Black microcrystalline glass as well as method and application thereof

Abstract

The invention provides black microcrystalline glass as well as a preparation method and application thereof, the black microcrystalline glass is prepared by using a coloring agent containing NiO and / or CoO in the composition, and the black microcrystalline glass shows a beautiful black appearance; meanwhile, the relative dielectric constant epsilon of the black microcrystalline glass at the frequency of 2.4 GHz and 5.0 GHz is 6 or below, and the dielectric loss is 0.005 or below; the requirements of the mobile phone cover plate glass applied to the communication technology can be met, and certain shading performance is realized in a visible light range.

Description

Technical Field

[0001] This application relates to the technical field of glass materials, and particularly relates to a black microcrystalline glass and its preparation method and uses. Background Art

[0002] In recent years, mobile phones applied to communication technologies need to have advantages such as faster data transmission speed, lower latency, energy saving, and cost reduction. Currently, traditional mobile phone cover materials are usually prepared from materials such as metals, glasses, ceramics, and polymers. Among them, metal materials have a shielding effect on mobile phone signals and have been gradually phased out; while ordinary glass and ceramic materials have insufficient scratch resistance, and the dielectric constant of ceramic materials is relatively high, which is not conducive to signal reception and transmission; polymer materials are not only not beautiful enough, but also have insufficient strength and are difficult to meet the requirements; and microcrystalline glass has gradually become the preferred choice for mobile phone cover materials due to its high strength, good scratch resistance, and high impact strength. However, future communication technologies have put forward strict requirements for the dielectric properties of mobile phone back cover materials. Therefore, the existing microcrystalline glass materials cannot meet the low dielectric property requirements of future communication technologies when applied to the backplane materials of intelligent communication devices. Summary of the Invention

[0003] The purpose of this application is to provide a black microcrystalline glass and its preparation method and uses. This microcrystalline glass has a beautiful black appearance, and at the same time, the dielectric constants at 2.4 GHz and 5 GHz frequencies are both lower than 6, and the dielectric losses are both below 0.005, which is sufficient to meet the requirements of the mobile phone cover glass for communication technologies; at the same time, it has a certain light-shielding performance in the visible light range.

[0004] In the first aspect, this application provides a black microcrystalline glass, which includes the following components in terms of mass percentage of oxides:

[0005] SiO 2 : 60.00 wt% - 75.00 wt%;

[0006] Al 2 O 3 : 2.00 wt% - 10.00 wt%;

[0007] P 2 O 5 : 1.50 wt% - 5.00 wt%;

[0008] ZrO 2 : 3.00 wt% - 10.00 wt%;

[0009] Na 2 O: 0.00 wt% - 4.00 wt%;

[0010] K 2O: 0.00 wt% to 1.00 wt%;

[0011] Li 2 O: 8.00 wt% to 14.00 wt%;

[0012] CaO: 0.00 wt% to 1.20 wt%;

[0013] B 2 O 3 : 0.00 wt% to 3.00 wt%;

[0014] The first colorant: at least one of NiO and CoO;

[0015] The second colorant: MnO 2 , Cr 2 O 3 and Ho 2 O 3 at least one of;

[0016] wherein, 0.01 wt% ≤ NiO + CoO ≤ 2.00 wt%;

[0017] 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%.

[0018] In some embodiments of the present application, the content of iron and / or titanium elements in the black series glass-ceramics is less than 1000 ppm.

[0019] In some embodiments of the present application, the content of NiO is 0.00 wt% to 1.00 wt% and / or the content of CoO is 0.00 wt% to 1.00 wt%.

[0020] In some embodiments of the present application, the content of MnO 2 is 0.00 wt% to 1.50 wt%; and / or the content of Cr 2 O 3 is 0.00 wt% to 4.00 wt%; and / or the content of Ho 2 O 3 is 0.00 wt% to 2.50 wt%.

[0021] In some embodiments of the present application, when the thickness of the black series glass-ceramics is 0.1 to 0.7 mm, L* in the color coordinates in the reflection mode in the CIELab color space is 16 to 30, preferably 16 to 29, more preferably 17 to 29; and / or a* is -4.5 to 5, preferably -4 to 5; and / or b* is -2 to 9.

[0022] In some embodiments of the present application, the black series glass-ceramics further contain CuO, Er 2 O 3 and / or Nd 2 O 3 ; preferably, based on the mass percentage of the oxide, the content of CuO is 0.00 wt% to 4.00 wt%;

[0023] and / or Er 2 O 3 has a content of 0.00 wt% to 4.00 wt%;

[0024] and / or Nd 2 O 3 has a content of 0.00 wt% to 4.00 wt%.

[0025] In some embodiments of the present application, the relative dielectric constant ε of the black series glass-ceramics at frequencies of 2.4 GHz and 5 GHz is both 6 or less.

[0026] In some embodiments of the present application, the relative dielectric constant ε of the black series glass-ceramics at frequencies of 2.4 GHz and 5 GHz is both 5.87 or less.

[0027] In some embodiments of the present application, the tangent value of the dielectric loss of the black series glass-ceramics at frequencies of 2.4 GHz and 5 GHz is both 5×10 -3 or less.

[0028] In some embodiments of the present application, the tangent value of the dielectric loss of the black series glass-ceramics at frequencies of 2.4 GHz and 5 GHz is both 1×10 -3 to 5×10 -3 .

[0029] In some embodiments of the present application, when the thickness of the black series glass-ceramics is 0.3 to 0.7 mm, the transmittance at 550 nm is 0 to 10%.

[0030] In some embodiments of the present application, the main crystal phases of the black series glass-ceramics include one or more of spodumene, lithium disilicate, lithium monosilicate, lithium phosphate, quartz, pyroxene, and nepheline; preferably, the main crystal phases of the black series glass-ceramics include one or more of spodumene, lithium disilicate, and quartz; and / or

[0031] The crystallinity of the black series glass-ceramics is 60 wt% - 100 wt%.

[0032] In a second aspect, the present application provides a method for preparing the above-mentioned black series glass-ceramics, comprising the following steps:

[0033] Step 1: Mix the raw materials for preparing the glass, melt them, and then cool and anneal to obtain a base glass;

[0034] Step 2: Heat-treat the base glass obtained in Step 1 to obtain the black series glass-ceramics.

[0035] In some embodiments of the present application, the heat treatment includes nucleation treatment and crystallization treatment.

[0036] In some embodiments of the present application, the heating rate of the nucleation treatment is 1 °C / min to 15 °C / min; and / or,

[0037] the temperature of the nucleation treatment is 500 °C to 600 °C; and / or,

[0038] the time of the nucleation treatment is 30 min to 600 min; and / or,

[0039] the heating rate of the crystallization treatment is 1 °C / min to 15 °C / min; and / or,

[0040] the temperature of the crystallization treatment is 600 °C to 850 °C; and / or,

[0041] the time of the crystallization treatment is 30 min to 600 min.

[0042] In a third aspect, the present application provides a strengthened black series glass-ceramics with a thickness of t, which includes double-sided strengthening layers and a tensile stress layer. The strengthening layers extend from the surface of the strengthened black series glass-ceramics towards the interior direction, wherein the double-sided strengthening layers are symmetrically distributed, and the thickness of each strengthening layer is not higher than 0.22t; when the thickness of the strengthened black series glass-ceramics is 0.1 - 0.7 mm, the color coordinates in the reflection mode in the CIELab color space are: L*: 15 - 30; a*: -5 - 5; b*: -2 - 10;

[0043] The strengthened black series glass-ceramics, in terms of mass percentage of oxides, includes the following components:

[0044] SiO 2 : 60.00 wt% to 75.00 wt%;

[0045] Al 2 O 3 : 2.00 wt% to 10.00 wt%;

[0046] P 2 O 5 : 1.50 wt% to 5.00 wt%;

[0047] ZrO 2 : 3.00 wt% to 10.00 wt%;

[0048] Na 2 O: 0.00 wt% to 21.00 wt%;

[0049] K 2 O: 0.00 wt% to 3.00 wt%;

[0050] Li 2 O: 1.00 wt% to 14.00 wt%;

[0051] CaO: 0.00 wt% to 1.20 wt%;

[0052] B 2 O 3 : 0.00 wt% to 3.00 wt%;

[0053] The first colorant: at least one of NiO and CoO;

[0054] The second colorant: MnO 2 , Cr 2 O 3 and Ho 2 O 3 at least one of;

[0055] wherein, 0.01 wt% ≤ NiO + CoO ≤ 2.00 wt%;

[0056] 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%;

[0057] The said tensile stress layer, calculated by the mass percentage of the oxide, comprises the following components:

[0058] SiO 2 : 60.00 wt% to 75.00 wt%;

[0059] Al 2 O 3 : 2.00 wt% to 10.00 wt%;

[0060] P 2 O 5 : 1.50 wt% to 5.00 wt%;

[0061] ZrO 2 : 3.00 wt% to 10.00 wt%;

[0062] Na 2 O: 0.00 wt% to 4.00 wt%;

[0063] K 2 O: 0.00 wt% to 1.00 wt%;

[0064] Li 2 O: 8.00 wt% to 14.00 wt%;

[0065] CaO: 0.00 wt% to 1.20 wt%;

[0066] B 2 O 3 : 0.00 wt% to 3.00 wt%;

[0067] The first colorant: at least one of NiO and CoO;

[0068] The second colorant: MnO 2 , Cr 2 O 3 , and Ho 2 O 3 at least one of;

[0069] wherein, 0.01 wt% ≤ NiO + CoO ≤ 2.00 wt%;

[0070] 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%.

