Colored microcrystalline glass and preparation method thereof

Abstract

The application discloses a kind of colored microcrystalline glass and preparation method, the colored microcrystalline glass is obtained by heat treatment from colored base material glass;The colored base material glass includes the glass composition of multiple different colors is melted into multiple different color glass liquid simultaneously forming as a whole to obtain, the colored base material glass has different color regions.

Description

Technical Field

[0001] The present application relates to the technical field of microcrystalline glass, and in particular to colored microcrystalline glass for electronic device housings, and specifically to a colored microcrystalline glass and a preparation method thereof. Background Art

[0002] Backplane glass, also known as the glass back cover of a mobile phone, is traditionally made primarily of metal and plastic. With the development and widespread adoption of 5G and wireless charging technologies, the signal shielding effect of metal backplanes has become increasingly prominent. Consequently, non-metallic materials are gradually replacing backplanes, with glass and glass-ceramics becoming the primary alternatives due to their superior performance. With the widespread adoption of smartphones, consumers are increasingly demanding not only performance and lifespan, but also visual effects and personalized appearance. Unlike front covers, backplanes do not necessarily require the same exceptional transmittance; their appearance can be customized. Consequently, the color selection and design of tinted glass or glass-ceramic back covers has become a hot topic for mobile phone manufacturers.

[0003] At present, the color design of mobile phone back covers mainly adopts film pasting, electroplating and spray painting. Both processes are post-processing on the transparent glass cover. The color has developed from the original single color to the popular gradient color and regional color. The diversified colors meet the pursuit of fashion of different consumers. The discoloration and cheap texture of film pasting and electroplating and spray painting have also caused terminal mobile phone manufacturers to gradually focus on the development of film color from the development of film color to the glass body, in order to achieve a three-dimensional, transparent and saturated color effect through the color of the glass body.

[0004] Existing research into the production of colored glass involves adding different colorants to glass components to create colored glass of varying colors. However, this method often produces only a single color, making the color of the glass itself very monotonous and difficult to meet market demand. Summary of the Invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of this application is to provide a colored micro-ceramic glass to achieve coloring of colored glass in different areas, so as to solve the technical problem in the prior art that colored glass cannot achieve controllable colors in different areas.

[0006] In order to solve the above technical problems, in the first aspect, the present application provides a colored microcrystalline glass, which is obtained by heat treating a colored substrate glass; the colored substrate glass comprises a plurality of different colored glass compositions melted into a plurality of different colored glass liquids and simultaneously molded into one, and the colored substrate glass has different color areas.

[0007] In some embodiments, multiple glass compositions of different colors are melted into glass liquids of different colors, and when formed, the following conditions are met: the absolute value of the temperature difference between the multiple glass liquids of different colors at a viscosity of 300P is less than or equal to 30°C, and the absolute value of the temperature difference at a viscosity of 600P is less than or equal to 40°C; this ensures that the colored substrate glass will not have defects such as breakage, flaws, cracks, etc. during the forming process and can be formed intact.

[0008] In some embodiments, when the multiple glass compositions of different colors are heat-treated after being formed, the absolute value of the temperature difference between the nucleation temperatures of the glass compositions of different colors is less than or equal to 20°C.

[0009] In some embodiments, when the multiple glass compositions of different colors are heat-treated after being formed, the absolute value of the temperature difference between the crystallization temperatures of the glass compositions of different colors is less than or equal to 20°C.

[0010] In some embodiments, after the glass compositions of different colors are formed and heat-treated, the absolute value of the difference between the average thermal expansion coefficients of the glass compositions of different colors is less than or equal to 0.8×10 -6 / K; can achieve uniform strengthening of colored micro-ceramic glass and has good strength performance.

[0011] In some embodiments, the glass compositions of various colors include the following components, calculated as a mole percentage of oxides:

[0012] SiO2: 66-71%;

[0013] Al2O3: 3.5~5.0%;

[0014] Na2O: 0-5.0%, not 0;

[0015] Li2O: 18-23%;

[0016] P2O5: 0.5~1.5%;

[0017] ZrO2: 1.5~4.0%;

[0018] At least one colorant, wherein the colorant comprises at least one of Au, Ag, Cr2O3, transition metal oxides, and rare earth metal oxides.

[0019] In some embodiments, the glass compositions of various colors further include the following components, calculated as a mole percentage of oxides:

[0020] K2O: 0~0.5%;

[0021] CaO: 0-1.5%;

[0022] B2O3: 0~2%.

[0023] In some embodiments, the number of glass compositions of different colors is 2 or more, or 3 or more.

[0024] In some embodiments, the compositions of the glass compositions of different colors differ partially or entirely in terms of the components other than the colorant and their contents.

[0025] In some embodiments, the colored substrate glass is formed by at least one of casting, calendering, overflow, float, and slot-drawing.

[0026] In some embodiments, multiple glass liquids of different colors are formed into one body in different regions.

[0027] In some embodiments, the plurality of differently colored glass compositions have the same primary crystalline phase after each forming and heat treatment.

[0028] In some embodiments, the main crystalline phase of the glass compositions of different colors after molding and heat treatment is a lithium-containing crystalline phase, including at least one of petalite, lithium monosilicate, lithium disilicate, and eucryptite.

[0029] In some embodiments, the heat treatment includes a nucleation treatment and a crystallization treatment.

[0030] In some embodiments, the nucleation treatment is performed by heating the colored substrate glass from room temperature to a nucleation temperature at a heating rate of 1 to 10° C. / min.

[0031] In some embodiments, the temperature of the nucleation treatment is 500-600° C., and the time of the nucleation treatment is 180-300 min.

[0032] In some embodiments, the crystallization treatment is to heat the colored substrate glass from a nucleation temperature to a crystallization temperature at a heating rate of 1 to 10° C. / min.

[0033] In some embodiments, the crystallization treatment temperature is 600-800° C., and the crystallization treatment time is 30-180 min.

[0034] In a second aspect, the present application provides a method for preparing the above-mentioned colored glass-ceramics, comprising the following steps:

[0035] Step 1: Components of a plurality of glass compositions of different colors are mixed separately and then melted to obtain glass liquids of various colors;

[0036] Step 2: Molding the glass liquids of various colors obtained in step 1 into one piece and annealing them to obtain colored substrate glass;

[0037] Step 3: Heat-treat the colored substrate glass obtained in step 2 to obtain colored microcrystalline glass.

[0038] In some embodiments, in step 1, the melting temperature is 1350-1650° C., and the melting time is 4-13 hours.

[0039] In some embodiments, in step 2, multiple glass liquids of different colors are formed into one body in different regions.

[0040] In some embodiments, in step 2, the molding method is at least one of casting molding, calendering molding, overflow molding, float molding, and narrow slit drawdown.

[0041] In some embodiments, in step 2, the annealing temperature is 450-500° C., and the annealing time is 12-48 hours.

[0042] In some embodiments, in step 3, the heat treatment includes a nucleation treatment and a crystallization treatment.

[0043] In some embodiments, the temperature of the nucleation treatment is 500-600° C., and the time of the nucleation treatment is 180-300 min.

