Transparent spinel glass ceramics, and method for producing the same and use thereof

Abstract

The present invention discloses a transparent spinel glass ceramic, which contains, based on the oxide molar percentage, 3.50-6.00 mol% Li2O and 2.00-4.00 mol% Na2O, and the crystal phase of the glass ceramic contains spinel crystals and zirconia crystals, but does not contain Li-containing crystals. The present invention optimizes the composition of the spinel glass ceramic material, introduces more Li ions and Na ions used for chemical strengthening of ion exchange into the spinel glass ceramic, obtains a spinel glass ceramic without impurity crystal phase, and ensures that the glass ceramic does not suffer from haze and devitrification, and the glass ceramic material has excellent transmittance. By introducing more Li ions and Na ions into the spinel glass ceramic composition, the obtained spinel glass ceramic can be chemically strengthened, and a transparent tempered glass ceramic with high CS, DOL_0, CT_AV and CT_LD is obtained, and the tempered glass ceramic shows excellent drop resistance.

Description

Technical Field

[0001] The present invention relates to the field of glass technology, and specifically to transparent spinel glass ceramics, and their preparation methods and uses.

Background Art

[0002] As electronic devices become thinner and lighter, the requirements for the performance of cover glass are increasing. Glass ceramics have attracted wide attention due to their good impact resistance, scratch resistance, abrasion resistance and other characteristics. Transparent spinel ceramics not only have performance characteristics such as high temperature resistance, corrosion resistance, abrasion resistance, impact resistance, high hardness, and excellent insulation properties possessed by general advanced ceramics, but also have optical properties similar to those of single crystal sapphire, and have good optical light transmittance in the wavelength ranges of ultraviolet, visible light, and infrared light. It is generally used as transparent armor, missile windows, cowlings, various substrate materials, new lamps, and viewing windows of equipment in various high-temperature, high-pressure, and corrosive environments. However, spinel glass ceramics generally cannot be toughened by chemical strengthening. Although they have the characteristic of high hardness, they have poor toughness and poor drop resistance. Especially when the thickness is small (≤1 mm), brittleness appears more significantly, and it is not suitable as an electronic cover glass that requires high impact resistance.

[0003] Electronic cover glass needs to have high CS, DOL_0, CT_AV and CT_LD. Especially with high CT_LD can good drop resistance performance be achieved. To obtain high CS, DOL_0, CT_AV and CT_LD, a certain amount of Li 2 O and Na 2 O need to be added to the composition of the glass. However, Li 2 O and Na 2As the addition amount of O increases, crystal phases that affect the optical properties of the glass ceramics, such as β-quartz, β-quartz solid solution, β-spodumene, etc., often precipitate in the glass. The precipitation of these crystals makes the glass ceramics prone to cloudiness and even devitrification, making it difficult to obtain ideal transparent spinel glass ceramics.

[0004] The problem that those skilled in the art need to solve urgently is to study new transparent spinel glass ceramics, which ensure excellent optical properties, while having more Li ions and Na ions used in chemical strengthening by ion exchange, and preparing strengthened glass ceramics with high CS, DOL_0, CT_AV and CT_LD using the transparent spinel glass ceramics, so as to achieve excellent drop resistance performance.

Summary of the Invention

[0005] The object of the present invention is to provide transparent spinel glass ceramics, which have a large amount of Li ions and Na ions used in chemical strengthening by ion exchange, do not contain impurity crystal phases that affect the transmittance of the glass ceramics, and have excellent transmittance. Using the transparent spinel glass ceramics, transparent strengthened glass ceramics with high CS, DOL_0, CT_AV and CT_LD can be manufactured by strengthening, and the obtained transparent strengthened glass ceramics have excellent drop resistance performance. At the same time, the present invention further provides a preparation method and use of the transparent spinel glass ceramics.

[0006] To solve the above technical problems, the present invention uses the following technical solutions. The present invention provides transparent spinel glass ceramics, based on the molar percentage of oxides, the glass ceramics comprise Li 2 O: 3.50 - 6.00 mol%, and Na 2 O: 2.00 - 4.00 mol%, and The crystal phase of the glass ceramics contains spinel crystals and zirconia crystals and does not contain Li-containing crystals.

[0007] Here, the crystal phase of the glass ceramics does not contain quartz and quartz solid solution.

[0008] Here, the glass ceramics exhibit a crystallinity of at least 30.00 wt%.

[0009] Here, the average size of the crystals in the glass ceramics is 15.00 nm or less.

[0010] Here, the spinel crystals include zinc spinel and magnesium spinel.

[0011] Here, when the thickness of the glass ceramics is 0.70 mm, the transmittance at a wavelength of 550.00 nm is greater than 85.00%.

[0012] Here, based on the molar percentage of oxides, the glass ceramics SiO 2 : 50.00 - 65.00 mol%, Al 2 O 3 : 14.50 - 25.00 mol%, MgO: 3.50 - 8.00 mol%, ZnO: 8.00 - 16.00 mol%, BaO: 0 - 2.00 mol%, and TiO 2 +ZrO 2 : 3.00 - 5.50 mol% further.

[0013] Here, based on the molar percentage of oxides, the glass ceramics 0.40 ≦ (Al 2 O 3 +ZnO+MgO+ZrO 2 +TiO 2 ) / (Li 2 O+Na 2 O+SiO 2It satisfies 0.70 ≥ (Al₂O₃ + ZnO + MgO + ZrO₂ + TiO₂) / (Li₂O + Na₂O + SiO₂ + BaO).

[0014] Here, based on the molar percentage of the oxides, the glass ceramics satisfy 0.43 ≤ (Al₂O₃ + ZnO + MgO + ZrO₂ + TiO₂) / (Li₂O + Na₂O + SiO₂ + BaO) ≤ 0.68. 2 ₂O₃ 3 ₂ + TiO₂) / (Li₂O + Na₂O + SiO₂ + BaO) ≤ 0.68. 2 ₂ 2 ) / (Li₂O + Na₂O + SiO₂ 2 ₂ + BaO) ≤ 0.68. 2 ₂ + BaO) ≤ 0.68. 2 ₂ + BaO) ≤ 0.68.

[0015] Here, based on the molar percentage of the oxides, the glass ceramics satisfy Na₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≥ 0.035, 2 ₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≥ 0.035, 2 ₂O + SiO₂ 2 ₂ + BaO) ≥ 0.035, 2 + BaO) ≥ 0.035, and / or Li₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≥ 0.054. 2 ₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≥ 0.054. 2 ₂O + SiO₂ 2 ₂ + BaO) ≥ 0.054. 2 + BaO) ≥ 0.054.

[0016] Here, based on the molar percentage of the oxides, the glass ceramics satisfy 0.035 ≤ Na₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≤ 0.070, 2 ₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≤ 0.070, 2 ₂O + SiO₂ 2 ₂ + BaO) ≤ 0.070, 2 + BaO) ≤ 0.070, and / or 0.054 ≤ Li₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≤ 0.090. 2 ₂O / (Li₂O + Na₂O + SiO₂ + BaO) ≤ 0.090. 2 ₂O + SiO₂ 2 ₂ + BaO) ≤ 0.090. 2 + BaO) ≤ 0.090.

[0017] Here, based on the molar percentage of the oxides, the glass ceramics contain the following components. SiO₂ 2 : 50.00 - 63.00 mol%, preferably 50.00 - 57.00 mol%, and / or Al₂O₃ 2 ₃3 : 14.50 to 20.00 mol%, preferably 15.00 to 19.00 mol%, and / or MgO: 3.90 to 7.60 mol%, preferably 4.00 to 7.50 mol% and / or ZnO: 8.00 to 15.50 mol%, preferably 9.00 to 15.20 mol%, and / or BaO: 0 to 1.50 mol%, preferably 1.00 to 1.35 mol%, and / or Li 2 O: 3.50 to 5.00 mol%, preferably 4.00 to 5.00 mol%, and / or Na 2 O: 2.30 to 3.60 mol%, preferably 3.00 to 3.60 mol%, and / or TiO 2 : 0 to 2.00 mol%, preferably 0.30 to 1.30 mol%, and / or ZrO 2 : 2.50 to 5.00 mol%, preferably 2.90 to 4.20 mol%.

[0018] The present invention further provides a method for preparing transparent spinel glass ceramics, and this preparation method includes step (1) compounding and mixing raw materials according to a recipe to prepare a glass precursor, and step (2) performing a nucleation treatment and a crystallization treatment on the obtained glass precursor in sequence to prepare the transparent spinel glass ceramics.

[0019] Here, in the step (2), when performing the nucleation treatment, the nucleation temperature is 700 to 800 °C, and the nucleation treatment time is 30 to 1440 min, when performing the crystallization treatment, the crystallization temperature is 900 to 1000 °C, and the crystallization treatment time is 5 to 1440 min.

[0020] Here, in the step (2), when performing the crystallization treatment, the temperature is raised to the crystallization temperature at a heating rate greater than 20 °C / min.

[0021] Here, in the step (2), when performing the crystallization treatment, the temperature is raised to the crystallization temperature at a heating rate of 25 °C / min or more, preferably at a heating rate of 30 °C / min or more.

[0022] Here, in the step (2), when performing the nucleation treatment, the temperature is raised to the nucleation temperature at a heating rate of 5 to 20 °C / min.

[0023] Here, in the step (2), when performing the nucleation treatment, the temperature is raised to the nucleation temperature at a heating rate of 10 °C / min.

[0024] The present invention further provides a strengthened glass ceramic, which is manufactured by chemically strengthening the transparent spinel glass ceramic by ion exchange, and the strengthened glass ceramic has a compressive stress region extending from its surface to the compression depth. Specifically, The strengthened glass ceramic can be obtained by performing one-step or multi-step ion exchange on the transparent spinel glass ceramic in a salt bath.

[0025] When performing one-step ion exchange, the composition of the salt bath is 50 to 100 wt% NaNO 3 + 0 to 50 wt% KNO 3 and the temperature of the ion exchange is 400 to 500 °C, and the time of the ion exchange is 0.5 to 48 h.