[0071] In a fourth aspect, the present application provides a strengthened black microcrystalline glass having a thickness of t, comprising a double-sided strengthening layer and a tensile stress layer, wherein the strengthening layer extends from the surface of the strengthened black microcrystalline glass toward the inside, wherein the double-sided strengthening layer is symmetrically distributed, and the thickness of each strengthening layer is not higher than 0.22t; the strengthened black microcrystalline glass has a color coordinate of 0.1 to 0.7 mm in a reflection mode in a CIELab color space: L*: 15 to 30; a*: -5 to 5; b*: -2 to 10;

[0072] The reinforced black glass-ceramics comprises the following components, measured by mass percentage of oxides:

[0073] SiO 2 : 60.00wt%~75.00wt%;

[0074] Al 2 O 3 : 2.00wt%~10.00wt%;

[0075] P 2 O 5 : 1.50wt%~5.00wt%;

[0076] ZrO 2 : 3.00wt%~10.00wt%;

[0077] Na 2 O: 0.00wt%~21.00wt%;

[0078] K 2 O: 0.00wt%~3.00wt%;

[0079] Li 2 O: 1.00wt%~14.00wt%;

[0080] CaO: 0.00wt%~1.20wt%;

[0081] B 2 O 3 : 0.00wt%~3.00wt%;

[0082] First colorant: at least one of NiO and CoO;

[0083] Secondary colorant: MnO 2 Cr 2 O 3 and Ho 2 O 3 At least one of the following;

[0084] Among them, 0.01wt%≤NiO+CoO≤2.00wt%;

[0085] 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%.

[0086] In some embodiments of the present application, the thickness t of the strengthened black series glass-ceramics described in the third aspect or the fourth aspect is 0.10 - 1.00 mm.

[0087] In some embodiments of the present application, the chemical strengthening process of the strengthened black series glass-ceramics described in the third aspect or the fourth aspect includes single-step chemical strengthening or multi-step chemical strengthening.

[0088] In some embodiments of the present application, in the strengthened black series glass-ceramics described in the third aspect or the fourth aspect, the single-step chemical strengthening uses a mixed salt bath containing NaNO 3 , KNO 3 and LiNO 3 . Preferably, the content of KNO 3 in the mixed salt bath is 0 - 100 wt%, the content of NaNO 3 is 0 - 100 wt%, and the content of LiNO 3 is 0 - 0.1 wt%.

[0089] In some embodiments of the present application, in the strengthened black series glass-ceramics described in the third aspect or the fourth aspect, the temperature of the single-step chemical strengthening is 380 - 530 °C, and the time of the single-step chemical strengthening is 15 min - 10 h.

[0090] In some embodiments of the present application, the single-rod static pressure strength of the strengthened black series glass-ceramics described in the third aspect or the fourth aspect is not less than 250 N, preferably 250 N - 500 N, more preferably 300 N - 500 N.

[0091] Fifth aspect, the present application provides an application of the black series glass-ceramics as described above, or the black series glass-ceramics prepared by the preparation method of the black series glass-ceramics as described above, or the strengthened black series glass-ceramics as described above in 2G, 3G, 4G, 5G, 5.5G, 6G communication devices, Bluetooth devices, and / or WIFI devices; especially applied to 5G, 5.5G, 6G communication devices.

[0092] Sixth aspect, the present application further provides an electronic device, including the black series glass-ceramics as described above, or the black series glass-ceramics prepared by the preparation method of the black series glass-ceramics as described above, or the strengthened black series glass-ceramics as described above.

[0093] In a seventh aspect, the present application further provides an electronic device, including a housing and a middle frame; the housing includes the black glass-ceramics as described above, or black glass-ceramics prepared by the preparation method of the above-mentioned black series glass-ceramics, or the above-mentioned strengthened black series glass-ceramics.

[0094] Advantages of the present application:

[0095] 1. In the present application, a variety of colorants containing NiO and / or CoO are added to the glass-ceramics to make black series glass-ceramics, which show a beautiful black appearance.

[0096] 2. In the present application, by controlling the composition of the colorants of the glass-ceramics, the prepared black series glass-ceramics have low dielectric constant and dielectric loss.

[0097] 3. In the present application, by controlling the composition of the oxide glass and the composition of the colorants, the prepared black series glass-ceramics can have a low dielectric loss of less than 0.005 at the frequencies required by the two conventional 5G communication technologies of 2.4 GHz and 5 GHz, and at the same time have a certain light-shielding performance in the visible light range. Description of the drawings

[0098] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0099] Figure 1 It is the XRD pattern of the glass-ceramics provided in Embodiment 3 and Comparative Example 3 of the present application.

[0100] Figure 2 It is a schematic diagram of the double-sided strengthening layer and the tensile stress layer of the strengthened glass-ceramics of the present application;

[0101] Reference numerals: 1 - strengthening layer, 2 - tensile stress layer. Detailed implementation manners

[0102] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0103] In this application, the main crystal phase (or also referred to as the major crystal phase) refers to the crystal phase that has a higher weight content than other crystal phases present in the glass-ceramics; the secondary crystal phase refers to the crystal phase in the glass-ceramics that has a weight content lower than that of the main crystal phase but higher than that of other crystal phases present in the glass-ceramics. In this application, the main crystal phase can be one or more. When there are multiple main crystal phases, the main crystal phases refer to multiple crystal phases arranged in descending order of weight content present in the glass-ceramics.

[0104] In this application, the crystallinity refers to the percentage of the total mass of the crystal phase or crystals in the glass-ceramics to the mass of the glass-ceramics, or also referred to as the total crystal phase content in the glass-ceramics.

[0105] In this application, the transmittance refers to the ratio of the radiant energy that is projected and transmitted through an object to the total radiant energy projected onto the object during the process where the incident light flux travels from the illuminated surface or the incident surface of the medium to the other side and exits.

[0106] In this application, the reflectivity refers to the percentage of the radiant energy reflected by an object to the total radiant energy.

[0107] In this application, nucleation refers to the growth of small crystal nuclei from the nucleating substances in the glass through heat treatment.

[0108] In this application, crystallization refers to the growth of a certain crystal on the basis of crystal nuclei in the glass through heat treatment.

[0109] In this application, the base glass refers to the glass that has not been subjected to nucleation treatment, crystallization treatment, and strengthening treatment.

[0110] In this application, visible light refers to light with a wavelength range of 360 nm to 740 nm.

[0111] In this application, glass-ceramics, also known as glass ceramics, are a type of solid composite material that contains both a glass phase and crystal phases (microcrystalline phase, crystalline phase) and is prepared by targeted and controlled crystallization of the base glass.

[0112] In this application, the dielectric constant refers to the relative dielectric constant, which is the main parameter reflecting the dielectric properties or polarization properties of the dielectric in a piezoelectric material under the action of an electrostatic field and is usually represented by ε.

[0113] In this application, the dielectric loss refers to the energy consumed per unit time by the dielectric under the action of an electric field. The size of the dielectric loss is usually measured by the tangent of the dielectric loss angle tg (dielectric loss factor).

[0114] Test method:

[0115] 1. Crystal phase and crystallinity test

[0116] In this application, the crystal phase and crystallinity of the glass-ceramics are tested and confirmed by an X-ray diffractometer. Specifically:

[0117] (1) XRD test: The glass-ceramics or strengthened glass-ceramics of this application are crushed and ground into samples with a particle size less than 75 μm, and the ground samples are tested using an X-ray diffractometer to obtain the XRD diffraction peak curve and XRD diffraction data. The X-ray diffractometer used in this invention is the XRD-6100 of Shimadzu. The incident angle range for testing is 2θ = 10 - 50, the scanning speed is 3° / min, the working voltage is 40 kV, and the working current is 30 mA.

[0118] (2) Determination of crystal phase: The XRD diffraction data is analyzed using data processing software (such as JADE Standard 8.6) to determine the crystal phase in the sample.

[0119] (3) Determination of crystallinity: The test results (RAW format) of XRD are imported into X-ray diffraction data software (such as the Rietveld refinement software Jade) for fitting and calculation, and then the crystallinity of the sample can be determined. Specifically, the ratio of the area of the fitted crystal phase peak to the area of all the fitted peaks is recorded as the crystallinity of the sample.

[0120] 2. Transmittance test

[0121] The transmittance of the glass to be tested at a wavelength of 550 nm is measured using a Shimadzu UV-2000 ultraviolet-visible spectrophotometer. Five pieces of the glass to be tested under the same conditions are measured respectively, and the average value of each test result is taken as the transmittance of the glass to be tested measured at a wavelength of 550 nm.

[0122] 3. CIE L*a*b* parameter test

[0123] In this application, it is measured using a Konica Minolta spectrophotometer CM-3600A of Japan and connected to the SpectraMagic NX spectral analysis software. Based on the D65 light source and a 10-degree standard observation angle, the test results in the reflection mode are converted into CIELab color space coordinates (L*; a*; and b*), and the measurement area is LAV (25.4 mm).

[0124] Five pieces of the glass to be tested under the same conditions are measured respectively, and the average value of each test result is taken as the L* value, a* value, and b* value of the glass to be tested.

[0125] 4. Dielectric property test

[0126] The dielectric constant and dielectric loss are measured with reference to GB / T1409-2006, and the test frequencies are 2.4 GHz and 5.0 GHz.

[0127] 5. Li 2 O component and B 2 O3 Test method for mass percentage of components

[0128] In this application, the mass percentage of Li 2 O component and B 2 O 3 component in the glass is tested according to the national standard GB / T 1549-2008.

[0129] 6. Determination of mass percentage of glass composition in this application

[0130] The composition of the glass in this application is measured by X-ray fluorescence spectrometer (XRF). The equipment used for the test is Thermo Scientific ARL TM PERFORM'X, the target material is Rh (rhodium), the tube voltage is 40KW, the current is 60mA, the collimator is 0.15, the crystal is selected as LiF200, the detector is selected as FPC, the test range is a 29mm circle, the analysis software is UniQuant non-standard analysis, and non-standard test is used during XRF test. The equipment cannot test the concentration of elements with atomic number 6 and below or their oxides in the glass. SiO 2 、Al 2 O 3 、P 2 O 5 、ZrO 2 、Na 2 O、K 2 O、CaO、NiO、CoO、Ho 2 O 3 、MnO 2 、Cr 2 O 3 etc. are the mass percentages of oxides that can be accurately measured by XRF. Li 2 O, B 2 O 3 are oxides that cannot be accurately measured by XRF.