[0044] In some embodiments, the crystallization treatment temperature is 600-800° C., and the crystallization treatment time is 30-180 min.

[0045] In some embodiments, the colored substrate glass is heated from room temperature to a nucleation temperature at a heating rate of 3 to 10° C. / min.

[0046] In some embodiments, the colored substrate glass is heated from the nucleation temperature to the crystallization temperature at a heating rate of 3 to 10° C. / min.

[0047] In a third aspect, the present application provides a strengthened colored micro-ceramic glass, which is obtained by chemically strengthening the colored micro-ceramic glass as described above or the colored micro-ceramic glass prepared by the above-mentioned method for preparing the colored micro-ceramic glass.

[0048] In some embodiments, chemical strengthening comprises single-step chemical strengthening or multi-step chemical strengthening.

[0049] In some embodiments, the single-step chemical strengthening uses a salt bath containing NaNO 3 , preferably with a content of 30-100 wt %.

[0050] In some embodiments, the temperature of the single-step chemical strengthening is 450-500°C.

[0051] In some embodiments, the time for single-step chemical strengthening is 1 to 15 hours.

[0052] In some embodiments, the multi-step chemical strengthening includes two steps of chemical strengthening, wherein the first step of chemical strengthening uses a salt bath containing NaNO3, preferably the content of NaNO3 is 30-100wt%; the second step of chemical strengthening uses a salt bath containing KNO3, preferably the content of KNO3 is 60-100wt%.

[0053] In some embodiments, the temperature of the first step chemical strengthening is 450-500° C., and the time of the first step chemical strengthening is 2-10 hours.

[0054] In some embodiments, the temperature of the second step chemical strengthening is 450-500° C., and the time of the second step chemical strengthening is 1-5 hours.

[0055] In some embodiments, at a thickness of 0.60 mm, the average single-rod static compressive strength of the strengthened colored glass-ceramics is greater than or equal to 300 N, preferably 320-450 N.

[0056] In some embodiments, at a thickness of 0.60 mm, the average drop resistance height of the strengthened colored glass-ceramics is greater than or equal to 1.80 m, preferably 1.80-2.50 m.

[0057] In a fourth aspect, the present application provides an application of the colored microcrystalline glass as described above, or the colored microcrystalline glass prepared by the above-mentioned method for preparing the colored microcrystalline glass, or the above-mentioned colored tempered microcrystalline glass in mobile phone back covers, electronic terminals, decorative parts, handicrafts, jewelry or portable digital devices.

[0058] In a fifth aspect, a consumer electronic product comprises: a housing comprising a front surface, a back surface and side surfaces; an electronic component at least partially located within the housing, the electronic component comprising at least a controller, a memory and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass arranged on the display, wherein at least a portion of the housing comprises the colored microcrystalline glass as described above, or the colored microcrystalline glass prepared by the method for preparing the colored microcrystalline glass as described above, or the strengthened colored microcrystalline glass as described above.

[0059] In a sixth aspect, an electronic device comprises the colored glass-ceramics as described above, the colored glass-ceramics prepared by the method for preparing the colored glass-ceramics as described above, or the strengthened colored glass-ceramics as described above.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] 1. The present application adopts a plurality of glass compositions of different colors to be melted into glass liquids of different colors and simultaneously molded into one body to obtain colored substrate glass with different color regions, and then heat-treated to obtain colored microcrystalline glass; thus, the colors of different regions of the colored glass can be controlled.

[0062] 2. The present application controls the absolute value of the temperature difference of each glass liquid after melting a plurality of glass compositions of different colors at a viscosity of 300P to be less than or equal to 30°C, and the absolute value of the temperature difference at a viscosity of 600P to be less than or equal to 40°C, thereby ensuring that the colored substrate glass can be perfectly formed without defects such as breakage, flaws, and cracks.

[0063] 3. In this application, a plurality of glass compositions of different colors are formed and heat-treated, and the absolute value of the difference between the average thermal expansion coefficients of the glass compositions of different colors is less than or equal to 0.8×10 -6 / K to achieve uniform strengthening of colored micro-ceramic glass with good strength performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 This is the molding diagram of the microcrystalline glass prepared in Example 4.

[0065] Figure 2 This is the forming diagram of the microcrystalline glass prepared in Comparative Example 2.

[0066] Figure 3 This is the DSC curve diagram of Example 2.

[0067] Figure 4 This is the DSC curve of Comparative Example 4.

[0068] Figure 5 This is the XRD pattern of the S11 component.

[0069] Figure 6 This is the viscosity-temperature curve of Example 1.

[0070] Figure 7 This is the viscosity-temperature curve of Comparative Example 1. DETAILED DESCRIPTION

[0071] This application will provide a clear and complete description of the technical solutions in the embodiments of this application in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of this application, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on this application are within the scope of protection of this application.

[0072] Unless otherwise indicated in specific circumstances in this application, the numerical ranges listed herein include upper and lower limits, as well as all integers and fractions within the range, and are not limited to the specific values ​​listed when defining the range. The term "and / or" herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0073] In a first aspect, the present application provides a colored glass-ceramic obtained by ceramicizing a colored substrate glass; the colored substrate glass is obtained by melting a plurality of differently colored glass compositions into a plurality of differently colored glass liquids and then simultaneously forming the glass into a single piece, wherein the colored substrate glass has regions of different colors. The term "formed into a single piece" as used herein should be understood to mean that the plurality of differently colored glass compositions are melted into glass liquids without mixing with each other. Instead, during forming, the glass liquids of different colors are bonded together with only their edges intact, and then formed into a single piece.

[0074] In some embodiments, the number of glass compositions of different colors is 2 or more, or 3 or more.

[0075] In some embodiments, the glass compositions of various colors include the following components, calculated as a mole percentage of oxides:

[0076] SiO2: 66-71%;

[0077] Al2O3: 3.5~5.0%;

[0078] Na2O: 0-5.0%, not 0;

[0079] Li2O: 18-23%;

[0080] P2O5: 0.5~1.5%;

[0081] ZrO2: 1.5~4.0%;

[0082] At least one colorant, wherein the colorant comprises at least one of Au, Ag, Cr2O3, transition metal oxides, and rare earth metal oxides.

[0083] In some embodiments, the colorant is used in an amount less than or equal to 3.00 mol%.

[0084] In some embodiments, the glass compositions of various colors further include the following components, calculated as a mole percentage of oxides:

[0085] K2O: 0~0.5%;

[0086] CaO: 0-1.5%;

[0087] B2O3: 0~2%.

[0088] Si02 is an oxide that forms a glass network backbone and can be used to stabilize the glass and glass-ceramic network structure. In some embodiments, the content of Si02 is from 66.00 mol% to 71.00 mol%, further preferred from 66.00 mol% to 70.00 mol%, for example, the content of Si02 can be 66.00 mol%, 66.50 mol%, 67.06 mol%, 67.30 mol%, 67.45 mol%, 67.62 mol%, 67.74 mol%, 67.76 mol%, 68.18 mol%, 68.24 mol%, 68.36 mol%, 68.46 mol%, 68.61 mol%, 68.89 mol%, 69.00 mol%, 69.15 mol%, 69.25 mol%, 69.50 mol%, 69.72 mol%, 69.92 mol%, 69.98 mol%, 70.29 mol%, 70.50 mol%, 71.00 mol%, and all ranges and sub-ranges between the aforementioned values. It is understood that in embodiments, any of the aforementioned ranges can be combined with any of the other ranges.

