example 3, Example 6, Example 8, Comparative Example 1 and Comparative Example 6.

[0042] Figure 3 It is a comparison chart of the DSC curves of the substrate glass of Example 8 and Comparative Example 6.

[0043] Figure 4 This is a transmittance curve of the microcrystalline glass of Example 8.

[0044] Figure 5 This is the transmittance curve of the microcrystalline glass of comparative example 6. DETAILED DESCRIPTION

[0045] This application will combine the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. 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 belong to the scope of protection of this application.

[0046] Unless otherwise specified 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 the range is limited. "And / or" referred to herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0047] 1. Explanation of some relevant terms involved in this application is as follows

[0048] 1. Base glass: refers to glass that has not been subjected to nucleation treatment, crystallization treatment, and strengthening treatment.

[0049] 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.

[0050] 3. Nucleation: Through heat treatment, the nucleating material in the glass grows small crystal nuclei.

[0051] 4. Crystallization: Glass grows a certain crystal based on the crystal nucleus through heat treatment.

[0052] 5. Transmittance: When light of a certain wavelength is irradiated onto 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.

[0053] 6. Crystallinity: It 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 content in the microcrystalline glass.

[0054] 7. Optical b value: used to characterize the yellow-blue value of a material. The optical b value in this application is the b value of transmitted light, and a positive optical b value indicates that the material is blue.

[0055] 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.

[0056] 9. Main surface: refers to the surface with the largest surface area in the glass brick or glass sheet, such as the upper and lower surfaces of the cover glass.

[0057] 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.

[0058] 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.

[0059] 2. Related detection methods involved in this application

[0060] 1. Synchronous thermal analysis test

[0061] After the substrate glass is crushed, ground and sieved through 200 meshes to obtain a sample, about 20 mg of the sample is 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 test curve of the sample. The differential thermal analyzer used in this application is a Mettler-Toledo TGA / DSC3+ thermogravimetric and synchronous thermal analyzer, and the standard used in the test is α-Al 2 O 3 The powder and sample container are platinum crucibles, the instrument is placed at an ambient temperature of 24°C and an air humidity of ≤40%.

[0062] 2. XRD test

[0063] (1) Test steps

[0064] The glass-ceramics are crushed and ground into samples with a particle size of less than 75 μm. The ground samples are tested using an X-ray diffractometer to obtain an XRD diffraction peak curve and XRD diffraction data.

[0065] The X-ray diffractometer was Shimadzu XRD-6100, the incident angle range used in the test was 2θ=10-50°, the scanning speed was 6° / min, the operating voltage was 40 kV, and the operating current was 30 mA.

[0066] (2) Determination of crystal phase

[0067] The XRD diffraction data were analyzed using Jade software (JADE Standard 8.6) to determine the crystalline phase in the glass-ceramic samples.

[0068] (3) Determination of crystallinity

[0069] The XRD test results (RAW format) are imported into the X-ray diffraction data Rietveld refinement software Jade for fitting and calculation to determine the crystallinity of the microcrystalline glass sample. Specifically, the ratio of the fitted crystalline phase peak area to the fitted total peak area is recorded as the crystallinity of the microcrystalline glass sample.

[0070] (4) Determination of average crystal size

[0071] The result data obtained by XRD test can be used to calculate the average crystal size of the sample according to the Scherrer formula D = Kλ / (βcosθ). Among them, 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 the Jade software, and Jade outputs a fitting report. According to the angle 2θ value and Peak FWHM value corresponding to each diffraction peak in the fitting report, the Peak FWHM value is converted into radians: β = (FWHM / 180×3.14), and the crystal size of each diffraction peak is calculated by the Scherrer formula D = Kλ / (βcosθ) and then averaged to obtain the average crystal size in the sample.

[0072] 3. Thickness test

[0073] The thickness of glass-ceramics is tested using a micrometer.

[0074] 4. Optical performance test

[0075] With reference to the national standard "GB / T 7962.12-2010 Test Method for Colorless Optical Glass Part 12: Spectral Transmittance", a haze meter was used to test the transmittance and optical b-value of the microcrystalline glass of the present application. Specifically, a haze meter was used to test the transmittance and optical b-value of 5 microcrystalline glass pieces of the same batch to light of different wavelengths. The average value of the transmittance of the 5 microcrystalline glass pieces measured at a wavelength of 550nm was taken, and recorded as the transmittance result of the microcrystalline glass at a wavelength of 550nm. The average value of the optical b-values ​​measured for the 5 microcrystalline glass pieces was taken, and recorded as the optical b-value result of the microcrystalline glass.

[0076] 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 light splitting method is a plane reflective grating, the wavelength range is 360nm to 740nm, the wavelength interval is 10nm, the illumination light source is a pulsed xenon lamp X4, the ambient temperature of the instrument is 24°C, and the air humidity is 40%.

[0077] 5. Young's modulus test

[0078] The UMS-100 ultrasonic material characterization system was used to test the Young's modulus of glass-ceramics by acoustic waves.

[0079] 6. Chemical etching effect test

[0080] (1) Etching test with hydrofluoric acid (HF) aqueous solution, HCl aqueous solution or NaOH aqueous solution

[0081] 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 mass per unit area of ​​microcrystalline glass under each test condition was calculated respectively.

[0082] The mass concentration of the HF aqueous solution used in the test of this application is 10wt% or 5wt%, and the test conditions are: the test temperature is 20°C, and the etching time or reaction time is 20min.

[0083] The mass concentration of the HCl aqueous solution used in the test of this application is 5wt%, and the test conditions are: the test temperature is 95°C, and the etching time or reaction time is 24h.

[0084] The mass concentration of the NaOH aqueous solution used in the test of this application is 5wt%, and the test conditions are: the test temperature is 95°C, and the etching time or reaction time is 6h.