[0131] Therefore, substituting the content values of Li 2 O and B 2 O 3 tested above into the XRF test results, the mass percentage of the complete glass components can be obtained.

[0132] 7. Single-rod static pressure strength test

[0133] In this application, the glass to be tested is placed on the bottom ring of a tensile testing machine (LT-850A). The testing software is started, and the moving speed of the extrusion rod (rod diameter 8 mm, indenter arc radius 10 mm) is set to 50 mm / min. Click "Start Test", and the extrusion rod will apply a force to the center of the glass to be tested at the set moving speed until cracks and breakage occur in the glass to be tested. The testing software will automatically read the force (N) at the time of glass breakage as the test result. Ten glass samples to be tested in the same state are taken for testing, and the average value of the test results is taken as the single-rod static pressure strength of the glass to be tested.

[0134] Glass-ceramics is a solid composite material formed by controlled crystallization of a base glass during heat treatment. Glass-ceramics contain a crystalline phase and a glass phase. Compared with glass materials without a crystalline phase, glass-ceramics usually have higher strength. This is because the crystalline phase has higher strength than the glass phase, absorbs more energy during fracture, and the crystalline phase can extend the path of crack propagation and hinder the expansion of cracks. Therefore, more impact energy can be consumed during the fracture and breakage process, improving the disadvantages of traditional glass being fragile and easily scratched. However, existing glass-ceramics often use iron-containing compounds and titanium-containing compounds as colorants to prepare glass-ceramics of various colors. The addition of iron-containing compounds and / or titanium-containing compounds to glass-ceramics will cause a significant increase in the dielectric constant of the glass-ceramics due to the presence of iron and / or titanium elements, improving the dielectric properties of the glass-ceramics and thus not being suitable for the dielectric property requirements of communication device housings. In addition, the increase in the dielectric constant and / or dielectric loss by NiO and / or CoO is much smaller than that by iron-containing compounds and / or titanium-containing compounds.

[0135] Based on this, this application proposes a black series of glass-ceramics with low dielectric properties suitable for communication devices. This black series of glass-ceramics is made black using a colorant containing NiO and / or CoO, and at the same time has a low dielectric constant and dielectric loss that meet the requirements of communication devices, and has a certain light-shielding performance in the visible light range.

[0136] In a first aspect, this application provides a black series of glass-ceramics, which includes the following components in terms of mass percentage of oxides:

[0137] SiO 2 : 60.00 wt% - 75.00 wt%;

[0138] Al 2 O 3 : 2.00 wt% - 10.00 wt%;

[0139] P 2 O 5 : 1.50 wt% - 5.00 wt%;

[0140] ZrO 2: 3.00 wt% to 10.00 wt%;

[0141] Na 2 O: 0.00 wt% to 4.00 wt%;

[0142] K 2 O: 0.00 wt% to 1.00 wt%;

[0143] Li 2 O: 8.00 wt% to 14.00 wt%;

[0144] CaO: 0.00 wt% to 1.20 wt%;

[0145] B 2 O 3 : 0.00 wt% to 3.00 wt%;

[0146] The first colorant: at least one of NiO and CoO;

[0147] The second colorant: MnO 2 , Cr 2 O 3 and Ho 2 O 3 at least one of;

[0148] Wherein, 0.01 wt% ≤ NiO + CoO ≤ 2.00 wt%;

[0149] 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%.

[0150] In this application, SiO 2 is the oxide that forms the glass network framework, used to stabilize the network structure of glass and glass-ceramics, and is used to form crystal phases such as lithium silicate, spodumene, β-spodumene and quartz in the lithium aluminosilicate system. In some embodiments of this application, based on the mass percentage of the oxide, the content of SiO 2 in the black series glass-ceramics is 60.00 wt% to 75.00 wt%, preferably 60.00 wt% to 73.00 wt%. In some embodiments of this application, based on the mass percentage of the oxide, the content of SiO 2The content can be: 60.00 wt%, 61.00 wt%, 62.00 wt%, 63.00 wt%, 64.00 wt%, 65.00 wt%, 66.00 wt%, 67.00 wt%, 68.00 wt%, 69.00 wt%, 70.00 wt%, 71.00 wt%, 72.00 wt%, 73.00 wt%, 74.00 wt% or 75.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0151] Al 2 O 3 For forming the glass skeleton, Al 2 O 3 Stabilizes the glass network structure, improves mechanical properties and chemical durability, and inhibits the phase separation of the glass, reducing the coefficient of thermal expansion. In some embodiments of the present application, based on the mass percentage of the oxide, the content of Al 2 O 3 in the black series of glass-ceramics is 2.00 wt% to 10.00 wt%, preferably 2.50 wt% to 10.00 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, the content of Al 2 O 3 in the black series of glass-ceramics can be: 2.00 wt%, 2.20 wt%, 2.50 wt%, 3.00 wt%, 3.60 wt%, 3.80 wt%, 4.00 wt%, 4.30 wt%, 4.70 wt%, 4.90 wt%, 5.00 wt%, 5.50 wt%, 5.80 wt%, 6.00 wt%, 6.50 wt%, 7.00 wt%, 7.50 wt%, 8.00 wt%, 8.50 wt%, 8.90 wt%, 9.00 wt%, 9.30 wt%, 9.50 wt%, 9.80 wt% or 10.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0152] Na 2 Na₂O is an external oxide of the glass network and can provide free oxygen to increase the oxygen-silicon ratio in the glass structure. In some embodiments of the present application, based on the mass percentage of the oxide, the content of Na 2 ₂O in the black series of glass-ceramics is 0.00 wt% to 4.00 wt%, preferably 0.00 wt% to 3.80 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, the content of Na 2The content of O can be 0.00 wt%, 0.30 wt%, 0.50 wt%, 0.80 wt%, 1.00 wt%, 1.10 wt%, 1.30 wt%, 1.50 wt%, 1.70 wt%, 1.90 wt%, 2.00 wt%, 2.20 wt%, 2.50 wt%, 2.70 wt%, 2.80 wt%, 2.90 wt%, 3.00 wt%, 3.10 wt%, 3.20 wt%, 3.30 wt%, 3.40 wt%, 3.50 wt%, 3.80 wt% or 4.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0153] Li 2 O is the main component of spodumene and lithium silicate crystals, and is also a necessary component for chemical strengthening. In some embodiments of the present application, based on the mass percentage of oxides, Li 2 The content of O in the black microcrystalline glass is 8.00 wt% to 14.00 wt%, preferably 8.00 wt% to 13.50 wt%. In some embodiments of the present application, based on the mass percentage of oxides, Li 2 The content of O can be: 8.00 wt%, 8.50 wt%, 9.00 wt%, 9.50 wt%, 10.00 wt%, 10.50 wt%, 11.00 wt%, 11.50 wt%, 12.00 wt%, 12.50 wt%, 13.00 wt%, 13.50 wt%, 13.80 wt% or 14.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0154] P 2 O 5 is a glass-forming oxide, which exists in the network structure in the form of phosphate tetrahedra [PO 4 . In some embodiments of the present application, based on the mass percentage of oxides, P 2 O 5 The content of is 1.50 wt% to 5.00 wt%, preferably 1.50 wt% to 4.50 wt%. In some embodiments of the present application, based on the mass percentage of oxides, P 2 O 5The content can be: 1.50 wt%, 2.00 wt%, 2.50 wt%, 2.90 wt%, 3.00 wt%, 3.30 wt%, 3.50 wt%, 4.00 wt%, 4.50 wt%, 4.80 wt% or 5.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0155] ZrO 2 can improve the viscosity, hardness, elastic modulus, refractive index, chemical stability of the glass and reduce the thermal expansion coefficient of the glass. In some embodiments of the present application, based on the mass percentage of oxides, ZrO in the black series glass-ceramics 2 content is 3.00 wt% to 10.00 wt%, preferably 3.00 wt% to 9.50 wt%. In some embodiments of the present application, based on the mass percentage of oxides, ZrO in the black series glass-ceramics 2 content can be: 3.00 wt%, 3.50 wt%, 3.80 wt%, 4.00 wt%, 4.50 wt%, 5.00 wt%, 5.50 wt%, 6.00 wt%, 6.50 wt%, 7.00 wt%, 7.50 wt%, 8.00 wt%, 8.50 wt%, 9.00 wt%, 9.50 wt%, 9.70 wt% or 10.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0156] B 2 O 3 helps to reduce the melting temperature of the base glass. B 2 O 3 with borate triangles [BO 3 and borate tetrahedrons [BO 4 as structural units, as the content of B 2 O 3 increases, the relative content of borate triangles and borate tetrahedrons changes, resulting in a reversal of the structure and properties. In some embodiments of the present application, based on the mass percentage of oxides, B in the black series glass-ceramics 2 O 3 content is 0.00 wt% to 3.00 wt%, preferably 0.00 wt% to 2.80 wt%. In some embodiments of the present application, based on the mass percentage of oxides, B in the black series glass-ceramics 2 O 3The content can be: 0.00 wt%, 0.10 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.40 wt%, 0.50 wt%, 0.60 wt%, 0.70 wt%, 0.90 wt%, 1.00 wt%, 1.30 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.10 wt%, 2.30 wt%, 2.50 wt%, 2.70 wt%, 2.90 wt% or 3.00 wt%, etc., and all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0157] K 2 O is an extra-network oxide. Adding K 2 O can reduce the crystallization tendency of the glass and increase the transparency and luster of the glass. In some embodiments of the present application, based on the mass percentage of the oxide, K in the black microcrystalline glass 2 The content of O is 0.00 wt% to 1.00 wt%, preferably 0.00 wt% to 0.09 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, K in the black microcrystalline glass 2 The content of O can be 0.00 wt%, 0.05 wt%, 0.08 wt%, 0.10 wt%, 0.12 wt%, 0.15 wt%, 0.20 wt%, 0.25 wt%, 0.30 wt%, 0.35 wt%, 0.40 wt%, 0.45 wt%, 0.50 wt%, 0.55 wt%, 0.58 wt%, 0.60 wt%, 0.65 wt%, 0.70 wt%, 0.75 wt%, 0.80 wt%, 0.85 wt%, 0.88 wt%, 0.90 wt%, 0.92 wt%, 0.95 wt%, 0.98 wt% or 1.00 wt%, etc., and all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0158] CaO can increase the chemical stability and mechanical strength of the glass, but the increase of CaO will increase the dielectric constant of the glass. In some embodiments of the present application, based on the mass percentage of oxides, the content of CaO in the black series of glass-ceramics is 0.00 wt% to 1.20 wt%, preferably 0.00 wt% to 1.18 wt%. In some embodiments of the present application, based on the mass percentage of oxides, the content of CaO in the black series of glass-ceramics can be 0.00 wt%, 0.10 wt%, 0.15 wt%, 0.20 wt%, 0.25 wt%, 0.30 wt%, 0.35 wt%, 0.40 wt%, 0.45 wt%, 0.50 wt%, 0.60 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.15 wt%, 1.18 wt%, 1.19 wt% or 1.20 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0159] In the present application, the black color and opacity of the black series of glass-ceramics and the strengthened black series of glass-ceramics both originate from the colorants; by controlling the component ratio of the colorants, low dielectric constant, dielectric loss and low visible light transmittance are achieved. In the present application, elements of the colorants such as Ni element, Co element, etc. exist in multiple valence states in the glass, and when calculating their contents, they are all converted into their oxides for calculation; specifically, the Ni element is converted into the content of NiO, and the Co element is converted into the content of CoO for calculation. In the present application, the colorant composition can include oxides such as NiO, MnO 2 , Cr 2 O 3 , CoO, Ho 2 O 3 and so on. The colorants are divided into the first colorant and the second colorant, where the first colorant is at least one of NiO and CoO, and the second colorant is at least one of MnO 2 , Cr 2 O 3 and Ho 2 O 3 . In the present application, the content of iron and / or titanium elements in the black series of glass-ceramics is less than 1000 ppm. Optionally, the iron and / or titanium elements are impurities. Optionally, the iron compounds and / or titanium compounds are all common iron-containing and / or titanium-containing coloring components in the art, specifically such as Fe 2 O 3 , TiO 2 , FeCl 3 and other compounds.