[0026] When performing two-step ion exchange, the composition of the first-step salt bath is 90 to 100 wt% NaNO 3 + 0 to 10 wt% KNO 3 and the temperature of the ion exchange is 400 to 500 °C, and the time of the ion exchange is 0.5 to 48 h, and the composition of the second-step salt bath is 0 to 10 wt% NaNO 3 + 90 to 100 wt% KNO3 It contains 3 , the temperature of ion exchange is 400 - 500 °C, and the time of ion exchange is 0.5 - 48 h.

[0027] To improve the service life of the salt bath, a salt bath protective agent accounting for 0.1 - 5.0 wt% of the mass percentage of the salt bath can be added to the salt bath, and the salt bath protective agent contains a substance for passivating, precipitating or absorbing Li + and contains a substance for passivating, precipitating or absorbing + .

[0028] Here, the depth DOL_0 of the compressive stress layer of the strengthened glass ceramics is 14% or more of the thickness of the strengthened glass ceramics, and the tensile stress line density CT_LD of the strengthened glass ceramics is 25000 MPa / mm or more.

[0029] Here, the tensile stress line density CT_LD of the strengthened glass ceramics is 25000 - 40000 MPa / mm, preferably 27000 - 40000 MPa / mm.

[0030] Here, the surface compressive stress CS of the strengthened glass ceramics is 650 MPa or more, preferably 680 MPa or more.

[0031] Here, the average tensile stress CT_AV of the strengthened glass ceramics is 35.0 MPa or more, preferably 39.0 MPa or more.

[0032] Here, the Vickers hardness of the strengthened glass ceramics is 740 HV0.3 or more.

[0033] Here, the fracture toughness of the strengthened glass ceramics is 1.500 MPa·m 1 / 2 or more, preferably 1.560 MPa·m 1 / 2 or more.

[0034] The present invention further provides an electronic terminal as a consumer product, and the electronic terminal includes a shell and electronic components partially located within the shell. The shell includes a front surface, a rear surface and side surfaces. The electronic component includes a display device, and the display device is located on the front surface of the shell or adjacent to the front surface. The front surface and / or the rear surface and / or the side surface include the strengthened glass ceramic material. The electronic terminal further includes a covering product that covers the front surface of the shell or is located on the display device, and the covering product includes the strengthened glass ceramic material. The electronic terminal serving as the consumer product includes a mobile phone, a tablet, a photovoltaic device, or other electronic terminals (such as an electronic wristwatch).

[0035] Both the transparent spinel glass ceramic material and the strengthened glass ceramic material in the present invention have excellent properties and can be included in / used in other products. For example, wristwatches, transparent armors, missile windows, cowlings, substrate materials, new lamps, viewing windows of equipment in high-temperature, high-pressure, and corrosive environments, display protection materials for portable smart electronic devices, and appearance case protection materials (portable smart electronic devices include mobile phones, tablets, electronic wristwatches, etc.), building products, transportation products (such as automobiles, trains, airplanes, seaplanes, etc.), appliance products, or any products that require a certain degree of transparency, scratch resistance, impact resistance, abrasion resistance, or a combination thereof. are any products.

[0036] Compared with the prior art, the present invention has the following beneficial effects. 1. The present invention optimizes the components of the spinel glass ceramic material, further introduces more Li ions and Na ions used for chemical strengthening by ion exchange into the spinel glass ceramic, and obtains a spinel glass ceramic without impurity crystal phases (such as impurity crystal phases of Li-containing crystal phases, quartz, quartz solid solutions, etc.), ensuring that no phenomena such as cloudiness and devitrification occur in the glass ceramic and that the glass ceramic material has excellent transmittance. By introducing more Li ions and Na ions into the spinel glass ceramics component, the obtained spinel glass ceramics can be chemically strengthened, and transparent strengthened glass ceramics with high CS, DOL_0, CT_AV, and CT_LD can be obtained. This strengthened glass ceramics exhibits excellent drop resistance.

[0037] 2. As a result of performing performance tests on the glass ceramics material obtained in the present invention, it was found that the transparent spinel glass ceramics material of the present invention has a high degree of crystallinity, thus bringing excellent mechanical properties to the glass ceramics material.

[0038] 3. The present invention further provides a method for preparing spinel glass ceramics. The process method provided by the present invention controls the process parameters of the crystallization process and the nucleation process, and sets the requirements for the heating rate parameter, so as to finally obtain spinel glass ceramics without impurity crystal phases (for example, impurity crystal phases such as Li-containing crystal phases, quartz, and quartz solid solutions), and ensure that the glass ceramics material has excellent optical properties.

Brief Description of the Drawings

[0039]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying out the Invention

[0040] Hereinafter, the present invention will be described in more detail with reference to examples and drawings. I. The related special names and related measurement methods according to the present invention are as follows. Glass ceramics, also called fine-crystalline glass, are solid composite materials that simultaneously contain a glass phase and a fine-crystalline phase, which are prepared by intentionally controlling the crystallization of a base glass.

[0041] Reinforced glass ceramics are solid composite materials obtained after the glass ceramics have undergone chemical strengthening treatment. When performing high-temperature chemical strengthening treatment, alkali metal ions with a large ionic radius in the salt bath (for example, potassium ions, sodium ions) replace alkali metal ions with a small ionic radius in the glass ceramics (for example, sodium ions, lithium ions), resulting in a difference in the volume of the exchanged ions and generating a compressive stress on the surface of the glass ceramics. The surface compressive stress CS is generated on the glass surface due to the effect of the large-radius alkali metal ions pushing and blocking the small-radius alkali metal ions on the surface of the glass ceramics after chemical strengthening, and is called the surface compressive stress.

[0042] The surface compressive stress CS is generated on the glass surface due to the effect of the large-radius alkali metal ions pushing and blocking the small-radius alkali metal ions on the surface of the glass ceramics after chemical strengthening, and is called the surface compressive stress.

[0043] The depth of the compressive stress layer DOL_0 refers to the distance from the surface of the strengthened glass ceramics to the position where the compressive stress is 0.

[0044] The tensile stress line density CT_LD is the ratio of the sum of the tensile stresses measured by the SLP stress meter to the thickness of the glass ceramics. After chemical strengthening, a tensile stress layer is formed inside the strengthened glass ceramics. The tensile stress layer has an upper boundary separated from the upper surface of the strengthened glass ceramics by a certain distance and a lower boundary separated from the lower surface of the strengthened glass ceramics by a certain distance. For a line segment that is perpendicular to both the upper and lower boundaries simultaneously within the tensile stress layer and whose upper and lower endpoints are respectively at the upper and lower boundaries, a curve is drawn with the magnitude of the tensile stress at a certain point on the line segment as the Y-axis and the distance from the corresponding point to the upper boundary as the X-axis, which is denoted as the tensile stress curve. The ratio of the definite integral of the tensile stress curve to the thickness of the strengthened glass ceramics is denoted as the tensile stress line density, that is, the ratio of the sum of the tensile stresses of the strengthened glass ceramics measured by the SLP-2000 stress meter to the glass thickness.

[0045] In chemically strengthened glass, the compressive stress and the tensile stress are in balance and equal. The SLP-2000 stress meter is used to more accurately measure the tensile stress region of the glass. By using the ratio of the tensile stress integral to the thickness, it represents the magnitude of the stress contained in the glass ceramics per unit thickness, and is used to represent the stress level of the chemically strengthened glass ceramics.

[0046] CT_AV refers to the average value of all the tensile stresses in the tensile stress region. The nucleation temperature is the temperature at which crystal nuclei are formed. The crystallization temperature is the temperature at which the growth rate of the target crystals can be controlled. The transmittance is when a certain wavelength irradiates the glass surface, and light undergoes reflection, absorption, and transmission. Among them, the ratio of the intensity of the transmitted part to the intensity of the incident light is the transmittance. Cloudiness means that the crystals in the glass ceramics are large or phase-separated, showing a semi-transparent state, which is a state between transparency and devitrification. Devitrification means that the crystals in the glass ceramics are large or phase - separated, completely losing the transparent characteristics of the glass, and no image on the back surface can be seen through the glass.

[0047] Test by differential scanning calorimetry (DSC) After pulverizing the sample, sieve it through a 200 - mesh sieve. The test conditions are from room temperature to 1100 °C with a heating rate of 10 °C / min. The test apparatus is the Mettler Toledo TGA / DSC3+ thermogravimetric and simultaneous thermal analyzer.

[0048] Test of transmittance First, wash the crystallized glass sheet with an ultrasonic cleaner, and the washing conditions include the following. The washing time is 5 - 10 min. The cleaning agent used is a general cleaning agent diluted 10 times. The washing temperature is 45 °C - 65 °C. The washing frequency is 20 kHz - 40 kHz.

[0049] Next, use a haze meter to measure the transmittance of the glass at different wavelengths, and measure according to the standard of "Part 12: Internal transmittance of spectrum in the measuring method of colorless optical glass - GB / T 7962.12 - 2010". The haze meter used in the present invention is the Konica Minolta spectrophotometer CM - 3600A.

[0050] Integral drop test First, attach 120 - mesh sandpaper to a 160 - g Huawei P30 model machine, place a 50×50×0.7 - mm tempered glass - ceramics sheet to be tested directly below the model machine, and drop the model machine from a predetermined height in the form of an impact.

[0051] The samples of each group are at least 10 or more. The dropping height starts from 0.4 m, and one dropping impact is applied to the sample. If it does not break, the height is increased by 0.1 m each time and dropped again until the glass breaks. When it breaks, the average value of the previous height is taken as the dropping resistance height.

[0052] In the present invention, for stress measurement, the FSM6000 and SLP2000 manufactured by Orihara Manufacturing Co., Ltd. are used to measure the surface high-pressure stress region and the deep-layer low-pressure stress region respectively. The stress curve is fitted using PMC software, and the corresponding test results can be obtained. Of course, other stress testers that can measure the surface high-pressure stress region and the deep-layer low-compression stress region may also be used.

[0053] Second, the present invention provides transparent spinel glass ceramics. Based on the molar percentage of oxides, the glass ceramics are Li 2 O: 3.50 to 6.00 mol%, and Na 2 O: 2.00 to 4.00 mol%, and the crystal phase of the glass ceramics contains spinel crystals and zirconia crystals, and does not contain Li-containing crystals.

