Tempered crystallized glass having high scratch resistance and its manufacturing method, chemically strengthened crystallized glass, glassware, and electronic device

Abstract

The present invention discloses a reinforced crystallized glass having high scratch resistance, the reinforced crystallized glass includes a compressive stress layer and a tensile stress layer, the main crystal phase of the reinforced crystallized glass is (Zn,Mg)Al2O4, the reinforced crystallized glass includes Na2O, the surface K2O concentration of the reinforced crystallized glass is 7.00wt% or more, optionally 7.00-15.00wt%, the depth of the reinforced crystallized glass from any surface of the reinforced crystallized glass to a position near the surface and having the same potassium (K) concentration as the center of the reinforced crystallized glass along the thickness direction of the glass is 0.07t or more, optionally 0.07t-0.10t, where t is the thickness of the reinforced crystallized glass. The present invention is based on intensive research into the inherent strength of crystallized glass and the stress characteristics obtained from the glass after strengthening, and by strengthening a specific system of crystallized glass with high inherent strength to satisfy specific stress characteristics, it is possible to finally obtain a strengthened crystallized glass with excellent scratch resistance, and this strengthened crystallized glass can achieve a scratch resistance effect comparable to that of sapphire glass.

Description

[Technical Field]

[0001] This invention claims priority based on a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on December 23, 2022, bearing application number 202211666239.3 and entitled "Toughened Crystallized Glass with High Scratch Resistance," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of glass material technology, and in particular to strengthened glass-ceramics with high scratch resistance. [Background technology]

[0003] Due to its excellent optical properties, glass is gradually replacing plastics as a protective cover for portable electronic devices. For protective covers and housing materials for portable electronic devices such as smartphones, smartwatches, and tablet devices, excellent scratch resistance is required. Currently, sapphire glass is a material with excellent pressure resistance and scratch resistance. However, sapphire glass is difficult to produce and process, has high processing costs, has a low tolerance for defects, and is prone to breakage. Conventional glass has poor scratch resistance, and even crystallized glass, which is glass with crystalline phases such as lithium disilicate or petalite precipitated in it, has limited scratch resistance and is therefore unable to meet the performance requirements of high-end products.

[0004] Zinc magnesium spinel crystals have a high Young's modulus and shear modulus, making them a preferred crystalline phase for improving the scratch resistance of glass.

[0005] Patent CN111615500A discloses a transparent zinc spinel-spinel glass-ceramic with spinel as the main crystalline phase, which has a Young's modulus of about 98.0 GPa to about 114.0 GPa and a hardness of about 9.0 GPa to about 11.2 GPa. The scratch resistance of the glass-ceramic disclosed in this patent is significantly improved compared to conventional crystallized glass, but further improvements in scratch resistance, Young's modulus, and hardness are required. Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a strengthened crystallized glass having high scratch resistance so as to solve the problem that the scratch resistance of the crystallized glass in the prior art is insufficient. [Means for solving the problem]

[0007] In order to solve the above technical problems, the present invention employs the following aspects.

[0008] In a first aspect, the present invention provides a strengthened glass-ceramic having high scratch resistance, the strengthened glass-ceramic comprising a compressive stress layer and a tensile stress layer, a (Zn,Mg)Al2O4 primary crystalline phase, Na2O, a surface K2O concentration of the strengthened glass-ceramic being 7.00 wt% or more, optionally 7.00 to 15.00 wt%, and a depth along the thickness of the strengthened glass-ceramic from any surface of the strengthened glass-ceramic to a position near the surface and having a potassium (K) concentration similar to that of the center of the strengthened glass-ceramic being 0.07t or more, optionally 0.07t to 0.10t, where t is the thickness of the strengthened glass-ceramic. Optionally, when the thickness is 0.7 mm, the strengthened glass-ceramic has a single-rod static pressure strength of 450 N or more, optionally 450 to 650 N.

[0009] Optionally, the Young's modulus of the strengthened glass-ceramics is 110 GPa or more, and optionally 110 to 130 GPa.

[0010] Optionally, the Vickers hardness of the strengthened crystallized glass is 750 kgf / mm 2 or more, and selectively 750 to 900 kgf / mm 2 and more selectively 800 to 900 kgf / mm 2 is.

[0011] Optionally, the average crystal grain size in the strengthened glass-ceramics is 15.00 nm or less, optionally 1.00 to 10.00 nm, and further optionally 4.50 to 8.00 nm.

[0012] Alternatively, in the strengthened crystallized glass, the crystalline content is 20.00 to 50.00 wt%, alternatively 25.00 to 50.00 wt%, and further alternatively 25.00 to 45.00 wt%.

[0013] Optionally, the secondary crystalline phase of the strengthened glass-ceramics includes one or more selected from tetragonal ZrO2, Zn2SiO4, and Mg2SiO4.

[0014] Optionally, the strengthened glass-ceramics is transparent in the visible light range.

[0015] Alternatively, an automatic pencil hardness tester with a Mohs hardness level 7 gem mineral hardness tester was fixed at a 45° angle, and the surface of the strengthened crystallized glass was scratched with a load of 750 g. When the scratched crystallized glass was observed under a microscope at 400x magnification, no scratches were found on the surface of the strengthened crystallized glass.

[0016] Optionally, the tensile stress layer of the strengthened glass-ceramics contains, in terms of mass percentage of oxides, 30.00%≦SiO2<35.00%, Al2O3: 30.00% to 40.00%, ZnO: 10.00% to 12.00%, MgO: 2.00% to 4.00%, ZrO2: 5.00% to 7.00%, Na2O: 2.00% to 9.00%, Li2O: 0 to 2.00%, and B2O3: 0 to 8.00%, where the components of the tensile stress layer of the strengthened glass-ceramics are: (1)X=((Na2O+B2O3) / ZrO2) / Al2O3, X≧2.00; (2)Y=ln[(Na2O+B2O3) / ZrO2], Y≧0; (3)Z=(SiO2+Al2O3-MgO-ZnO) / (Li2O+Na2O+B2O3), 4.00≦Z≦10.00; In the formulas (1) to (3), oxide represents the mass percentage of the oxide component; Meet the following.

[0017] Optionally, the components of the tensile stress layer of the strengthened crystallized glass further include: (4)W=(0.8×(Al2O3-SiO2)+1.5×(ZnO-MgO)) / ZrO2, 0≦W≦3.00; In formula (4), oxide represents the mass percentage of the oxide component; Meet the following.

[0018] Optionally, in the tensile stress layer of the strengthened crystallized glass, the mass percentage of SiO2 is 32.00% to 34.95%, and / or the mass percentage of Al2O3 is 32.00% to 38.00%, and / or ZnO is 10.00% to 11.48%, and / or MgO is 2.50% to 3.50%, and / or ZrO2 is 5.40% to 6.50%, and / or Na2O is 2.50% to 8.50%, and / or B2O3 is 2.50 to 8.00%.

[0019] Optionally, the tensile stress layer of the strengthened glass-ceramics further contains 0 to 3.00 wt % of BaO and / or 0 to 2.00 wt % of Y2O3.

[0020] Optionally, the strengthened glass-ceramics is essentially free of TiO2 and P2O5.

[0021] Alternatively, the strengthened glass-ceramics is obtained by chemically strengthening glass-ceramics, and the composition of the chemically strengthened glass-ceramics is essentially the same as the composition of the tensile stress layer of the strengthened glass-ceramics in terms of oxide mass percentage.

[0022] Alternatively, the chemically strengthened crystallized glass is placed in a salt bath containing a potassium salt at 380°C to 550°C to carry out a chemical strengthening treatment, the chemical strengthening treatment time being 1 hour to 96 hours, optionally 1 hour to 48 hours, thereby obtaining the strengthened crystallized glass, and the potassium salt including one or more selected from potassium nitrate, potassium sulfate, and potassium carbonate, optionally potassium nitrate.

[0023] In a second aspect, the present invention further provides chemically strengthened glass-ceramics for producing the aforementioned strengthened glass-ceramics, wherein the main crystalline phase of the chemically strengthened glass-ceramics is (Zn,Mg)Al2O4, and in the chemically strengthened glass-ceramics, the molar percentage of Al2O3 is greater than the sum of the molar percentages of MgO and ZnO in terms of oxide molar percentages, and the theoretical crystallinity of the chemically strengthened glass-ceramics is at least 30.00 wt% or more, and optionally 30.00 wt% to 50.00 wt%. When the chemically strengthened glass-ceramics satisfies the theoretical crystallinity, the dissociation energy U per unit volume of the residual glass phase in the glass-ceramics is 71.00 kJ cm. -3 or more, and selectively 71.00 kJ cm -3 ~134.00kJ·cm -3 is.

[0024] Optionally, the chemically strengthened crystallized glass contains, in terms of oxide mass percentage, 30.00%≦SiO2<35.00%, Al2O3: 30.00% to 40.00%, ZnO: 10.00% to 12.00%, MgO: 2.00% to 4.00%, ZrO2: 5.00% to 7.00%, Na2O: 2.00% to 9.00%, Li2O: 0 to 2.00%, and B2O3: 0 to 8.00%, and the components of the chemically strengthened crystallized glass are: (1)X=((Na2O+B2O3) / ZrO2) / Al2O3, X≧2.00; (2)Y=ln[(Na2O+B2O3) / ZrO2], Y≧0; (3)Z=(SiO2+Al2O3-MgO-ZnO) / (Li2O+Na2O+B2O3), 4.00≦Z≦10.00; In the formulas (1) to (3), oxide represents the mass percentage of the oxide component; Meet the following.

[0025] Optionally, the components of the chemically strengthened crystallized glass further include: (4)W=(0.8×(Al2O3-SiO2)+1.5×(ZnO-MgO)) / ZrO2, 0≦W≦3.00; In formula (4), oxide represents the mass percentage of the oxide component; Meet the following.

[0026] Optionally, the Young's modulus of the chemically strengthened crystallized glass is 110 GPa or more, and optionally 110 to 140 GPa.

[0027] Preferably, the average crystal grain size of the chemically strengthened crystallized glass is 15.00 nm or less, preferably 1.00 to 10.00 nm, and more preferably 4.50 to 8.00 nm.

[0028] Alternatively, in the chemically strengthened crystallized glass, the crystalline content is 20.00 to 50.00 wt%, alternatively 25.00 to 50.00 wt%, and further alternatively 25.00 to 45.00 wt%.

[0029] Optionally, the secondary crystalline phase of the chemically strengthening glass-ceramics includes one or more selected from tetragonal ZrO2, Zn2SiO4, and Mg2SiO4.

[0030] Optionally, the chemically strengthened crystallized glass further contains 0 to 3.00 wt% of BaO and / or 0 to 2.00 wt% of Y2O3.

[0031] Optionally, the chemically strengthened crystallized glass is essentially free of TiO2 and P2O5.

[0032] In a third aspect, the present invention further provides glassware produced from the above-mentioned strengthened glass-ceramics or the above-mentioned chemically strengthened glass-ceramics.

[0033] In a fourth aspect, the present invention further provides an electronic device comprising the strengthened glass-ceramics or the chemically strengthened glass-ceramics. [Effects of the Invention]

[0034] Compared with the prior art, the present invention has the following advantageous effects:

[0035] The present invention pursues intensive research into the intrinsic strength of glass-ceramics and the stress characteristics of tempered glass. By tempering specific systems of glass-ceramics with high intrinsic strength to meet specific stress characteristics, the resulting tempered glass-ceramics exhibit excellent scratch resistance. In the present invention, the high surface K2O concentration and high potassium-sodium exchange depth of the tempered glass-ceramics endow the tempered glass-ceramics with excellent surface and deep stress characteristics. Combined with the inherently high intrinsic strength of the glass-ceramics, the mechanical properties of the tempered glass-ceramics of the present invention are significantly improved, enabling the tempered glass-ceramics to achieve scratch resistance comparable to that of sapphire glass. Based on its excellent mechanical properties and scratch resistance, the tempered glass-ceramics of the present invention can meet the application requirements for cover glass in high-end electronic products.