[0089] Al203 can also stabilize the network and can also increase the strength of the glass structure, increasing the glass's scratch and drop resistance. In some embodiments, the content of Al203 is from 3.50 mol% to 5.00 mol%, for example, the content of Al203 can be 3.50 mol%, 3.75 mol%, 3.95 mol%, 3.97 mol%, 3.98 mol%, 3.99 mol%, 4.01 mol%, 4.02 mol%, 4.04 mol%, 4.07 mol%, 4.11 mol%, 4.18 mol%, 4.19 mol%, 4.20 mol%, 4.21 mol%, 4.26 mol%, 4.27 mol%, 4.50 mol%, 4.75 mol%, 4.86 mol%, 4.90 mol%, 5.00 mol%, and all ranges and sub-ranges between the aforementioned values. It is understood that in embodiments, any of the aforementioned ranges can be combined with any of the other ranges.

[0090] In some embodiments, the content of Na2O is within 5.00 mol% and is not 0. For example, the content of Na2O can be 0.28 mol%, 0.29 mol%, 0.31 mol%, 1.00 mol%, 1.41 mol%, 1.42 mol%, 1.43 mol%, 1.44 mol%, 1.45 mol%, 1.47 mol%, 1.64 mol%, 1.67 mol%, 3.02 mol%, 3.10 mol%, 3.12 mol%, 3.15 mol%, 4.20 mol%, 4.67 mol%, 5.00 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0091] Li2O is the lithium required to form the lithium silicate crystal phase when the substrate glass is ceramicized to form glass-ceramics. In some embodiments, the content of Li2O is 18.00 mol% to 23.00 mol%. For example, the content of Li2O can be 18.00 mol%, 18.58 mol%, 18.74 mol%, 19.12 mol%, 19.50 mol%, 20.61 mol%, 20.66 mol%, 20.67 mol%, 20.74 mol%, 20.76 mol%, 20.80 mol%, 20.81 mol%, 20.96 mol%, 20.99 mol%, 21.06 mol%, 21.09 mol%, 21.13 mol%, 21.28 mol%, 21.49 mol%, 21.84 mol%, 22.01 mol%, 22.60 mol%, 22.72 mol%, 22.77 mol%, 23.00 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges may be combined with any other ranges.

[0092] In some embodiments, the content of KO is 0 mol% to 0.50 mol%. For example, the content of KO can be 0 mol%, 0.01 mol%, 0.08 mol%, 0.09 mol%, 0.12 mol%, 0.15 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0093] PO can be used as a nucleating agent to form bulk nucleation. In some embodiments, the content of PO is 0.50 mol% to 1.50 mol%. For example, the content of PO can be 0.50 mol%, 0.67 mol%, 0.72 mol%, 0.80 mol%, 0.82 mol%, 0.83 mol%, 0.84 mol%, 0.85 mol%, 0.95 mol%, 0.98 mol%, 0.99 mol%, 1.00 mol%, 1.03 mol%, 1.06 mol%, 1.08 mol%, 1.21 mol%, 1.50 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0094] ZrO2 is generally present in the glass system as a nucleating agent. In some embodiments, the content of ZrO2 is 1.50 mol% to 4.00 mol%. For example, the content of ZrO2 can be 1.50 mol%, 1.62 mol%, 1.68 mol%, 1.70 mol%, 1.72 mol%, 1.74 mol%, 1.85 mol%, 2.50 mol%, 2.54 mol%, 2.58 mol%, 2.59 mol%, 2.62 mol%, 2.66 mol%, 2.67 mol%, 3.10 mol%, 3.25 mol%, 3.46 mol%, 3.67 mol%, 3.77 mol%, 4.00 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0095] CaO can increase the chemical stability and mechanical strength of the glass. In some embodiments, the content of CaO is 0 to 1.5 mol%. For example, the content of CaO can be 0, 0.10 mol%, 0.20 mol%, 0.53 mol%, 0.75 mol%, 0.77 mol%, 0.78 mol%, 0.79 mol%, 0.85 mol%, 0.86 mol%, 0.89 mol%, 0.97 mol%, 1.00 mol%, 1.34 mol%, 1.49 mol%, 1.50 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0096] B2O3 helps lower the melting temperature of the substrate glass. In some embodiments, the content of B2O3 is 0 to 2.00 mol%. For example, the content of B2O3 can be 0, 0.29 mol%, 0.30 mol%, 0.31 mol%, 0.62 mol%, 1.20 mol%, 1.42 mol%, 1.49 mol%, 1.51 mol%, 1.52 mol%, 1.54 mol%, 1.80 mol%, 1.87 mol%, 2.00 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0097] In some embodiments, the colorant includes at least one of Au, Ag, Cr2O3, transition metal oxides, and rare earth metal oxides. The colorant is a common coloring substance in the art, such as Au, Ag, Cr2O3, transition metal oxides, and rare earth metal oxides. The colorant may be one or more of Fe2O3, Er2O3, NiO, MnO2, Cr2O3, CoO, Ho2O3, Nd2O3, and Cu2O, but is not limited to the above colorants. Similarly, the colors presented by the colored micro-ceramics of the present application include, but are not limited to, red, pink, yellow, green, blue, purple, and black. Colorants can be used alone or in combination. For example, when used alone, Fe2O3 gives the glass a black or smoky gray color, Er2O3 gives it a pink color, NiO gives it a brown or green color, MnO2 gives it a reddish-brown color, Cr2O3 gives it a green color, CoO gives it a blue color, Ho2O3 gives it a yellow color, Nd2O3 gives it a purple-red color, and Cu2O gives it a sky blue color. When used in combination, Fe2O3 can be mixed with MnO2 and NiO, or with MnO2, NiO, and Cr2O3. Mixing Fe2O3 with MnO2, Cr2O3, or NiO can deepen the color of the base glass, glass-ceramics, or glass-ceramics products. In some embodiments, the amount of colorant used is less than or equal to 3.00 mol%. In some embodiments, the amount of colorant used can be 0, 0.01 mol%, 0.02 mol%, 0.05 mol%, 0.20 mol%, 0.30 mol%, 0.48 mol%, 0.49 mol%, 0.51 mol%, 0.65 mol%, 0.97 mol%, 1.50 mol%, 1.80 mol%, 2.00 mol%, 2.10 mol%, 2.30 mol%, 2.50 mol%, 2.70 mol%, 2.90 mol%, 3.00 mol%, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0098] In some embodiments, the number of glass compositions of different colors is 2 or more, or 3 or more. In some embodiments, the composition of the glass compositions of different colors, except for the colorant, and the content thereof are partially or completely different.