[0160] In some embodiments of the present application, in the black microcrystalline glass, the content of NiO + CoO is 0.01 wt% to 2.00 wt% based on the mass percentage of the oxide. In some embodiments of the present application, based on the mass percentage of the oxide, the content of NiO + CoO can be 0.01 wt%, 0.03 wt%, 0.05 wt%, 0.08 wt%, 0.10 wt%, 0.13 wt%, 0.15 wt%, 0.17 wt%, 0.19 wt%, 0.20 wt%, 0.23 wt%, 0.28 wt%, 0.30 wt%, 0.33 wt%, 0.38 wt%, 0.40 wt%, 0.45 wt%, 0.48 wt%, 0.50 wt%, 0.53 wt%, 0.57 wt%, 0.60 wt%, 0.65 wt%, 0.70 wt%, 0.75 wt%, 0.80 wt%, 0.85 wt%, 0.90 wt%, 0.95 wt%, 0.99 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt%, 1.50 wt%, 1.60 wt%, 1.70 wt%, 1.80 wt%, 1.90 wt% or 2.00 wt%, etc., and all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0161] In some embodiments of the present application, in the black microcrystalline glass, MnO 2 + Cr 2 O 3 + Ho 2 O 3 The content of is 0.01 wt% to 8.00 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, MnO 2 + Cr 2 O 3 + Ho 2 O 3The content can be 0.01wt%, 0.03wt%, 0.05wt%, 0.08wt%, 0.10wt%, 0.13wt%, 0.15wt%, 0.17wt%, 0.19wt%, 0.20wt%, 0.30wt%, 0.50wt%, 0.80wt%, 1.00wt%, 1.20wt%, 1.50wt%, 1.80wt%, 2.00wt%, 2.30wt%, 2.70wt%, 2.90wt%, 3.00wt%, 3.50wt%, 4.00wt%, 4.50wt%, 5.00wt%, 5.50wt%, 6.00wt%, 6.30wt%, 6.80wt%, 7.00wt%, 7.30wt%, 7.70wt%, 7.90wt% or 8.00wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0162] In some embodiments of the present application, based on the mass percentage of the oxide, the content of NiO in the black series glass-ceramics is 0.00wt% to 1.00wt%. In some embodiments of the present application, based on the mass percentage of the oxide, the content of NiO in the black series glass-ceramics can be 0.00wt%, 0.01wt%, 0.05wt%, 0.09wt%, 0.15wt%, 0.20wt%, 0.30wt%, 0.50wt%, 0.70wt%, 0.80wt%, 0.90wt% or 1.00wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0163] In some embodiments of the present application, based on the mass percentage of the oxide, the content of CoO in the black series glass-ceramics is 0.00wt% to 1.00wt%. In some embodiments of the present application, based on the mass percentage of the oxide, the content of CoO in the black series glass-ceramics can be 0.00wt%, 0.01wt%, 0.05wt%, 0.09wt%, 0.15wt%, 0.20wt%, 0.30wt%, 0.50wt%, 0.70wt%, 0.80wt%, 0.90wt% or 1.00wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0164] In some embodiments of the present application, based on the mass percentage of the oxide, MnO in the black series glass-ceramics 2The content of [MnO] is 0.00 wt% to 1.50 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, MnO in the black series of glass-ceramics 2 The content can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt% or 1.50 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0165] In some embodiments of the present application, based on the mass percentage of the oxide, Cr in the black series of glass-ceramics 2 O 3 The content of [Cr₂O₃] is 0.00 wt% to 4.00 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, Cr in the black series of glass-ceramics 2 O 3 The content can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt%, 1.50 wt%, 1.70 wt%, 1.90 wt%, 2.00 wt%, 2.30 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.20 wt%, 3.50 wt%, 3.80 wt% or 4.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0166] In some embodiments of the present application, based on the mass percentage of the oxide, Ho in the black series of glass-ceramics 2 O 3 The content of [Ho₂O₃] is 0.00 wt% to 2.50 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, Ho in the black series of glass-ceramics 2 O 3The content can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.40 wt%, 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.40 wt%, 1.70 wt%, 1.90 wt%, 2.00 wt%, 2.10 wt%, 2.20 wt%, 2.30 wt%, 2.40 wt% or 2.50 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0167] In some embodiments of the present application, calculated by mass percentage of the oxide, the black series glass-ceramics further contain CuO, Er 2 O 3 and / or Nd 2 O 3 。In some embodiments of the present application, calculated by mass percentage of the oxide, the content of CuO in the black series glass-ceramics is 0.00 wt% to 4.0 wt%, preferably 0.00 wt% to 3.90 wt%. In some embodiments of the present application, calculated by mass percentage of the oxide, the content of CuO in the black series glass-ceramics can be 0.00 wt%, 0.20 wt%, 0.50 wt%, 0.80 wt%, 1.00 wt%, 1.10 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.50 wt%, 3.80 wt%, or 4.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0168] In some embodiments of the present application, calculated by mass percentage of the oxide, the Er 2 O 3 content in the black series glass-ceramics is 0.00 wt% to 4.0 wt%, preferably 0.00 wt% to 3.90 wt%. In some embodiments of the present application, calculated by mass percentage of the oxide, the Er 2 O 3The content can be 0.00 wt%, 0.50 wt%, 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.50 wt%, 3.80 wt%, 3.90 wt% or 4.00 wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0169] In some embodiments of the present application, in terms of the mass percentage of the oxide, Nd in the black series of glass-ceramics 2 O 3 has a content of 0.00 wt% to 4.00 wt%. In some embodiments of the present application, in terms of the mass percentage of the oxide, Nd in the black series of glass-ceramics 2 O 3 has a content that can be 0.00 wt%, 0.20 wt%, 0.40 wt%, 0.80 wt%, 1.00 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.20 wt%, 3.50 wt%, 3.80 wt% or 4.00 wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0170] In the black series of glass-ceramics of the present application, a clarifying agent can also be added. Examples of the clarifying agent include common ones in the art such as NaCl, Na 2 SO 4 , SnO 2 , As 2 O 3 , Sb 2 O 3 , NaNO 3 , KNO 3 and / or CeO 2 etc. In some embodiments of the present application, the addition amount of the clarifying agent is 0 to 1.0 wt% of the glass mass.

[0171] In some embodiments of the present application, the relative dielectric constant ε of the black microcrystalline glass at a frequency of 2.4 GHz and / or 5 GHz is 6 or less, preferably 5.87 or less. In some embodiments of the present application, the relative dielectric constant ε of the black microcrystalline glass at a frequency of 2.4 GHz may be 1.00, 1.50, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.20, 5.50, 5.83, 5.87, 5.90, 5.98 or 6.00, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range. In some embodiments of the present application, the relative dielectric constant ε of the black microcrystalline glass at a frequency of 5 GHz may be 1.00, 1.50, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.20, 5.50, 5.83, 5.87, 5.90, 5.98 or 6.00, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0172] In some embodiments of the present application, the tangent value of the dielectric loss of the black microcrystalline glass at a frequency of 2.4 GHz and / or 5 GHz is 5×10 -3 or less, preferably 1.00×10 -3 ~5×10 -3 . In some embodiments of the present application, the tangent value of the dielectric loss of the black microcrystalline glass at a frequency of 2.4 GHz may be 1.00×10 -3 , 1.50×10 -3 , 1.80×10 -3 , 2.00×10 -3 , 2.20×10 -3 , 2.50×10 -3 , 2.80×10 -3 , 2.90×10 -3 , 3.00×10 -3 , 3.50×10 -3 , 3.90×10 -3 , 4.00×10 -3 , 4.30×10 -3 , 4.50×10 -3 , 4.90×10 -3 or 5.00×10 -3etc., and all ranges and sub-ranges between the above values. It should be understood that, in an embodiment, any of the above ranges can be combined with any other range. In some embodiments of the present application, the tangent value of the dielectric loss of the black series glass-ceramics at a frequency of 5 GHz can be 1.00×10 -3 、1.50×10 -3 、1.80×10 -3 、2.00×10 -3 、2.20×10 -3 、2.50×10 -3 、2.80×10 -3 、2.90×10 -3 、3.00×10 -3 、3.50×10 -3 、3.90×10 -3 、4.00×10 -3 、4.30×10 -3 、4.50×10 -3 、4.90×10 -3 or 5.00×10 -3 etc., and all ranges and sub-ranges between the above values. It should be understood that, in an embodiment, any of the above ranges can be combined with any other range.