[0036] The present invention optimizes the composition of chemically strengthened glass-ceramics by adjusting the relationship between the oxides and the content of each oxide in the composition. On the other hand, the melting difficulty of the substrate glass and the heat treatment temperature required to produce the desired chemically strengthened glass-ceramics using the substrate glass are reduced, thereby easing the difficulty of mass-producing chemically strengthened glass-ceramics. The glass composition provided by the present invention allows for mass production of the substrate glass using conventional methods such as continuous melting and rolling, ensuring the formability of the substrate glass. Furthermore, when the substrate glass corresponding to the glass composition of the present invention is heat-treated at a temperature of 800°C or less, it is possible to obtain transparent chemically strengthened glass-ceramics whose main crystalline phase is a zinc-magnesium spinel solid solution and which has excellent optical properties. Compared to the prior art, the composition provided by the present invention significantly reduces the heat treatment temperature, further easing the difficulty of mass-producing spinel glass-ceramics and improving the mass productivity of spinel glass-ceramics. On the other hand, the synergistic effect of specific oxide components allows the desired content of the target main crystalline phase (Zn,Mg)Al2O4 to be obtained, while improving the intrinsic strength of the residual glass phase in the chemically strengthened glass-ceramics. By combining the main crystalline phase (Zn,Mg)Al2O4, which has a high Young's modulus and shear modulus, with the residual glass phase, which has a high intrinsic strength, the final chemically strengthened glass-ceramics has high intrinsic strength and better mechanical properties, such as scratch resistance, than conventional spinel-based glass-ceramics. [Brief explanation of the drawings]

[0037] [Figure 1] FIG. 1 is a TGA curve diagram of the substrate glass in Example S4. [Figure 2] FIG. 2 shows the XRD spectrum of the sample of chemically strengthened crystallized glass of Example S1. [Figure 3] FIG. 3 is a transmittance curve diagram of the sample of chemically strengthened crystallized glass of Example S1. [Figure 4]Figure 4 shows scratch resistance graphs obtained by performing scratch resistance tests on the chemically strengthened crystallized glass of Example S1 under different conditions, where (a) corresponds to the test condition R1: Mohs hardness level 7 gem mineral hardness tester, load 250g, (b) corresponds to the test condition R2: Mohs hardness level 7 gem mineral hardness tester, load 500g, and (c) corresponds to the test condition R3: Mohs hardness level 6 gem mineral hardness tester, load 750g. [Figure 5] Figure 5 is a scratch damage effect diagram obtained by conducting a scratch damage test on the chemically strengthened crystallized glass of Examples S2 and S8 under test condition R4, where test condition R4 is a gem mineral hardness tester with a Mohs hardness level of 7 and a load of 750 g, (d) corresponds to the chemically strengthened crystallized glass of Example S2, and (e) corresponds to the chemically strengthened crystallized glass of Example S8. [Figure 6] FIG. 6 is a scratch test result diagram of the tempered crystallized glass of Example S1 under test condition R4, where test condition R4 is a Mohs hardness level 7 gem mineral hardness tester with a load of 750 g. [Figure 7] Figure 7 shows the scratch resistance graphs obtained by conducting scratch resistance tests on the tempered crystallized glass and sapphire glass of Examples S2 and S8 under test condition R5. Here, test condition R5 is a gem mineral hardness tester with a Mohs hardness level of 8 and a load of 750 g, where (g) corresponds to the tempered crystallized glass of Example S2, (h) corresponds to the tempered crystallized glass of Example S8, and (i) corresponds to sapphire glass. [Figure 8] Figure 8 shows the scratch resistance test results for the tempered crystallized glasses of Comparative Examples D1 and D2 under test condition R4, where test condition R4 is a gem mineral hardness tester with a Mohs hardness level of 7 and a load of 750 g, (j) corresponds to the tempered crystallized glass of Comparative Example D1, and (k) corresponds to the tempered crystallized glass of Comparative Example D2. [Figure 9]Figure 9 is a scratch damage effect diagram obtained by conducting a scratch damage test on the chemically strengthened crystallized glass of Comparative Example D6 under test condition R3, where test condition R3 was a gem mineral hardness tester with a Mohs hardness level of 6 and a load of 750 g, (l) corresponds to the pattern that appears on the head of the scratch on the chemically strengthened crystallized glass of Comparative Example D6, and (m) corresponds to the fish scale pattern in the center of the scratch on the chemically strengthened crystallized glass of Comparative Example D6. [Figure 10] FIG. 10 is a scratch resistance diagram of the tempered crystallized glass of Comparative Example D6, obtained by performing a scratch resistance test under test condition R3, where test condition R3 is a Mohs hardness level 6 gem mineral hardness tester with a load of 750 g. [Figure 11] FIG. 11 is an SEM image of the chemically strengthened crystallized glass of Example S3 of the present invention. [Figure 12] FIG. 12 is a graph showing the relationship between the concentration functions of Na2O and K2O measured by a thickness cross-sectional electron probe in the strengthened crystallized glass of Example S1. [Figure 13] FIG. 13 is a graph showing the relationship between the concentration functions of Na2O and K2O measured by a thickness cross-sectional electron probe in the strengthened crystallized glass of Example S2. [Figure 14] FIG. 14 is a graph showing the relationship between the concentration functions of Na2O and K2O measured by a thickness cross-sectional electron probe in the strengthened crystallized glass of Example D2. DETAILED DESCRIPTION OF THE INVENTION

[0038] First, the following describes the relevant special names and relevant measurement methods according to the present invention.

[0039] Base glass: Glass that has not been subjected to nucleation, crystallization, or strengthening processes.

[0040] Glass-ceramics: Also known as glass-ceramics, these are solid composite materials that contain both a glass phase and a crystalline phase (also called a microcrystalline phase, crystallized phase, or crystalline phase) prepared by specifically controlling the crystallization of a substrate glass.

[0041] Strengthened glass-ceramics: A solid composite material obtained by chemically strengthening glass-ceramics. During high-temperature chemical strengthening, alkali metal ions with small ionic radii (e.g., sodium ions and lithium ions) in the glass-ceramics are replaced with alkali metal ions with large ionic radii (e.g., potassium ions and sodium ions) in the salt bath or molten salt, resulting in a difference in volume due to ion exchange, which creates compressive stress on the surface of the glass-ceramics.

[0042] Residual glass phase: The amorphous phase in a glass-ceramic system, which includes both the crystalline phase and the residual glass phase in the glass-ceramic system.

[0043] Dissociation energy: Generally, this refers to the energy required for dissociation. It is the minimum amount of energy absorbed from the outside when breaking down a molecule in its lowest energy state into completely independent atoms, and is also the energy required to break a bond.

[0044] Nucleation: The growth of small crystal nuclei in nucleating substances in glass by heat treatment.

[0045] Crystallization: Heat treatment causes crystals to grow from nuclei.

[0046] Crystalline Phase: The crystalline phase is the microscopic structure of a crystal and is determined by the conformation of the polymer chains and their arrangement in the crystal.

[0047] Theoretical Crystallinity: The theoretical maximum degree of crystallinity for a glass-ceramic formulation.

[0048] Average grain size: Using an X-ray diffractometer, measure the crystallized glass sample, and calculate the data obtained from XRD measurement according to the Scherrer formula D = Kλ / (β cos θ), to obtain the average grain size, where λ is the X-ray wavelength, i.e., 0.154056 nm, β is the half-width of the diffraction peak, K = 0.89, and θ is the Bragg diffraction angle. For example, the RAW file output from the XRD instrument is curve-fitted using Jade software, and Jade outputs a fitting report. Based on the angle 2θ value corresponding to each diffraction peak in the fitting report and the Peak FWHM value (diffraction peak half-width), the Peak FWHM value is converted to radians, i.e., β = (FWHM / 180 × 3.14), and the grain size of each diffraction peak is calculated according to the Scherrer formula D = Kλ / (β cos θ), and then averaged to obtain the average grain size. The X-ray diffraction apparatus used in the present invention is an XRD-6100 manufactured by Shimadzu Corporation, the target material is copper, the diffraction angle range used in the measurement is 2θ = 10 to 80°, the scanning speed is 0.2° / min, the operating voltage is 40 kV, and the operating current is 30 mA.

[0049] Crystal content: The percentage of the total mass of crystals in the total mass of the glass-ceramic, also known as the actual crystallinity. Note that crystalline phases and crystal grains both refer to the crystals precipitated in the glass-ceramic, but are described differently.

[0050] Transmittance: The ratio of the radiant energy transmitted through an object to the total radiant energy incident on the object during the process of an incident light beam exiting the irradiated surface or medium from the incident surface to another surface. In the examples and comparative examples of the present invention, the transmittance of crystallized glass at a wavelength of 550 nm refers to the average value of the transmittance measured at a wavelength of 550 nm for multiple glass samples from the same batch. Measurements are performed on at least five crystallized glass samples from each batch.

[0051] Refractive index: the ratio of the propagation speed of light in a vacuum to the propagation speed of light in the medium. In the present invention, the refractive index of the crystallized glass piece is measured using a monocular Abbe refractometer (WYA-2WAJ, BELL Analytical Instruments Co., Ltd.) with a wavelength set to 589 nm.

[0052] b-value: The yellow / blue value of a material. In the examples of the present invention, the b-value is the b-value of transmitted light. A positive b-value indicates a strong blue tint of the material. This is measured using a spectrophotometer CM-3600A manufactured by Konica Minolta Japan.

[0053] Vickers hardness: A standard for expressing the hardness of materials proposed by Robert L. Smith and George E. Sandland of the UK at Vickers Ltd in 1921.

[0054] Sample thickness measurement: Measured using a micrometer. Although the degree of ion exchange varies in a gradient from the surface to the center in the thickness direction, the total Na-K and / or Li-Na exchange amount generally does not exceed 1% of the total mass of the sample, and the difference in ionic radius is at the pm level. Therefore, the expansion effect in the thickness direction is extremely slight, and it can be approximately assumed that the thickness does not change. In other words, the change in thickness of the crystallized glass piece before and after chemical strengthening is so small that it can be ignored.

[0055] Optical property measurement: The haze, b value, and transmittance of the crystallized glass are measured using specialized measuring equipment in accordance with GB / T 7962.12-2010, "Measuring Methods for Colorless Optical Glasses, Part 12: Spectral Transmittance." In this study, the haze and b value are measured using a spectrophotometer CM-3600A manufactured by Konica Minolta Japan. In this study, the transmittance and its curve are measured using a UV-2000 UV-Visible Spectrophotometer manufactured by Shimadzu Corporation.

[0056] Crystalline content measurement method: An X-ray diffractometer is used to measure the crystallized glass sample, and the XRD measurement results are obtained. The X-ray diffractometer measurement result file (RAW format) is imported into Rietveld X-ray diffraction data refinement software (e.g., Gsas, Fullprof, Maud), fitting and calculation are performed, and the ratio of the fitted crystalline phase peak area to the fitted total peak area is the crystalline content. The X-ray diffractometer used in this invention is a Shimadzu XRD-6100, the target material is copper, the diffraction angle range used in the measurement is 2θ = 10 ~ 80 °, the scanning speed is 0.2 ° / min, the operating voltage is 40 kV, and the operating current is 30 mA.

[0057] Density measurement: The density of the crystallized glass sample was measured according to the principle of "Archimedes' method", and the measuring instrument was ALFA MIRAGE electronic hydrometer SD-200L.

[0058] Measurement of Young's modulus: The measuring instrument is a UMS-100 ultrasonic material characterization system.

[0059] Differential scanning calorimetry (DSC) measurements were performed using a Mettler-Toledo TGA / DSC3+ thermogravimetric and simultaneous thermal analyzer. The sample was powdered and passed through a 200-mesh sieve. The measurement conditions were room temperature to 1100°C, with a heating rate of 10°C / min. The standard material used for the measurements was α-Al2O3 powder. The temperature of the instrument's installation environment was 24°C, and the air humidity was 40%.