[0085] (2) Etching test of mixed acid solution

[0086] In the mixed acid solution used in the present application: 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 balance is water. Among them, the surfactant is sodium dodecyl sulfate.

[0087] The above reagents for preparing the mixed acid solution have the following sources: surfactant: sodium dodecyl sulfate, purity ≥40%; diethylenetriaminepentaacetic acid, purity ≥13.0%; hydrofluoric acid, purity ≥40%; phosphoric acid, purity ≥85%; nitric acid, purity ≥65%.

[0088] The test conditions for etching treatment using a mixed acid solution adopted in this application are as follows: 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 rate of the spray equipment to 500L / min, and allow the spray equipment to 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.

[0089] 7. Density test

[0090] This application uses the electronic density balance SD-200L of Japan ALFAMIRAGE to test the density of microcrystalline glass.

[0091] 8. Refractive index test

[0092] This application uses the Abbe refractometer WYA-2WAJ produced by Shanghai Lichen Bangxi Instrument Technology Co., Ltd. to test the refractive index of microcrystalline glass.

[0093] 3. Glass-ceramics and its preparation method and application scheme

[0094] In the prior art, in order to improve the chemical etching efficiency of microcrystalline glass, a high-concentration etching solution and high temperature are usually used to increase the etching speed of the etching solution on the microcrystalline glass. However, high temperature conditions will not only lead to the deterioration of the working environment, but also cause the etching solution to boil and evaporate, which will not only further increase the consumption of high-concentration etching solution, but also cause harm to the health of operators and the environment.

[0095] 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 of a relatively low concentration, which 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 a specific composition and structure, which 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 of a relatively low concentration, which is beneficial to improving the chemical etching thinning rate of the glass-ceramic, and then is beneficial to improving the production efficiency of ultra-thin glass-ceramic products or customized glass-ceramic products. The microcrystalline glass can quickly react with a low-concentration etching solution, and the etching rate is relatively fast. Even at room temperature, the microcrystalline glass can achieve a relatively fast etching rate, which can effectively improve the etching conditions while accelerating the etching rate and reducing the consumption of the etching solution. At the same time, chemical etching and thinning using the microcrystalline glass of the present application 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.

[0096] 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 contains the following components, expressed in molar percentage based on oxides:

[0097] SiO2 :55.00~65.00mol%、P 2 O 5 :1.00~3.00mol%、ZrO 2 :2.00~5.00mol%、Li 2 O: 25.00~32.00mol%, Al 2 O 3 :0~2.00mol%, MgO: 0~2.00mol%, Na 2 O: 0-3.00 mol%, K 2 O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta 2 O 5 :0~1.00mol%、La 2 O 3 :0~1.00mol%;

[0098] The composition of the glass-ceramics satisfies the following conditions: 2×Li 2 O+9×ZrO 2 +1.2×CaO≥88.00mol%, preferably ≥90.00mol%, wherein each oxide chemical formula represents the molar percentage content of the corresponding component in the microcrystalline glass composition. By optimizing the composition of microcrystalline glass, each component in the microcrystalline glass satisfies a specific content and content relationship, and the synergistic effect between the components is brought into play, thereby ensuring that a specific structure can be formed inside the microcrystalline glass, and then ensuring that the microcrystalline glass contains a large amount of lithium disilicate crystal phase, ensuring that the microcrystalline glass has high intrinsic strength and excellent optical properties, while also significantly improving the chemical etching thinning effect of the microcrystalline glass, so that the microcrystalline glass can achieve a relatively excellent chemical etching thinning effect in an acidic liquid with a lower concentration and a lower temperature, which is beneficial to improving the chemical etching thinning rate of the microcrystalline glass, and then beneficial to improving the production efficiency of microcrystalline glass such as ultra-thin microcrystalline glass products or customized microcrystalline glass products.

[0099] Lithium disilicate (Li 2 Si 2 O 5 ) phase is based on [Si 2 O 5] Orthorhombic crystals in a tetrahedral array, 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 path of cracks to be distorted when passing through the crystals, thereby preventing the expansion of the cracks and improving the strength and fracture toughness of the glass-ceramics. At the same time, the refractive index of lithium disilicate crystals is close to that of the glass matrix (such as the base glass for preparing glass-ceramics), which 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 are easier to chemically etch and thin compared to other glass-ceramics.

[0100] In the glass system of this application, SiO 2 As a glass network forming oxide, it is an indispensable component of the glass network structure. 2 As an important component of lithium disilicate crystal phase, it is also indispensable. However, excessive SiO 2 It will increase the viscosity of the glass liquid, making it difficult to melt the glass. Therefore, in order to meet the requirements of glass formability and achieve the desired crystallization effect of this application, SiO 2 The content is controlled at 55.00~65.00mol%.

[0101] In some embodiments of the present application, in the glass-ceramics, SiO 2 The content of SiO 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, SiO 2 The content 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 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.

[0102] In the glass system of this application, Al 2 O 3 As an optional component, it is an intermediate oxide for glass formation, an appropriate amount of Al 2 O 3 It can stabilize the network structure, but excessive Al 2 O 3 This will increase the viscosity of the glass liquid, leading to the precipitation of other crystalline phases such as petalite, and reduce the content of the main crystalline phase, lithium disilicate. Therefore, in order to meet the desired crystalline phase structure, the Al 2 O 3 The content is 0 to 2.00 mol%.

[0103] In some embodiments of the present application, in the glass-ceramics, Al 2 O 3 The content of Al may be 0 to 2.00 mol%, 0.10 to 1.80 mol%, 0 to 1.50 mol%, 0.20 to 1.60 mol%, 0.00 to 0.50 mol%, or 1.30 to 1.50 mol%. In some embodiments, Al 2 O 3 The content of 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 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.