[0054] The present invention conducts research aiming at the components of the glass ceramics material. In order for the glass ceramics material to be toughened by chemical strengthening and obtain high CS, DOL_0, CT_AV and CT_LD, and improve the impact resistance and dropping resistance performance, it is necessary to add alkali metal oxides, especially Li 2 O (lithium oxide) and Na 2 O (sodium oxide) to the components. However, with the increase in the addition amounts of Li 2 O and Na 2 O, impurity crystals that affect the optical properties of the glass ceramics from the glass, such as crystal phases such as β-quartz, β-quartz solid solution, and β-spodumene, often precipitate. Figure 3 shows this well. Li 2As the content of O increases, in Fig. 3, the single peak formed from spinel gradually becomes a plurality of peaks (spinel peak + other impurity crystal phases). Due to the precipitation of these impurity crystals, the glass after crystallization is prone to clouding and further devitrification, which seriously affects the optical properties of the glass ceramics.

[0055] To address this problem, the prior art generally uses a method of reducing the addition amounts of Li 2 O and Na 2 O to avoid the excessive precipitation of crystal phases such as β - quartz, β - quartz solid solution, and β - spodumene, and further avoid the clouding and devitrification of the glass ceramics. However, with this method, the CS, DOL_0, CT_AV, and CT_LD obtained by strengthening the glass ceramics are relatively low, making it difficult to achieve excellent drop resistance performance.

[0056] In order to obtain transparent strengthened spinel glass ceramics with high CS, DOL_0, CT_AV, and CT_LD and improve the drop resistance performance of the spinel glass ceramics, the present invention optimizes the components.

[0057] The present invention can obtain spinel glass ceramics without impurity crystal phases (such as impurity crystal phases of Li - containing crystal phases, quartz, quartz solid solution, etc.) when introducing more Li 2 O and Na 2 O, ensuring that no phenomena such as clouding and devitrification occur in the glass ceramics and that the glass ceramic material has excellent transmittance. By introducing more Li ions and Na ions into the spinel glass ceramic components, the obtained spinel glass ceramics can be chemically strengthened, and transparent strengthened glass ceramics with high CS, DOL_0, CT_AV, and CT_LD can be obtained, and this transparent strengthened glass ceramics exhibits excellent drop resistance performance.

[0058] In the transparent spinel glass ceramics provided by the present invention, Li 2The content of O is 3.50 to 6.00 mol% and all ranges and sub-ranges therebetween, for example, 3.50 to 5.00 mol%, 4.50 to 5.00 mol%, 4.50 to 5.50 mol%, 3.50 to 4.50 mol%, 4.00 to 5.00 mol%, 4.50 to 6.00 mol%, 5.00 to 6.00 mol%, 5.50 to 6.00 mol%, 3.50 to 4.00 mol%, 3.50 to 4.40 mol%, 3.80 to 5.50 mol%, 3.90 to 4.00 mol%, 3.60 to 4.40 mol%, 4.80 to 5.90 mol%, etc. In some embodiments, Li 2 The content of O may be 3.50 mol%, 3.60 mol%, 3.70 mol%, 3.80 mol%, 3.90 mol%, 4.00 mol%, 4.10 mol%, 4.20 mol%, 4.30 mol%, 4.40 mol%, 4.50 mol%, 4.60 mol%, 4.70 mol%, 4.80 mol%, 4.90 mol%, 5.00 mol%, 5.10 mol%, 5.20 mol%, 5.30 mol%, 5.40 mol%, 5.50 mol%, 5.60 mol%, 5.70 mol%, 5.80 mol%, 5.90 mol%, 6.00 mol%, etc.

[0059] Na 2 The content of O is 2.00 to 4.00 mol% and all ranges and sub-ranges therebetween, for example, 2.30 to 3.60 mol%, 3.00 to 3.60 mol%, 2.5 to 3.00 mol%, 2.40 to 3.80 mol%, 2.00 to 2.60 mol%, 2.00 to 2.80 mol%, 2.50 to 3.20 mol%, 2.50 to 3.60 mol%, 2.50 to 3.10 mol%, 2.50 to 3.40 mol%, 2.50 to 3.80 mol%, 2.80 to 3.50 mol%, 2.10 to 3.90 mol%, etc. In some embodiments, Na 2The content of O may be 2.00 mol%, 2.10 mol%, 2.20 mol%, 2.30 mol%, 2.40 mol%, 2.50 mol%, 2.60 mol%, 2.70 mol%, 2.80 mol%, 2.90 mol%, 3.00 mol%, 3.10 mol%, 3.20 mol%, 3.30 mol%, 3.40 mol%, 3.50 mol%, 3.60 mol%, 3.70 mol%, 3.80 mol%, 3.90 mol%, 4.00 mol% or the like.

[0060] In some embodiments, the crystalline phase of the glass ceramics does not contain quartz and quartz solid solution. The presence of quartz and quartz solid solution affects the optical properties of the spinel glass ceramics, making the crystallized glass cloudy and more prone to devitrification.

[0061] In some embodiments, the glass ceramics exhibit a crystallinity of at least 30.00 wt%, and the average size of the crystals in the glass ceramics is 15.0 nm or less. By controlling to obtain a sufficiently high crystallinity, the inherent strength of the glass ceramics can be significantly improved. At the same time, by controlling the crystal size so that the crystal size is sufficiently small, the light transmittance of the glass ceramics can be significantly improved, ensuring that the glass ceramics have excellent optical properties. The glass ceramics of the present invention exhibit a crystallinity of at least 30.00 wt%, including 30.00 wt% and above and all ranges and sub-ranges therebetween, such as 30.00 - 50.00 wt% , including 30.00 - 40.00 wt%, 40.00 - 50.00 wt%, 35.00 - 40.00 wt%, 30.00 - 44.00 wt%, 31.00 - 35.00 wt%, 42.00 - 45.00 wt%, 31.00 - 37.00 wt%, 30.00 - 38.00 wt%, 30.00 - 39.00 wt%, etc. In some embodiments, the crystallinity of the glass ceramics of the present invention is 30.00 wt%, 31.00 wt%, 32.00 wt%, 33.00 wt%, 34.00 wt%, 35.00 wt%, 36.00 wt%, 37.00 wt%, 38.00 wt%, 39.00 wt%, 40.00 wt%, 41.00 wt%, 42.00 wt%, 43.00 wt%, 44.00 wt%, 45.00 wt%, 46.00 wt%, 47.00 wt%, 48.00 wt%, 49.00 wt%, 50.00 wt%, etc. Also, the average size of the crystals in the glass ceramics of the present invention is 15.0 nm or less, including 15.0 nm or less and all ranges and sub - ranges therebetween, for example 5.0 - 10.0 nm, 5.0 - 11.0 nm, 5.0 - 13.0 nm, 4.0 - 10.0 nm, 3.0 - 15.0 nm, 6.0 - 13.0 nm, 7.0 - 12.0 nm, 2.0 - 10.0 nm, 5.0 - 14.0 nm, 4.0 - 9.0 nm, etc. In some embodiments, the average size of the glass ceramic crystals of the present invention may be 2.0 nm, 3.0 nm, 4.0 nm, 5.0 nm, 6.0 nm, 7.0 nm, 9.0 nm, 10.0 nm, 11.0 nm, 12.0 nm, 13.0 nm, 14.0 nm, 15.0 nm, etc.

[0062] In some examples, the spinel crystals include zinc spinel and magnesium spinel, and / or a solid solution of zinc spinel (ZnAl 2 O 4 ) and magnesium spinel (MgAl 2 O 4 ). Zinc spinel (ZnAl 2 O 4 ) is a cubic mineral. On the Mohs hardness scale, the hardness of spinel is 7.5 - 8, and the measured density is 4.38 - 4.60 g / cm 3and under ambient pressure, the Young's modulus of zinc spinel is 290 GPa, the shear modulus is 146 GPa, and the refractive index is 1.79 - 1.80. Zinc spinel (ZnAl 2 O 4 ) forms a solid solution with magnesium spinel (MgAl 2 O 4 ), and the properties of the solid solution spinel are almost the same as those of zinc spinel (ZnAl 2 O 4 ). The differences are: (comparison between magnesium spinel and zinc spinel): (a) a lower refractive index (magnesium spinel: 1.72 vs. zinc spinel: 1.79 - 1.80); (b) a lower density (magnesium spinel: 3.6 - 4.1 g / cm 3 vs. zinc spinel: 4.4 - 4.6 g / cm 3 ); (c) a lower Young's modulus (magnesium spinel: 283 GPa vs. zinc spinel: 290 GPa); (d) a higher shear modulus (magnesium spinel: 155 GPa vs. zinc spinel: 146 GPa). Since the composite microcrystalline glass is a function of the mechanical performance of each component phase, the high hardness, high density, and high elastic constant of zinc magnesium spinel result in the mechanical performance of the composite microcrystalline glass being superior to that of the precursor glass. Zinc magnesium spinel microcrystalline glass exhibits excellent crack propagation resistance and scratch resistance.

[0063] In some embodiments, when the glass ceramics has a thickness of 0.7 mm, the transmittance at a wavelength of 550 nm is greater than 85.00%. The glass ceramics of the present invention is transparent within the visible light range and exhibits a transmittance of at least about 85.00% at a wavelength of 550 nm. The glass ceramics of the present invention has a transmittance at a wavelength of 550 nm greater than 85.00%, including all ranges and sub - ranges above and between 85.00%, for example, 86.00%, 87.00%, 88.00%, 89.00%, 90.00%, 91.00%, 92.00%, 93.00%, etc.

[0064] In some embodiments, based on the molar percentage of oxides, the glass ceramics described in the present invention SiO2 : 50.00 to 65.00 mol%, Al 2 O 3 : 14.50 to 25.00 mol%, MgO: 3.50 to 8.00 mol%, ZnO: 8.00 to 16.00 mol%, BaO: 0 to 2.00 mol%, and, TiO 2 +ZrO 2 : 3.00 to 5.50 mol% is further included. Furthermore, based on the molar percentage of the oxides, the glass ceramics described in the present invention SiO 2 : 50.00 to 63.00 mol%, preferably 50.00 to 57.00 mol%, and / or Al 2 O 3 : 14.50 to 20.00 mol%, preferably 15.00 to 19.00 mol%, and / or MgO: 3.90 to 7.60 mol%, preferably 4.00 to 7.50 mol%, and / or ZnO: 8.00 to 15.50 mol%, preferably 9.00 to 15.20 mol%, and / or BaO: 0 to 1.50 mol%, preferably 1.00 to 1.35 mol%, and / or Li 2 O: 3.50 to 5.00 mol%, preferably 4.00 to 5.00 mol%, and / or Na 2 O: 2.30 to 3.60 mol%, preferably 3.00 to 3.60 mol%, and / or TiO 2 : 0 to 2.00 mol%, preferably 0.30 to 1.30 mol%, and / or ZrO 2 : 2.50 to 5.00 mol%, preferably 2.90 to 4.20 mol% is further included.