[0099] In view of the fact that defects such as cracking, flaws, and cracks do not occur in the process of preparing the colored base glass from the plurality of different colored glass compositions in the integral forming, the temperature at which the viscosity is 300 P and the temperature at which the viscosity is 600 P on the viscosity-temperature curve are used to characterize the properties of the base glass when the plurality of different colored glass compositions are melted into a plurality of different colored glass liquids and then formed. In some embodiments, the plurality of different colored glass compositions, when melted into a plurality of different colored glass liquids, satisfy the following conditions when formed: the absolute value of the temperature difference between the plurality of different colored glass liquids at a viscosity of 300 P is less than or equal to 30°C, and the absolute value of the temperature difference between the plurality of different colored glass liquids at a viscosity of 600 P is less than or equal to 40°C. Preferably, the absolute value of the temperature difference between the plurality of different colored glass liquids at a viscosity of 300 P can be less than or equal to 30°C, less than or equal to 28°C, less than or equal to 25°C, less than or equal to 23°C, less than or equal to 20°C, less than or equal to 18°C, less than or equal to 15°C, less than or equal to 10°C, less than or equal to 5°C, less than or equal to 3°C, less than or equal to 1°C, and all ranges and sub-ranges between the above values. Further preferably, the absolute value of the temperature difference between the plurality of different colored glass liquids at a viscosity of 600 P is less than or equal to 40°C, less than or equal to 30°C, less than or equal to 20°C, less than or equal to 10°C, less than or equal to 8°C, less than or equal to 5°C, less than or equal to 3°C, less than or equal to 1°C, and all ranges and sub-ranges between the above values. It should be understood that any of the above ranges can be combined with any other range in embodiments.

[0100] In the present application, the forming method of the colored base glass is not fixedly required, as long as the purpose of the present application can be achieved. In some embodiments, the forming method of the colored base glass can be at least one of casting forming, calendering forming, overflow forming, float forming, and narrow slit down-draw forming. Preferably, the forming method of the colored base glass is casting forming.

[0101] In some embodiments, the plurality of different colored glass liquids are formed integrally in different regions when casting formed. Specifically, the plurality of different colored glass liquids are formed integrally in different regions in the same mold, and the forming conditions of the plurality of different colored glass liquids in this forming process are completely the same.

[0102] In some embodiments, the main crystal phase of each of the plurality of different colored glass compositions after the forming heat treatment is the same.

[0103] In some embodiments, the main crystal phase of each of the plurality of different colored glass compositions after the forming heat treatment includes a lithium-containing crystal phase, as long as the lithium-containing crystal phase that can be formed in the present field is included, and specifically can include at least one of petalite, lithium metasilicate, lithium disilicate, and eucryptite.

[0104] In some embodiments, when multiple glass compositions of different colors are individually formed and heat-treated, the absolute value of the temperature difference between the nucleation temperatures of the glass compositions of different colors is less than or equal to 20°C. In some embodiments, when multiple glass compositions of different colors are individually formed and heat-treated, the absolute value of the temperature difference between the nucleation temperatures of the glass compositions of different colors is less than or equal to 18°C, less than or equal to 15°C, less than or equal to 13°C, less than or equal to 11°C, less than or equal to 9°C, less than or equal to 7°C, less than or equal to 5°C, less than or equal to 3°C, less than or equal to 1°C, etc., and all ranges and sub-ranges therebetween. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0105] In some embodiments, when multiple glass compositions of different colors are individually formed and heat-treated, the absolute value of the temperature difference between the crystallization temperatures of the glass compositions of different colors is less than or equal to 20°C. In some embodiments, when multiple glass compositions of different colors are individually formed and heat-treated, the absolute value of the temperature difference between the crystallization temperatures of the glass compositions of different colors is less than or equal to 18°C, less than or equal to 15°C, less than or equal to 13°C, less than or equal to 11°C, less than or equal to 9°C, less than or equal to 7°C, less than or equal to 5°C, less than or equal to 3°C, less than or equal to 1°C, etc., and all ranges and sub-ranges therebetween. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0106] In some embodiments, after the glass compositions of different colors are formed and heat-treated, the absolute value of the difference between the average thermal expansion coefficients of the glass compositions of different colors is less than or equal to 0.8×10 -6 In some embodiments, after the glass compositions of different colors are formed and heat-treated, the absolute value of the difference between the average thermal expansion coefficients of the glass compositions of different colors is less than or equal to 0.6×10 -6 / K, less than or equal to 0.5×10 -6 / K, less than or equal to 0.4×10 -6 / K, less than or equal to 0.3×10 -6 / K, less than or equal to 0.1×10 -6 / K, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0107] In some embodiments, the colored substrate glass is subjected to a heat treatment to prepare a colored microcrystalline glass, and the heat treatment includes a nucleation treatment and a crystallization treatment. In some embodiments, the temperature of the nucleation treatment is 500-600°C, and the time of the nucleation treatment is 180-300 minutes. In some embodiments, the temperature of the nucleation treatment can be 500°C, 520°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, etc., and all ranges and sub-ranges between the above values. In some embodiments, the time of the nucleation treatment can be 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, 300 minutes, etc., and all ranges and sub-ranges between the above values. In some embodiments, the temperature of the crystallization treatment is 600-800°C, and the time of the crystallization treatment is 30-180 minutes. In some embodiments, the crystallization temperature may 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., etc., and all ranges and sub-ranges therebetween. In some embodiments, the crystallization time may be 30 min, 50 min, 60 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, etc., and all ranges and sub-ranges therebetween.

[0108] In some embodiments, the nucleation treatment is to heat the colored substrate glass from room temperature to the nucleation temperature at a heating rate of 1 to 10°C / min. In some embodiments, 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, etc., and all ranges and sub-ranges between the above values. In some embodiments, the crystallization treatment is to heat the colored substrate glass from the nucleation temperature to the crystallization temperature at a heating rate of 1 to 10°C / min. In some embodiments, 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, 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 ranges.

[0109] In a second aspect, the present application provides a method for preparing the above-mentioned colored glass-ceramics, comprising the following steps:

[0110] Step 1: Components of a plurality of glass compositions of different colors are mixed separately and then melted to obtain glass liquids of various colors;

[0111] Step 2: Molding the glass liquids of various colors obtained in step 1 into one piece and annealing the pieces to obtain colored substrate glass with different color regions;

[0112] Step 3: Heat-treat the colored substrate glass obtained in step 2 to obtain colored microcrystalline glass.

[0113] In some embodiments, in step 1, the melting temperature is 1350-1650°C and the melting time is 4-13 hours. In some embodiments, in step 1, the melting temperature can be 1350°C, 1400°C, 1450°C, 1500°C, 1550°C, 1600°C, 1650°C, etc., and all ranges and sub-ranges between the above values. In some embodiments, in step 1, the melting time is 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0114] In some embodiments, in step 2, the glass liquids of different colors are molded into one piece in different regions. Specifically, the glass liquids of different colors are molded into one piece in different regions of the same mold. During this molding process, the molding conditions of the glass liquids of different colors are exactly the same.