[0104] In the glass system of the present application, P 2 O 5 It is a nucleating agent and an essential component. When its content is too little or too much, the crystallization effect will be poor, and it is difficult to ensure that the microcrystalline glass that meets the desired optical properties and intrinsic strength is obtained. For example, it may cause the microcrystalline glass to be not transparent enough. Therefore, in order to ensure that the microcrystalline glass that meets the specific structure desired by the present application is obtained, the P 2 O 5 The content is 1.00~3.00mol%.

[0105] In some embodiments of the present application, in the glass-ceramics, P 2 O 5 The content of may be 1.00 to 3.00 mol%, 1.50 to 2.50 mol%, 1.80 to 1.90 mol%, 1.60 to 2.00 mol%, or 1.50 to 3.00 mol%. In some embodiments, P 2 O 5 The content of can be 1.00mol%, 1.20mol%, 1.40mol%, 1.50mol%, 1.60mol%, 1.70mol%, 1.80mol%, 1.87mol%, 1.86mol%, 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 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.

[0106] In the glass system of this application, ZrO 2 It is an intermediate oxide in the formation of glass and is also an essential component. Adding a certain amount of ZrO 2 The content of ZrO can improve the alkali resistance of microcrystalline glass, but the acid resistance will be reduced. 2 It is conducive to the efficient chemical etching and thinning of microcrystalline glass in acid solution, and can also reduce the crystal size and increase the toughness of 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 glass, make the microcrystalline glass have higher intrinsic strength and optical properties, and improve the chemical etching effect of microcrystalline glass, it is necessary to control the content of ZrO 2 The content is 2.00~5.00mol%.

[0107] In some embodiments of the present application, in the glass-ceramics, ZrO 2 The content of ZrO may be 2.00 to 5.00 mol%, 3.00 to 4.50 mol%, 2.50 to 5.00 mol%, 4.50 to 5.00 mol%, or 3.00 to 5.00 mol%. In some embodiments, ZrO 2The content can be 2.00mol%, 2.50mol%, 3.00mol%, 3.10mol%, 3.31mol%, 3.50mol%, 3.72mol%, 4.00mol%, 4.21mol%, 4.44mol%, 4.50mol%, 4.57mol%, 4.61mol%, 4.63mol%, 4.66mol%, 4.68mol%, 4.72mol% or 5.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the 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.

[0108] In the glass system of the present application, MgO, as an optional component, can play a role in regulating the glass phase composition in the microcrystalline glass. However, excessive MgO will affect the growth of crystals, thereby affecting the structure of the microcrystalline glass, affecting the mechanical strength or optical properties of the 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%.

[0109] In some embodiments of the present application, in the glass-ceramics, the content of MgO 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, 0.10mol%, 0.20mol%, 0.30mol%, 0.40mol%, 0.46mol%, 0.50mol%, 0.60mol%, 0.70mol%, 0.80mol%, 0.87mol%, 0.90mol%, 1.00mol%, 1.06mol%, 1.10mol%, 1.20mol%, 1.30mol%, 1.34mol%, 1.40mol%, 1.50mol%, 1.57mol%, 1.60mol%, 1.70mol%, 1.80mol%, 1.89mol% or 2.00mol%, 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 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.

[0110] In the glass system of this application, Na 2 O is an optional component, which belongs to the network extracellular oxide and can provide free oxygen. 2O is beneficial to improve the viscosity of glass and promote the melting and clarification of glass liquid, but excessive Na 2 O will affect the network structure of the glass, and thus affect the performance of the microcrystalline glass. Therefore, in order to ensure that the microcrystalline glass meets the desired structure, it is necessary to control the Na 2 The O content is 0 to 3.00 mol%.

[0111] In some embodiments of the present application, in the glass-ceramics, Na 2 The content of O may be 0 to 3.00 mol%, 0.10 to 2.80 mol%, 0.50 to 2.50 mol%, 1.00 to 2.00 mol%, 0 to 0.50 mol%, or 0.50 to 2.59 mol%. In some embodiments, Na 2 The content of O can be 0, 0.10mol%, 0.20mol%, 0.30mol%, 0.40mol%, 0.50mol%, 0.56mol%, 0.80mol%, 1.00mol%, 1.48mol%, 1.50mol%, 2.00mol%, 2.50mol%, 2.59mol%, 2.80mol% or 3.00mol%, 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 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.

[0112] In the glass system of this application, K 2 O is an optional component. Appropriate amount of K 2 O can reduce the viscosity of the glass liquid and promote the formation of crystals, but if it contains too much K 2 O, it is easy to cause the glass crystal to coarsen, reducing the transmittance of the microcrystalline glass and microcrystalline glass products. Therefore, in order to ensure that the microcrystalline glass obtains better optical properties and high intrinsic strength, the present application controls K 2 The O content is 0 to 1.00 mol%.

[0113] In some embodiments of the present application, in the glass-ceramics, K 2 The content of O may be 0 to 1.00 mol%, 0.10 to 0.90 mol%, 0 to 0.50 mol%, 0.50 to 1.00 mol%, or 0 to 0.92 mol%. In some embodiments, K 2The content of O can be 0, 0.10mol%, 0.20mol%, 0.21mol%, 0.36mol%, 0.40mol%, 0.50mol%, 0.60mol%, 0.69mol%, 0.72mol%, 0.80mol%, 0.92mol% or 1.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the 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.

[0114] In the glass system of this application, Li 2 O is lithium disilicate crystal phase (Li 2 Si 2 O 5 ) is an essential component, which directly affects the content of lithium disilicate crystal phase in microcrystalline glass. As a network oxide formed by glass, it can provide free oxygen, improve the viscosity of glass liquid, and promote the melting and clarification of glass liquid. At the same time, it can also provide lithium ions for ion exchange with molten salt bath, which is an important factor affecting the stress level that can be obtained in glass. However, excessive Li 2 The addition of O may lead to poor stability of the glass crystallization process, or even cause the precipitation of other crystalline phases, affecting the structure of the glass-ceramics. Therefore, in order to ensure that the glass-ceramics meets the desired structure, has excellent optical properties and high intrinsic strength, and improves the chemical etching thinning effect of the glass-ceramics, it is necessary to control the Li 2 The O content is between 25.00 and 32.00 mol%.