[0065] In the present invention, SiO 2 (Silicon dioxide) and Al 2 O 3Aluminum oxide is the main component that constitutes the network structure of glass. With sufficient SiO 2 and Al 2 O 3 , it is possible to ensure that the glass has a high network structure strength, which is advantageous for ensuring that the glass has high intrinsic strength and thermal stability. If the content of SiO 2 and Al 2 O 3 is too high, the difficulty of melting and manufacturing the glass will increase. Al 2 O 3 not only supplies Al elements for the precipitation of spinel crystals but also can increase the surface compressive stress during chemical strengthening treatment.

[0066] MgO (magnesium oxide) and ZnO (zinc oxide) can provide the necessary Mg elements and Zn elements for the spinel crystals formed in the glass-ceramics. Here, MgO can increase the high-temperature viscosity of the glass liquid, reduce the crystallization tendency and crystallization rate, and improve the chemical stability and mechanical strength of the glass. ZnO, as a network intermediate, can consume free oxygen in the glass to form [ZnO 4 and enter the structural network of the glass, making the structure of the glass more stable. If its usage amount is too large, the glass is likely to crystallize. Therefore, by adjusting the ratio of MgO to ZnO, the precipitation rate of crystals can be controlled.

[0067] BaO (barium oxide) promotes the melting of the glass, but if its content is too high, secondary bubbles are likely to occur and clarification becomes difficult.

[0068] TiO 2 (titanium oxide) and ZrO 2 (zirconium oxide) are used as nucleating agents. ZrO 2 can increase the viscosity and chemical stability of the glass. If the content is too high, the glass becomes difficult to melt. TiO 2It can improve the chemical stability of the glass and at the same time improve the uniformity of glass melting production. However, if the content is too high, it will color the glass and increase the glass refractive index. TiO 2 and ZrO 2 The combination with brings about a good nucleation effect.

[0069] The content of SiO 2 is 50.00 - 65.00 mol% and all ranges and sub - ranges therebetween, such as 50.00 - 63.00 mol%, 50.00 - 65.00 mol%, 5 0.00 - 60.00 mol%, 51.00 - 63.00 mol%, 52.00 - 65.00 mol%, 53.00 - 65.00 mol%, 55.00 - 65.00 mol%, 50.00 - 57.00 mol%, 52.00 - 57.00 mol%, etc. are included. In some embodiments, the content of SiO 2 may be 50.00 mol%, 51.00 mol%, 52.00 mol%, 53.00 mol%, 54.00 mol%, 55.00 mol%, 56.00 mol%, 57.00 mol%, 58.00 mol%, 59.00 mol%, 60.00 mol%, 61.00 mol%, 62.00 mol%, 63.00 mol%, 64.00 mol%, 65.00 mol%, etc.

[0070] The content of Al 2 O 3 is 14.50 - 25.00 mol% and all ranges and sub - ranges therebetween, such as 14.50 - 20.00 mol%, 15.00 - 19.00 mol%, 14.50 - 20.00 mol%, 15.50 - 20.00 mol%, 15.00 - 24.00 mol%, 14.90 - 23.00 mol%, 16.00 - 24.00 mol%, 17.00 - 25.00 mol%, 18.00 - 25.00 mol%, etc. are included. In some embodiments, the content of Al 2 O 3The content may be, for example, 14.50 mol%, 14.90 mol%, 15.00 mol%, 15.50 mol%, 16.00 mol%, 17.00 mol%, 18.00 mol%, 19.00 mol%, 20.00 mol%, 23.00 mol%, 24.00 mol%, 25.00 mol%, etc.

[0071] The content of MgO is from 3.50 to 8.00 mol% and all ranges and sub-ranges therebetween, such as 4.00 to 7.50 mol%, 3.90 to 7.60 mol%, 3.50 to 4.00 mol%, 3.50 to 5.00 mol%, 3.50 to 6.00 mol%, 3.50 to 7.00 mol%, 4.50 to 6.00 mol%, 5.50 to 8.00 mol%, 6.50 to 8.00 mol%, etc. In some embodiments, the content of MgO may be, for example, 3.50 mol%, 3.90 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 7.60 mol%, 8.00 mol%, etc.

[0072] The content of ZnO is from 8.00 to 16.00 mol% and all ranges and sub-ranges therebetween, such as 8.00 to 15.50 mol%, 9.00 to 15.20 mol%, 8.00 to 13.00 mol%, 9.00 to 16.00 mol%, 10.00 to 16.00 mol%, 8.00 to 10.00 mol%, 8.00 to 11.00 mol%, 8.00 to 12.00 mol%, 9.00 to 14.00 mol%, 9.00 to 12.00 mol%, etc. In some embodiments, the content of ZnO may be, for example, 8.00 mol%, 9.00 mol%, 10.00 mol%, 11.00 mol%, 12.00 mol%, 13.00 mol%, 14.00 mol%, 15.20 mol%, 15.50 mol%, 16.00 mol%, etc.

[0073] The content of BaO is 0 to 2.00 mol% and all ranges and sub-ranges therebetween, such as 0 to 1.50 mol%, 1.00 to 1.40 mol%, 0 to 1.00 mol%, 1.00 to 2.00 mol%, 1.10 to 2.00 mol%, 1.20 to 2.00 mol%, 1.10 to 1.50 mol%, 1.20 to 1.80 mol%, etc. In some embodiments, the content of BaO may be 0 mol%, 1.00 mol%, 1.10 mol%, 1.20 mol%, 1.40 mol%, 1.50 mol%, 1.80 mol%, 2.00 mol%, etc.

[0074] TiO 2 +ZrO 2 The content of + ZrO is 3.00 to 5.50 mol% and all ranges and sub-ranges therebetween, such as 3.00 to 5.00 mol%, 3.50 to 5.00 mol%, 4.50 to 5.00 mol%, 3.10 to 4.50 mol%, 3.30 to 4.70 mol%, 3.70 to 4.50 mol%, 3.10 to 4.80 mol%, 4.00 to 5.00 mol %, 3.00 to 4.20 mol%, 3.20 to 5.10 mol%, 3.40 to 5.40 mol%, 3.70 to 5.20 mol%, 3.00 to 4.00 mol%, etc. In some embodiments, TiO 2 +ZrO 2 The content of + ZrO may be 3.00 mol%, 3.10 mol%, 3.20 mol%, 3.30 mol%, 3.40 mol%, 3.50 mol%, 3.70 mol%, 4.00 mol%, 4.20 mol%, 4.50 mol%, 4.70 mol%, 4.80 mol%, 5.00 mol%, 5.10 mol%, 5.20 mol%, 5.40 mol%, 5.50 mol%, etc.

[0075] TiO 2The content is 0 to 2.00 mol% and all ranges and sub-ranges therebetween, such as 0.10 to 1.00 mol%, 0.50 to 1.00 mol%, 0.20 to 1.90 mol%, 0.40 to 1.20 mol%, 0.60 to 1.50 mol%, 0.80 to 1.00 mol%, 0.30 to 1.80 mol%, 0.20 to 1.50 mol%, 0.30 to 1.30 mol%, 0.10 to 1.70 moll%, etc. In some embodiments, TiO 2 The content may be 0 mol%, 0.10 mol%, 0.20 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.60 mol%, 0.80 mol%, 0.90 mol%, 1.00 mol%, 1.20 mol%, 1.30 mol%, 1.50 mol%, 1.70 mol%, 1.80 mol%, 1.90 mol%, 2.00 mol%, etc.

[0076] The content of ZrO 2 is 2.50 to 5.00 mol% and all ranges and sub-ranges therebetween, such as 2.60 to 4.50 mol%, 2.70 to 4.50 mol%, 2.90 to 4.20 mol%, 2.90 to 3.50 mol%, 2.80 to 3.70 mol%, 2.50 to 3.10 mol%, 2.60 to 4.60 mol%, 3.50 to 5.00 mol%, 4.50 to 5.00 mol%, 3.10 to 4.50 mol%, 3.20 to 4.30 mol%, 2.90 to 3.80 mol%, 2.70 to 3.80 mol%, etc. In some embodiments, the content of ZrO 2 may be 2.50 mol%, 2.60 mol%, 2.70 mol%, 2.80 mol%, 2.90 mol%, 3.10 mol%, 3.20 mol%, 3.50 mol%, 3.70 mol%, 3.80 mol%, 4.20 mol%, 4.30 mol%, 4.50 mol%, 4.60 mol%, 5.00 mol%, etc.

[0077] After the blending of the materials is completed, it is necessary to further add a clarifying agent to the blended materials. The clarifying agent is not particularly limited, and sodium chloride (NaCl), tin oxide, etc. can be used. The amount of the clarifying agent used does not exceed 2 wt% of the weight of the blended materials. For example, when the weight of the blended materials formulated according to the recipe is 1 kg, the amount of the clarifying agent added does not exceed 20 g. The clarifying agent is an auxiliary component added separately during blending.