[0060] Single-rod static pressure: Place the tempered glass-ceramic on the bottom ring of the tensile testing machine (LT-850A), start the measurement software, set the pressure rod (rod diameter 8 mm, indenter arc radius 10 mm) to a speed of 50 mm / min, and click Start Measurement. The pressure rod will apply force to the center of the glass-ceramic piece being measured at the set speed until the glass-ceramic cracks and shatters. The measurement software automatically reads the force (N) at which the glass shatters as the measurement result. Ten glass-ceramic samples in the same condition are measured, and the average of the measurement results is taken as the single-rod static pressure strength of the glass-ceramic.

[0061] Scratch test: The measuring instrument is an automatic pencil hardness tester (ZIPANG MOTOR). Measurement method: The scratch test is performed by fixing the Mohs hardness tester at a 45° angle, contacting its tip with the surface of the glass sample, and moving the glass mounting table at a speed of 60 mm / min under a predetermined load. The wiped glass sample to be measured is placed on the glass mounting table, and the predetermined load is set by placing a weight of the corresponding weight on it. The gem mineral hardness tester numbers 6 to 8 used in this invention correspond to Mohs hardness levels 6 to 8, respectively. After the scratch test is completed, the scratched glass sample is placed under a 400x microscope, and the condition of the scratches is observed and photographed for recording. The hardness of the glass sample to be tested is determined based on the presence and condition of scratches. The presence of scratches indicates that the hardness of the glass sample to be tested is lower than that measured by the hardness tester, while the absence of scratches indicates that the hardness of the glass sample to be tested is higher than that measured by the hardness tester.

[0062] Electron probe measurement: The measuring device is a Shimadzu EPMA-1720 electron probe. Component analysis of a microscopic area is performed using characteristic X-rays generated by applying an electron beam to the sample. In this invention, the depth of the compressive stress layer formed by potassium-sodium exchange in chemically strengthened glass-ceramics is measured using the electron probe.

[0063] Measurement of surface K2O concentration: The surface K2O concentration is equal to the mass of K2O divided by the total mass of oxides, where the total mass of oxides includes oxides that can be accurately measured by XRF, such as SiO2, Al2O3, P2O5, ZrO2, Na2O, and K2O, but does not include oxides that cannot be accurately measured by XRF, such as Li2O and B2O3. The surface K2O concentration of the strengthened crystallized glass of the present invention was measured using an X-ray fluorescence spectrometer (XRF) using a Thermo Scientific ARL® PERFORM'X. The target material was Rh (rhodium), the tube voltage was 40 kW, the current was 60 mA, the collimator was 0.15, the crystal was LiF200, the detector was FPC, the measurement range was a 29 mm circle, and the analysis software was UniQuant, for standardless analysis. Although standardless measurement was used during XRF measurement, the mass of elements with atomic numbers below 6 and their oxides in the glass was not measured. That is, in the present invention, when the K2O concentration obtained by XRF measurement is calculated, the total mass of oxides does not include the mass of elements in the glass with atomic numbers of 6 or less and their oxides.

[0064] Vickers hardness (HV) measurement: Chemically strengthened tempered glass-ceramic pieces were cut into small pieces measuring 50 mm long x 50 mm wide x 0.7 mm thick. Glass samples with clean surfaces and no visible scratches, dents, cracks, or other damage were selected as test specimens, and the Vickers hardness of the tempered glass-ceramic was measured using a Vickers hardness tester. Measurement conditions: load 300 gf, load time 10 s, indentation validity in accordance with GB / T 16534. Three different locations on the surface of the same sample were selected for measurement, and the average of the three measurements was used as the final measurement result. The Vickers hardness tester used in this invention was a digital low-load Vickers hardness tester (Beijing Science and Technology Co., Ltd., VTD405).

[0065] 2. Highly scratch-resistant tempered glass-ceramics and chemically tempered glass-ceramics

[0066] As a result of examining the components of conventional crystallized glass, the present inventors have found that zinc-magnesium spinel crystals have high Young's modulus and shear modulus, making them a preferred crystalline phase for improving the scratch resistance of glass. However, the scratch resistance of conventional transparent spinel crystallized glass is not sufficient to meet the application requirements for protective covers for high-end products, and further improvement is required.

[0067] The present invention provides a strengthened crystallized glass having high scratch resistance, the strengthened crystallized glass including a compressive stress layer and a tensile stress layer, the main crystalline phase of the strengthened crystallized glass being (Zn,Mg)Al2O4. The strengthened crystallized glass includes Na2O. The surface K2O concentration of the strengthened crystallized glass is 7.00 wt% or more, optionally 7.00 to 15.00 wt%. In the strengthened crystallized glass, the depth along the thickness direction of the glass from any surface of the strengthened crystallized glass to a position near the surface and having a potassium (K) concentration similar to that of the center of the strengthened crystallized glass is 0.07t or more, optionally 0.07t to 0.10t, where t is the thickness of the strengthened crystallized glass.

[0068] The present invention has been developed through extensive research into the intrinsic strength of glass-ceramics and the stress characteristics obtained in tempered glass, and has achieved specific stress characteristics by tempering a specific system of chemically strengthened glass-ceramics with high intrinsic strength, ultimately obtaining tempered glass-ceramics with excellent scratch resistance. In the present invention, the high surface K2O concentration and high potassium-sodium exchange depth of the tempered glass-ceramics endow the tempered glass-ceramics with excellent surface stress characteristics and deep layer stress characteristics, which, when combined with the inherently high intrinsic strength of chemically strengthened glass-ceramics, ultimately significantly improve the mechanical properties of the tempered glass-ceramics of the present invention, enabling the tempered glass-ceramics to achieve scratch resistance comparable to that of sapphire glass.

[0069] After the chemical strengthening ion exchange process, the composition on the surface of the glass-ceramics may be different from that of the freshly formed glass-ceramics (i.e., the glass-ceramics for chemical strengthening that has not been ion-exchanged). That is, the composition of the compressive stress layer formed by ion exchange on the surface of the strengthened glass-ceramics may be different from that of the glass-ceramics for chemical strengthening. This is because, during the ion exchange, one type of alkali metal ion (e.g., Li) in the freshly formed glass-ceramics is present. + or Na + ) is a large alkali metal ion (e.g., Na + or K + ) is substituted, for example, Na in glass + In the enrichment salt bath, + and was replaced by K + and / or Li in the glass + Na in the enriched salt bath + is exchanged with Na + However, in the embodiment, the composition of the glass-ceramics at or near the center of the depth of the glass product still has the composition of the newly formed glass-ceramics. That is, the composition of the tensile stress layer in the strengthened glass-ceramics that has not undergone ion exchange still has the composition of the glass-ceramics for chemical strengthening. As a result, the potassium concentration at the center of the strengthened glass-ceramics still has the potassium concentration of the composition of the glass-ceramics for chemical strengthening.

[0070] While the chemical strengthening process involves the exchange of alkali metal ions, the main crystalline phase of the chemically strengthened glass-ceramics of the present invention is (Zn,Mg)Al2O4, and the secondary crystalline phase contains one or more selected from tetragonal ZrO2, Zn2SiO4, and Mg2SiO4. Since these phases do not contain alkali metals and are not involved in ion exchange, the composition of the crystalline phases remains essentially unchanged before and after strengthening. Therefore, the main crystalline phase of the strengthened glass-ceramics obtained by chemical strengthening remains (Zn,Mg)Al2O4, and the secondary crystalline phase contains one or more selected from tetragonal ZrO2, Zn2SiO4, and Mg2SiO4.

[0071] In some embodiments of the present invention, the surface K2O concentration of the strengthened glass-ceramics is 7.00 wt% or more, and optionally 7.00 to 15.00 wt%. In some embodiments, the surface K2O concentration is 7.00 wt% to 8.00 wt%, 7.00 wt% to 9.00 wt%, 7.00 wt% to 10.00 wt%, 7.00 wt% to 11.00 wt%, 7.00 wt% to 12.00 wt%, 7.00 wt% to 13.00 wt%, 7.00 wt% to 14.00 wt%, 7.00 wt% to 15.00 wt%, 8.00 wt% to 9.00 wt%, 7.00 wt% to 10.00 wt%, 7.00 wt% to 11.00 wt%, 7.00 wt% to 12.00 wt%, 7.00 wt% to 13.00 wt%, 7.00 wt% to 14.00 wt%, 7.00 wt% to 15.00 wt%, 8.00 wt% to 8.00 wt%, 7 ... 0.00wt% to 10.00wt%, 9.00wt% to 14.00wt%, 9.00wt% to 13.00wt%, 7.00wt%, 8.00wt%, 9.00wt%, 10.00wt%, 11.00wt%, 12.00wt%, 13.00wt%, 14.00wt%, 15.00wt%, etc., and all ranges and subranges therebetween.

[0072] In the strengthened crystallized glass, the depth along the thickness of the glass from any surface of the strengthened crystallized glass to a position near the surface and having a potassium (K) concentration similar to that of the center of the strengthened crystallized glass is 0.07t or more, and optionally 0.07t to 0.10t, where t is the thickness of the strengthened crystallized glass. In some embodiments, the depth along the thickness of the glass from any surface of the strengthened crystallized glass to a position near the surface and having a potassium (K) concentration similar to that of the center of the strengthened crystallized glass may be 0.07t to 0.08t, 0.07t to 0.09t, 0.08t to 0.09t, 0.08t to 0.10t, 0.09t to 0.10t, 0.07t, 0.08t, 0.09t, 0.10t, etc., and all ranges and subranges therebetween. For example, when the thickness of the strengthened crystallized glass is 0.7 mm, the depth along the thickness direction of the glass from any surface of the strengthened crystallized glass to a position near the surface and having the same potassium (K) concentration as the center of the strengthened crystallized glass is 49.00 μm or more, optionally 49.00 μm to 70.00 μm, further 49.00 μm to 55.00 μm, 49.00 μm to 60.00 μm. μm, 49.00 μm to 55.00 μm, 50.00 μm to 60.00 μm, 50.00 μm to 70.00 μm, 60.00 μm to 70.00 μm, 55.00 μm to 70.00 μm, 65.00 μm to 70.00 μm, 49.00 μm, 50.00 μm, 55.00 μm, 60.00 μm, 65.00 μm, 70.00 μm, etc., and all ranges and subranges therebetween. Note that, in embodiments, any of the above ranges can be combined with any other range. In the present invention, the greater the depth from any surface of the strengthened crystallized glass to a position near that surface that has a potassium (K) concentration similar to that of the center of the strengthened crystallized glass, the deeper the K ions in the salt bath penetrate into the crystallized glass when chemical strengthening is performed, and therefore the deeper the compressive stress layer formed in the strengthened crystallized glass by potassium-sodium exchange (referring to the exchange between potassium ions in the salt bath and Na ions in the crystallized glass) is.

[0073] In some embodiments of the present invention, when the thickness is 0.7 mm, the single-rod static pressure strength of the strengthened glass-ceramics is 450 N or more, optionally 450 to 650 N. In some embodiments, the single-rod static pressure strength of the strengthened glass-ceramics may be 450 N to 500 N, 450 N to 600 N, 450 N to 490 N, 480 N to 570 N, 470 N to 610 N, 520 N to 650 N, 540 N to 630 N, 450 N, 500 N, 550 N, 600 N, 650 N, etc., and all ranges and subranges therebetween. Note that in some embodiments, any of the above ranges can be combined with any other range.

[0074] In some embodiments of the present invention, the Young's modulus of the chemically strengthened glass-ceramics is 110.00 GPa or more, and optionally 110.00 GPa to 140.00 GPa. In addition, in the present invention, after chemical strengthening treatment, the Young's modulus of the glass-ceramics increases appropriately, so the Young's modulus of the strengthened glass-ceramics is 110 GPa or more, and optionally 110 to 140 GPa. In some embodiments, the Young's modulus of the strengthened glass-ceramics may be 110 GPa to 140 GPa, 110 GPa to 115 GPa, 110 GPa to 120 GPa, 110 GPa to 125 GPa, 115 GPa to 128 GPa, 121 GPa to 129 GPa, 114 GPa to 127 GPa, 113 GPa to 129 GPa, 126 GPa to 130 GPa, 110 GPa, 115 GPa, 118 GPa, 120 GPa, 123 GPa, 126 GPa, 130 GPa, 135 GPa, 140 GPa, etc., and all ranges and subranges therebetween. Note that, in embodiments, any of the above ranges may be combined with any other range.