[0115] In some embodiments of the present application, in the glass-ceramics, Li 2 The content of O may be 25.00 to 32.00 mol%, 27.00 to 30.00 mol%, 26.00 to 32.00 mol%, 28.00 to 30.00 mol%, 27.00 to 31.00 mol%, 29.00 to 32.00 mol%, or 25.00 to 30.00 mol%. In some embodiments, Li 2The content of O 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 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.

[0116] In the glass system of 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 a sharp drop in the crystallinity of the glass, affecting the intrinsic strength of the microcrystalline glass, and also affecting 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%.

[0117] In some embodiments of the present application, in the glass-ceramics, the content of CaO can be 0-2.00mol%, 0.10-1.90mol%, 0-1.83mol%, 0.5-1.50mol%, 0.60-1.00mol%, 0.80-2.00mol% or 0-0.80mol%. In some embodiments, the content of CaO can be 0, 0.10mol%, 0.30mol%, 0.50mol%, 0.60mol%, 0.80mol%, 0.90mol%, 0.92mol%, 0.93mol%, 0.94mol%, 1.00mol%, 1.50mol%, 1.80mol%, 1.83mol%, 1.90mol% or 2.00mol%, 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 microcrystalline glass with the desired properties of the present application can be obtained.

[0118] In the glass system of the present application, SrO is an optional component, which is an alkaline earth metal oxide. An appropriate amount of SrO can play a role in adjusting the glass phase composition in the microcrystalline glass, which is beneficial to increase the density of the microcrystalline glass and reduce the expansion softening point of the microcrystalline glass, thereby facilitating hot bending. However, the introduction of excessive SrO will deteriorate the optical properties of the microcrystalline glass. Therefore, in order to make the microcrystalline glass meet excellent optical properties and high intrinsic strength, while improving the hot bending effect of the microcrystalline glass, the SrO content is controlled to be 0-2.00 mol%.

[0119] 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%, 0.6 0mol%, 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.

[0120] In the glass system of this application, Ta 2 O 5 It is an optional component that can improve the mechanical strength of glass. However, excessive Ta 2 O 5 Therefore, in order to make the microcrystalline glass meet excellent optical properties and high intrinsic strength, it is necessary to control the Ta 2 O 5 The content is 0-1.00 mol%. In some embodiments of the present application, in the glass-ceramics, Ta 2 O 5 The content of Ta may be 0 to 1.00 mol%, 0.5 to 0.9 mol%, 0 to 0.50 mol%, 0.3 to 0.80 mol%, or 0 to 0.46 mol%. In some embodiments, Ta 2 O 5The content of 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 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.

[0121] In the glass system of this application, La 2 O 3 It is an optional component that can increase the density and Young's modulus of glass. However, excessive La 2 O 3 Therefore, in order to make the microcrystalline glass meet excellent optical properties and high intrinsic strength, it is necessary to control La 2 O 3 The content is 0 to 1.00 mol%.

[0122] In some embodiments, La 2 O 3 The content of La may be 0 to 1.00 mol%, 0.10 to 0.90 mol%, 0 to 0.60 mol%, 0.20 to 0.80 mol%, 0.30 to 0.70 mol%, 0 to 0.53 mol%, or 0.60 to 1.00 mol%. In some embodiments, La 2 O 3 The content of can be 0, 0.10mol%, 0.20mol%, 0.27mol%, 0.30mol%, 0.40mol%, 0.50mol%, 0.53mol%, 0.60mol%, 0.70mol%, 0.80mol%, 0.89mol%, 0.90mol% or 1.00mol%, or can be all ranges and sub-ranges between any two of the above specific values, as long as the microcrystalline glass with the 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 glass system of the present application, the components of the microcrystalline glass are also optimized and adjusted so that the components of the microcrystalline glass meet the following conditions: 2×Li 2 O+9×ZrO 2 +1.2×CaO≥88.00mol%, preferably 2×Li 2 O+9×ZrO2 +1.2×CaO≥90.00mol%, wherein each oxide chemical formula represents the molar percentage content of the corresponding component in the microcrystalline glass component. By making the composition of the microcrystalline glass satisfy this relationship, while ensuring that the microcrystalline glass obtains high intrinsic strength and excellent optical properties, the chemical etching thinning effect of the microcrystalline glass can be significantly improved, so that the microcrystalline glass can achieve a relatively excellent chemical etching thinning effect in a relatively low concentration of acidic liquid.

[0124] In some embodiments of the present application, in the glass-ceramics, calculated by molar percentage of oxides, 2×Li 2 O+9×ZrO 2 The value of +1.2×CaO may be 88.00 mol% to 105.00 mol%, 90.00 mol% to 99.00 mol%, 89.00 mol% to 104.00 mol%, 90.00 mol% to 103.00 mol%, 99.00 to 105.00 mol%, 88.00 mol% to 105.00 mol%, 92.00 mol% to 105.00 mol%, 94.00 mol% to 104.00 mol%, 98.00 mol% to 103.00 mol%, or 88.00 mol% to 98.00 mol%. In some embodiments, 2×Li 2 O+9×ZrO 2 The value of +1.2×CaO can be 88.00mol%, 89.00mol%, 90.00mol%, 90.18mol%, 91.00mol%, 92.00mol%, 93.00mol%, 94.00mol%, 94.23mol%, 95.00mol%, 96.00mol%, 97.00mol%, 97.75mol%, 98.00mol%, 98.08mol%, 99.00mol%, 99.63mol%. %, 100.00mol%, 100.41mol%, 100.55mol%, 101.00mol%, 101.02mol%, 101.09mol%, 101.49mol%, 101.66mol%, 101.83mol%, 102.00mol%, 103.00mol% or 105.00mol%, 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 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.