[0115] In some embodiments, in step 2, the forming method can be at least one of casting, calendering, overflow, float glass, and slot draw. Preferably, in step 2, the forming method is casting.

[0116] In some embodiments, in step 2, the annealing temperature is 450-500°C and the annealing time is 12-48 hours. In some embodiments, in step 2, the annealing temperature can be 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, etc., and all ranges and sub-ranges between the above values. In some embodiments, in step 2, the annealing time can be 12h, 14h, 16h, 18h, 20h, 23h, 25h, 27h, 29h, 32h, 35h, 38h, 40h, 42h, 44h, 46h, 48h, 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 ranges.

[0117] In some embodiments, in step 3, the heat treatment comprises a nucleation treatment and a crystallization treatment. In some embodiments, the temperature of the nucleation treatment is 500-600 °C, and the holding time of the nucleation treatment is 180-300 min. In some embodiments, the temperature of the nucleation treatment can be 500 °C, 520 °C, 540 °C, 560 °C, 580 °C, 600 °C, and all ranges and sub-ranges between the above recited values. In some embodiments, the holding time of the nucleation treatment can be 180 min, 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, and all ranges and sub-ranges between the above recited values. In some embodiments, the temperature of the crystallization treatment is 600-800 °C, and the holding time of the crystallization treatment is 30-180 min. In some embodiments, the temperature of the crystallization treatment can be 600 °C, 620 °C, 640 °C, 660 °C, 680 °C, 700 °C, 730 °C, 750 °C, 770 °C, 790 °C, 800 °C, and all ranges and sub-ranges between the above recited values. In some embodiments, the holding time of the crystallization treatment can be 30 min, 50 min, 70 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, and all ranges and sub-ranges between the above recited values. In some embodiments, the colored base material glass is heated from room temperature to the temperature of the nucleation treatment at a heating rate of 3-10 °C / min. In some embodiments, the colored base material glass is heated from the temperature of the nucleation treatment to the temperature of the crystallization treatment at a heating rate of 3-10 °C / min. In some embodiments, the heating rate can be 3 °C / min, 5 °C / min, 7 °C / min, 9 °C / min, 10 °C / min, and all ranges and sub-ranges between the above recited values, regardless of whether the temperature is the temperature of the nucleation treatment or the temperature of the crystallization treatment. It should be understood that in embodiments, any of the above recited ranges can be combined with any other range.

[0118] In some embodiments, in step 3, when the plurality of different colored glass compositions are each heat treated after being shaped, the absolute value of the temperature difference between the nucleation temperatures of each of the different colored glass compositions is less than or equal to 20 °C. In some embodiments, in step 3, when the plurality of different colored glass compositions are each heat treated after being shaped, the absolute value of the temperature difference between the nucleation temperatures of each of the different colored glass compositions is less than or equal to 18 °C, less than or equal to 15 °C, less than or equal to 13 °C, less than or equal to 11 °C, less than or equal to 9 °C, less than or equal to 7 °C, less than or equal to 5 °C, less than or equal to 3 °C, less than or equal to 1 °C, and all ranges and sub-ranges between the above recited values. It should be understood that in embodiments, any of the above recited ranges can be combined with any other range.

[0119] In some embodiments, in step 3, when the plurality of glass compositions of different colors are individually formed and heat-treated, the absolute value of the temperature difference between the crystallization temperatures of the glass compositions of different colors is less than or equal to 20°C. In some embodiments, in step 3, when the plurality of glass compositions of different colors are individually formed and heat-treated, the absolute value of the temperature difference between the crystallization temperatures of the glass compositions of different colors is less than or equal to 18°C, less than or equal to 15°C, less than or equal to 13°C, less than or equal to 11°C, less than or equal to 9°C, less than or equal to 7°C, less than or equal to 5°C, less than or equal to 3°C, less than or equal to 1°C, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0120] In some embodiments, in step 3, after the multiple glass compositions of different colors are formed and heat-treated, the absolute value of the difference between the average thermal expansion coefficients of the glass compositions of different colors is less than or equal to 0.8×10 -6 In some embodiments, when the colored substrate glass is heat-treated, the absolute value of the difference between the average thermal expansion coefficients of the substrate glass in different color regions is less than or equal to 0.6×10 -6 / K, less than or equal to 0.5×10 -6 / K, less than or equal to 0.4×10 -6 / K, less than or equal to 0.3×10 -6 / K, less than or equal to 0.1×10 -6 / K, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0121] In a third aspect, the present application provides a strengthened colored micro-ceramic glass, which is obtained by chemically strengthening the colored micro-ceramic glass as described above or the colored micro-ceramic glass prepared by the above-mentioned method for preparing the colored micro-ceramic glass.

[0122] In some embodiments, chemical strengthening includes single-step chemical strengthening or multi-step chemical strengthening. In some embodiments, the single-step chemical strengthening adopts a salt bath containing NaNO3, and preferably the content of the NaNO3 is 30-100wt%. In some embodiments, the temperature of the single-step chemical strengthening is 450-500°C. In some embodiments, the temperature of the single-step chemical strengthening can be 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, etc., and all ranges and sub-ranges between the above values. In some embodiments, the time of the single-step chemical strengthening is 1-15h. In some embodiments, the time of the single-step chemical strengthening is 1h, 3h, 5h, 7h, 9h, 10h, 12h, 13h, 14h, 15h, etc., and all ranges and sub-ranges between the above values. It should be understood that in the embodiment, any of the above ranges can be combined with any other ranges.

[0123] In some embodiments, the multi-step chemical strengthening includes a two-step chemical strengthening, wherein the first step chemical strengthening uses a salt bath containing NaNO3, preferably the NaNO3 content is 30-100 wt%; the second step chemical strengthening uses a salt bath containing KNO3, preferably the KNO3 content is 60-100 wt%. In some embodiments, the temperature of the first step chemical strengthening is 450-500°C, and the time of the first step chemical strengthening is 2-10 hours. In some embodiments, the temperature of the first step chemical strengthening can be 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, etc., and all ranges and sub-ranges between the above values. In some embodiments, the time of the first step chemical strengthening can be 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0124] In some embodiments, the temperature of the second chemical strengthening step is 450-500°C, and the time of the second chemical strengthening step is 1-5 hours. In some embodiments, the temperature of the second chemical strengthening step can be 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, etc., and all ranges and sub-ranges between the above values. In some embodiments, the time of the second chemical strengthening step can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc., and all ranges and sub-ranges between the above values. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0125] In some embodiments, at a thickness of 0.60 mm, the average single-rod static compressive strength of the strengthened colored glass-ceramics is greater than or equal to 300 N, preferably 320-450 N. In some embodiments, at a thickness of 0.60 mm, the average single-rod static compressive strength of the strengthened colored glass-ceramics may be 300-450 N, 300-430 N, 300-410 N, or 310-400 N, and may also be 300 N, 330 N, 350 N, 380 N, 390 N, or 400 N, as well as all ranges and sub-ranges therebetween. It should be understood that in embodiments, any of the above ranges may be combined with any other ranges.