[0075] In some embodiments of the present invention, the Vickers hardness of the strengthened glass-ceramics is 750 kgf / mm 2 or more, and selectively 750 to 900 kgf / mm 2 and more selectively 800 to 900 kgf / mm 2 In some embodiments, the Vickers hardness of the strengthened glass-ceramics is 750 kgf / mm2 ~810kgf / mm 2 , 800kgf / mm 2 ~820kgf / mm 2 , 810kgf / mm 2 ~850kgf / mm 2 , 840kgf / mm 2 ~880kgf / mm 2 , 860kgf / mm 2 ~890kgf / mm 2 , 870kgf / mm 2 ~900kgf / mm 2 , 850kgf / mm 2 ~880kgf / mm 2 , 830kgf / mm 2 ~845kgf / mm 2 , 860kgf / mm 2 ~875kgf / mm 2 , 750kgf / mm 2 , 800kgf / mm 2 , 820kgf / mm 2 , 845kgf / mm 2 , 860kgf / mm 2 , 870kgf / mm 2 , 885kgf / mm 2 , 890kgf / mm 2 and all ranges and subranges therebetween, as defined above. Note that, in practice, any of the above ranges can be combined with any other range.

[0076] In some embodiments of the present invention, the average grain size of the chemically strengthened glass-ceramics is 15.00 nm or less, optionally 1.00 to 10.00 nm, and more preferably 4.50 to 8.00 nm. In the present invention, the chemical strengthening process does not significantly change the grain size, so the average grain size of the strengthened glass-ceramics is 15.00 nm or less. In some embodiments, the average grain size is 1.00 nm to 4.00 nm, 1.00 nm to 9.00 nm, 1.00 nm to 13.00 nm, 3.00 nm to 5.00 nm, 6.00 nm to 10.00 nm, 7.00 nm to 9.00 nm, 5.00 nm to 6.00 nm, 5.00 nm to 7.00 nm, 5.00 nm to 8.00 nm, 6.00 nm to 8.00 nm, 8.00 nm to 10.00 nm, or 7.00 nm to 12.00 nm. 00 nm, 1.00 nm, 2.00 nm, 3.00 nm, 4.00 nm, 5.00 nm, 6.00 nm, 7.00 nm, 8.00 nm, 9.00 nm, 10.00 nm, 11.00 nm, 12.00 nm, 13.00 nm, 14.00 nm, 15.00 nm, etc., and all ranges and subranges therebetween, optionally from 1.00 to 10.00 nm, and more optionally from 4.50 to 8.00 nm, etc. In the preferred embodiment, any of the above ranges can be combined with any other range.

[0077] In some embodiments of the present invention, the crystalline content of the chemically strengthened glass-ceramics is 20.00 to 50.00 wt%, optionally 25.00 to 50.00 wt%, and even more optionally 25.00 to 45.00 wt%. The primary crystalline phase of the chemically strengthened glass-ceramics of the present invention is (Zn,Mg)Al2O4, and the secondary crystalline phase contains one or more selected from tetragonal ZrO2, Zn2SiO4, and Mg2SiO4. Since it does not contain alkali metal ions, it is not involved in ion exchange. Therefore, the crystalline content of the strengthened glass-ceramics is maintained at 20.00 to 50.00 wt%, optionally 25.00 to 50.00 wt%, and even more optionally 25.00 to 45.00 wt%. In some embodiments, the crystalline content of the strengthened glass-ceramics may be 20.00 wt%, 25.00 wt%, 28.00 wt%, 30.00 wt%, 33.00 wt%, 35.00 wt%, 38.00 wt%, 40.00 wt%, 43.00 wt%, 45.00 wt%, 48.00 wt%, 50.00 wt%, etc., and all ranges and subranges therebetween. Note that, in embodiments, any of the above ranges may be combined with any other range.

[0078] In some embodiments of the present invention, when the thickness is 0.7 mm, the transmittance of the chemically strengthened glass-ceramics for light with a wavelength of 550 nm is 85.00% or more, and optionally 89.00% or more. Furthermore, in the present invention, the transmittance of the glass-ceramics remains essentially unchanged after chemical strengthening. Therefore, the strengthened glass-ceramics is transparent in the visible light range and still has essentially the same transmittance as the chemically strengthened glass-ceramics.

[0079] In some embodiments, when the thickness is 0.7 mm, the transmittance of the chemically strengthened crystallized glass for light with a wavelength of 550 nm may be 85.00% to 89.00%, 85.00% to 96.00%, 85.00% to 90.00%, 88.00% to 95.00%, 88.00% to 96.00%, 88.00% to 99.00%, 86.00%, 87.00%, 88.00%, 89.00%, 90.00%, 91.00%, 92.00%, 93.00%, 94.00%, 95.00%, 96.00%, etc., and all ranges and subranges therebetween. Note that in the embodiments, any of the above ranges can be combined with any other range.

[0080] In some embodiments of the present invention, a gemstone mineral hardness tester measuring 7 on the Mohs hardness scale is fixed at a 45° angle using an electric pencil hardness tester, and the surface of the strengthened crystallized glass is scratched with a load of 750 g. The scratched crystallized glass is observed under a microscope at 400x magnification, and no scratches are found on the surface of the strengthened crystallized glass.

[0081] After the chemical strengthening ion exchange process, the composition of the surface of the crystallized glass may be different from that of the freshly formed crystallized glass (i.e., the crystallized glass for chemical strengthening that has not been subjected to ion exchange). However, in an embodiment, the composition of the crystallized glass at or near the center of the depth of the glass product still has the composition of the freshly formed crystallized glass. That is, in the present invention, the composition of the tensile stress layer of the strengthened crystallized glass still has the composition of the crystallized glass for chemical strengthening.

[0082] In some embodiments of the present invention, the tensile stress layer of the strengthened glass-ceramics or the glass-ceramics for chemical strengthening contains, in terms of oxide mass percentage, 30.00%≦SiO2<35.00%, Al2O3: 30.00% to 40.00%, ZnO: 10.00% to 12.00%, MgO: 2.00% to 4.00%, ZrO2: 5.00% to 7.00%, Na2O: 2.00% to 9.00%, Li2O: 0 to 2.00%, and B2O3: 0 to 8.00%, and at the same time, the components of the tensile stress layer of the strengthened glass-ceramics or the glass-ceramics for chemical strengthening are: (1)X=((Na2O+B2O3) / ZrO2) / Al2O3, X≧2.00; (2)Y=ln[(Na2O+B2O3) / ZrO2], Y≧0; (3)Z=(SiO2+Al2O3-MgO-ZnO) / (Li2O+Na2O+B2O3), 4.00≦Z≦10.00; In the formulas (1) to (3), oxide represents the mass percentage of the oxide component; Meet the following.

[0083] Optionally, the tensile stress layer of the strengthened glass-ceramics or the components of the chemically strengthened glass-ceramics further comprise: (4)W=(0.8×(Al2O3-SiO2)+1.5×(ZnO-MgO)) / ZrO2, 0≦W≦3.00; In formula (4), oxide represents the mass percentage of the oxide component; Meet the following.

[0084] In some embodiments of the present invention, in the tensile stress layer of the strengthened crystallized glass or the crystallized glass for chemical strengthening, the mass percentage of SiO2 is 32.00% to 34.95%, and / or the mass percentage of Al2O3 is 32.00% to 38.00%, and / or ZnO is 10.00% to 11.48%, and / or MgO is 2.50% to 3.50%, and / or ZrO2 is 5.40% to 6.50%, and / or Na2O is 2.50% to 8.50%, and / or B2O3 is 2.50 to 8.00%.

[0085] In some embodiments of the present invention, the tensile stress layer of the strengthened glass-ceramics or the glass-ceramics for chemical strengthening further contains 0 to 3.00 wt % of BaO and / or 0 to 2.00 wt % of Y2O3.

[0086] In some embodiments of the present invention, the strengthened glass-ceramics or the chemically strengthened glass-ceramics is essentially free of TiO2 and P2O5.

[0087] The present invention optimizes the composition of chemically strengthened crystallized glass, adjusting the relationship between each oxide and the content of each oxide in the composition system. As a result of examining each oxide component of chemically strengthened crystallized glass, the present invention has found that there is a certain correlation between each oxide component, and this correlation affects the structure and performance of chemically strengthened crystallized glass, and is related to the scratch resistance of the crystallized glass required for the present invention, as well as other performances of the crystallized glass.

[0088] The inventors have investigated the dissociation energy of aluminum oxide, which is extremely high, G = 134 KJ cm -3Therefore, increasing the Al2O3 content in spinel glass-ceramics can increase the alumina saturation of the crystalline phase while improving the dissociation energy of the residual glass phase, which is beneficial for improving the intrinsic strength of the residual glass phase. Furthermore, the atomic density of glass increases with increasing aluminum coordination number, and increasing the Al2O3 content has been found to be beneficial for improving the density of glass-ceramics. However, using aluminum oxide instead of silicon oxide makes the glass more difficult to melt and form, necessitating the addition of fluxing components such as alkali metal oxides, alkaline earth metal oxides, and boron oxide. Alkali metal oxides provide alkali metal ions to strengthen glass-ceramics through chemical strengthening, and also provide free oxygen to affect the glass network structure. While boron oxide has a good fluxing effect, its coordination structure is affected by the free oxygen provided by the alkali metal and / or alkaline earth metal. Too much boron oxide reduces the proportion of boron-oxygen tetrahedra and boron-oxygen triangles in the glass phase, transforming part of the glass phase from its original three-dimensional cage structure to a two-dimensional layered structure, weakening the glass network. At the same time, too much boron oxide adversely affects the optical properties of the glass. Zinc oxide, magnesium oxide, and aluminum oxide are components of the desired primary crystalline phase ((Zn,Mg)Al2O4), with ZrO2 acting as a nucleating agent. The relationship between the contents of these oxides not only determines the content of the primary crystalline phase in chemically strengthened glass-ceramics, but also the structure and inherent strength of the residual glass phase in chemically strengthened glass-ceramics.

[0089] Based on this, the present inventors have unintentionally discovered that by adjusting the glass-ceramic formulation based on the dosage range of each oxide, it is possible to reduce the difficulty of melting the substrate glass and the heat treatment temperature when using the substrate glass to produce the desired chemically strengthened glass-ceramic. The glass formulation provided by the present invention can be mass-produced to obtain the substrate glass using conventional methods such as continuous melting and rolling, ensuring the formability of the glass. Furthermore, when the substrate glass corresponding to the glass formulation of the present invention is heat-treated at a temperature of 800°C or less, it is possible to obtain transparent chemically strengthened glass-ceramic with excellent optical properties, with a zinc-magnesium spinel solid solution as the main crystalline phase. Compared to the prior art, the formulation provided by the present invention significantly reduces the heat treatment temperature, further easing the difficulty of mass-producing spinel glass-ceramic and improving the mass productivity of spinel glass-ceramic. Meanwhile, the synergistic effect of the specific oxide components allows the desired main crystalline phase (Zn,Mg)Al2O4 to be obtained and improving the intrinsic strength of the residual glass phase in the chemically strengthened glass-ceramic. By combining the main crystalline phase (Zn,Mg)Al2O4, which has a high Young's modulus and shear modulus, with the residual glass phase, which has high intrinsic strength, the resulting chemically strengthened glass-ceramics has high intrinsic strength and superior scratch resistance to conventional spinel-based glass-ceramics. The scratch resistance of the tempered glass-ceramics obtained by strengthening the chemically strengthened glass-ceramics of the present invention is comparable to that of sapphire glass, and can meet the requirements for cover glass in high-end electronic products.