[0173] In some embodiments of the present application, the thickness of the black series glass-ceramics is not particularly limited. For example, it can be 0.1 - 0.7 mm; preferably 0.15 - 0.7 mm. In some embodiments of the present application, the thickness of the black series glass-ceramics can be 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm or 0.7 mm, etc., and all ranges and sub-ranges between the above values. It should be understood that, in an embodiment, any of the above ranges can be combined with any other range.

[0174] In some embodiments of the present application, for the black microcrystalline glass with a thickness of 0.1 to 0.7 mm, the color coordinates in the reflection mode in the CIELab color space are: L*: 15 to 30; a*: -5 to 5; b*: -2 to 10. In some embodiments of the present application, with a thickness of 0.1 to 0.7 mm and in the reflection mode in the CIELab color space, the L* of the black microcrystalline glass can be 15 to 30, 17 to 29, 20 to 28, 21 to 27, 23 to 28, 24 to 28, 25 to 29, or 25 to 27, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, with a thickness of 0.1 to 0.7 mm and in the reflection mode in the CIELAB color space, the a* of the black microcrystalline glass can be -5 to 5, -3 to 4, -3 to 3, -2 to 5, -1 to 5, -0.5 to 5, -0.5 to 1, -0.5 to 0.5, or -0.1 to 0.5, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, with a thickness of 0.1 to 0.7 mm and in the reflection mode in the CIELab color space, the b* of the black microcrystalline glass can be -2 to 10, -2 to 8, -2 to 6, -2 to 3, -2 to 1, -1.5 to 1, -1.5 to 0.5, -2.5 to 1.5, or -1.1 to 0.5, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0175] In the present application, the black microcrystalline glass has a certain light-shielding performance in the visible light range; for example, with a thickness of 0.1 to 0.7 mm, the transmittance of the black microcrystalline glass at 550 nm is 0 to 10%. In some embodiments of the present application, with a thickness of 0.1 to 0.7 mm, the transmittance of the black microcrystalline glass at 550 nm can be 0.00%, 0.05%, 0.10%, 0.40%, 0.70%, 0.90%, 1.00%, 1.50%, 1.80%, 2.00%, 2.50%, 3.00%, 3.50%, 4.10%, 4.70%, 5.00%, 5.50%, 6.00%, 6.50%, 7.00%, 7.50%, 8.00%, 8.50%, 9.00%, 9.50%, or 10.00%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0176] In some embodiments of the present application, the main crystal phases of the black series glass-ceramics include one or more of spodumene, lithium disilicate, lithium monosilicate, lithium phosphate, quartz, pyroxene, and nepheline. In some embodiments of the present application, the main crystal phases of the black series glass-ceramics include one or more of spodumene, lithium disilicate, and quartz. In some embodiments of the present application, the main crystal phase of the black glass-ceramics is spodumene and / or lithium disilicate.

[0177] In some embodiments of the present application, the crystallinity of the black series glass-ceramics is 60 wt%-100 wt%. In some embodiments of the present application, the crystallinity of the black series glass-ceramics can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 82 wt%, 83 wt%, 85 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 94 wt%, 96 wt%, 98 wt%, 99 wt%, or 100 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0178] In a second aspect, the present application provides a method for preparing the black series glass-ceramics as described above, comprising the following steps:

[0179] Step 1: Mix the raw materials for preparing the glass, melt them, and then cool and anneal to obtain a base glass;

[0180] Step 2: Heat-treat the base glass obtained in Step 1 to obtain the black series glass-ceramics.

[0181] In the preparation method of the present application, the melting temperature is 1400°C - 1650°C, and the melting time is 5 h - 24 h. In some embodiments of the present application, the melting temperature can be 1400°C, 1450°C, 1500°C, 1550°C, 1600°C, or 1650°C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, the melting time can be 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 12 h, 15 h, 17 h, 20 h, 21 h, or 24 h, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0182] In the preparation method of the present application, the temperature of the annealing treatment is 400°C - 500°C, and the time of the annealing treatment is 10h - 24h. In some embodiments of the present application, the temperature of the annealing treatment can be 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 470°C, 480°C, 490°C or 500°C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, the time of the annealing treatment can be 10h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0183] In the preparation method of the present application, the base glass can be prepared by using the forming methods in the prior art, and the present application has no limitation on this. For example, the forming methods of the base glass can include but are not limited to the float method, overflow method, rolling method or casting process. Exemplarily, after mixing each component evenly according to the formula and melting and forming, cooling and annealing treatment are carried out to obtain the base glass. The preparation process of the base glass is the prior art, so it will not be described in detail one by one in the present application. The composition of the base glass in the present application is the same as that of the obtained glass-ceramics.

[0184] In the preparation method of the present application, the base glass is subjected to heat treatment, and the heat treatment includes nucleation treatment and crystallization treatment.

[0185] In the preparation method of the present application, the heating rate of the nucleation treatment is 1°C / min to 15°C / min. In some embodiments of the present application, the heating rate of the nucleation treatment can be 1°C / min, 3°C / min, 5°C / min, 7°C / min, 9°C / min, 10°C / min, 11°C / min, 12°C / min, 13°C / min, 14°C / min or 15°C / min, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0186] In the preparation method of the present application, the temperature of the nucleation treatment is 500 - 600 °C and / or the time of the nucleation treatment is 30 min - 600 min. In some embodiments of the present application, the temperature of the nucleation treatment can be 500 °C, 520 °C, 540 °C, 550 °C, 560 °C, 570 °C, 580 °C, 590 °C or 600 °C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, the time of the nucleation treatment can be 30 min, 60 min, 90 min, 180 min, 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, 350 min, 400 min, 450 min, 500 min, 550 min or 600 min, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0187] In the preparation method of the present application, the heating rate of the crystallization treatment is 1 - 15 °C / min. In some embodiments of the present application, the heating rate of the crystallization treatment can be 1 °C / min, 3 °C / min, 5 °C / min, 7 °C / min, 9 °C / min, 10 °C / min, 11 °C / min, 12 °C / min, 13 °C / min, 14 °C / min or 15 °C / min, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0188] In the preparation method of the present application, the temperature of the crystallization treatment is 600 - 850 °C and / or the time of the crystallization treatment is 30 min - 600 min. In some embodiments of the present application, the temperature of the crystallization treatment can be 600 °C, 620 °C, 640 °C, 650 °C, 660 °C, 670 °C, 680 °C, 700 °C, 720 °C, 740 °C, 760 °C, 780 °C, 800 °C or 850 °C, etc., as well as all ranges and sub-ranges between the above values. In some embodiments of the present application, the time of the crystallization treatment can be 30 min, 50 min, 60 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 240 min, 280 min, 300 min, 320 min, 360 min, 380 min, 400 min, 450 min, 500 min, 540 min, 560 min, 580 min or 600 min, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0189] Before and / or after heat treatment, those skilled in the art can also perform other conventional steps to obtain a substrate glass and / or a glass-ceramic sample that meets the required specifications or requirements. For example, shaping, cutting (such as cutting with a multi-wire saw), CNC machining (computer numerical control, i.e., a numerically controlled machine tool), thinning, or polishing steps can be performed. In this application, there is no limitation on the size processing of the substrate glass and / or the glass-ceramic sample. For example, it can be 50mm×50mm×0.7mm, 300mm×120mm×0.7mm, etc.

[0190] In a third aspect, the present application provides a strengthened black glass-ceramic with a thickness of t, which includes a double-sided strengthening layer and a tensile stress layer. The strengthening layer extends from the surface of the strengthened black glass-ceramic towards the interior direction, where the double-sided strengthening layer is symmetrically distributed, and the thickness of each strengthening layer is not higher than 0.22t; when the strengthened black glass-ceramic has a thickness of 0.1 - 0.7mm, the color coordinates in the reflection mode in the CIELab color space are: L*: 15 - 30; a*: -5 - 5; b*: -2 - 10;

[0191] The strengthened black glass-ceramic includes the following components in terms of mass percentage of oxides:

[0192] SiO 2 : 60.00wt% - 75.00wt%;

[0193] Al 2 O 3 : 2.00wt% - 10.00wt%;

[0194] P 2 O 5 : 1.50wt% - 5.00wt%;

[0195] ZrO 2 : 3.00wt% - 10.00wt%;

[0196] Na 2 O: 0.00wt% - 21.00wt%;

[0197] K 2 O: 0.00wt% - 3.00wt%;

[0198] Li 2 O: 1.00wt% - 14.00wt%;

[0199] CaO: 0.00wt% - 1.20wt%;

[0200] B 2 O3 : 0.00 wt% to 3.00 wt%;

[0201] First colorant: at least one of NiO and CoO;

[0202] Second colorant: MnO 2 , Cr 2 O 3 and Ho 2 O 3 at least one of;

[0203] wherein, 0.01 wt% ≤ NiO + CoO ≤ 2.00 wt%;

[0204] 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%;

[0205] In this application, the strengthened black glass-ceramics are obtained by chemically strengthening the aforementioned black glass-ceramics; since the chemical strengthening only occurs on the surface of the body of the black glass-ceramics, and the thickness of the strengthened layer formed after chemical strengthening is much smaller than the thickness of the black glass-ceramics; therefore, the composition of the compressive stress layer and the center of the strengthened black glass-ceramics is almost exactly the same or exactly the same as the glass composition of the black glass-ceramics. In some embodiments of this application, the compressive stress layer of the strengthened black glass-ceramics, calculated by mass percentage of oxides, includes the following components: SiO 2 : 60.00 wt% to 75.00 wt%; Al 2 O 3 : 2.00 wt% to 10.00 wt%; P 2 O 5 : 1.50 wt% to 5.00 wt%; ZrO 2 : 3.00 wt% to 10.00 wt%; Na 2 O: 0.00 wt% to 4.00 wt%; K 2 O: 0.00 wt% to 1.00 wt%; Li 2 O: 8.00 wt% to 14.00 wt%; CaO: 0.00 wt% to 1.20 wt%; B 2 O 3 : 0.00 wt% to 3.00 wt%; First colorant: at least one of NiO and CoO; Second colorant: MnO 2 , Cr 2 O 3 and Ho 2 O 3at least one; wherein, 0.01 wt% ≤ NiO + CoO ≤ 2.00 wt%; 0.01 wt% ≤ MnO 2 + Cr 2 O 3 + Ho 2 O 3 ≤ 8.00 wt%.