[0125] In some embodiments of the present application, the SiO in the microcrystalline glass is calculated according to the content expressed as a molar percentage of the oxide basis. 2 The content and Li 2 The content of O meets the following conditions: SiO 2 +Li 2 O=89.00-96.00mol%. By making the glass-ceramics satisfy the composition of the relationship, it is beneficial to ensure that the desired content of lithium disilicate crystals are precipitated in the glass-ceramics, and the precipitation of other crystals, such as petalite crystals, can be effectively reduced, which is beneficial to ensure that the glass-ceramics obtains higher intrinsic strength and excellent optical properties, and is also beneficial for the glass-ceramics to obtain a higher stress level after chemical strengthening. At the same time, it is also beneficial to ensure that the substrate glass does not lose transparency when the glass-ceramics is prepared by heat treatment, or to ensure that the substrate glass does not lose transparency during the melting process.

[0126] In some embodiments, in the glass-ceramics, SiO 2 +Li 2 The value of O may be 89.00 to 96.00 mol%, 90.00 to 95.00 mol%, 91.00 to 93.00 mol%, 90.50 to 93.50 mol%, 90.00 to 92.00 mol%, or 91.00 to 95.00 mol%. In some embodiments, SiO 2 +Li 2 The value of O 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 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.

[0127] In some embodiments of the present application, the SiO in the microcrystalline glass is calculated according to the content expressed as a molar percentage of the oxide basis. 2 The content and Li 2 The content of O meets the following conditions: SiO 2 / Li 2O = 2.00 ~ 2.50. By making the glass-ceramics satisfy the composition of this relationship, it is beneficial to reduce the crystal size of the glass-ceramics and improve the optical properties of the glass-ceramics; at the same time, it is beneficial to ensure the precipitation of the main crystal phase lithium disilicate crystals and can effectively reduce the precipitation of other crystal phases, such as petalite crystals, which is beneficial to ensure that the glass-ceramics obtains a higher intrinsic strength and is also beneficial for the glass-ceramics to obtain a higher stress level after chemical strengthening.

[0128] In some embodiments, in the glass-ceramics, SiO 2 / Li 2 The value of O may be 2.00 to 2.50, 2.05 to 2.25, 2.00 to 2.30, or 2.10 to 2.35. In some embodiments, SiO 2 / Li 2 The value of O may 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 may be any range and sub-range 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.

[0129] In some embodiments of the present application, the component contents in the microcrystalline glass also satisfy the following conditions, calculated according to the contents expressed as molar percentages of the oxides: (Li 2 O+ZrO 2 ) / (SiO 2 +Al 2 O 3 +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 with higher intrinsic strength.

[0130] In some embodiments, in the glass-ceramics, calculated by molar percentage of oxides, (Li 2 O+ZrO 2 ) / (SiO 2 +Al 2 O 3 +CaO) may have a value of 0.50 to 0.60, 0.51 to 0.59, 0.55 to 0.60, 0.50 to 0.55, 0.52 to 0.58, 0.53 to 0.57, 0.54 to 0.56, or 0.51 to 0.55. In some embodiments, (Li 2 O+ZrO2 ) / (SiO 2 +Al 2 O 3 +CaO) can 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 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.

[0131] In some embodiments of the present application, the content of the components in the microcrystalline glass also satisfies the following conditions, calculated according to the content expressed as a molar percentage of the oxide: (2×Li 2 O-6×P 2 O 5 ) / SiO 2 ≥0.70. By making the glass-ceramics satisfy the composition of this relational expression, it is helpful to ensure that a desired content of lithium disilicate crystal phase is precipitated in the glass-ceramics, thereby ensuring that the glass-ceramics has high intrinsic strength.

[0132] In some embodiments, in the glass-ceramics, calculated by molar percentage of oxides, (2×Li 2 O-6×P 2 O 5 ) / SiO 2 The value of may be 0.70 to 1.00, 0.80 to 0.90, 0.70 to 0.80, or 0.90 to 1.00. In some embodiments, (2×Li 2 O-6×P 2 O 5 ) / SiO 2 The value of 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 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.

[0133] In some embodiments of the present application, the microcrystalline glass comprises the following components, expressed in terms of molar percentage based on oxides: SiO 2 :60.50~64.00mol%、P 2 O 5 :1.50~2.50mol%、ZrO 2 :4.00~5.00mol%、Li2 O: 28.00-31.00 mol%, Al 2 O 3 :0~1.50mol%, MgO: 0~2.00mol%, Na 2 O: 0-3.00 mol%, K 2 O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta 2 O 5 :0~1.00mol%、La 2 O 3 :0~1.00mol%.

[0134] In some embodiments of the present application, the crystallinity of the glass-ceramics is ≥ 60.00wt%, preferably 60.00-90.00wt%. The "crystallinity of 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 performance 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 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.

[0135] In some embodiments of the present application, "lithium disilicate crystalline phase is 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.

[0136] In some embodiments of the present application, non-limiting examples of other possible crystalline phases in the microcrystalline glass include, but are not limited to: petalite crystalline phase and / or lithium phosphate crystalline phase. In some embodiments, the microcrystalline glass further comprises a petalite crystalline phase, preferably the weight percentage of the petalite crystalline phase in the microcrystalline glass is less than or equal to 20%, more preferably, the weight percentage of the petalite crystalline phase in the microcrystalline glass may be less than or equal to 15%, less than or equal to 10%, or less than or equal to 5%.

[0137] In some embodiments of the present application, in the glass-ceramics, the average crystal size is ≤100.00nm, preferably the average crystal size is less than or equal to 50nm. Meeting a smaller average crystal size is conducive to ensuring the excellent optical properties of the glass-ceramics. In some embodiments, in the glass-ceramics, the average crystal size can be 5-100nm, 10-90nm, 5-30nm, 10-40nm, 5-50nm, 18.70-26.80nm, 20.10-25.60nm, 22.80-23.00nm or 10-30nm. 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 desired properties of the present application can be obtained.