[0090] SiO2 is a glass network-forming oxide and is an essential component for forming the glass network structure. Appropriately increasing the SiO2 content can increase the stability and mechanical strength of the glass, but excessive SiO2 increases the viscosity of the substrate glass, making it more difficult to melt the glass and reducing the formability of the substrate glass. In the present invention, the mass percentage of SiO2 is 30.00% to 35.00%, which is advantageous for improving the stability, formability, and mechanical strength performance of the glass in a balanced manner. In some embodiments, the SiO2 content can be 30.00%-31.00%, 30.00%-32.00%, 30.00%-33.00%, 32.00%-34.95%, 31.00%-34.95%, 31.00%-34.00%, 30.00%, 30.50%, 31.00%, 31.50%, 32.00%, 32.50%, 33.00%, 33.50%, 34.00%, 34.50%, 34.95%, etc., and all ranges and subranges therebetween. Note that any of the above ranges can be combined with any other range in the present embodiment.

[0091] Al2O3 is an intermediate oxide during glass formation and can improve the chemical stability of glass. Al2O3 is one of the components that form the zinc-magnesium spinel crystalline phase after crystallization of the substrate glass and directly affects the content of the main crystalline phase (Zn,Mg)Al2O4. At the same time, [AlO4] has a larger volume than [SiO4], providing more space for ion exchange and promoting the progress of chemical strengthening. Furthermore, Al2O3 has a significant impact on the intrinsic strength of the residual glass phase due to its extremely high dissociation energy. However, excessive Al2O3 increases the viscosity of the substrate glass, thereby reducing the formability of the substrate glass. In the present invention, the mass percentage of Al2O3 is 30.00 to 40.00%. In some embodiments, the Al2O3 content is between 30.00% and 31.00%, between 30.00% and 32.00%, between 30.00% and 33.00%, between 32.00% and 35.00%, between 31.00% and 35.00%, between 31.00% and 34.00%, between 33.00% and 36.00%, between 32.00% and 38.00%, between 30.00% and 35.00%. 00%, 34.00%-39.00%, 35.00%-40.00%, 36.00%-40.00%, 30.00%, 31.00%, 32.00%, 33.00%, 34.00%, 35.00%, 37.00%, 38.00%, 39.00%, 40.00%, etc., and all ranges and subranges therebetween. Note that in embodiments, any of the above ranges can be combined with any other range.

[0092] ZnO provides the zinc necessary to form a zinc-magnesium spinel crystalline phase after crystallization of the substrate glass. ZnO can reduce the thermal expansion coefficient of the glass and increase its chemical stability, thermal stability, and refractive index. In the present invention, the mass percentage of ZnO is 10% to 12%. In some embodiments, the ZnO content can be 10.00% to 11.00%, 10.00% to 11.40%, 11.00% to 12.00%, 11.50% to 12.00%, 10.00%, 10.50%, 11.00%, 11.48%, 11.50%, 12.00%, etc., and all ranges and subranges therebetween. Note that, in embodiments, any of the above ranges can be combined with any other range.

[0093] MgO provides the magnesium necessary for the substrate glass to crystallize and form a zinc-magnesium spinel crystalline phase. MgO can slow the hardening rate of the glass and improve its forming performance. Furthermore, MgO can reduce the crystallization tendency and crystallization rate, increase the high-temperature viscosity of the glass, and improve the chemical stability and mechanical strength of the glass. In the present invention, the mass percentage of MgO is 2% to 4%. In some embodiments, the MgO content may be 2.00% to 3.00%, 3.00% to 4.00%, 2.00% to 2.50%, 2.50% to 3.00%, 2.50% to 4.00%, 3.50% to 4.00%, 2.00%, 2.50%, 3.00%, 3.50%, 4.00%, etc., and all ranges and subranges therebetween. Note that, in the present invention, any of the above ranges can be combined with any other range.

[0094] ZrO2 has a high cationic charge and a strong electric field strength, which provides a significant accumulation effect in the glass structure and functions as a nucleating agent in the substrate glass. At the same time, ZrO2 can further increase the strength and toughness of the glass-ceramics and improve their corrosion resistance against acids and alkalis. In addition, ZrO2 is the second crystalline phase in the glass-ceramics of this system. However, due to the extreme difficulty of melting ZrO2, excessive ZrO2 cannot be uniformly dispersed in the substrate glass, which can easily result in melting defects such as unmelted material and precipitation. In the present invention, the mass percentage of ZrO2 is 5% to 7%. In some embodiments, the ZrO content can be 5.00%-6.00%, 5.50%-6.00%, 5.50%-7.00%, 6.00%-7.00%, 6.50%-7.00%, 5.00%, 5.40%, 5.50%, 6.00%, 6.50%, 7.00%, etc., and all ranges and subranges therebetween. Note that any of the above ranges can be combined with any other range in the present embodiment.

[0095] The tensile stress layer of the strengthened glass-ceramics or the chemically strengthened glass-ceramics of the present invention contains one or more alkali metal oxides, such as Li2O and Na2O, which promote chemical strengthening of the glass-ceramics through the ion exchange process and improve the mechanical strength properties of the glass-ceramics. At the same time, alkali metal oxides act as network modifiers during glass formation, providing free oxygen, which destroys the glass network structure and further affects the intrinsic strength of the glass. However, destroying the glass network structure is beneficial for reducing the high-temperature viscosity of the glass and facilitating the melting and fining of the glass liquid.

[0096] To balance various influences and ensure that the glass-ceramics meet the desired performance, the mass percentage of Na2O in the present invention is 2.00% to 9.00%. + is an ion exchange component necessary for chemical strengthening processes, and K has a large ionic radius in the molten salt bath. + and Na, which has a small ionic radius in glass-ceramics. +The exchange reaction between NaO and NaO generates surface compressive stress on the surface of the crystallized glass, further improving the strength and scratch resistance of the crystallized glass. In some embodiments, the NaO content may be 2.00% to 3.00%, 2.00% to 5.00%, 2.00% to 8.00%, 2.50% to 8.50%, 3.00% to 6.00%, 4.00% to 9.00%, 2.00% to 7.00%, 5.00% to 8.00%, 6.00% to 9.00%, 2.00%, 2.50%, 3.00%, 4.00%, 5.00%, 6.00%, 7.00%, 8.00%, 8.50%, 9.00%, etc., and all ranges and subranges therebetween. Note that, in the embodiments, any of the above ranges may be combined with any other range.

[0097] In the present invention, the mass percentage of Li2O is 0.00% to 2.00%. + and Li with a small ionic radius in the glass-ceramic + The exchange reaction between LiO and LiO forms deep stress in the crystallized glass, improving the strength and scratch resistance of the crystallized glass, as well as improving the impact resistance of the crystallized glass. In some embodiments, the LiO content may be 0.00-1.00%, 0.00-1.50%, 1.00-1.50%, 1.00-2.00%, 1.50-2.00%, 0.00%, 1.00%, 1.50%, 2.00%, etc., and all ranges and subranges therebetween. Note that, in the embodiments, any of the above ranges may be combined with any other range.

[0098] B2O3 functions as a flux in the glass-forming process. The free oxygen provided by alkali metals or alkaline earth metals influences the coordination of boron oxide, converting it from a boron-oxygen triangle to a boron-oxygen tetrahedron composed of bridging oxygen atoms. This transforms part of the glass phase from its original two-dimensional layer structure to a three-dimensional cage structure, reinforcing the glass network. B2O3 reduces the high-temperature viscosity of glass, accelerates glass fining, and reduces the crystallization ability of glass, effectively alleviating the difficulty of melting the base glass due to high aluminum oxide content. However, excessive B2O3 reduces the chemical stability and mechanical strength of glass, affecting its optical properties. In this invention, the mass percentage of B2O3 is 0-8%. In some embodiments, the B2O3 content may be 1.00% to 6.00%, 2.00% to 3.00%, 1.00% to 4.00%, 1.00% to 5.00%, 2.00% to 5.00%, 2.50% to 8.00%, 3.00% to 6.00%, 4.00% to 9.00%, 2.00% to 7.00%, 5.00% to 8.00%, 6.00% to 9.00%, 0.00%, 1.00%, 2.00%, 2.50%, 3.00%, 4.00%, 5.00%, 6.00%, 7.00%, 8.00%, etc., and all ranges and subranges therebetween. Note that any of the above ranges may be combined with any other range in the present embodiment.

[0099] In some embodiments, the value of X=((Na2O+B2O3) / ZrO2) / Al2O3 can be 2.00-3.00, 2.00-4.00, 2.00-5.00, 2.00-6.00, 2.00-7.00, 2.00-8.00, 2.00-9.00, 2.00-10.00, 3.00-4.00, 3.00-6.00, 3.00-9.00, 5.00-9.00, 6.00-9.00, 8.00-9.00, 2.00, 3.00, 4.00, 5.00, 6.00, 7.00, 8.00, 9.00, 10.00, etc., and all ranges and subranges therebetween. It should be noted that in embodiments, any of the above ranges can be combined with any other range.

[0100] In some embodiments, the value of Y = ln[(Na2O + B2O3) / ZrO2] can be 0.00-0.10, 0.00-1.00, 0.00-0.30, 0.00-0.60, 0.00-0.90, 0.00-0.40, 0.10-0.90, 0.30-0.70, 0.30-0.90, 0.20-0.50, 0.40-0.80, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.10, etc., and all ranges and subranges therebetween. Note that, in some embodiments, any of the above ranges can be combined with any other range.

[0101] In some embodiments, the value of Z=(SiO2+Al2O3-MgO-ZnO) / (Li2O+Na2O+B2O3) is 4.00-10.00, 4.00-5.00, 4.00-6.00, 4.00-7.00, 4.00-8.00, 4.00-9.00, 5.00-6.00, 5.00-7.00, 5.00-8.00, 5.00-9.00, 5.00-10.00, 6.00-7.00, 6.00-8.00, 6.00-9.00, 6.00-10 ... 0.00 to 7.00, 6.00 to 8.00, 6.00 to 9.00, 6.00 to 10.00, 7.00 to 8.00, 7.00 to 9.00, 7.00 to 10.00, 8.00 to 9.00, 8.00 to 10.00, 9.00 to 10.00, 4.00, 5.00, 6.00, 7.00, 8.00, 9.00, 10.00, etc., and all ranges and subranges therebetween. Note that, in embodiments, any of the above ranges can be combined with any other range.

[0102] In some embodiments of the present invention, the content of each oxide in the tensile stress layer of the strengthened glass-ceramics or the glass-ceramics for chemical strengthening is further (4)W=(0.8×(Al2O3-SiO2)+1.5×(ZnO-MgO)) / ZrO2, 0≦W≦3.00; Meet the requirements. In formula (4), "oxide" represents the mass percentage of the oxide component. By adjusting the content relationship of Al2O3, SiO2, ZnO, MgO, and ZrO2 to satisfy formula (4) while satisfying the range of each oxide and the requirements of formulas (1) to (3), it is possible to ensure that the transparent crystallized glass has excellent optical properties.

[0103] In some embodiments, the value of W = (0.8 × (Al2O3-SiO2) + 1.5 × (ZnO-MgO)) / ZrO2 can be 0.00-3.00, 0.00-1.00, 0.00-2.00, 1.00-2.00, 1.00-3.00, 2.00-3.00, 0.00-0.50, 0.00-1.50, 0.00-2.50, 1.00-1.50, 1.00-2.50, 2.00-2.50, 2.5.00-3.00, 0.00, 0.50, 1.00, 1.50, 2.00, 2.50, 3.00, etc., and all ranges and subranges therebetween. Note that any of the above ranges can be combined with any other range in the embodiments. In some embodiments of the present invention, the strengthened glass-ceramics is obtained by subjecting chemically strengthened glass-ceramics to a chemical strengthening treatment.

[0104] In some embodiments of the present invention, in the chemically strengthened glass-ceramics, the molar percentage of Al2O3 is greater than the sum of the molar percentages of MgO and ZnO in terms of oxides, and the theoretical crystallinity of the chemically strengthened glass-ceramics is at least 30.00 wt% or more, and optionally 30.00 wt% to 50.00 wt%. When the chemically strengthened glass-ceramics satisfies the theoretical crystallinity, the dissociation energy U per unit volume of the residual glass phase in the chemically strengthened glass-ceramics is 71.00 KJ cm. -3 or more, and selectively 71.00 KJ cm -3 ~134.00KJ·cm -3 is.