[0078] In some embodiments, based on the molar percentage of the oxides, in the glass ceramics, 0.40 ≦ (Al 2 O 3 +ZnO+MgO+ZrO 2 +TiO 2 ) / (Li 2 O+Na 2 O+SiO 2 +BaO) ≦ 0.70. In the present invention, by configuring the crystallizable glass to have such a specific ratio, the glass ceramics manufactured using these crystallizable glasses can have the above-mentioned properties of the present invention including the composition and / or amount and / or structure of zinc spinel and magnesium spinel. For example, by defining that the composition of the glass ceramics satisfies the above molar ratio and the glass ceramics contain zinc spinel, magnesium spinel, and a glass phase, it can affect the properties and / or characteristics of the glass ceramics manufactured therefrom. For example, the crystallinity of the glass ceramics can be improved, it can have better inherent strength, and at the same time, a higher transmittance can be obtained, and ion exchange can be carried out quickly and efficiently. By adjusting the crystallizable glass in this way, this ratio enables the actual conversion process (for example, the temperature and / or time of nucleation and crystallization) to be carried out, and reproducibly and surely enables the formation of glass ceramics characterized by the required excellent optical properties and inherent strength. (Al 2 O 3 +ZnO+MgO+ZrO 2 +TiO 2 ) / (Li 2O + Na 2 O + SiO 2 (The ratio of (Al 2 O 3 + ZnO + MgO + ZrO 2 + TiO 2 ) / (Li 2 O + Na 2 O + SiO 2 + BaO) includes ratios of 0.40 to 0.70 and all ranges and sub - ranges therebetween, for example, 0.41 - 0.51, 0.43 - 0.68, 0.42 - 0.60, 0.43 - 0.55, 0.44 - 0.58, 0.42 - 0.68, 0.45 - 0.69, 0.46 - 0.62, 0.41 - 0.54, 0.43 - 0.54, 0.44 - 0.59, 0.49 - 0.70, etc. In some embodiments, (Al

[0079] In some examples, based on the molar percentage of oxides, in the glass - ceramics, Na 2 O / (Li 2 O + Na 2 O + SiO 2 + BaO) ≥ 0.035, and / or Li 2 O / (Li 2 O + Na 2 O + SiO 2 + BaO) ≥ 0.054 is satisfied. Further, the relationship between Na 2 O and Li 2 O and other components is studied, and Na 2 O and Li 2By controlling the usage amount between O and other components within the range of such a predetermined ratio, it is possible to ensure that the glass ceramics have excellent ion exchange ability, and it is guaranteed that the obtained transparent spinel glass ceramics can obtain high CS, DOL_0, CT_AV, and CT_LD through chemical strengthening of ion exchange.

[0080] Na 2 O / (Li 2 O+Na 2 O+SiO 2 +BaO) ratio is 0.035 or more and all ranges and sub-ranges therebetween, such as 0.035 - 0.070, 0.039 - 0.058, 0.035 - 0.051, 0.035 - 0.052, 0.035 - 0.055, 0.040 - 0.060, 0.055 - 0.060, 0.038 - 0.052, etc. are included. In some embodiments, Na 2 O / (Li 2 O+Na 2 O+SiO 2 +BaO) ratio may be 0.035, 0.036, 0.037, 0.038, 0.039, 0.040, 0.043, 0.045, 0.048, 0.050, 0.051, 0.052, 0.055, 0.058, 0.060, 0.063, 0.065, 0.068, 0.070, etc.

[0081] Li 2 O / (Li 2 O+Na 2 O+SiO 2 +BaO) ratio is 0.054 or more and all ranges and sub-ranges therebetween, such as 0.054 - 0.090, 0.055 - 0.080, 0.056 - 0.074, 0.058 - 0.073, 0.056 - 0.071, 0.059 - 0.077, 0.055 - 0.065, 0.055 - 0.075, etc. are included. In some embodiments, Li 2 O / (Li 2 O+Na 2 O+SiO 2The ratio of (+BaO) may be 0.054, 0.055, 0.056, 0.058, 0.059, 0.060, 0.063, 0.065, 0.068, 0.070, 0.071, 0.073, 0.074, 0.075, 0.077, 0.080, 0.083, 0.085, 0.088, 0.090, etc.

[0082] Third, the present invention provides a method for preparing transparent spinel glass ceramics, Step (1) Mixing raw materials according to a recipe to prepare a glass precursor, and Step (2) Sequentially performing a nucleation treatment and a crystallization treatment on the obtained glass precursor to prepare the transparent spinel glass ceramics.

[0083] In the present invention, the raw materials are formulated and mixed according to the recipe for 30 minutes. After uniform mixing, a clarifying agent is added as needed, melted in a platinum crucible at 1650 °C for 20 hours, then put into a molding die for molding, cooled to 900 °C, then put into an annealing furnace at 600 °C for annealing for 6 hours, and then cooled to room temperature together with the furnace to obtain a glass precursor. Sequentially performing a nucleation treatment and a crystallization treatment on the glass precursor can prepare transparent spinel glass ceramics.

[0084] To obtain the transparent spinel glass ceramic product of the present invention, when performing the nucleation treatment, the nucleation temperature is 700 - 800 °C, the nucleation treatment time is 30 - 1440 min, when performing the crystallization treatment, the crystallization temperature is 900 - 1000 °C, and the crystallization treatment time is 5 - 1440 min. The nucleation treatment time here is the time for heat preservation after raising the temperature of the crystallization furnace to the set nucleation temperature according to the set heating rate. The crystallization treatment time here is the time for heat preservation after raising the temperature of the crystallization furnace to the set crystallization temperature according to the set heating rate.

[0085] Put the glass precursor into a crystallization furnace. First, heat it up to the nucleation temperature at a heating rate of 5 - 20 °C / min, hold it for 30 - 1440 min to perform the nucleation treatment, form a sufficient number of crystal nuclei, ensure the crystallinity of the glass ceramics. After the nucleation treatment is completed, heat it up to the crystallization temperature at a heating rate greater than 20 °C / min, hold it for 5 - 1440 min to perform the crystallization treatment, precipitate the required zinc spinel and magnesium spinel, and at the same time effectively suppress the precipitation of the impurity crystal phase. After the crystallization treatment, lower the temperature to room temperature together with the furnace. By adjusting the heating rate, temperature, and time at different treatment stages according to the glass ceramics composition within the above range, it can be ensured that no impurity crystal phase that affects the transmittance of the spinel glass ceramics precipitates, and no clouding and devitrification phenomena occur in the glass ceramics.

[0086] The nucleation temperature includes 700 - 800 °C and all ranges and sub - ranges therebetween, such as 710 - 790 °C, 700 - 720 °C, 700 - 730 °C, 700 - 740 °C, 700 - 750 °C, 700 - 760 °C, 730 - 800 °C, 740 - 800 °C, 750 - 800 °C, 760 - 800 °C, etc. The nucleation treatment time includes 30 - 1440 min and all ranges and sub - ranges therebetween, such as 30 - 300 min, 30 - 200 min, 30 - 700 min, 30 - 500 min, 60 - 120 min, 80 - 144 min, 90 - 1200 min, 100 - 1100 min, 300 - 440 min, 100 - 500 min, 200 - 600 min, 300 - 540 min, 100 - 440 min, 300 - 440 min, etc.

[0087] The crystallization temperature includes 900 - 1000 °C and all ranges and sub - ranges therebetween, such as 900 - 980 °C, 900 - 960 °C, 900 - 950 °C, 900 - 930 °C, 920 - 950 °C, 910 - 1000 °C, 920 - 1000 °C, 930 - 1000 °C, 940 - 1000 °C, etc. The crystallization treatment time includes 5 - 1440 min and all ranges and sub - ranges therebetween, such as 5 - 100 min, 5 - 150 min, 5 - 200 min, 50 - 300 min, 100 - 440 min, 90 - 340 min, 200 - 1240 min, 800 - 1040 min, 500 - 740 min, 900 - 1040 min, 200 - 340 min, 100 - 300 min, 500 - 1440 min, etc.

[0088] In some embodiments, the heating rate during the crystallization process affects the crystal phase composition in the glass - ceramics and ultimately affects the performance of the glass - ceramics product. Different heating rates can bring different structures and properties to the glass - ceramics product. When the glass precursor obtained based on the recipe of the present invention undergoes crystallization treatment and the heating rate is maintained within the range of 0 - 20 °C / min, the precipitation of impurity crystal phases such as Li - containing crystal phases (such as β - spodumene), quartz, and quartz solid solution in the glass - ceramics is extremely slow. According to the research of the present inventors, in the system of spinel micro - crystals, the presence of impurity crystal phases such as β - quartz, β - quartz solid solution, and β - spodumene has a profound impact on the optical properties of the spinel glass - ceramics material. After crystallization, clouding phenomenon occurs in the glass - ceramics material, and even devitrification occurs, significantly reducing the transmittance of the obtained glass - ceramics product. This is not desirable for cover glass products. When the heating rate is greater than 20 °C / min, preferably 25 °C / min or more, more preferably 30 °C / min or more, the Li ions introduced into the glass component are always retained in the glass phase that is easy to ion - exchange, and other impurity crystal phases that affect the optical properties of the glass - ceramics do not precipitate, and do not affect the transmittance of the spinel glass - ceramics. This part is specifically as shown in Figures 4 and 5.

[0089] As can be seen from FIG. 4, when performing the crystallization treatment, if the heating rate is maintained within the range of 0 to 20 ° C / min, impurity crystals will precipitate in the glass (extra characteristic peaks clearly appear in the XRD spectrum), mainly crystal phases such as β-quartz, β-quartz solid solution, and β-spodumene. As can be understood in combination with FIG. 5, these impurity crystal phases precipitated in the glass have a profound impact on the optical properties of the glass, causing cloudiness and even devitrification of the glass. When performing the crystallization treatment, if the heating rate is greater than 20 ° C / min and is 30 ° C / min, no impurity crystals will precipitate and the glass will remain in a transparent state. When performing the crystallization treatment of the present invention, the heating rate is greater than 20 ° C / min and 35 ° C / min or less, as well as all ranges and sub-ranges therebetween, such as 21 to 30 ° C / min, 22 to 25 ° C / min, 25 to 30 ° C / min, 23 to 28 ° C / min, 22 to 30 ° C / min, 23 to 30 ° C / min, 24 to 30 ° C / min, 25 to 28 ° C / min, 21 to 35 ° C / min, etc. In some embodiments, when performing the crystallization treatment, the heating rate may be 21 ° C / min, 22 ° C / min, 23 ° C / min, 24 ° C / min, 25 ° C / min, 28 ° C / min, 30 ° C / min, 35 ° C / min, etc.