[0126] In some embodiments, the average drop resistance height of the strengthened colored glass-ceramics is greater than or equal to 1.8 m, preferably 1.80-2.5 m. In some embodiments, at a thickness of 0.60 mm, the average drop resistance height of the strengthened colored glass-ceramics can be 1.82-2.5 m, 1.85-2.5 m, 1.90-2.3 m, or 1.92-2.2 m, and can also be 1.80 m, 1.82 m, 1.85 m, 1.87 m, 1.89 m, 1.90 m, 1.93 m, 1.95 m, 1.98 m, 2.0 m, 2.2 m, 2.3 m, or 2.5 m, and all ranges and sub-ranges therebetween. It should be understood that in embodiments, any of the above ranges can be combined with any other ranges.

[0127] In a fourth aspect, the present application provides an application of the colored microcrystalline glass as described above, or the colored microcrystalline glass prepared by the above-mentioned colored microcrystalline glass preparation method, or the above-mentioned strengthened colored microcrystalline glass in mobile phone back covers, electronic terminals, decorative parts, handicrafts, jewelry or portable digital devices.

[0128] In a fifth aspect, a consumer electronic product comprises: a housing comprising a front surface, a back surface and side surfaces; an electronic component at least partially located within the housing, the electronic component comprising at least a controller, a memory and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass arranged on the display, wherein at least a portion of the housing comprises the colored microcrystalline glass as described above, or the colored microcrystalline glass prepared by the method for preparing the colored microcrystalline glass as described above, or the strengthened colored microcrystalline glass as described above.

[0129] In a sixth aspect, an electronic device comprises the colored glass-ceramics as described above, the colored glass-ceramics prepared by the method for preparing the colored glass-ceramics as described above, or the strengthened colored glass-ceramics as described above.

[0130] In the seventh aspect, the test method, the relevant measurement methods involved in this application are explained as follows.

[0131] Thermal analysis (DSC) test:

[0132] The test was conducted using a Mettler-Toledo TGA / DSC 3+ simultaneous thermal analyzer in accordance with JY / T 0589.5-202. The standard material used was α-Al2O3 powder, and the sample container was a platinum crucible. The instrument was maintained at an ambient temperature of 24°C and an air humidity of 40%. The glass was ground and sieved through a 200-mesh sieve to obtain the test sample. Approximately 20 mg of the sample was weighed and heated from room temperature to 900°C at a rate of 10°C / min under a nitrogen atmosphere to obtain the DSC curve.

[0133] Viscosity-temperature test:

[0134] The test was performed in accordance with ASTM C965-96 (Reapproved 2017) using a combination of an Orton RSV-1700 and a Brookfield DV2TLV viscometer (USA).

[0135] Average thermal expansion coefficient test:

[0136] Thermal expansion coefficient (α 20℃-300℃ ) The test was carried out in accordance with the test method of GB / T7962.16-2010; the testing instrument was the German Lindsay vertical mode thermal expansion instrument (L75VD 1000).

[0137] XRD test:

[0138] The glass-ceramic sample was ground into a fine glass powder with a particle size of less than 75 μm using a grinding mill. The powder was then tested using an X-ray diffractometer (Shimadzu XRD-6100) to obtain an XRD diffraction peak curve. The X-ray diffractometer used in the present invention was a Shimadzu XRD-6100, with a copper target, an incident angle range of 2θ = 10-80°, a scanning speed of 0.02-6° / min, an operating voltage of 40 kV, and an operating current of 30 mA.

[0139] Test method for crystal content:

[0140] Import the X-ray diffractometer test result file (RAW format) into the X-ray diffraction data Rietveld refinement software (such as Gsas, Fullprof, Maud), perform fitting and calculation, and you can get the crystal content / crystallinity in the microcrystalline glass sample. The ratio of the fitted crystal phase peak area to the fitted total peak area is the crystal content, which is also referred to as crystallinity in this application.

[0141] Glass thickness:

[0142] Determined by laser thickness gauge testing. The thickness change of glass-ceramics before and after chemical strengthening is very small and can be ignored.

[0143] Vickers hardness test:

[0144] The test was carried out in accordance with the standard "GB / T 37900-2019 Ultra-thin glass hardness and fracture toughness test method - Small load Vickers hardness indentation method".

[0145] Single rod static pressure strength test:

[0146] Place the glass sample to be tested on the bottom ring of the tensile testing machine (LT-850A), start the test software, and set the movement speed of the extrusion rod (rod diameter 8mm, indenter arc radius 10mm) to 50mm / min. Click to start the test. The extrusion rod will apply force to the center of the glass sample to be tested at the set movement speed until the glass sample cracks and breaks.

[0147] The test software will automatically read the force (N) when the glass sample breaks as the test result.

[0148] Take 10 glass samples under the same conditions for testing, and take the average value of the test results as the average single-rod static pressure strength of the glass samples to be tested.

[0149] Average drop height test:

[0150] Average drop height: The average value obtained by dividing the sum of the drop heights measured for multiple glass samples by the number of samples measured. It is used to characterize the glass's resistance to cracking on the contact surface.

[0151] Take at least 10 glass samples from each batch for testing, and take the average drop height of all glass samples. The formula is as follows:

[0152] Where n is the number of glass samples tested in each batch, and hi is the drop resistance height of a single glass sample tested.

[0153] Among them, the test method for the drop resistance of glass samples is:

[0154] Step 1: Place the glass sample to be tested, which is 50mm x 50mm x 0.7mm in length, width and thickness, on the front of the 187g model machine;

[0155] Step 2: Place the model phone on a Green Figure LT-SKDL-CD drop machine with the glass sample facing the sandpaper. Drop it from a certain drop height, impacting the 80-grit sandpaper directly below the model phone, simulating a normal mobile phone drop.

[0156] If the glass sample does not break, the drop height of the model machine is increased in a certain pattern. For example, the drop height starts from 0.4m and the sample is dropped once. If it does not break, the drop height is increased by 0.1m each time until the glass sample breaks.

[0157] Step 3: Record the last drop height of the glass sample when it breaks as the anti-drop height. For example, if the drop height when it breaks is 0.5m, the anti-drop height of the sample is 0.4m.

[0158] In the eighth aspect, the present application is described below through specific embodiments.

[0159] Example 1

[0160] Step 1: Prepare the raw materials for the glass compositions S2 and S4 listed in Table 1, respectively, and mix them in a V-type mixer for 30 minutes to obtain the S2 mixture and the S4 mixture. The two mixtures are then transferred to different platinum-rhodium crucibles and melted in a lifting furnace to obtain two glass liquids of different colors; the melting temperature is 1550°C, and the melting time is 5 hours.

[0161] Step 2: Cool the two different colored glass liquids obtained in step 1 to an appropriate temperature, and then pour them into the mold from both sides to form them into one piece; after cooling to 800°C, place them in an annealing furnace and anneal them at 500°C for 13 hours; then cool them to room temperature in the furnace to obtain colored substrate glass with different color areas;

[0162] Step 3: heat-treating the colored substrate glass obtained in step 2 to obtain colored glass-ceramics;

[0163] The heat treatment includes nucleation treatment and crystallization treatment; the temperature and time of the nucleation treatment and crystallization treatment are shown in Table 4 below.