[0138] In some embodiments of the present application, the density of the microcrystalline glass is ≥2.50 g / cm 3 , a higher density is conducive to ensuring that the microcrystalline glass meets high intrinsic strength. In some embodiments, the density of the microcrystalline glass can be 2.50-2.70 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 may be 2.50 g / cm 3 , 2.51g / cm 3 , 2.52g / cm 3, 2.53g / cm 3 , 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 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.

[0139] 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 a higher intrinsic strength, which is beneficial for obtaining higher mechanical strength properties. In some embodiments, the Young's modulus of the glass-ceramics may be 100.00 to 130.00 GPa, 105.00 to 125.00 GPa, 108 to 130 GPa, 110.00 to 125.00 GPa, 114 to 130 GPa, or 110.00 to 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 desired properties of the present application can be obtained.

[0140] In some embodiments of the present application, the refractive index of the microcrystalline glass is ≤1.60, preferably 1.50 to 1.60.

[0141] In some embodiments of the present application, the microcrystalline glass is transparent in the visible light range; at a thickness of 0.5 mm, for light with a wavelength of 550 nm, the transmittance of the microcrystalline glass is ≥ 85.00%; preferably, the transmittance at 550 nm is ≥ 90.00%; and more preferably, the transmittance is 90.00-93.00%. Microcrystalline glass with a higher transmittance can ensure good light transmittance and good transparency, and is suitable for use in display cover glass that has requirements for display effects. In some embodiments, at a thickness of 0.5 mm, for light of a wavelength of 550 nm, 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 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 desired properties of the present application can be obtained.

[0142] In some embodiments of the present application, at a thickness of 0.5 mm, the optical b value of the glass-ceramics is less than or equal to 1.00; preferably, the optical b value is less than 0.80. In some embodiments, the optical b value of the 0.5 mm thick glass-ceramics 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-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.

[0143] In some embodiments of the present application, a microcrystalline glass having one side provided with a protective film on one of the two main surfaces is placed in a mixed acid solution at 20°C to contact with it, thereby achieving etching thinning, the etching rate of the microcrystalline glass is ≥7.00μm / min, preferably 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 microcrystalline glass sample before etching - thickness of microcrystalline glass sample after etching) / etching time. "Contact" refers to a 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 not in contact with the solution, a protective film may be placed on the surface before the glass-ceramic contacts the etching solution to isolate the contact of the etching solution with the glass-ceramic, and the protective film still exists after contact with the etching solution and can be easily removed. Any applicable method may 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, it is preferred that the surfactant include sodium dodecyl sulfate. In the present application, it is preferred to perform etching thinning under the condition of chamfering to ensure that the side without the protective film is uniformly etched, but it is not limited to such an etching process. The glass-ceramic described in the present application can be used for chemical etching thinning processes commonly used in the art. 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.

[0144] In some embodiments of the present application, when the microcrystalline glass is placed in a hydrofluoric acid aqueous solution with a mass concentration of 10% at 20°C for 20 minutes, the change in the mass per unit area of ​​the microcrystalline glass is greater than or equal to 28.00 mg / cm 2Preferably, the change in mass per unit area of ​​the microcrystalline glass is 30.00 to 50.00 mg / cm 2 In some embodiments, under the above conditions, the change in the mass per unit area of ​​the microcrystalline glass 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 50.00mg / cm 2 , or may be 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 microcrystalline glass still has a relatively efficient chemical etching thinning effect, which is beneficial to improving the etching thinning efficiency.

[0145] In the present application, a method for preparing the aforementioned microcrystalline glass is also provided, which comprises the following steps:

[0146] A substrate glass is provided, wherein the substrate glass comprises the following components expressed in terms of molar percentage on an oxide basis: SiO 2 :55.00~65.00mol%、P 2 O 5 :1.00~3.00mol%、ZrO 2 :2.00~5.00mol%、Li 2 O: 25.00~32.00mol%, Al 2 O 3 :0~2.00mol%, MgO: 0~2.00mol%, Na 2 O: 0-3.00 mol%, K 2 O: 0~1.00mol%, CaO: 0~2.00mol%, SrO: 0~2.00mol%, Ta 2 O 5 :0~1.00mol%、La 2 O 3 :0~1.00mol%, wherein, in terms of the content expressed as a molar percentage based on the oxide, the composition of the substrate glass satisfies: 2×Li 2 O+9×ZrO 2 +1.2×CaO≥88.00mol%;

[0147] The substrate glass is subjected to heat treatment for crystallization to obtain a glass-ceramic, and the glass-ceramic 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 glass-ceramic. It should be understood that the glass-ceramic is prepared by heat treatment of the substrate glass. Therefore, in terms of the molar percentage of oxides, the composition of the substrate glass used is the same as or substantially the same as that of the glass-ceramic.

[0148] In some embodiments of the present application, calculated in terms of the molar percentage of oxides, the composition of the substrate glass further satisfies: SiO 2 +Li 2 O = 89.00 - 96.00 mol%, preferably, SiO 2 +Li 2 O = 90.00 - 95.00 mol%; and / or,

[0149] SiO 2 / Li 2 O = 2.00 - 2.50, preferably, SiO 2 / Li 2 O = 2.00 - 2.30; and / or,

[0150] (Li 2 O + ZrO 2 ) / (SiO 2 +Al 2 O 3 +CaO) ≥ 0.50, preferably, (Li 2 O + ZrO 2 ) / (SiO 2 +Al 2 O 3 +CaO) ranges from 0.50 to 0.60; and / or,

[0151] (2×Li 2 O - 6×P 2 O 5 ) / SiO 2 ≥ 0.70, preferably, (2×Li 2 O - 6×P 2 O 5 ) / SiO 2 ranges from 0.70 to 1.00;

[0152] In the above relationships, each oxide chemical formula represents the molar percentage content of the corresponding component in the composition of the substrate glass.