[0206] In some embodiments of the present application, based on the mass percentage of the oxide, the content of SiO in the strengthened black series glass-ceramics 2 can be: 60.00 wt%, 62.00 wt%, 65.00 wt%, 68.00 wt%, 70.00 wt%, 71.00 wt%, 72.00 wt%, 73.00 wt%, 74.00 wt% or 75.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0207] In some embodiments of the present application, based on the mass percentage of the oxide, the content of Al in the strengthened black series glass-ceramics 2 O 3 can be: 2.00 wt%, 2.20 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.30 wt%, 3.50 wt%, 3.80 wt%, 4.00 wt%, 4.10 wt%, 4.30 wt%, 4.40 wt%, 4.70 wt%, 4.90 wt%, 5.00 wt%, 5.30 wt%, 5.50 wt%, 5.70 wt%, 5.90 wt%, 6.00 wt%, 6.50 wt%, 6.80 wt%, 7.00 wt%, 7.50 wt%, 8.00 wt%, 8.30 wt%, 8.50 wt%, 8.80 wt%, 9.00 wt%, 9.20 wt%, 9.50 wt%, 9.80 wt% or 10.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0208] In some embodiments of the present application, based on the mass percentage of the oxide, the content of P in the strengthened black series glass-ceramics 2 O 5 is 1.50 wt% to 5.00 wt%, preferably 1.50 wt% to 4.50 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, the content of P in the strengthened black series glass-ceramics 2 O 5The content can be: 1.50 wt%, 2.00 wt%, 2.50 wt%, 2.90 wt%, 3.00 wt%, 3.30 wt%, 3.50 wt%, 4.00 wt%, 4.50 wt%, 4.80 wt% or 5.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0209] In some embodiments of the present application, based on the mass percentage of the oxide, Li in the strengthened black series glass-ceramics 2 The content of O is 1.00 wt% to 14.00 wt%, preferably 1.00 wt% to 13.50 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, Li in the strengthened black series glass-ceramics 2 The content of O can be 1.00 wt%, 1.50 wt%, 2.00 wt%, 2.50 wt%, 3.00 wt%, 3.50 wt%, 4.00 wt%, 4.50 wt%, 5.00 wt%, 5.50 wt%, 6.00 wt%, 6.50 wt%, 7.00 wt%, 7.50 wt%, 8.00 wt%, 8.50 wt%, 9.00 wt%, 9.30 wt%, 9.50 wt%, 9.80 wt%, 10.00 wt%, 11.00 wt%, 12.00 wt%, 13.00 wt% or 14.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0210] In some embodiments of the present application, based on the mass percentage of the oxide, Na in the strengthened black series glass-ceramics 2 O is 0.00 wt% to 21.00 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, Na in the strengthened black series glass-ceramics 2O can be 0.00 wt%, 0.30 wt%, 0.50 wt%, 0.80 wt%, 1.00 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.50 wt%, 3.80 wt%, 4.00 wt%, 4.50 wt%, 5.00 wt%, 5.50 wt%, 6.00 wt%, 6.50 wt%, 7.00 wt%, 7.50 wt%, 8.00 wt%, 8.50 wt%, 9.00 wt%, 9.50 wt%, 10.00 wt%, 10.50 wt%, 11.00 wt%, 11.50 wt%, 12.00 wt%, 12.50 wt%, 13.00 wt%, 13.50 wt%, 14.00 wt%, 14.50 wt%, 15.00 wt%, 15.50 wt%, 16.00 wt%, 16.50 wt%, 17.00 wt%, 17.50 wt%, 18.00 wt%, 18.50 wt%, 19.00 wt%, 19.50 wt%, 19.80 wt%, 20.00 wt% or 21.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0211] In some embodiments of the present application, in terms of the mass percentage of the oxide, K in the strengthened black series glass-ceramics 2 O is 0.00 wt% to 3.00 wt%. In some embodiments of the present application, in terms of the mass percentage of the oxide, K in the strengthened black series glass-ceramics 2 O can be 0.00 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.30 wt%, 2.60 wt%, 2.80 wt%, 2.90 wt% or 3.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0212] In some embodiments of the present application, in terms of the mass percentage of the oxide, ZrO in the strengthened black series glass-ceramics 2 is 3.00 wt% to 10.00 wt%. In some embodiments of the present application, in terms of the mass percentage of the oxide, ZrO in the strengthened black series glass-ceramics 2It can be 3.00 wt%, 3.50 wt%, 4.00 wt%, 4.50 wt%, 5.00 wt%, 5.50 wt%, 6.00 wt%, 6.50 wt%, 7.00 wt%, 7.50 wt%, 8.00 wt%, 8.50 wt%, 8.80 wt%, 9.00 wt%, 9.50 wt%, 9.80 wt% or 10.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0213] In some embodiments of the present application, based on the mass percentage of the oxide, CaO in the strengthened black series glass-ceramics is 0.00 wt% to 1.20 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, CaO in the strengthened black series glass-ceramics can be 0.00 wt%, 0.30 wt%, 0.5 wt%, 1.00 wt%, 1.10 wt%, 1.15 wt%, 1.18 wt% or 1.20 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0214] In some embodiments of the present application, based on the mass percentage of the oxide, B 2 O 3 in the strengthened black series glass-ceramics is 0.00 wt% to 3.00 wt%. In some embodiments of the present application, based on the mass percentage of the oxide, B 2 O 3 in the strengthened black series glass-ceramics can be 0.00 wt%, 0.30 wt%, 0.50 wt%, 1.00 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.20 wt%, 2.50 wt%, 2.80 wt% or 3.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0215] In some embodiments of the present application, based on the mass percentage of the oxide, the content of NiO in the strengthened black series glass-ceramics can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt% or 1.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0216] In some embodiments of the present application, based on the mass percentage of the oxide, the content of CoO in the strengthened black series glass-ceramics can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt% or 1.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0217] In some embodiments of the present application, based on the mass percentage of the oxide, MnO in the strengthened black series glass-ceramics 2 The content can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt% or 1.50 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0218] In some embodiments of the present application, based on the mass percentage of the oxide, Cr in the strengthened black series glass-ceramics 2 O 3 The content can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt%, 1.50 wt%, 1.70 wt%, 1.90 wt%, 2.00 wt%, 2.50 wt%, 3.00 wt%, 3.50 wt% or 4.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0219] In some embodiments of the present application, based on the mass percentage of the oxide, Ho in the strengthened black series glass-ceramics 2 O 3The content can be 0.00 wt%, 0.01 wt%, 0.05 wt%, 0.09 wt%, 0.15 wt%, 0.20 wt%, 0.30 wt%, 0.50 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt%, 1.00 wt%, 1.10 wt%, 1.20 wt%, 1.30 wt%, 1.40 wt%, 1.50 wt%, 1.80 wt%, 2.00 wt%, 2.20 wt%, 2.30 wt%, 2.40 wt% or 2.50 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0220] In some embodiments of the present application, the strengthened black series glass-ceramics provided by the present application further contain CuO, Er 2 O 3 and / or Nd 2 O 3 .

[0221] Among them, calculated by the mass percentage of the oxide, the content of CuO in the strengthened black series glass-ceramics can be 0.00 wt% to 4.00 wt%, preferably 0.00 wt% to 3.90 wt%. In some embodiments of the present application, calculated by the mass percentage of the oxide, the content of CuO in the strengthened black series glass-ceramics can be 0.00 wt%, 0.20 wt%, 0.40 wt%, 0.60 wt%, 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.40 wt%, 1.60 wt%, 1.80 wt%, 2.00 wt%, 2.30 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.30 wt%, 3.50 wt%, 3.80 wt% or 4.00 wt%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0222] Among them, calculated by the mass percentage of the oxide, the content of Er 2 O 3 in the strengthened black series glass-ceramics is 0.00 wt% to 4.00 wt%, preferably 0.00 wt% to 3.90 wt%. In some embodiments of the present application, calculated by the mass percentage of the oxide, the content of Er 2 O 3The content can be 0.00 wt%, 0.20 wt%, 0.40 wt%, 0.60 wt%, 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.40 wt%, 1.60 wt%, 1.80 wt%, 2.00 wt%, 2.30 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.50 wt%, 3.80 wt% or 4.00 wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0223] Among them, in the strengthened black series glass-ceramics, Nd in terms of mass percentage of the oxide 2 O 3 The content is 0.00 wt% to 4.00 wt%. In some embodiments of the present application, in the strengthened black series glass-ceramics, Nd in terms of mass percentage of the oxide 2 O 3 The content can be 0.00 wt%, 0.20 wt%, 0.40 wt%, 0.60 wt%, 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.40 wt%, 1.60 wt%, 1.80 wt%, 2.00 wt%, 2.20 wt%, 2.50 wt%, 2.80 wt%, 3.00 wt%, 3.20 wt%, 3.50 wt%, 3.80 wt% or 4.00 wt% etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0224] In some embodiments of the present application, the thickness t of the strengthened black series glass-ceramics of the present application is not particularly limited. For example, it can be 0.1 to 0.7 mm; preferably 0.15 to 0.7 mm. In some embodiments of the present application, the thickness t of the strengthened black glass-ceramics can be 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm or 0.7 mm etc., as well as all ranges and sub-ranges between the above values. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0225] In the present application, the chemical strengthening process of the strengthened black series glass-ceramics includes single-step chemical strengthening or multi-step chemical strengthening.