[0090] The heating rate during the nucleation process affects the formation of crystal nuclei and the number of crystal nuclei, and ultimately affects the crystallinity of the glass ceramics and the inherent strength of the glass ceramics. When performing the nucleation treatment of the present invention, the heating rate is 5 to 20 ° C / min and all ranges and sub-ranges therebetween, such as 5 to 10 ° C / min, 10 to 20 ° C / min, 11 to 20 ° C / min, 12 to 15 ° C / min, 9 to 20 ° C / min, 13 to 20 ° C / min, 10 to 19 ° C / min, 9 to 17 ° C / min, etc. In some embodiments, when performing the nucleation treatment, the heating rate may be 5 ° C / min, 9 ° C / min, 10 ° C / min, 11 ° C / min, 12 ° C / min, 13 ° C / min, 15 ° C / min, 16 ° C / min, 17 ° C / min, 19 ° C / min, 20 ° C / min, etc.

[0091] 3. The present invention further provides strengthened glass ceramics. The strengthened glass ceramics of the present invention are produced by chemically strengthening the transparent spinel glass ceramics through ion exchange, and the strengthened glass ceramics have a compressive stress region extending from the surface to the compression depth. The strengthened glass ceramics include a compressive stress layer located on the surface and a tensile stress layer located inside. The compressive stress layer is a compressive stress region formed by chemical strengthening, and the tensile stress layer is a region that has not been ion-exchanged. The composition of the tensile stress layer of the strengthened glass ceramics is the same as that of the transparent spinel glass ceramics.

[0092] Specifically, when implementing, the strengthened glass ceramics can be obtained by performing one-step or multi-step ion exchange on the transparent spinel glass ceramics in a salt bath.

[0093] The transparent spinel glass ceramics can be chemically strengthened. In the process of chemical strengthening by ion exchange of the glass ceramics, the glass ceramics can perform K -Na + -Na + 、Na + -Li + binary ion exchange, whereby the glass ceramics obtain a composite compressive stress layer after ion exchange, and the strengthened glass ceramics after strengthening have a compressive stress region extending from the surface to the compression depth.

[0094] The transparent spinel glass ceramics can use multiple ion exchange processes to improve the performance of the glass ceramics. By using ion exchange salt baths with different ion concentrations, a stress curve is generated at the selected depth, and strengthened glass ceramics with excellent stress characteristics can be obtained.

[0095] The crystalline phases of the toughened glass ceramics provided by the present invention include spinel crystals and zirconia crystals, and do not contain Li-containing crystals, quartz, and quartz solid solutions. The spinel crystals include zinc spinel and magnesium spinel, and / or a solid solution of zinc spinel (ZnAl 2 O 4 ) and magnesium spinel (MgAl 2 O 4 ). The toughened glass ceramics exhibit a crystallinity of at least 30.00 wt%, and the average size of the crystals in the toughened glass ceramics is 15.0 nm or less. When the thickness of the toughened glass ceramics is 0.7 mm, the transmittance at 550 nm is greater than 85.00%.

[0096] The depth of the compressive stress layer DOL_0 of the toughened glass ceramics of the present invention is 14% or more of the thickness of the toughened glass ceramics. As the contents of Li 2 O and Na 2 O increase, the glass ceramics have more Na ions and Li ions available for ion exchange and can form a higher compressive stress layer depth.

[0097] When the glass ceramics have a thickness of 0.7 mm, the range of DOL_0 is 100.0 μm or more, including all ranges and sub-ranges between 100.0 μm and, for example, 100.0 - 125.0 μm, 100.0 - 127.0 μm, 100.0 - 135.0 μm, 100.0 - 140.0 μm, 100.0 - 112.0 μm, 100.0 - 115.0 μm, 100.0 - 116.0 μm, 100.0 - 112.0 μm, 104.0 - 120.0 μm, 106.0 - 111.0 μm, 108.0 - 120.0 μm, 104.0 - 120.0 μm, 108.0 - 120.0 μm, etc. In some embodiments, DOL_0 may be 100.0 μm, 104.0 μm, 106.0 μm, 108.0 μm, 111.0 μm, 112.0 μm, 115.0 μm, 116.0 μm, 120.0 μm, 125.0 μm, 127.0 μm, 135.0 μm, 140.0 μm, etc.

[0098] The tensile stress line density CT_LD of the tempered glass ceramics of the present invention is 25,000 MPa / mm or more, including 25,000 MPa / mm or more and all ranges and sub-ranges therebetween, such as 25,000 - 40,000 MPa / mm, 27,000 - 40,000 MPa / mm, 25,000 - 38,000 MPa / mm, 25,000 - 37,000 MPa / mm, 25,000 - 39,000 MPa / mm, 27,000 - 38,000 MPa / mm, 27,000 - 39,000 MPa / mm, 28,000 - 38,000 MPa / mm, etc. In some embodiments, CT_LD may be 25,000 MPa / mm, 27,000 MPa / mm, 28,000 MPa / mm, 37,000 MPa / mm, 38,000 MPa / mm, 39,000 MPa / mm, 40,000 MPa / mm, etc.

[0099] The surface compressive stress CS of the tempered glass ceramics of the present invention is 650 MPa or more, including CS being 650 MPa or more and all ranges and sub-ranges therebetween, for example, preferably 680 MPa or more, preferably 700 MPa or more, preferably 750 MPa or more, preferably 800 MPa or more, preferably 900 MPa or more, preferably 1000 MPa or more, preferably 700 - 800 MPa, preferably 750 - 800 MPa, preferably 760 - 870 MPa, preferably 710 - 860 MPa, preferably 700 - 900 MPa, preferably 800 - 1000 MPa, preferably 850 - 1000 MPa, etc. In some embodiments, CS may be 650 MPa, 680 MPa, 700 MPa, 710 MPa, 750 MPa, 760 MPa, 800 MPa, 850 MPa, 860 MPa, 870 MPa, 900 MPa, 1000 MPa, etc.

[0100] The average tensile stress CT_AV of the tempered glass ceramics of the present invention is 35.0 MPa or more, and it includes CT_AV being 35.0 MPa or more and all ranges and sub-ranges therebetween, for example, preferably 39.0 MPa or more, preferably 40.0 MPa or more, preferably 45.0 MPa or more, preferably 50.0 MPa or more, preferably 55.0 MPa or more, preferably 60.0 MPa or more, preferably 65.0 MPa or more, preferably 70.0 MPa or more, preferably 75.0 MPa or more, preferably 39.0 MPa to 65.0 MPa, preferably 35.0 MPa to 65.0 MPa, preferably 35.0 MPa to 55.0 MPa, preferably 35.0 MPa to 70.0 MPa, etc. In some embodiments, CT_AV may be 35.0 MPa, 39.0 MPa, 40.0 MPa, 45.0 MPa, 50.0 MPa, 55.0 MPa, 60.0 MPa, 65.0 MPa, 70.0 MPa, 75.0 MPa, etc.

[0101] The Vickers hardness of the tempered glass ceramics of the present invention is 740 HV0.3 or more. Here, 740 in 740 HV0.3 represents the Vickers hardness, and 0.3 means that the load value used for measurement is 0.3 kg. It includes 740 HV0.3 or more and all ranges and sub-ranges therebetween, for example, preferably 760 HV0.3 or more, preferably 770 HV0.3 or more, preferably 780 HV0.3 or more, preferably 790 HV0.3 or more, preferably 800 HV0.3 or more, preferably 820 HV0.3 or more, preferably 830 HV0.3 or more, preferably 740 HV0.3 to 780 HV0.3, preferably 740 HV0.3 to 830 HV0.3, etc. In some embodiments, the Vickers hardness may be 740 HV0.3, 760 HV0.3, 770 HV0.3, 780 HV0.3, 790 HV0.3, 800 HV0.3, 820 HV0.3, 830 HV0.3, etc.

[0102] The fracture toughness of the tempered glass ceramics of the present invention is 1.500 MPa·m 1 / 2 or more, and the fracture toughness of the tempered glass ceramics is 1.500 MPa·m 1 / 2The above and all ranges and sub-ranges therebetween, for example, preferably 1.560 MPa·m 1 / 2 or more, preferably 1.500 - 1.560 MPa·m 1 / 2 , preferably 1.600 - 1.700 MPa·m 1 / 2 , preferably 1.500 - 1.590 MPa·m 1 / 2 , preferably 1.540 - 1.600 MPa·m 1 / 2 , preferably 1.500 - 1.610 MPa·m 1 / 2 , preferably 1.500 - 1.630 MPa·m 1 / 2 , preferably 1.500 - 1.700 MPa·m 1 / 2 and the like are included. In some embodiments, the fracture toughness of the toughened glass ceramics is 1.500 MPa·m 1 / 2 , 1.540 MPa·m 1 / 2 , 1.560 MPa·m 1 / 2 , 1.590 MPa·m 1 / 2 , 1.600 MPa·m 1 / 2 , 1.610 MPa·m 1 / 2 , 1.630 MPa·m 1 / 2 , 1.700 MPa·m 1 / 2 and so on may be acceptable.

[0103] In the present invention, whether the transparent spinel glass ceramics select single ion exchange or multiple ion exchanges, since the glass ceramics already have improved intrinsic strength, toughened glass ceramic products with better performance can be obtained after ion exchange.

[0104] The salt bath used in the present invention contains at least one of potassium salt and sodium salt. Regarding the salts used for ion exchange, nitrates are common, but any suitable salt or salt combination can be used.

[0105] When performing one-step ion exchange, the composition of the salt bath is 50 - 100 wt% NaNO 3 + 0 - 50 wt% KNO 3It includes, the temperature of ion exchange is 400 - 500 °C, and the time of ion exchange is 0.5 - 48 h. Here, the "time of ion exchange" refers to the time for chemically strengthening the glass ceramics by putting them into a salt bath at a predetermined temperature and mixing ratio.

[0106] Here, the temperature of ion exchange includes 400 - 500 °C and all ranges and sub - ranges therebetween, for example, 400 - 500 °C, 400 - 410 °C, 400 - 420 °C, 400 - 430 °C, 400 - 440 °C, 400 - 450 °C, 400 - 460 °C, 400 - 470 °C, 410 - 450 °C, 430 - 500 °C, 440 - 500 °C, etc. The ion exchange time includes 0.5 - 48 h and all ranges and sub - ranges therebetween, for example, 0.5 - 46 h, 1 - 10 h, 1 - 5 h, 1 - 40 h, 7 - 30 h, 9 - 29 h, 10 - 41 h, 6 - 32 h, 9 - 27 h, 4 - 33 h, 5 - 27 h, 6 - 38 h, etc.