[0153] In the present application, the substrate glass can be prepared by a conventional preparation method. For example, the molding method of the substrate glass can include but is not limited to: float, overflow, rolling or pouring. Exemplarily, in the substrate glass preparation method of the present application, the raw material components and the clarifier are first mixed, melted at 1550℃~1680℃, and the melting time is 5h or more. Then, the melted glass liquid is cast into a forming mold, cooled to 850℃~950℃, and then the obtained molded and cooled glass sample is placed in an annealing furnace at 450℃~500℃ for annealing for 12~48h, and then cooled to room temperature to obtain a substrate glass sample. Further, 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 each raw material.

[0154] 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 min, and the crystallization treatment temperature is 600-750° C., and the crystallization treatment time is 5-1440 min.

[0155] 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 may be any range and sub-range 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. 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 may be any range and sub-range 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. In some embodiments, the nucleation time may be 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 microcrystalline glass with the desired performance 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 microcrystalline glass with the desired performance 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 microcrystalline glass with the desired performance of the present application can be obtained.

[0156] In some embodiments of the present application, the heating rate of the heat treatment process is 3 to 15°C / min, preferably 3 to 10°C / min. For example, the temperature is increased from room temperature to the nucleation treatment temperature at a heating rate of 3 to 15°C / min, and / or, the temperature is increased 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 may 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 may 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.

[0157] In some embodiments of the present application, the 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.

[0158] In some embodiments of the present application, the glass-ceramic can be obtained by chemically strengthening the glass-ceramic, and the composition at the center of the depth of the chemically strengthened glass-ceramic is the same as that of the glass-ceramic. It should be understood that after chemical strengthening, the composition at the surface of the glass-ceramic product may be different from the composition of the glass-ceramic before it undergoes the ion exchange process, compared to the glass-ceramic before chemical strengthening. This is because when ion exchange is performed, a type of alkali metal ion (for example, Li + Or Na + ) are replaced by larger alkali metal ions (e.g., Na + or K + ) is replaced. However, in an embodiment, the glass composition and phase assembly at the depth center or near the depth center of the microcrystalline glass product will still have the composition and phase assembly of the newly formed microcrystalline glass. That is to say, 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 microcrystalline glass that has been chemically strengthened are the same or substantially the same as those of the newly formed microcrystalline glass.

[0159] In the present application, the microcrystalline glass has high intrinsic strength and excellent optical properties. The chemically strengthened microcrystalline glass or anti-glare microcrystalline glass prepared using the microcrystalline glass also has excellent performance and can be used in electronic devices or electronic products, mainly electronic devices and electronic products that need to install glass products. The electronic devices or electronic products include but are not limited to mobile phones, tablet computers, televisions, computer displays and smart wearable devices.

[0160] The microcrystalline glass with excellent performance provided in the present application or the chemically strengthened microcrystalline glass 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 screen 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 microcrystalline glass required. 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 work surfaces, other surfaces, appliance doors, floor tiles, wall panels or storage containers. Other surfaces can include but are not limited to exterior wall surfaces, stair tread surfaces, column veneers or counter surfaces, etc., and storage containers can include but are not limited to cups, plates, medicine bottles or beverage bottles, etc.

[0161] 4. The technical solution of this application is explained below through specific embodiments

[0162] Example 1

[0163] Step 1: Substrate Glass Preparation

[0164] According to the raw material ratio, 1000g of raw materials were configured (the raw materials were configured according to the formula of Example 1 in Table 1), and 5g of sodium chloride was added to the configured raw materials, and 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, and then poured into a molding mold to be formed and cooled into glass bricks, cooled to about 900°C, and then placed in a 460°C annealing furnace for annealing for 12 hours, and then cooled to room temperature with the furnace to obtain a base material glass brick.

[0165] Step 2: Glass-ceramic preparation

[0166] The base glass brick obtained in step 1 is subjected to nucleation treatment and crystallization treatment in sequence. The process conditions of the nucleation treatment and crystallization treatment are shown in Table 3, and a transparent micro-ceramic glass brick can be prepared.

[0167] Specifically, the substrate glass brick is placed in a crystallization furnace, 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, the nucleation treatment time is 4h, and then heated 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 1.5h. Here, the nucleation treatment time refers to the time of keeping warm after the crystallization furnace is heated to the set nucleation treatment temperature at the set heating rate. The crystallization treatment time refers to the time of keeping warm after the crystallization furnace is heated to the set crystallization treatment temperature at the set heating rate.

[0168] Step 3: Glass-ceramic sample processing

[0169] After shaping, cutting and polishing the glass-ceramic sample 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 50mm×50mm×0.5mm glass-ceramic polished sheet.

[0170] Examples 2 to 12 and comparative examples 1 to 6 were prepared using the components in Tables 1 to 2 to prepare the corresponding substrate glass. Then, nucleation treatment and crystallization treatment were performed according to Tables 3 to 4 to obtain the corresponding microcrystalline glass. Subsequently, chemical etching thinning tests were performed, and the test results are shown in Tables 5 to 6.

[0171]

[0172]

[0173]

[0174]

[0175] From the above table and attached figures, we can see that:

[0176] Examples 1-12 adjust the components of the microcrystalline glass, which not only ensures the preparation of microcrystalline glass with higher crystallinity and higher density, and 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 lower b-value, which is conducive to improving the commercial application of the microcrystalline glass.

[0177] from Figure 2 It can be seen that the main crystalline phase in the glass-ceramics obtained in the embodiment and the comparative example is lithium disilicate. Figure 4 and Figure 5 By comparison, it can be seen that the optical transmittance of the microcrystalline glass obtained by the glass formula scheme of Example 8 is better than that of Comparative Example 6. By comparing Table 5 and Table 6, it can be seen that 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 relatively low. This shows that the microcrystalline glass of the embodiment has improved the chemical etching thinning effect, even at higher temperatures, and still maintains good acid and alkali resistance.