[0164] The colored microcrystalline glass obtained above is shaped, cut and ground to obtain colored microcrystalline glass sheets of required specifications, such as 50mm×50mm×0.7mm (specification dimensions) in length, width and thickness, and relevant performance tests are performed.

[0165] The 50 mm × 50 mm × 0.7 mm colored glass-ceramics sheet obtained above was polished and then immersed in a salt bath for chemical strengthening to obtain strengthened colored glass-ceramics; the composition of the salt bath and the strengthening process conditions are shown in Table 7 below.

[0166] Examples 2-6 were prepared under the same operating conditions as Example 1, except that the glass compositions used to prepare the colored glass-ceramics were different, as shown in Tables 1-3, and the molding and heat treatment processes were different, as shown in Table 4. The performance parameters of the colored glass-ceramics of Examples 1-6 are shown in Table 4, and the performance parameters of the strengthened colored glass-ceramics prepared using the colored glass-ceramics of Examples 1-6 are shown in Table 7.

[0167] Comparative Examples 1-4 were prepared under the same operating conditions as Example 1, except that the glass compositions used to prepare the colored glass-ceramics were different, as shown in Tables 1-3, and the molding and heat treatment processes were different, as shown in Table 6. Comparative Examples 1-2 failed to produce intact colored glass-ceramics because they did not achieve complete integral molding. Although Comparative Example 4 was able to achieve integral molding, it also failed to produce intact colored glass-ceramics.

[0168] In addition, Example 7

[0169] Step 1: Prepare the raw materials of the glass compositions S20, S21, and S22 listed in Table 3, respectively, and mix them in a V-type mixer for 30 minutes to obtain an S20 mixture, an S21 mixture, and an S22 mixture. The three mixtures are then transferred to different platinum-rhodium crucibles and melted in a lifting furnace to obtain three different colored glass liquids; the melting temperature is 1550° C., and the melting time is 5 hours.

[0170] Step 2: Cool the three different colored glass liquids obtained in step 1 to an appropriate temperature, and then pour them into the mold from different positions to form them into one piece; after cooling to 800°C, place them in an annealing furnace and anneal them at 500°C for 13 hours; then cool them to room temperature in the furnace to obtain colored substrate glass with different color areas;

[0171] Step 3: The colored substrate glass obtained in step 2 is subjected to heat treatment to obtain colored microcrystalline glass; the heat treatment includes nucleation treatment and crystallization treatment; the temperature and time of the nucleation treatment and crystallization treatment are shown in Table 5 below.

[0172] The colored microcrystalline glass obtained above is shaped, cut and ground to obtain colored microcrystalline glass sheets of required specifications, such as 50mm×50mm×0.7mm (specification dimensions) in length, width and thickness, and relevant performance tests are performed.

[0173] The 50 mm × 50 mm × 0.7 mm colored microcrystalline glass slices obtained above were polished and then immersed in a salt bath for chemical strengthening to obtain strengthened colored microcrystalline glass; the composition of the salt bath and the strengthening process conditions are shown in Table 8 below.

[0174] Comparative Example 5

[0175] Glass composition S23 and glass composition S19 in Table 3 are used to prepare colored microcrystalline glass. Glass composition S23 is a formula for preparing microcrystalline glass with the main crystal phases of ZnAl2O4 and MgAl2O4. Although the viscosity-temperature difference between glass composition S23 and glass composition S19 can meet the conditions, their nucleation and crystallization temperatures are very different, and overall uniform crystallization cannot be carried out, and colored microcrystalline glass cannot be prepared.

[0176] Table 1. Glass composition, its own heat treatment process and related performance parameters

[0177]

[0178]

[0179] Table 2. Glass composition, its own heat treatment process and related performance parameters

[0180]

[0181]

[0182] Table 3. Glass composition, its own heat treatment process and related performance parameters

[0183]

[0184]

[0185] Table 4. Molding and ceramic process conditions and performance parameters of colored microcrystalline glass of Examples 1-6

[0186]

[0187] Table 5. Molding and ceramic process conditions and performance parameters of the colored microcrystalline glass of Example 7

[0188]

[0189] Table 6. Molding and ceramic process conditions and performance parameters of colored microcrystalline glass of comparative examples 1-5

[0190]

[0191] Table 7. Composition of the salt bath, strengthening process conditions and performance parameters of the strengthened colored glass-ceramics of Examples 1-6

[0192]

[0193]

[0194] Table 8. Composition, strengthening process conditions and performance parameters of the salt bath for strengthening the colored glass-ceramics of Example 7

[0195]

[0196] Table 9. Composition, strengthening process conditions and performance parameters of the salt bath for strengthening the colored microcrystalline glass of Comparative Example 3

[0197] Composition (mol%) Comparative Example 3 Chemically enhanced salt bath <![CDATA[69.97wt%KNO3+30wt%NaNO3+0.03wt%LiNO3]]> Chemical strengthening temperature (℃) 470 Chemical strengthening temperature (℃) 6 Average single rod static pressure strength (N) 137 Average drop resistance height (m) 0.86

[0198] From the above table and attached figures we can see that:

[0199] (1) The two or more components in the embodiment must satisfy the requirement that the temperature difference is less than 30°C when the viscosity is 300P and the temperature difference is less than 40°C when the viscosity is 600P, so that when preparing glass-ceramics with different colors in different areas, various colored glasses can be well formed in the mold. Figure 1 As can be seen from the figure, the connection between the two different color areas in the glass-ceramic is very well formed, and is not much different from the surface of ordinary single-color glass-ceramic. Figure 3 This also demonstrates that the two different colored glass compositions in Example 2 have similar DSC curves, enabling glass compositions of different color regions and compositions to be molded under the same conditions. Furthermore, Tables 4 and 5 demonstrate that the glass-ceramics prepared in this example exhibit high strength and excellent strength properties.

[0200] (2) The two or more components in the embodiment must satisfy the requirement that the absolute value of the temperature difference between the nucleation temperatures is less than 20°C, and the absolute value of the temperature difference between the crystallization temperatures is less than 20°C, so as to ensure that the microcrystalline glass prepared in the embodiment can achieve uniform crystallization of various colored glasses in different regions, laying the foundation for subsequent chemical strengthening.

[0201] (3) The difference in thermal expansion coefficient between two or more formulations in the embodiment must be less than 0.8×10 -6 / K, so that the glass-ceramics prepared in the embodiment can be uniformly strengthened during chemical strengthening, and the chemical strengthening process will not have an adverse effect on the original performance of the glass-ceramics.

[0202] (4) Comparative Example 1 does not meet the condition that the temperature difference is less than 30°C when the viscosity is 300P, and Comparative Example 2 does not meet the condition that the temperature difference is less than 30°C when the viscosity is 300P and the temperature difference is less than 40°C when the viscosity is 600P, resulting in problems with the microcrystalline glass of these comparative examples from the very beginning of molding. Some comparative examples have problems at the joints during the molding process.