[0107] The composition of the salt bath is 50 - 100 wt% of NaNO 3 and all ranges and sub - ranges therebetween, for example, 50 - 60 wt%, 50 - 70 wt%, 50 - 80 wt%, 50 - 90 wt%, 60 - 100 wt%, 70 - 100 wt%, 80 - 100 wt%, 50 - 89 wt%, 64 - 88 wt%, 90 - 100 wt%, etc., and 0 - 50 wt% of KNO 3 and all ranges and sub - ranges therebetween, for example, 0 - 40 wt%, 0 - 30 wt%, 0 - 20 wt%, 0 - 10 wt%, 0 - 14 wt%, 0 - 15 wt%, 0 - 35 wt%, 0 - 45 wt%, 5 - 40 wt%, 20 - 30 wt%, etc.

[0108] When performing two - stage ion exchange, the composition of the salt bath in the first stage is 90 - 100 wt% NaNO 3 + 0 - 10 wt% KNO 3 It includes, the temperature of ion exchange is 400 - 500 °C, and the time of ion exchange is 0.5 - 48 h, The composition of the salt bath in the second stage is 0 - 10 wt% NaNO 3 + 90 - 100 wt% KNO 3It includes, and the temperature of ion exchange is 400 - 500 °C, and the time of ion exchange is 0.5 - 48 h.

[0109] Here, the temperature of ion exchange includes 400 - 500 °C and all ranges and sub - ranges therebetween, for example, 400 - 500 °C, 400 - 410 °C, 400 - 420 °C, 400 - 430 °C, 400 - 440 °C, 400 - 450 °C, 400 - 460 °C, 400 - 470 °C, 410 - 450 °C, 430 - 500 °C, 440 - 500 °C, etc. The ion exchange time includes 0.5 - 48 h and all ranges and sub - ranges therebetween, for example, 0.5 - 46 h, 1 - 10 h, 1 - 5 h, 1 - 40 h, 7 - 30 h, 9 - 29 h, 10 - 41 h, 6 - 32 h, 9 - 27 h, 4 - 33 h, 5 - 27 h, 6 - 38 h, etc.

[0110] The composition of the salt bath in the first stage is 90 - 100 wt% NaNO 3 and all ranges and sub - ranges therebetween, for example, 91 - 100 wt%, 92 - 100 wt%, 93 - 100 wt%, 94 - 100 wt%, 95 - 100 wt%, 96 - 100 wt%, 97 - 100 wt%, 98 - 100 wt%, 99 - 100 wt%, etc. Further, 0 - 10 wt% KNO 3 and all ranges and sub - ranges therebetween, for example, 0 - 1 wt%, 0 - 2 wt%, 0 - 3 wt%, 0 - 4 wt%, 5 - 10 wt%, 2 - 10 wt%, 6 - 9 wt%, 3 - 8 wt%, 2 - 9 wt%, 1 - 8 wt%, etc.

[0111] The composition of the salt bath in the second stage is 0 - 10 wt% NaNO 3 and all ranges and sub - ranges therebetween, for example, 0 - 1 wt%, 0 - 2 wt%, 0 - 3 wt%, 0 - 4 wt%, 2 - 10 wt%, 3 - 5 wt%, 5 - 10 wt%, 6 - 10 wt%, 2 - 7 wt%, 3 - 7 wt%, etc. Further, 90 - 100 wt% KNO 3 and all ranges and sub - ranges therebetween , for example, 91 - 100 wt%, 92 - 100 wt%, 93 - 100 wt%, 94 - 100 wt%, 95 - 100 wt%, 96 - 100 wt%, 97 - 100 wt%, 98 - 100 wt%, etc.

[0112] To improve the service life of the salt bath, a salt bath protective agent accounting for 0.1-5 wt% of the mass percentage of the salt bath can be added to the salt bath, and the salt bath protective agent contains Li + and substances for passivating, precipitating or absorbing it. For example, substances for passivating, precipitating or absorbing Li + such as phosphates, silicates, carbonates, etc. can be used as the salt bath protective agent, whereby the concentration of Li + exchanged in the salt bath is increased, thereby avoiding affecting the ion exchange performance provided by the salt bath and the service life of the salt bath. The salt bath protective agent includes 0.1-5.0 wt% and all ranges and sub-ranges therebetween, for example, 0.1-4.0 wt%, 0.1-3.0 wt%, 0.1-2.0 wt%, 0.1-1.0 wt%, 0.2-5.0 wt%, 0.5-5.0 wt%, 4.1-5.0 wt%, 3.1-5.0 wt%, 2.6-4.5 wt%, 0.7-3.5 wt%, 0.8-2.5 wt%, 0.9-1.5 wt%, 0.8-2.5 wt%, etc.

[0113] IV. The present invention further provides an electronic terminal as a consumer product. The electronic terminal as a consumer product provided by the present invention includes a shell and electronic parts partially located within the shell, the shell includes a front surface, a rear surface and side surfaces, the electronic parts include a display device, and the display device is located on the front surface of the shell or adjacent to the front surface, the front surface and / or the rear surface and / or the side surfaces include the strengthened glass ceramics material, the electronic terminal further includes a covering product covering the front surface of the shell or located on the display device, and the covering product includes the strengthened glass ceramics material, the electronic terminal as a consumer product includes a mobile phone, a tablet, a photovoltaic device, or other electronic terminals (such as electronic wristwatches).

[0114] The transparent spinel glass-ceramic material and the reinforced glass-ceramic material in the present invention both have excellent properties and can be included in / used in other products. For example, watches, transparent armor, missile windows, cowlings, substrate materials, new lamps, viewing windows of equipment in high-temperature, high-pressure, and corrosive environments, display protection materials and appearance case protection materials for portable smart electronic devices (portable smart electronic devices include mobile phones, tablet computers, electronic watches, etc.), building products, transportation products (such as automobiles, trains, airplanes, seaplanes, etc.), appliance products, or any product that requires a certain degree of transparency, scratch resistance, impact resistance, abrasion resistance, or a combination thereof.

[0115] V. Hereinafter, the present invention will be described by way of specific examples. Table 1 shows the recipes of the glass-ceramics of Schemes 1-6 of the present invention.

[0116] [Table 1]

[0117] Table 2 shows the recipes of the glass-ceramics of Schemes 7-12 of the present invention.

[0118] [Table 2]

[0119] Table 3 shows the recipes of the glass-ceramics of Comparative Schemes 13-16 of the present invention.

[0120] [Table 3]

[0121] Table 4 shows the properties of the glass-ceramics prepared in Examples 1-2 and Comparative Examples 13-16 and the corresponding reinforced glass-ceramics.

[0122] [Table 4]

[0123] Remarks: DOL_0 is the depth of the compressive stress generated after the Li ions in the glass ceramics are exchanged with the Na ions in the salt bath. DOL_2 is the depth of the compressive stress generated after the Na ions in the glass ceramics are exchanged with the K ions in the salt bath. "450 - 3H" means that the ion exchange temperature is 450 °C and the ion exchange time is 3 h, and other similar expressions have similar meanings. "100%NaNO 3 " means 100 wt% of NaNO 3 and other similar expressions have similar meanings.

[0124] Table 5 shows the properties of the glass ceramics prepared in Examples 3 - 7 and the corresponding strengthened glass ceramics.

[0125]

Table 5

[0126] Remarks: DOL_0 is the depth of the compressive stress generated after the Li ions in the glass ceramics are exchanged with the Na ions in the salt bath. DOL_2 is the depth of the compressive stress generated after the Na ions in the glass ceramics are exchanged with the K ions in the salt bath. "450 - 3H" means that the ion exchange temperature is 450 °C and the ion exchange time is 3 h, and the meanings of other similar expressions are similar. "100%NaNO 3 " means 100 wt% of NaNO 3 and other similar expressions have similar meanings.

[0127] Table 6 shows the properties of the glass ceramics prepared in Examples 8 - 12 and the corresponding strengthened glass ceramics.

[0128]

Table 6

[0129] Remarks: DOL_0 is the depth of the compressive stress generated after the Li ions in the glass ceramics are exchanged with the Na ions in the salt bath. DOL_2 is the depth of the compressive stress generated after the Na ions in the glass ceramics are exchanged with the K ions in the salt bath. "450-3H" means that the ion exchange temperature is 450 °C and the ion exchange time is 3 h, and the meanings of other similar expressions are similar. "100%NaNO 3 " means 100 wt% of NaNO 3 and other similar expressions have similar meanings.

[0130] Table 7 shows the glass ceramics prepared in Comparative Examples 1 to 6.

[0131]

Table 7

[0132] Remarks: The precipitated quartz solid solution in the above comparative examples is mainly β-quartz solid solution.

[0133] Table 8 shows the glass ceramics prepared in Comparative Examples 7 to 12.

[0134]

Table 8

[0135] Remarks: The precipitated quartz solid solution in the above comparative examples is mainly β-quartz solid solution.

[0136] Taking Example 1 as an example, according to the recipe of Scheme 1, raw materials are blended and mixed for 30 minutes. The total amount of the mixed materials is 1000 g. After uniform mixing, 5 g of a clarifying agent (NaCl) is added, melted in a platinum crucible at 1650 °C for 20 hours, then put into a molding die for molding, cooled to 900 °C, then put into an annealing furnace at 600 °C for annealing for 6 hours, and then cooled to room temperature together with the furnace to obtain a glass precursor. According to the corresponding process conditions in the above table, nucleation treatment and crystallization treatment are sequentially performed on the glass precursor to manufacture a glass-ceramics product. Chemical strengthening is performed on the obtained glass-ceramics according to the corresponding strengthening process conditions in the above table to manufacture a strengthened glass-ceramics product.

[0137] As can be seen from Tables 1 to 6, in the glass recipes of Comparative Examples 13 to 16, since the contents of Li 2 O and Na 2 O are lower than those in Examples 1 to 12, after the prepared glass-ceramics are subjected to strengthening treatment, the obtained CT_LD is much lower than that in Examples 1 to 12, and some do not even reach 20000 MPa / mm. The drop height resistance of the strengthened glass-ceramics prepared from the glass-ceramics of Examples 1 to 12 is significantly higher than that of Comparative Examples 13 to 16.