[0105] In some embodiments, the theoretical crystallinity of the chemically strengthened glass-ceramics may be 30.00 wt% to 40.00 wt%, 30.00 wt% to 60.00 wt%, 30.00 wt% to 70.00 wt%, 35.00 wt% to 45.00 wt%, 32.00 wt% to 48.00 wt%, 41.00 wt% to 49.00 wt%, 30.00 wt%, 35.00 wt%, 40.00 wt%, 45.00 wt%, 50.00 wt%, etc., and all ranges and subranges therebetween. Note that, in embodiments, any of the above ranges may be combined with any other range.

[0106] The theoretical crystallinity refers to the theoretically highest degree of crystallization when a base glass of a certain composition forms a specific crystalline phase. The theoretical crystallinity is the theoretically highest crystallinity, and is an important parameter for reliably obtaining crystallized glass having the required content of the target crystalline phase by performing preliminary basic control of the components of the main crystalline phase.

[0107] Because different types of glass-ceramics have different crystalline phases and degrees of crystallization, the methods for calculating their theoretical degrees of crystallization also differ. The theoretical degrees of crystallization for different glass-ceramics are determined by two components: a nucleating agent, such as ZrO2, and oxides that constitute specific crystalline phases. In the present invention, the primary crystalline phase of the chemically strengthened glass-ceramics is a zinc-magnesium spinel solid solution (Zn,Mg)Al2O4, and the secondary crystalline phase includes one or more selected from tetragonal ZrO2, Zn2SiO4, and Mg2SiO4. Therefore, the theoretical degree of crystallization for the glass-ceramics of the present invention is determined by two components: a nucleating agent, such as ZrO2, and oxides that constitute the crystalline phase: Al2O3, MgO, and ZnO.

[0108] The primary crystalline phase of the chemically strengthened glass-ceramics of the present invention is a zinc-magnesium spinel solid solution (Zn,Mg)Al2O4. The composition of the crystalline phase, expressed in terms of oxide molar percentage, is MgO / Al2O3 = 1 in MgAl2O4 and ZnO / Al2O3 = 1 in ZnAl2O4. To achieve high crystallinity and good strengthening effects, a portion of Al2O3 must remain in the residual glass phase after the complete formation of ZnAl2O4 and / or MgAl2O4. Because [AlO4] tetrahedra have a larger volume than [SiO4] tetrahedra, an appropriate amount of Al2O3 remains in the residual glass phase, providing more space for ion exchange during the chemical strengthening process and facilitating the progress of ion exchange. Furthermore, in the chemically strengthened glass-ceramics of the present invention, the molar percentage of Al2O3 is greater than the sum of the molar percentages of ZnO and MgO.

[0109] In some embodiments of the present invention, when the chemically strengthened glass-ceramics satisfy the theoretical crystallinity, the dissociation energy U per unit volume of the residual glass phase in the chemically strengthened glass-ceramics is 71.00 kJ cm -3 or more, and selectively 71.00 KJ cm -3 ~134.00kJ·cm -3 In some embodiments, the dissociation energy U per unit volume of the residual glass phase in the chemically strengthened glass-ceramics is 71.00 KJ cm -3 ~75.00KJ·cm -3 , 71.00 KJ·cm -3 ~80.00KJ·cm -3 , 71.00 KJ·cm -3 ~90.00KJ·cm -3 , 71.00 KJ·cm -3 ~100.00KJ·cm -3 , 71.00 KJ·cm -3 ~110.00KJ·cm -3 , 71.00 KJ·cm -3 ~120.00KJ·cm -3 , 71.00 KJ·cm -3 ~130.00KJ·cm -3 , 80.00KJ·cm -3~90.00KJ·cm -3 , 80.00KJ·cm -3 ~100.00KJ·cm -3 , 80.00KJ·cm -3 ~110.00KJ·cm -3 , 80.00KJ·cm -3 ~120.00KJ·cm -3 , 80.00KJ·cm -3 ~130.00KJ·cm -3 , 90.00KJ·cm -3 ~100.00KJ·cm -3 , 90.00KJ·cm -3 ~110.00KJ·cm -3 , 90.00KJ·cm -3 ~120.00KJ·cm -3 , 90.00KJ·cm -3 ~130.00KJ·cm -3 , 100.00KJ·cm -3 ~110.00KJ·cm -3 , 100.00KJ·cm -3 ~120.00KJ·cm -3 , 100.00KJ·cm -3 ~130.00KJ·cm -3 , 71.00 KJ·cm -3 , 80.00KJ·cm -3 , 90.00KJ·cm -3 , 100.00KJ·cm -3 , 110.00KJ·cm -3 , 120.00KJ·cm -3 , 134.00KJ·cm -3 etc., and all ranges and subranges between the above values. Note that, in practice, any of the above ranges can be combined with any other range.

[0110] The calculation of the dissociation energy U per unit volume of the residual glass phase will be explained below using the spinel-based crystallized glass of the present invention as an example.

[0111] In a glass formulation, assuming that the molar percentage of Al2O3 is a, the molar percentage of ZnO is b, and the molar percentage of MgO is c, then a>b+c. After zinc magnesium spinel crystallized glass having the theoretical crystallinity is produced from the base glass of this formulation, the dissociation energy U per unit volume of the residual glass phase is calculated as follows:

[0112] 1. Determine the mole percentages of ZnO, MgO, and Al2O3 in the residual glass phase.

[0113] This is the theoretical crystallinity, which is the degree of crystallinity reached when both ZnO and MgO participate in the precipitation of spinel. Therefore, all ZnO and MgO are present in the crystalline phase, meaning that the content of ZnO and MgO in the residual glass phase is 0. Since a > b + c, Al2O3 (a - (b + c)) remains in the residual glass phase, and the molar percentage of Al2O3 in the residual glass phase is calculated based on the content of each oxide in the residual glass phase.

[0114] 2. Determine the mole percentage of other oxides in the residual glass phase, excluding Al2O3, ZnO, and MgO.

[0115] (1) Nucleating agents generally precipitate before crystals. For example, the nucleating agent ZrO2 precipitates tiny crystal grains less than 1 nm in size during the nucleation step of glass-ceramics, and crystals grow on them. The nucleating agent TiO2 forms titanate crystal nuclei during the nucleation step of glass-ceramics, and under their guidance, crystals grow and cover them. Since the nucleating agent is generally located at the center of the crystals, theoretically, all of the nucleating agent is present within the crystalline phase, and the content of nucleating agent in the residual glass phase is zero.

[0116] (2) Except for the oxides constituting the crystalline phase and the nucleating agent, all other oxides in the base glass are theoretically present in the residual glass phase. The mole percentages of each oxide in the residual glass phase are calculated based on the content of each oxide in the residual glass phase.

[0117] 3. In the residual glass phase, the mole percentage of a certain oxide is defined as n i and the dissociation energy coefficient of the oxide is defined as U i Then, Makishima and Mackenzie define U i The values ​​can be obtained as shown in Table 1 below.

[0118] If the dissociation energy per unit volume of the residual glass phase is defined as U, then (Formula 1) U=ΣU i ×n i U i is the dissociation energy coefficient, with units of kJ cm -3 and n i is the mole percentage of a given oxide in the residual glass phase.

[0119] [Table 1]

[0120] In some embodiments of the present invention, the tensile stress layer of the strengthened glass-ceramics or the glass-ceramics for chemical strengthening further contains 0 to 3.00 wt% BaO and / or 0 to 2.00 wt% Y2O3.

[0121] As a high-field-strength cation, Y2O3 cooperates with Al2O3 to increase the atomic density of glass and also improve the hardness and Young's modulus of glass-ceramics. In the present invention, the mass percentage of Y2O3 is 0.00-2.00%. In some embodiments, the Y2O3 content may be 0.00-1.00%, 0.00-1.50%, 1.00%-1.50%, 1.00%-2.00%, 1.50%-2.00%, 0.00, 1.00%, 1.50%, 2.00%, etc., and all ranges and subranges therebetween. Note that, in the present invention, any of the above ranges may be combined with any other range.

[0122] BaO has a good fluxing effect, and this effect is particularly remarkable in this system. At the same time, BaO increases the refractive index of the glass phase, improving the optical properties of the glass. In the present invention, the mass percentage of BaO is 0 to 3.00%. In some embodiments, the BaO content can be 0.00-3.00, 0.00-1.00, 0.00-2.00, 1.00-2.00, 1.00-3.00, 2.00-3.00, 0.00-0.50, 0.00-1.50, 0.00-2.50, 1.00-1.50, 1.00-2.50, 2.00-2.50, 2.5.00-3.00, 0.00, 0.50, 1.00, 1.50, 2.00, 2.50, 3.00, etc., and all ranges and subranges therebetween. Note that, in certain embodiments, any of the above ranges can be combined with any other range.

[0123] In some embodiments of the present invention, the strengthened glass-ceramics or chemically strengthened glass-ceramics are essentially free of TiO2 and / or P2O5. Here, "essentially free" means that TiO2 and / or P2O5 are not actively added or blended into the glass, but may be present in small amounts as contaminants. The inventors have found that adding TiO2 to the formulation of the present invention results in undesirable color. To obtain the desired transparent glass-ceramics, TiO2 is selectively not included.

[0124] In the present invention, the chemically strengthened crystallized glass is produced by the following method.

[0125] Step 1: Obtaining a substrate glass, the substrate glass containing, in terms of mass percentage of oxides, the following components: 30.00%≦SiO2<35.00%, Al2O3: 30.00% to 40.00%, ZnO: 10.00% to 12.00%, MgO: 2.00% to 4.00%, ZrO2: 5.00% to 7.00%, Na2O: 2.00% to 9.00%, Li2O: 0 to 2.00%, and B2O3: 0 to 8.00%, wherein the content of each oxide in the substrate glass is further (1)X=((Na2O+B2O3) / ZrO2) / Al2O3, X≧2.00; (2)Y=ln[(Na2O+B2O3) / ZrO2], Y≧0; (3)Z=(SiO2+Al2O3-MgO-ZnO) / (Li2O+Na2O+B2O3), 4.00≦Z≦10.00; In the formulas (1) to (3), oxide represents the mass percentage of the oxide component; Meet the following.

[0126] Step 2: The substrate glass is heat-treated to obtain the chemically strengthened crystallized glass, and the heat treatment includes a nucleation treatment and / or a crystallization treatment. The heat treatment of the substrate glass may be a single-stage heat treatment, or a two-stage or multi-stage heat treatment. A single-stage heat treatment means that nucleation and the desired crystal growth are carried out directly in a single-stage heating process, without a separate nucleation treatment, and is understood to mean that the crystallization treatment is carried out directly. A two-stage heat treatment means that a two-stage heating process is carried out, first a nucleation treatment, i.e., a nucleation treatment, and then the desired crystal growth treatment, i.e., a crystallization treatment.

[0127] The substrate glass has the composition of the chemically strengthened crystallized glass in terms of mass percentage of oxides.

[0128] Optionally, in step 2, when nucleation treatment is performed, the nucleation temperature is 650 to 850°C, optionally 650 to 750°C, and the nucleation treatment time is 0 to 72 hours, optionally 0 to 24 hours.

[0129] Optionally, in step 2, when crystallization is performed, the crystallization temperature is 700 to 1000°C, optionally 700 to 850°C, and the crystallization time is 0.1 to 72 hours, optionally 0.1 to 24 hours.

[0130] Optionally, in step 2, when the heat treatment is performed, the temperature rise rate is controlled to 5 to 30° C. / min, and optionally to 5 to 15° C. / min.

[0131] Optionally, the content of each oxide in the substrate glass may further be: (4)W=(0.8×(Al2O3-SiO2)+1.5×(ZnO-MgO)) / ZrO2,0≦W≦3.00; In formula (4), oxide represents the mass percentage of the oxide component; Meet the following.

[0132] Optionally, the substrate glass further contains 0 to 3.00 wt% BaO and / or 0 to 2.00 wt% Y2O3.

[0133] Optionally, the substrate glass is essentially free of TiO2 and / or P2O5.