[0226] In some embodiments of the present application, in the single-step chemical strengthening, a salt bath containing NaNO 3 is used; preferably, the content of the NaNO 3 is 20 to 100 wt%;

[0227] Alternatively, in some other embodiments, the single-step chemical strengthening uses a mixed salt bath containing NaNO 3 and KNO 3 . Preferably, the content of KNO 3 in the mixed salt bath is 70-100 wt%, and the content of NaNO 3 is 0-30 wt%; or the single-step chemical strengthening uses a mixed salt bath containing NaNO 3 , KNO 3 and LiNO 3 . Preferably, the content of KNO 3 in the mixed salt bath is 70-100 wt%, the content of NaNO 3 is 0-30 wt%, and the content of LiNO 3 is 0-0.1 wt%.

[0228] In some embodiments of the present application, the temperature of the single-step chemical strengthening is 380°C to 500°C, and the time of the single-step chemical strengthening is 1 h to 10 h.

[0229] In some embodiments of the present application, the multi-step chemical strengthening includes two-step chemical strengthening. Among them, the first-step chemical strengthening uses a salt bath containing NaNO 3 ; the second-step chemical strengthening uses a salt bath containing KNO 3 . Preferably, the first-step chemical strengthening uses a salt bath containing 100 wt% NaNO 3 ; the second-step chemical strengthening uses a salt bath containing 99.9-100 wt% KNO 3 and 0-0.1 wt% LiNO 3 .

[0230] In some embodiments of the present application, in the two-step chemical strengthening, the temperature of the first-step chemical strengthening is 380-500°C, and the time of the first-step chemical strengthening is 1-10 h; the temperature of the second-step chemical strengthening is 380-500°C, and the time of the second-step chemical strengthening is 1-5 h.

[0231] In some embodiments of the present application, the single-rod static pressure strength of the black series glass-ceramics to be strengthened is not less than 250 N, preferably 250 N to 500 N, more preferably 260 N to 500 N, and still more preferably 300 N to 500 N.

[0232] Fourthly, the present application provides an application of the black series glass-ceramics as described above, or the black series glass-ceramics prepared by the preparation method of the black series glass-ceramics as described above, or the strengthened black series glass-ceramics as described above in 2G, 3G, 4G, 5G, 5.5G, 6G communication devices, Bluetooth devices, and / or WIFI devices; especially applied to 5G, 5.5G, 6G communication devices.

[0233] In a fifth aspect, the present application further provides an electronic device, including the above-mentioned black series microcrystalline glass, or the black series microcrystalline glass prepared by the preparation method of the above-mentioned black series microcrystalline glass, or the above-mentioned strengthened black series microcrystalline glass. In the present application, the electronic device includes a housing and a middle frame; the housing includes the above-mentioned black series microcrystalline glass, or the black series microcrystalline glass prepared by the preparation method of the above-mentioned black series microcrystalline glass, or the above-mentioned strengthened black series microcrystalline glass. The electronic device may be at least one of a mobile phone, a tablet computer, a handheld game console, a portable digital device (such as a digital camera), a vehicle-mounted central control, an electronic whiteboard glass, a smart home, and smart wearables (such as smart bracelets, smart watches, and smart glasses).

[0234] To facilitate those skilled in the art to better understand the innovative points of the present application, the technical solutions of the present application will be further described in detail below in conjunction with embodiments. The embodiments of the present application described in detail below are exemplary and are only used to explain the present application and should not be construed as a limitation to the present application.

[0235] Example 1

[0236] According to the formula of Example 1 in Table 1, each raw material component was accurately weighed in proportion and fully mixed to obtain a mixture, and the total weight of each raw material component was 2000 g; the mixture was placed in a platinum crucible and heated to 1550 °C in a high-temperature melting furnace for melting, and the melting time was 10 h. After removing bubbles, the glass melt was poured into a mold for cooling and forming. After cooling to 800 °C, it was placed in an annealing furnace at 500 °C for annealing for 12 hours, and then cooled to room temperature with the furnace to obtain the base glass.

[0237] The above-obtained base glass was heated to the nucleation temperature at a heating rate of 10 °C / min for nucleation treatment; then it was heated to the crystallization temperature at a heating rate of 10 °C / min for crystallization treatment; a microcrystalline glass brick was obtained. After the microcrystalline glass brick was successively subjected to cold processing treatments such as cutting, CNC machining (the model of the CNC instrument and equipment used in the present application is: RCG500S), and polishing, a microcrystalline glass of 50 mm × 50 mm × 0.7 mm was made.

[0238] The nucleation temperature, nucleation treatment time, crystallization temperature, and crystallization treatment time are shown in Table 2 respectively.

[0239] Examples 2 to 10

[0240] The same operations as in Example 1 were carried out, except for the compositions of the respective raw materials for preparing the microcrystalline glass shown in Table 1 and the conditions of the nucleation treatment and crystallization treatment shown in Table 2.

[0241] Comparative Examples 1 to 7

[0242] The operation was carried out under the same conditions as in Example 1, except for the compositions of the raw materials for preparing the glass-ceramics shown in Table 3 and the conditions of nucleation treatment and crystallization treatment shown in Table 4.

[0243] The performances of the glass-ceramics of the above Examples 1-10 and Comparative Examples 1-7 were tested respectively, and the result data are shown in Table 2 and Table 4 respectively.

[0244] The glass-ceramics of the above Examples 1-10 and Comparative Examples 1-7 were respectively subjected to chemical strengthening treatment to obtain strengthened glass-ceramics; the chemical strengthening process conditions are shown in Tables 5-6 respectively.

[0245] The single-rod static pressure strength and the content of Na 2 O / wt% in the strengthened layer after strengthening of the strengthened glass-ceramics prepared in the above Examples 1-10 were respectively tested; the results are shown in Table 5. The single-rod static pressure strength of the strengthened glass-ceramics prepared in the above Comparative Examples 1-7 was respectively tested; the results are shown in Table 6.

[0246] Among them, the XRD patterns of the glass-ceramics provided in Example 3 and the glass-ceramics provided in Comparative Example 3 are as Figure 1 shown. It can be seen from this figure that the main crystal phases of the glass-ceramics provided in this application are spodumene and lithium disilicate, while the main crystal phases of the glass-ceramics provided in Comparative Example 3 are spodumene, lithium disilicate and quartz.

[0247] Table 1

[0248]

[0249] Table 2

[0250]

[0251]

[0252] Table 4

[0253]

[0254] Table 5

[0255]

[0256] Table 6

[0257]

[0258] The black series glass-ceramics prepared in the examples of this application have a dielectric constant of less than 6 and a dielectric loss of less than 0.005 at a frequency of 2.4 GHz or 5 GHz, which can meet the requirements of 5G applications.

[0259] It can be seen from the comparison between Example 3 and Comparative Example 4 that when the content of CaO exceeds the composition range of this application, the dielectric constant of the black series of glass-ceramics prepared thereby significantly increases at a frequency of 2.4 GHz or 5 GHz; meanwhile, the dielectric constant of the black series of glass-ceramics at a frequency of 2.4 GHz or 5 GHz is greater than 6, and the dielectric loss is all above 0.005, which cannot meet the requirements of 5G applications.

[0260] It can be seen from the comparison between Example 3 and Comparative Example 5 that when the content of CoO exceeds the composition range of this application, the dielectric constant of the black series of glass-ceramics prepared thereby significantly increases at a frequency of 2.4 GHz or 5 GHz; the dielectric constant of the black series of glass-ceramics at a frequency of 2.4 GHz or 5 GHz is greater than 6, and the dielectric loss is all above 0.005, which cannot meet the requirements of 5G applications.

[0261] It can be seen from the comparison between Example 1 and Comparative Example 6 that when the content of NiO exceeds the composition range of this application, the dielectric constant of the black series of glass-ceramics prepared thereby significantly increases at a frequency of 2.4 GHz or 5 GHz; the dielectric constant of the black series of glass-ceramics at a frequency of 2.4 GHz or 5 GHz is greater than 6, and the dielectric loss is all above 0.005, which cannot meet the requirements of 5G applications.

[0262] It can be seen from the comparison between Example 2 and Comparative Example 7 that when the contents of CoO and NiO exceed the composition range of this application, the dielectric constant of the black series of glass-ceramics prepared thereby significantly increases at a frequency of 2.4 GHz or 5 GHz; the dielectric constant of the black series of glass-ceramics at a frequency of 2.4 GHz or 5 GHz is greater than 6, and the dielectric loss is all above 0.005, which cannot meet the requirements of 5G applications.

[0263] It can be seen from the comparison between the examples and Comparative Examples 1-3 that TiO 2 and / or Fe 2 O 3 is added to the glass composition to prepare a black series of glass-ceramics, and its dielectric constant and dielectric loss increase greatly, which are not suitable for the requirements of 5G applications.

[0264] The above is only the specific implementation manner of this application, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by this invention should be covered by the protection scope of this application. Therefore, the protection scope of this application should be subject to the protection scope of the claims.

Claims

1. A black microcrystalline glass, wherein the black microcrystalline glass has a color coordinate of L*: 15-30; a*: -5-5; b*: -2-10 in a reflection mode in a CIELab color space at a thickness of 0.1-0.7 mm; characterized in that: Calculated by mass percentage of oxides, it includes the following components: SiO2: 60.00wt%~75.00wt%; Al2O3: 2.00wt%~10.00wt%; P2O5: 1.50wt%~5.00wt%; ZrO2: 3.00wt%~10.00wt%; Na2O: 0.00wt%~4.00wt%; K2O: 0.00wt%~1.00wt%; Li2O: 8.00wt%~14.00wt%; CaO: 0.00wt%~1.20wt%; B2O3: 0.00wt%~3.00wt%; First colorant: at least one of NiO and CoO; Second colorant: at least one of MnO2, Cr2O3 and Ho2O3; Among them, 0.01wt%≤NiO+CoO≤2.00wt%; 0.01wt%≤MnO2+Cr2O3+Ho2O3≤8.00wt%.