[0138] A bulk drop test was performed on the strengthened glass-ceramics of Comparative Examples 13, 15 and Examples 5, 6, 11, 12. 10 samples of each were taken, and the test results are as shown in Figure 1. As can be seen from Figure 1, the drop effects of Comparative Example 13 and Comparative Example 15 are low, and the drop heights are concentrated between 0.7 and 1.7 m. In Examples 5, 6, 11, 12, since the content of Li 2 O in the recipe is high, the tensile stress line density CT_LD after strengthening treatment increases significantly, the stress depth DOL_0 also increases significantly, and the drop height improves significantly. At the same time, the CT_LD of Example 12 and Example 6 are almost the same. As can be seen from this, the drop height of Example 12 with a high degree of crystallinity is clearly high, and among the 10 pieces of glass dropped, only 2 pieces of glass have a drop height of less than 2 m. As can be seen from this, in the strengthened glass-ceramics, the drop height is related to the degree of crystallinity and C Associated with both T_LD, the present invention ensures crystallinity while adding more Li 2 O to ensure that the strengthened CT_LD is high and the drop resistance effect is high.

[0139] As can be seen from Tables 7-8, the heating rate of the crystallization process has a significant impact on the type of crystal phase of the glass ceramics. In Comparative Examples 1-12, the crystallization heating rate is less than 20 °C / min, an impurity crystal phase of quartz solid solution occurs in the crystal phase of the glass ceramics material, and the size of the crystal grains is significantly large. Although the crystallinity increases, the transmittance decreases significantly, and furthermore, a situation where the refractive index cannot be measured occurs. Such glass ceramics cannot meet the requirements as a cover material.

[0140] The glass precursor obtained by the recipe of Embodiment 8 was subjected to microcrystallization treatment at different crystallization heating rates (5 °C / min, 20 °C / min, 30 °C / min). The photographs of the obtained glass ceramics are shown in Fig. 5, the XRD spectra of the obtained glass ceramics are shown in Fig. 4, and the transmittance of the obtained glass ceramics at a light wavelength of 550 nm is shown in Fig. 6. As can be seen from Figs. 4-6, when the heating rate is within the range of 0-20 °C / min during the crystallization treatment, impurity crystals precipitate in the glass (extra characteristic peaks appear significantly in the XRD spectrum), the glass ceramics become cloudy, and even devitrification occurs. When the heating rate is 30 °C / min during the crystallization treatment, no impurity crystals precipitate and the glass remains in a transparent state.

[0141] The present invention optimizes the composition of the spinel glass ceramics material, further introduces more Li ions and Na ions used for chemical strengthening by ion exchange into the spinel glass ceramics, and obtains spinel glass ceramics without impurity crystal phases (such as impurity crystal phases such as Li-containing crystal phases, quartz, and quartz solid solutions), ensuring that the glass ceramics do not exhibit phenomena such as cloudiness and devitrification and that the glass ceramics material has excellent transmittance.

[0142] By introducing more Li ions and Na ions into the spinel glass ceramics component, the obtained spinel glass ceramics can be chemically strengthened, and transparent strengthened glass ceramics with high CS, DOL_0, CT_AV, and CT_LD can be obtained, and this strengthened glass ceramics exhibits excellent drop resistance.

[0143] As a result of conducting property tests on the glass ceramics material obtained in the present invention, it was found that the transparent spinel glass ceramics material of the present invention has a high degree of crystallinity, thus bringing excellent mechanical properties to the glass ceramics material.

[0144] The present invention further provides a method for preparing spinel glass ceramics. The process method provided by the present invention controls the process parameters of the crystallization process and the nucleation process, and sets the requirements for the heating rate parameter, so as to obtain spinel glass ceramics without impurity crystal phases (for example, impurity crystal phases such as Li-containing crystal phases, quartz, and quartz solid solutions), and ensure that the glass ceramics material has excellent optical properties.

[0145] Finally, the above embodiments are only for explaining the technical solution of the present invention and do not limit the technical solution. Those skilled in the art should understand that modifications or equivalent substitutions made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention are also included within the scope of the claims of the present invention.

Claims

1. 1. A transparent spinel glass-ceramic comprising: On an oxide mole percentage basis, the glass-ceramics include Li ２ O:3.50~6.00mol%、 Na ２ O:2.00~4.00mol%、 SiO ２ :50.00~65.00mol%、 Al ２ O ３ :14.50~25.00mol%、 MgO: 3.50 to 8.00 mol%, ZnO: 8.00 to 16.00 mol%, BaO: 0 to 2.00 mol%, and TiO ２ + ZrO ２ : Contains 3.00 to 5.50 mol%, A transparent spinel glass-ceramic, characterized in that the crystal phase of the glass-ceramic contains spinel crystals and zirconia crystals, and does not contain Li-containing crystals.

2. 2. The transparent spinel glass-ceramic of claim 1, wherein the crystalline phase of the glass-ceramic is free of quartz and quartz solid solutions.

3. 2. The transparent spinel glass-ceramic of claim 1, wherein the glass-ceramic exhibits a crystallinity of at least 30.00 wt. %.

4. 2. The transparent spinel glass-ceramic of claim 1, characterized in that the average size of the crystals in the glass-ceramic is less than or equal to 15.00 nm.

5. 2. The transparent spinel glass-ceramics of claim 1, wherein the spinel crystals include zinc spinel and magnesium spinel.

6. 2. The transparent spinel glass ceramic according to claim 1, wherein the glass ceramic has a transmittance of more than 85.00% at a wavelength of 550.00 nm when the glass ceramic has a thickness of 0.70 mm.

7. On an oxide mole percentage basis, the glass-ceramics include 0.40≦(Al ２ O ３ +ZnO+MgO+ZrO ２ + TiO ２ ) / (Li ２ O+Na ２ O+SiO ２ 2. The transparent spinel glass-ceramic according to claim 1, characterized in that:

8. On an oxide mole percentage basis, the glass-ceramics include 0.43≦(Al ２ O ３ +ZnO+MgO+ZrO ２ + TiO ２ ) / (Li ２ O+Na ２ O+SiO ２ 8. The transparent spinel glass-ceramics according to claim 7, characterized in that:

9. On an oxide mole percentage basis, the glass-ceramics include Na ２ O / (L) ２ O+1 ２ O+SiOO ２ +B1O)≧0.035、 and / or Li ２ O / (Li ２ O+Na ２ O+SiO ２ 2. The transparent spinel glass-ceramic according to claim 1, characterized in that:

10. On an oxide mole percentage basis, the glass-ceramics include 0.035≦N ２ O / (L) ２ O+1 ２ O+SiOO ２ +B1O)≦0.070、 and / or 0.054≦Li ２ O / (Li ２ O+Na ２ O+SiO ２ 10. The transparent spinel glass-ceramics according to claim 9, characterized in that:

11. The glass-ceramics comprise, on an oxide mole percentage basis, the following components: SiO ２ : 50.00 to 63.00 mol %, and / or A ２ O ３ : 14.50 to 20.00 mol %, and / or MgO: 3.90 to 7.60 mol %; and / or ZnO: 8.00 to 15.50 mol %, and / or BaO: 0 to 1.50 mol %, and / or Li ２ O: 3.50 to 5.00 mol %, and / or Na ２ O: 2.30 to 3.60 mol %, and / or TiO ２ : 0 to 2.00 mol %, and / or ZrO ２ : 2.50 to 5.00 mol%, 2. The transparent spinel glass ceramic according to claim 1 .

12. The glass-ceramics comprise, on an oxide mole percentage basis, the following components: SiO ２ : 50.00 to 57.00 mol %, and / or A ２ O ３ : 15.00 to 19.00 mol %, and / or MgO: 4.00 to 7.50 mol %; and / or ZnO: 9.00 to 15.20 mol %, and / or BaO: 1.00 to 1.35 mol %, and / or Li ２ O: 4.00 to 5.00 mol %, and / or Na ２ O: 3.00 to 3.60 mol %, and / or TiO ２ : 0.30 to 1.30 mol %, and / or ZrO ２ : 2.90 to 4.20 mol%, 2. The transparent spinel glass ceramic according to claim 1 .

13. 1. A method for producing a transparent spinel glass-ceramic, comprising the steps of: Step (1) blending and mixing raw materials according to a recipe to produce a glass precursor; Step (2) subjecting the obtained glass precursor to a nucleation treatment and a crystallization treatment in sequence to produce the transparent spinel glass-ceramic according to any one of claims 1 to 12. A method for producing a transparent spinel glass-ceramic, comprising:

14. In the step (2), When performing the nucleation treatment, the nucleation temperature is 700 to 800° C., and the nucleation treatment time is 30 to 1440 min. The method according to claim 13, characterized in that, when the crystallization treatment is performed, the crystallization temperature is 900 to 1000° C., and the crystallization treatment time is 5 to 1440 min.

15. 15. The method according to claim 14, wherein in the step (2), when the crystallization treatment is performed, the temperature is increased to the crystallization temperature at a rate of more than 20° C. / min.

16. 16. The method according to claim 15, wherein in the step (2), when the crystallization treatment is performed, the temperature is increased to the crystallization temperature at a rate of 25° C. / min or more.

17. The method according to claim 14, wherein in the step (2), when the nucleation treatment is performed, the temperature is increased to the nucleation temperature at a rate of 5 to 20° C. / min.

18. 18. The method according to claim 17, wherein in the step (2), when the nucleation treatment is performed, the temperature is increased to the nucleation temperature at a rate of 10° C. / min.

19. A reinforced glass-ceramic, 13. The reinforced glass-ceramic, characterized in that the reinforced glass-ceramic has a compressive stress region extending from its surface to a compression depth, the reinforced glass-ceramic includes a compressive stress layer located on the surface and a tensile stress layer located inside, the composition of the tensile stress layer being the same as that of the transparent spinel glass-ceramic according to any one of claims 1 to 12.

20. Use of the transparent spinel glass-ceramics according to any one of claims 1 to 12 in watches, transparent armor, missile windows, cowlings, substrate materials, lamps, observation windows for equipment in high temperature and pressure corrosive environments, automobiles, trains, airplanes, marine aircraft, building materials, and portable smart electronic devices.

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