[0134] In the present invention, the method for forming the substrate glass includes, but is not limited to, a float process, an overflow process, a rolling process, or a casting process. For example, the components are uniformly mixed according to the formulation, melt-molded, and then cooled and annealed to obtain the substrate glass. For example, the substrate glass raw material is melted at a melting temperature of 1480°C to 1650°C, the molten glass liquid is molded, and after molding, the glass is cooled and annealed to obtain the substrate glass. Alternatively, the annealing temperature is 500°C to 650°C, and the annealing is performed for 12 to 48 hours.

[0135] In the present invention, when manufacturing a substrate glass, a fining agent may be added to the raw materials for manufacturing the substrate glass, and the fining agent may include one or more of NaCl, Na2SO4, SnO2, As2O3, Sb2O3, NaNO3, KNO3, CeO2, and (NH4)2SO4, and optionally include one or more of NaCl, SnO2, NaNO3, and CeO2, but is not limited thereto. Based on the total mass of the raw materials for the substrate glass, the amount of the fining agent added is 0.01 wt% to 2.00 wt%, and optionally 0.01 wt% to 1.50 wt%.

[0136] In some embodiments of the present invention, chemically strengthened crystallized glass is subjected to chemical strengthening treatment by placing the chemically strengthened crystallized glass in a salt bath containing potassium salt at 380°C to 550°C, and the chemical strengthening treatment time is 1 hour to 96 hours, optionally 1 hour to 48 hours, to obtain the strengthened crystallized glass, and the potassium salt includes one or more selected from potassium nitrate, potassium sulfate, and potassium carbonate, optionally potassium nitrate.

[0137] In some embodiments, the potassium salt-containing salt bath is 100 wt% potassium salt, optionally 100 wt% potassium nitrate, or a mixed salt of potassium salt and sodium salt, optionally a mixed salt of potassium nitrate and sodium nitrate. The salt bath may further contain 0-1 wt% lithium salt, optionally 0-1 wt% lithium nitrate. The chemical strengthening treatment may be a single-stage chemical strengthening treatment, or a two-stage or multi-stage chemical strengthening treatment.

[0138] In some embodiments, the duration of the chemical strengthening treatment is between 1.00 hours and 5.00 hours, between 1.00 hours and 6.00 hours, between 3.00 hours and 10.00 hours, between 5.00 hours and 10.00 hours, between 7.00 hours and 12.00 hours, between 9.00 hours and 24.00 hours, between 12.00 hours and 36.00 hours, between 24.00 hours and 44.00 hours, between 8.00 hours and 24.00 hours, between 9.00 hours and 44.00 hours, between 25.00 hours and 36.00 hours. h, 22.00 h to 37.00 h, 48.00 h to 96.00 h, 6.00 h, 8.00 h, 12.00 h, 14.00 h, 24.00 h, 32.00 h, 36.00 h, 22.00 h, 18.00 h, 28.00 h, 42.00 h, 48.00 h, 60 h, 65 h, 70 h, 80 h, 90 h, 96 h, etc., and all ranges and subranges therebetween.

[0139] In some embodiments, the temperature of the salt bath used in the chemical strengthening process may be 380°C to 400°C, 400°C to 450°C, 450°C to 500°C, 500°C to 550°C, 400°C to 420°C, 450°C, 480°C, 500°C, 510°C, 530°C, 540°C, 550°C, etc., and all ranges and subranges therebetween.

[0140] Third, the present invention further provides glassware made from the above-mentioned tempered glass-ceramics or the above-mentioned chemically tempered glass-ceramics.

[0141] The glassware of the present invention may be regular or irregular, and can be manufactured as required by those skilled in the art.

[0142] Fourth, the present invention further provides an electronic device comprising the above-mentioned strengthened glass-ceramics or the above-mentioned chemically strengthened glass-ceramics.

[0143] The electronic device according to the present invention includes at least one of a mobile phone, a display (e.g., an in-vehicle display, an in-aircraft display, etc.), a tablet, a digital wristwatch, a smart wearable device (e.g., a smart band, a smart watch, a smart glasses), and a television, but is not limited to these. In the electronic device of the present invention, a layer may or may not be provided on the surface of the cover component.

[0144] Illustratively, the electronic device provided by the present invention comprises: a case including a front surface, a back surface, and sides; an electronic component at least partially disposed within the case, the electronic component including at least a controller, a memory, and a display, the display being disposed on or adjacent to a front surface of the case; a covering substrate disposed above the display; Here, at least a portion of at least one of the case or the covering substrate contains any one of the above-mentioned chemically strengthened crystallized glass or strengthened crystallized glass.

[0145] The chemically strengthened crystallized glass and strengthened crystallized glass of the present invention have excellent properties and can be included / applied not only to other products but also to any product that requires a certain level of transparency, scratch resistance, or other combinations.

[0146] V. Specific Examples

[0147] Example S1:

[0148] (1) Manufacturing of substrate glass: According to the formula, 1000g of raw materials were mixed and mixed uniformly for 30 minutes, after which 5g of NaCl was added as a fining agent. The resulting mixture was placed in a platinum crucible and melted at 1650℃ for 5 hours, then poured into a mold and cooled to 900℃, placed in an annealing furnace at 620℃ for 12 hours, and then cooled to room temperature to obtain the substrate glass.

[0149] (2) Production of crystallized glass (i.e., crystallized glass for chemical strengthening): The substrate glass is subjected to heat treatment, and the temperature is raised to a nucleation temperature of 690°C at a heating rate of 10°C / min, with a nucleation treatment time of 240 minutes. The temperature is then raised to a crystallization temperature of 760°C at a heating rate of 10°C / min, with a crystallization treatment time of 240 minutes. This results in a crystallized glass block. Here, the nucleation treatment time refers to the time during which the crystallization furnace is heated to the set nucleation temperature at a set heating rate and then maintained at that temperature. The crystallization treatment time refers to the time during which the crystallization furnace is heated to the set crystallization temperature at a set heating rate and then maintained at that temperature.

[0150] (3) Cold working treatment: The above-mentioned crystallized glass block is subjected to a cold working treatment, which includes shaping and slicing, to obtain crystallized glass pieces of a desired size, for example, 50 mm in length x 50 mm in width x 0.7 mm in thickness.

[0151] After the slicing process, CNC processing, grinding processing, and polishing processing may be performed sequentially, or after the slicing process, at least one method from among CNC processing, grinding processing, and polishing processing may be selected to perform modification processing on the glass pieces.

[0152] In Example S1, the crystallized glass sample (ie, crystallized glass piece for chemical strengthening) for measuring the physical property parameters of the crystallized glass and for chemical strengthening is a polished piece measuring 50 mm long x 50 mm wide x 0.7 mm thick.

[0153] (4) Preparation of tempered crystallized glass: The above-mentioned crystallized glass pieces for chemical strengthening are placed in 100 wt% KNO3 at 480°C to carry out one-stage chemical strengthening ion exchange, and the strengthening time is 6 hours (i.e., 360 minutes), thereby obtaining tempered crystallized glass.

[0154] Examples S2 to S10: The other conditions are the same as those in Example S1, except that the component contents and related parameters are adjusted as shown in Tables 2 and 4, respectively.

[0155] Comparative examples D1~D7: The other conditions are the same as those in Example S1, except that the component contents and related parameters are adjusted as shown in Tables 3 and 5, respectively.

[0156] Tables 2 to 7 show the formulation tables for the examples and comparative examples, the characteristic parameters of the chemically strengthened crystallized glass and the characteristic parameters of the strengthened crystallized glass for the examples and comparative examples, the scratch resistance experiment plan, and the scratch test results for the chemically strengthened crystallized glass and the strengthened crystallized glass for the examples and comparative examples.

[0157]

Table 2

[0158]

Table 3

[0159]

Table 4

[0160]

Table 5

[0161]

Table 6

[0162]

Table 7

[0163] As can be seen from the above results, the present invention strictly controls the content of each oxide in Examples S1 to S10 and adjusts the content of important oxides in X, Y, and Z, thereby imparting a high residual glass phase dissociation energy to the resulting chemically strengthened glass-ceramics. This allows the desired spinel crystals of the present invention to form in the chemically strengthened glass-ceramics while maintaining excellent optical properties. By combining a primary crystalline phase (Zn,Mg)Al2O4 with a high Young's modulus and shear modulus with a residual glass phase with high intrinsic strength, the final chemically strengthened glass-ceramics has high intrinsic strength and superior scratch resistance compared to conventional spinel-based glass-ceramics. Furthermore, by strengthening the chemically strengthened glass-ceramics to meet specific stress characteristics, the strengthened glass-ceramics are endowed with excellent surface stress characteristics and deep layer stress characteristics. Finally, the mechanical properties of the strengthened glass-ceramics of the present invention are significantly improved, allowing the strengthened glass-ceramics to achieve scratch resistance comparable to that of sapphire glass.

[0164] The chemically strengthened crystallized glass of Example S1 of the present invention passed scratch tests using a gem hardness scale of 7 (Mohs hardness level 7) under loads of 250g and 500g, and a gem hardness scale of 6 (Mohs hardness level 6) under loads of 750g, and no scratches were found on the scratched crystallized glass surface. The scratch effect is shown in Figure 4.

[0165] The chemically strengthened crystallized glass of Examples S2 and S8 of the present invention passed the scratch test using a gem hardness scale number 7 (Mohs hardness level 7) under a load of 750g, and no scratches were found on the scratched crystallized glass surface. The scratch effect is shown in Figure 5.

[0166] As can be seen from Table 7 and FIGS. 4 and 5, all of the chemically strengthened crystallized glasses according to the present invention have good scratch resistance.

[0167] The tempered crystallized glass of Example S1 of the present invention passed the scratch test using a gem hardness scale number 7 (Mohs hardness level 7) under a load of 750g, and there were no scratches on the scratched crystallized glass surface. The scratch effect is shown in Figure 6.

[0168] In a scratch test using a 750g load and a gem mineral hardness scale No. 8 (Mohs hardness level 8) on the strengthened crystallized glass of Examples S2 and S8 of the present invention, the scratch resistance of the scratched crystallized glass surface was similar to that of sapphire glass measured under the same conditions. The scratch resistance is shown in Figure 7. This indicates that the scratch resistance of the strengthened crystallized glass of Examples S2 and S8 of the present invention is comparable to that of sapphire glass.

[0169] As can be seen from Table 7 and Figures 6 and 7, the use of tempered glass-ceramics obtained by tempering the chemically tempered glass-ceramics of the present invention has improved scratch resistance compared to chemically tempered glass-ceramics. The scratch resistance achieved by the tempered glass-ceramics of the present invention is comparable to that of sapphire glass, and can meet the demand for cover glass for high-end electronic products.

[0170] Comparative Examples D1 to D7 were unable to fully meet the requirements of the glass composition of the present invention, and the stress characteristics after strengthening also did not meet the requirements of the present invention. The final chemical strengthening crystallized glass and strengthened crystallized glass were all different from those of the present invention, and the scratch resistance was clearly inferior to that of the examples of the present invention.

[0171] The tempered crystallized glass of comparative examples D1 and D2 failed to pass the scratch test using a 750g load and a gem mineral hardness scale of No. 7 (Mohs hardness level 7). All scratched crystallized glass had obvious scratches on the surface. The scratch effect is shown in Figure 8. Comparing the tempered crystallized glass of D1 and D2, the scratch resistance of the tempered crystallized glass of D1 is superior to that of D2.

[0172] The dissociation energy per unit volume of the residual glass phase in comparative example D5 is relatively high, 75.46 kJ cm -3 However, in this proposal, the improvement in dissociation energy is due to the large amount of Li contained in the system. Through testing, the present inventors found that this proposal does not allow for the production of transparent chemically strengthened crystallized glass samples by heat treatment.

[0173] Comparative Example D6 is a mainstream glass-ceramic product in the current cover market. The chemically strengthened glass-ceramic of Comparative Example D6 failed to pass a scratch test using a gem hardness scale No. 6 (Mohs hardness level 6) under a load of 750g. There were obvious scratches on the scratched glass-ceramic surface, which were deep and wide, and had fish scale patterns or scratch debris. The scratch effect is shown in Figure 9. The strengthened glass-ceramic of Comparative Example D6 still failed to pass a scratch test using a gem hardness scale No. 6 (Mohs hardness level 6) under a load of 750g. There were obvious scratches on the scratched glass-ceramic surface. The scratch effect is shown in Figure 10.