[0203] Fracture makes it impossible to form a variety of colored glass in the mold; Figure 2This is demonstrated by the fact that due to the large difference in viscosity between the different color areas at the molding temperature, they cannot be tightly connected, resulting in fractures near the structure.

[0204] (5) Although Comparative Example 3 meets the requirements of viscosity, nucleation temperature and crystallization temperature, it does not meet the requirements of the present application for the difference in thermal expansion coefficient. This means that although Comparative Example 3 can be formed when preparing microcrystalline glasses of different color areas, after chemical strengthening, the strengthened dimensional expansion of the microcrystalline glasses of different color areas is inconsistent, and the surface stress of the microcrystalline glasses after strengthening is uneven, which ultimately deteriorates the performance of the microcrystalline glasses.

[0205] (6) Although Comparative Example 4 meets the condition that the temperature difference is less than 30°C when the viscosity is 300P and the temperature difference is less than 40°C when the viscosity is 600P, Comparative Example 4 does not meet the condition that the absolute value of the temperature difference between the crystallization temperatures is less than 20°C. Figure 4 It can be clearly seen that the temperature ranges for nucleation and crystallization of the different color regions in Comparative Example 4 are very different, which leads to inconsistent heat treatment conditions theoretically required for the different color regions in this comparative example. Ultimately, the degree of crystallization of the different color regions under the same heat treatment conditions is quite different, and there is a very obvious difference in appearance. One color region is completely crystallized and transparent, while the other color region is in a semi-crystalline state. This shows that it is difficult to achieve controllable molding of the different color regions in Comparative Example 4 under the same conditions.

[0206] (7) Comparative Example 5 is a comparison of different crystal phases. Although Comparative Example 5 meets the viscosity requirements of this application, it does not meet the conditions of the heat treatment process of this application. If heat treatment is carried out according to the ceramicization conditions of S23, S19 will become devitrified and no colored microcrystalline glass can be obtained.

[0207] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the technical solutions. Those skilled in the art should understand that modifications or equivalent replacements of the technical solutions of the present invention that do not depart from the purpose and scope of the technical solutions of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A colored micro-ceramic glass, characterized in that: The colored glass-ceramics are obtained by ceramicizing colored substrate glass; the colored substrate glass comprises a plurality of different colored glass compositions melted into a plurality of different colored glass liquids and then simultaneously molded into one piece, and the colored substrate glass has different color regions; The compositions of the glass compositions of different colors are partially or completely different in composition and content of the components other than the colorant; A plurality of different colored glass compositions are melted into a plurality of different colored glass liquids, which satisfy the following conditions during molding: the absolute value of the temperature difference between the plurality of different colored glass liquids at a viscosity of 300P is less than or equal to 30°C, and the absolute value of the temperature difference between the plurality of different colored glass liquids at a viscosity of 600P is less than or equal to 40°C; When the glass compositions of different colors are heat-treated after being formed, the absolute value of the temperature difference between the nucleation temperatures of the glass compositions of different colors is less than or equal to 20°C; When the glass compositions of different colors are heat-treated after being formed, the absolute value of the temperature difference between the crystallization temperatures of the glass compositions of different colors is less than or equal to 20°C; After the glass compositions of different colors are formed and ceramicized, the absolute value of the difference between the average thermal expansion coefficients of the glass compositions of different colors is less than or equal to 0.8×10 -6 / K; Calculated in mole percentages of oxides, glass compositions of various colors include the following components: SiO2: 66~71%; Al2O3: 3.5~5.0%; Na2O: 0~5.0%, not 0; Li2O: 18~23%; P2O5: 0.5~1.5%; ZrO2: 1.5~4.0%; At least one colorant, wherein the colorant comprises at least one of Au, Ag, transition metal oxides, and rare earth metal oxides.

2. The colored glass-ceramics according to claim 1, characterized in that: Calculated by mole percentage of oxides, the glass compositions of various colors also include the following components: K2O: 0~0.5%; CaO: 0~1.5%; B2O3: 0~2%.

3. The colored glass-ceramics according to any one of claims 1 to 2, characterized in that: There are two or more glass compositions of different colors.

4. The colored glass-ceramics according to any one of claims 1 to 2, characterized in that: The colored substrate glass is formed by at least one of casting, rolling, overflow, float, and slot-drawing.

5. The colored glass-ceramics according to any one of claims 1 to 2, characterized in that: Glass liquids of various colors are molded into one piece in different areas.

6. The colored glass-ceramics according to any one of claims 1 to 2, characterized in that: The main crystal phase of the glass compositions of various colors after molding and heat treatment is the same.

7. The colored glass-ceramics according to claim 6, characterized in that: The main crystal phase of the glass compositions of various colors after being formed and heat-treated is a lithium-containing crystal phase, including at least one of petalite, lithium monosilicate, lithium disilicate, and eucryptite.

8. A method for preparing colored micro-ceramic glass, characterized in that: The method of preparing the colored glass-ceramics according to any one of claims 1 to 7 comprises the following steps: Step 1: Components of a plurality of glass compositions of different colors are mixed separately and then melted to obtain glass liquids of various colors; Step 2: Molding the glass liquids of various colors obtained in step 1 into one piece and annealing them to obtain colored substrate glass; Step 3: Heat-treat the colored substrate glass obtained in step 2 to obtain colored microcrystalline glass.

9. The preparation method according to claim 8, characterized in that: In step 2, glass liquids of various colors are formed into one piece in different areas.

10. The preparation method according to claim 9, characterized in that: In step 2, the molding method is at least one of casting molding, calendering molding, overflow molding, float molding, and narrow slit drawdown.

11. A strengthened colored microcrystalline glass, obtained by chemically strengthening the colored microcrystalline glass as described in any one of claims 1 to 7 or the colored microcrystalline glass prepared by the preparation method of the colored microcrystalline glass as described in any one of claims 8 to 10.

12. The strengthened colored glass-ceramics according to claim 11, characterized in that: Chemical strengthening includes single-step chemical strengthening or multi-step chemical strengthening.

13. Use of the colored microcrystalline glass as described in any one of claims 1 to 7, or the colored microcrystalline glass prepared by the preparation method of the colored microcrystalline glass as described in any one of claims 8 to 10, or the colored reinforced microcrystalline glass as described in claim 11 in electronic terminals, decorative parts, handicrafts, and jewelry.

14. A consumer electronic product comprising: a housing comprising a front surface, a back surface, and side surfaces; an electronic assembly at least partially located within the housing, the electronic assembly including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass arranged on the display, wherein at least a portion of the outer shell comprises the colored microcrystalline glass according to any one of claims 1 to 7, the colored microcrystalline glass prepared by the method for preparing the colored microcrystalline glass according to any one of claims 8 to 10, or the strengthened colored microcrystalline glass according to claim 11.

15. An electronic device comprising the colored microcrystalline glass described in any one of claims 1 to 7, or the colored microcrystalline glass prepared by the method for preparing the colored microcrystalline glass described in any one of claims 8 to 10, or the strengthened colored microcrystalline glass described in claim 11.

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