[0178] From the above tests, it can be seen that the microcrystalline glass of the present application can achieve efficient chemical etching thinning in a relatively low concentration HF solution, which is not only beneficial to improve the chemical etching thinning rate of the microcrystalline glass, and thus to improve 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.

[0179] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application rather than to limit the technical solution. Ordinary technicians in this field should understand that those modifications or equivalent substitutions of the technical solution of the present application that do not depart from the purpose and scope of the technical solution of the present application should be included in the scope of the claims of the present application.

Claims

1. A chemically strengthened glass-ceramic, characterized in that: The chemically strengthened glass-ceramics 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 chemically strengthened glass-ceramics; the composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer contains the following components, expressed as a molar percentage based on an oxide: 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: 0-2.00 mol%, Na2O: 0~3.00mol%, K2O: 0~1.00mol%, CaO: 0-2.00 mol%, SrO: 0-2.00 mol%, Ta2O5: 0~1.00mol%, La2O3: 0~1.00mol%; The composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer satisfies the following requirements, expressed in molar percentage based on oxides: 2×Li2O+9×ZrO2+1.2×CaO≥88.00mol%, preferably ≥90.00mol%, wherein each oxide chemical formula respectively represents the molar percentage content of the corresponding component in the composition at the center of the chemically strengthened glass-ceramics or the tensile stress layer.

2. The chemically strengthened glass-ceramics according to claim 1, characterized in that: Calculated according to the content expressed as a molar percentage of the oxide basis, the content of SiO2 and the content of Li2O in the composition at the center of the chemically strengthened microcrystalline glass or the composition of the tensile stress layer meet the following conditions: SiO2+Li2O=89.00~96.00mol%; Preferably, SiO2+Li2O=90.00~95.00mol%.

3. The chemically strengthened glass-ceramics according to claim 1 or 2, characterized in that: Calculated according to the content expressed as a molar percentage of the oxide basis, the content of SiO2 and the content of Li2O in the composition at the center of the chemically strengthened microcrystalline glass or the composition of the tensile stress layer meet the following conditions: SiO2 / Li2O=2.00~2.50; preferably, SiO2 / Li2O=2.00~2.

30.

4. The chemically strengthened glass-ceramics according to any one of claims 1 to 3, characterized in that: The composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer, calculated based on the content expressed as a molar percentage of the oxide basis, also satisfies the following conditions: (Li2O+ZrO2) / (SiO2+Al2O3+CaO)≥0.50; preferably, the value of (Li2O+ZrO2) / (SiO2+Al2O3+CaO) is 0.50~0.60, wherein each oxide chemical formula respectively represents the molar percentage content of the corresponding component in the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer.

5. The chemically strengthened glass-ceramics according to any one of claims 1 to 4, characterized in that: The composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer, calculated based on the content expressed as a molar percentage of the oxide basis, also satisfies the following conditions: (2×Li2O-6×P2O5) / SiO2≥0.70, preferably, the value of (2×Li2O-6×P2O5) / SiO2 is 0.70~1.00, wherein each oxide chemical formula respectively represents the molar percentage content of the corresponding component in the center of the chemically strengthened microcrystalline glass or the composition of the tensile stress layer.

6. The chemically strengthened glass-ceramics according to any one of claims 1 to 5, characterized in that: Expressed as mole percentage on an oxide basis: The composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer comprises 58.00 to 65.00 mol % SiO2, preferably 60.00 to 64.00 mol % SiO2; And / or, the composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer contains 26.00 to 32.00 mol % of Li2O, preferably 27.00 to 31.00 mol % of Li2O; And / or, the composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer contains 2.50 to 5.00 mol % ZrO2, preferably 3.00 to 5.00 mol % ZrO2; And / or, the composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer contains 1.50 to 3.00 mol % of P2O5, preferably 1.50 to 2.50 mol % of P2O5.

7. The chemically strengthened glass-ceramics according to any one of claims 1 to 6, characterized in that: The composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer includes the following components, expressed as a molar percentage based on oxides: 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 chemically strengthened glass-ceramics according to any one of claims 1 to 7, characterized in that: The chemically strengthened glass-ceramics has a crystallinity of ≥60.00 wt%, preferably 60.00 wt% to 90.00 wt%; and / or, In the chemically strengthened glass-ceramics, the average crystal size is less than or equal to 100 nm, preferably the average crystal size is less than or equal to 50 nm, and more preferably the average crystal size is 10 to 40 nm.

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

60.

10. The chemically strengthened glass-ceramics according to any one of claims 1 to 9, characterized in that: The Young's modulus of the chemically strengthened glass-ceramics is ≥100 GPa, preferably the Young's modulus is 108 to 130 GPa, and more preferably the Young's modulus is 114 to 130 GPa.

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

8.

12. A method for preparing the chemically strengthened 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 terms of 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%, La2O3: 0-1.00 mol%, wherein, in terms of content expressed in terms of molar percentage based on oxides, the composition of the substrate glass satisfies: 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; The glass-ceramics is obtained by chemical strengthening treatment to obtain chemically strengthened glass-ceramics, and the composition at the center of the chemically strengthened glass-ceramics or the composition of the tensile stress layer is the same as or substantially the same as that of the glass-ceramics.

13. The method for preparing chemically strengthened glass-ceramics according to claim 12, 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 min, the crystallization treatment temperature is 600-750° C., and the crystallization treatment time is 5-1440 min.

14. An electronic device, characterized in that: The electronic device comprises the chemically strengthened glass-ceramics according to any one of claims 1 to 12 or the chemically strengthened glass-ceramics produced by the method for producing the chemically strengthened glass-ceramics according to any one of claims 13 to 14.

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