[0174] As can be seen from Table 7 and Figures 8 to 10, the scratch resistance of the chemically strengthened crystallized glasses and strengthened crystallized glasses of Comparative Examples D1 to D7 is clearly inferior to the scratch resistance of the chemically strengthened crystallized glasses and strengthened crystallized glasses of the present invention.

[0175] Furthermore, because the heat treatment temperatures of all the examples of the present invention are lower than those of Comparative Examples D1 to D5, the substrate glass obtained using the formulation of the present invention has a zinc-magnesium spinel solid solution as the main crystalline phase when the heat treatment temperature is below 800°C, and a transparent chemically strengthened glass-ceramic with excellent optical properties can be obtained. Compared with the prior art, the chemically strengthened glass-ceramic composition provided by the present invention significantly reduces the heat treatment temperature, further easing the difficulty of mass-producing spinel glass-ceramic and improving the mass productivity of spinel glass-ceramic. This demonstrates the high mass productivity of the chemically strengthened glass-ceramic formulation of the present invention. At the same time, because the formulation of the present invention contains relatively little lithium, the raw material costs are much lower than those of the mainstream lithium aluminosilicate glass-ceramic, and the future application prospects are good.

[0176] Finally, the above-described embodiments do not limit the technical solutions of the present invention, but are only used to explain the technical solutions of the present invention. Those skilled in the art can understand that any modifications or equivalent replacements of the technical solutions of the present invention that do not deviate from the spirit and scope of the present invention are included in the claims of the present invention.

Claims

1. A tempered crystallized glass having high scratch resistance and including a compressive stress layer and a tensile stress layer, The main crystalline phase of the strengthened glass-ceramics is (Zn, Mg)Al ２ O ４ and the strengthened glass-ceramics contains Na ２ O is contained, and the surface K of the strengthened crystallized glass is ２ The O concentration is 7.00 wt% or more, In the strengthened crystallized glass, a depth along the thickness direction of the glass from any surface of the strengthened crystallized glass to a position near the surface and having a potassium (K) concentration similar to that of the center of the strengthened crystallized glass is 0.07t or more, where t is the thickness of the strengthened crystallized glass, The tensile stress layer of the strengthened glass-ceramics contains, in mass percentage of oxides, 30.00%≦SiO 2 <35.00%, Al 2 O 3 : 30.00% to 40.00%, ZnO: 10.00% to 12.00%, MgO: 2.00% to 4.00%, ZrO 2 : 5.00% to 7.00%, Na 2 O: 2.00% to 9.00%, Li 2 O: 0 to 2.00%, and B 2 O 3 : 0 to 8.00%, and the components of the tensile stress layer of the strengthened glass-ceramics are: (4) W=(0.8×(Al 2 O 3 −SiO 2 )+1.5×(ZnO−MgO)) / ZrO 2 , 0≦W≦2.50; In formula (4), the oxide satisfies the mass percentage of the oxide component. A tempered crystallized glass having high scratch resistance, characterized by:

2. When the thickness is 0.7 mm, the single rod static pressure strength of the strengthened crystallized glass is 450 N or more; 2. The tempered crystallized glass having high scratch resistance according to claim 1.

3. The Young's modulus of the strengthened crystallized glass is 110 GPa or more.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

4. The Vickers hardness of the strengthened crystallized glass is 750 kgf / mm ２ That's all.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

5. In the strengthened crystallized glass, the average crystal grain size is 15.00 nm or less, and / or In the strengthened crystallized glass, the crystalline content is 20.00 to 50.00 wt %.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

6. The secondary crystalline phase of the strengthened glass-ceramics is tetragonal ZrO ２ , Zn ２ SiO ４ , Mg ２ SiO ４ One or more selected from 2. The tempered crystallized glass having high scratch resistance according to claim 1.

7. The strengthened glass-ceramics is transparent within the visible light range.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

8. An automatic pencil hardness tester was used to fix a gem mineral hardness tester with a Mohs hardness level of 7 at a 45° angle, and the surface of the strengthened crystallized glass was scratched with a load of 750 g. When the scratched crystallized glass was observed under a microscope at 400x magnification, no scratches were found on the surface of the strengthened crystallized glass.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

9. The components of the tensile stress layer of the strengthened crystallized glass are (1)X=((Na ２ O+B ２ O ３ ) / ZrO ２ ) / Al ２ O ３ 、X≧2.00; (2)Y=ln[(Na ２ O+B ２ O ３ ) / ZrO ２ ]、Y≧0; (3)Z=(SiO ２ +AS ２ O ３ -MO-ZﻎO) / (L- ２ O+1 ２ O+B ２ O ３ ),4.00≦Z≦10.00; In formulas (1) to (3), oxide represents the mass percentage of the oxide component; 2. The tempered crystallized glass having high scratch resistance according to claim 1, wherein the following is satisfied:

10. The surface K 2 O concentration of the strengthened glass-ceramics is 7.00 to 15.00 wt %, and / or In the strengthened crystallized glass, the depth along the thickness direction of the glass from any surface of the strengthened crystallized glass to a position near the surface and having a potassium (K) concentration similar to that of the center of the strengthened crystallized glass is 0.07t to 0.10t, and / or The single rod static pressure strength of the strengthened glass-ceramics is 450 to 650 N, and / or The Young's modulus of the strengthened glass-ceramics is 110 to 140 GPa, and / or The Vickers hardness of the strengthened glass-ceramics is 750 to 900 kgf / mm 2 , and / or In the strengthened crystallized glass, the average crystal grain size is 1.00 to 10.00 nm, and / or In the strengthened crystallized glass, the crystalline content is 25.00 to 50.00 wt %.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

11. In the tensile stress layer of the strengthened glass-ceramics, SiO ２ and / or Al ２ O ３ and / or ZnO is 10.00% to 11.48% and / or MgO is 2.50% to 3.50% and / or ZrO ２ is 5.40% to 6.50%, and / or Na ２ O is 2.50% to 8.50%, and / or B ２ O ３ is 2.50 to 8.00%, 2. The tempered crystallized glass having high scratch resistance according to claim 1.

12. The tensile stress layer of the strengthened crystallized glass further contains 0 to 3.00 wt % of BaO and / or 0 to 2.00 wt % of Y. ２ O ３ Including, 2. The tempered crystallized glass having high scratch resistance according to claim 1.

13. The strengthened crystallized glass contains TiO ２ and P ２ O ５ is basically not included, 2. The tempered crystallized glass having high scratch resistance according to claim 1.

14. The Vickers hardness of the strengthened crystallized glass is 800 to 900 kgf / mm 2 , and / or In the strengthened crystallized glass, the average crystal grain size is 4.50 to 8.00 nm, and / or In the strengthened crystallized glass, the crystalline content is 25.00 to 45.00 wt%.

2. The tempered crystallized glass having high scratch resistance according to claim 1.

15. A method for producing the tempered crystallized glass having high scratch resistance according to any one of claims 1 to 14, comprising: The tempered glass-ceramics is obtained by subjecting the chemically tempered glass-ceramics to a chemical tempering treatment, and specifically, The chemically strengthened crystallized glass is subjected to a chemical strengthening treatment by being placed in a salt bath containing a potassium salt at 380°C to 550°C, and the chemical strengthening treatment is carried out for 1 hour to 96 hours to obtain the strengthened crystallized glass, and the potassium salt includes one or more selected from potassium nitrate, potassium sulfate, and potassium carbonate.

1. A method for producing tempered crystallized glass having high scratch resistance, comprising:

16. The chemical strengthening treatment time is 1 hour to 48 hours, and / or The potassium salt is potassium nitrate.

16. The method for producing tempered crystallized glass having high scratch resistance according to claim 15.

17. A chemically strengthened crystallized glass for producing the strengthened crystallized glass having high scratch resistance according to any one of claims 1 to 14, The main crystalline phase of the chemically strengthened glass-ceramics is (Zn, Mg)Al ２ O ４ In the glass-ceramics for chemical strengthening, the oxide molar percentage is Al ２ O ３ is greater than the sum of the molar percentages of MgO and ZnO, and the theoretical crystallinity of the chemically strengthened crystallized glass is at least 30.00 wt% or more. When the chemically strengthened crystallized glass satisfies the theoretical crystallinity, the dissociation energy U per unit volume of the residual glass phase in the chemically strengthened crystallized glass is 71.00 kJ cm －３ That's all, The chemically strengthened crystallized glass contains, in terms of oxide mass percentage, 30.00%≦SiO 2 <35.00%, Al 2 O 3 : 30.00% to 40.00%, ZnO: 10.00% to 12.00%, MgO: 2.00% to 4.00%, ZrO 2 : 5.00% to 7.00%, Na 2 O: 2.00% to 9.00%, Li 2 O: 0 to 2.00%, and B 2 O 3 : 0 to 8.00%. The components of the chemically strengthened crystallized glass are: (4) W=(0.8×(Al 2 O 3 −SiO 2 )+1.5×(ZnO−MgO)) / ZrO 2 , 0≦W≦2.50; In formula (4), the oxide represents the mass percentage of the oxide component. A chemically strengthened crystallized glass characterized by:

18. The components of the chemically strengthened crystallized glass are (1)X=((Na ２ O+B ２ O ３ ) / ZrO ２ ) / Al ２ O ３ 、X≧2.00; (2)Y=ln[(Na ２ O+B ２ O ３ ) / ZrO ２ ]、Y≧0; (3)Z=(SiO ２ +AS ２ O ３ -MO-ZﻎO) / (L- ２ O+1 ２ O+B ２ O ３ ),4.00≦Z≦10.00; In formulas (1) to (3), oxide represents the mass percentage of the oxide component; 18. The glass-ceramics for chemical strengthening according to claim 17, which satisfies the above.

19. The Young's modulus of the chemically strengthened crystallized glass is 110 GPa or more, and / or In the chemically strengthened crystallized glass, the average crystal grain size is 15.00 nm or less, and / or In the chemically strengthened crystallized glass, the crystalline content is 20.00 to 50.00 wt %, and / or The secondary crystalline phase of the chemically strengthened crystallized glass is tetragonal ZrO ２ , Zn ２ SiO ４ , Mg ２ SiO ４ and / or The chemically strengthened crystallized glass further contains 0 to 3.00 wt % of BaO and / or 0 to 2.00 wt % of Y. ２ O ３ and / or The chemically strengthened crystallized glass contains TiO ２ and P ２ O ５ and / or The theoretical crystallinity of the chemically strengthened crystallized glass is 30.00 wt% to 50.00 wt%, and / or the dissociation energy U per unit volume of the residual glass phase in the chemically strengthened glass-ceramics is 71.00 kJ·cm −3 to 134.00 kJ·cm −3 ; The chemically strengthened crystallized glass according to claim 17, characterized in that:

20. The Young's modulus of the chemically strengthened crystallized glass is 110 to 140 GPa, and / or In the chemically strengthened crystallized glass, the average crystal grain size is 1.00 to 10.00 nm, and / or In the chemically strengthened crystallized glass, the crystal content is 25.00 to 50.00 wt %; The chemically strengthened crystallized glass according to claim 17, characterized in that:

21. In the chemically strengthened crystallized glass, the average crystal grain size is 4.50 to 8.00 nm, and / or In the chemically strengthened crystallized glass, the crystal content is 25.00 to 45.00 wt %; The chemically strengthened crystallized glass according to claim 17, characterized in that:

22. A glassware manufactured from the tempered crystallized glass having high scratch resistance according to any one of claims 1 to 14.

23. A glass instrument manufactured from the glass-ceramics for chemical strengthening according to claim 17.

24. An electronic device comprising the strengthened crystallized glass having high scratch resistance according to any one of claims 1 to 14.

25. An electronic device comprising the glass-ceramics for chemical strengthening according to claim 17.

Images