2. The black-based microcrystalline glass according to claim 1, characterized in that: The content of iron and / or titanium in the black glass-ceramics is less than 1000 ppm.

3. The black-based microcrystalline glass according to any one of claims 1 to 2, characterized in that: The content of NiO is 0.00 wt% to 1.00 wt% and / or the content of CoO is 0.00 wt% to 1.00 wt%.

4. The black-based microcrystalline glass according to any one of claims 1 to 3, characterized in that: The content of MnO2 is 0.00wt% to 1.50wt%; and / or the content of Cr2O3 is 0.00wt% to 4.00wt%; and / or the content of Ho2O3 is 0.00wt% to 2.50wt%.

5. The black-based microcrystalline glass according to any one of claims 1 to 4, characterized in that: The black microcrystalline glass has a color coordinate of L* of 16 to 30, preferably 16 to 29, and more preferably 17 to 29 in the reflection mode in the CIELab color space at a thickness of 0.1 to 0.7 mm; and / or a* of -4.5 to 5, preferably -4 to 5; and / or b* of -2 to 9.

6. The black-based microcrystalline glass according to any one of claims 1 to 5, characterized in that: The black glass-ceramics further contains CuO, Er2O3 and / or Nd2O3; preferably, the content of CuO is 0.00wt% to 4.00wt% in terms of the mass percentage of the oxide; and / or the content of Er2O3 is 0.00wt% to 4.00wt%; And / or the content of Nd2O3 is 0.00wt% to 4.00wt%.

7. The black-based microcrystalline glass according to any one of claims 1 to 6, characterized in that: The relative dielectric constant ε of the black-based microcrystalline glass at frequencies of 2.4 GHz and 5 GHz is less than 6.

8. The black-based microcrystalline glass according to any one of claims 1 to 7, characterized in that: The relative dielectric constant ε of the black glass-ceramics at frequencies of 2.4 GHz and 5 GHz is both 5.87 or less.

9. The black-based microcrystalline glass according to any one of claims 1 to 8, characterized in that: The dielectric loss tangent value of the black microcrystalline glass at the frequency of 2.4 GHz and 5 GHz is 5×10 -3 the following.

10. The black-based glass-ceramics according to any one of claims 1 to 9, characterized in that: The dielectric loss tangent value of the black microcrystalline glass at the frequency of 2.4 GHz and 5 GHz is 1×10 -3 ~5×10 -3 .

11. The black-based glass-ceramics according to any one of claims 1 to 10, characterized in that: The black series microcrystalline glass has a transmittance of 0 to 10% at 550 nm when the thickness is 0.1 to 0.7 mm.

12. The black-based microcrystalline glass according to any one of claims 1 to 11, characterized in that: The main crystalline phase of the black series glass-ceramics includes one or more of petalite, lithium disilicate, lithium monosilicate, lithium phosphate, quartz, pyroxene and nepheline; preferably, the main crystalline phase of the black series glass-ceramics includes one or more of petalite, lithium disilicate and quartz; and / or The crystallinity of the black glass-ceramics is 60wt% to 100wt%.

13. The method for preparing black glass-ceramics according to any one of claims 1 to 12, characterized in that: The following steps are involved: Step 1: Mix the raw materials for preparing glass, melt them, cool them and perform annealing to obtain substrate glass; Step 2: Heat-treat the substrate glass obtained in step 1 to obtain black microcrystalline glass.

14. The method for preparing black microcrystalline glass according to claim 13, characterized in that: The heat treatment includes nucleation treatment and crystallization treatment; further, the heating rate of the nucleation treatment is 1°C / min to 15°C / min; and / or, the temperature of the nucleation treatment is 500°C to 600°C; and / or, the time of the nucleation treatment is 30min to 600min; and / or, the heating rate of the crystallization treatment is 1°C / min to 15°C / min; and / or, the temperature of the crystallization treatment is 600°C to 850°C; and / or, the time of the crystallization treatment is 30min to 600min.

15. A strengthened black glass-ceramic with a thickness of t, comprising a double-sided strengthening layer and a tensile stress layer, wherein the strengthening layer extends from the surface of the strengthened black glass-ceramic toward the inside, wherein the double-sided strengthening layer is symmetrically distributed, and the thickness of each strengthening layer is not more than 0.22t; the color coordinates of the strengthened black glass-ceramic in the reflection mode in the CIELab color space at a thickness of 0.1 to 0.7 mm are: L*: 15 to 30; a*: -5 to 5; b*: -2 to 10; The reinforced black glass-ceramics comprises the following components, measured by mass percentage of oxides: SiO2: 60.00wt%~75.00wt%; Al2O3: 2.00wt%~10.00wt%; P2O5: 1.50wt%~5.00wt%; ZrO2: 3.00wt%~10.00wt%; Na2O: 0.00wt%~21.00wt%; K2O: 0.00wt%~3.00wt%; Li2O: 1.00wt%~14.00wt%; CaO: 0.00wt%~1.20wt%; B2O3: 0.00wt%~3.00wt%; First colorant: at least one of NiO and CoO; Second colorant: at least one of MnO2, Cr2O3 and Ho2O3; in, 0.01wt%≤NiO+CoO≤2.00wt%; 0.01wt%≤MnO2+Cr2O3+Ho2O3≤8.00wt%; The tensile stress layer, measured in terms of oxide mass percentage, comprises the following components: SiO2: 60.00wt%~75.00wt%; Al2O3: 2.00wt%~10.00wt%; P2O5: 1.50wt%~5.00wt%; ZrO2: 3.00wt%~10.00wt%; Na2O: 0.00wt%~4.00wt%; K2O: 0.00wt%~1.00wt%; Li2O: 8.00wt%~14.00wt%; CaO: 0.00wt%~1.20wt%; B2O3: 0.00wt%~3.00wt%; First colorant: at least one of NiO and CoO; Second colorant: at least one of MnO2, Cr2O3 and Ho2O3; Among them, 0.01wt%≤NiO+CoO≤2.00wt%; 0.01wt%≤MnO2+Cr2O3+Ho2O3≤8.00wt%.

16. A strengthened black glass-ceramic with a thickness of t, comprising a double-sided strengthening layer and a tensile stress layer, wherein the strengthening layer extends from the surface of the strengthened black glass-ceramic toward the inside, wherein the double-sided strengthening layer is symmetrically distributed, and the thickness of each strengthening layer is not more than 0.22t; the color coordinates of the strengthened black glass-ceramic in the reflection mode in the CIELab color space at a thickness of 0.1 to 0.7 mm are: L*: 15 to 30; a*: -5 to 5; b*: -2 to 10; The reinforced black glass-ceramics comprises the following components, measured by mass percentage of oxides: SiO2: 60.00wt%~75.00wt%; Al2O3: 2.00wt%~10.00wt%; P2O5: 1.50wt%~5.00wt%; ZrO2: 3.00wt%~10.00wt%; Na2O: 0.00wt%~21.00wt%; K2O: 0.00wt%~3.00wt%; Li2O: 1.00wt%~14.00wt%; CaO: 0.00wt%~1.20wt%; B2O3: 0.00wt%~3.00wt%; First colorant: at least one of NiO and CoO; Second colorant: at least one of MnO2, Cr2O3 and Ho2O3; in, 0.01wt%≤NiO+CoO≤2.00wt%; 0.01wt%≤MnO2+Cr2O3+Ho2O3≤8.00wt%.

17. The tempered black glass-ceramics according to claim 15 or 16, characterized in that: t is 0.10~0.70mm.

18. The tempered black glass-ceramics according to claim 15 or 16, characterized in that: The chemical strengthening process of strengthening the black series microcrystalline glass includes single-step chemical strengthening or multi-step chemical strengthening.

19. The tempered black glass-ceramics according to claim 18, characterized in that: The single-step chemical strengthening adopts a mixed salt bath containing NaNO3, KNO3 and LiNO3; preferably, the content of KNO3 in the mixed salt bath is 0-100wt%, the content of NaNO3 is 0-100wt%, and the content of LiNO3 is 0-0.1wt%.

20. The tempered black glass-ceramics according to any one of claims 18 to 19, characterized in that: The temperature of the single-step chemical strengthening is 380-530° C., and the time of the single-step chemical strengthening is 15 min-10 h.

21. The tempered black glass-ceramics according to any one of claims 15 to 20, characterized in that: The single rod static pressure strength of the reinforced black glass-ceramics is not less than 250N, preferably 250N to 500N, and more preferably 300N to 500N.

22. Application of the black glass-ceramics as described in any one of claims 1 to 12, or the black glass-ceramics prepared by the method for preparing black glass-ceramics as described in any one of claims 13 to 14, or the strengthened black glass-ceramics as described in any one of claims 15 to 21 in 2G, 3G, 4G, 5G, 5.5G, 6G communication equipment, Bluetooth equipment and / or WIFI equipment; especially in 5G, 5.5G, 6G communication equipment.

23. An electronic device, characterized in that: The invention comprises the black glass-ceramics according to any one of claims 1 to 12 or the black glass-ceramics prepared by the method for preparing the black glass-ceramics according to any one of claims 13 to 14 or the strengthened black glass-ceramics according to any one of claims 15 to 21.

24. An electronic device, characterized in that: It comprises an outer shell and a middle frame; the outer shell comprises the black glass-ceramic described in any one of claims 1 to 12, or the black glass-ceramic prepared by the method for preparing the black glass-ceramic described in any one of claims 13 to 14, or the strengthened black glass-ceramic described in any one of claims 15 to 21.

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