3D hot bendable microcrystalline glass, preparation method and application thereof

Abstract

The application belongs to the technical field of glass-ceramics material, and particularly relates to a 3D hot-bendable glass-ceramics, a preparation method and application thereof. The application provides a 3D hot-bendable glass-ceramics, which comprises petalite crystal phase, lithium disilicate crystal phase and quartz crystal phase. The total crystal phase content of the 3D hot-bendable glass-ceramics is 40-70%, wherein the sum of the petalite crystal phase content and the lithium disilicate crystal phase content accounts for 50-70% of the total crystal phase content, and the quartz crystal phase content accounts for 4-10% of the total crystal phase content. The 3D hot-bendable glass-ceramics has the petalite crystal phase, the lithium disilicate crystal phase and the quartz crystal phase before hot bending, and the proportion of each crystal phase is controlled in a suitable range, so that a pleasing white appearance is presented, and the 3D hot-bendable glass-ceramics can be 3D hot-bent at 810 DEG C to be formed into a 3D glass-ceramics and a three-dimensional product.

Description

Technical Field

[0001] This invention belongs to the field of microcrystalline glass material technology, and relates to a 3D heat-bendable microcrystalline glass, its preparation method and application. Due to its pleasing white appearance, good mechanical properties and dimensional stability, it is particularly suitable as an external component for portable communication or information equipment. Background Technology

[0002] The casings of mobile phones and other electronic devices are typically made of materials such as polymers and ceramics, taking into account various factors such as aesthetics, scratch resistance, processability, and cost. Portable devices, in particular, are mostly constructed from composite materials such as plastics and resins. However, using plastics and resins for the casing results in problems such as poor heat dissipation and susceptibility to scratches; while using ceramics results in problems such as high density, poor impact resistance, and increased phone weight.

[0003] Glass-ceramics are composite materials containing both glassy and microcrystalline phases, prepared through targeted and controlled heat treatment of a substrate glass. They primarily utilize the crystalline phase precipitated within the glass to inhibit the propagation of microcracks, thereby improving the glass's brittleness to some extent. Compared to ordinary glass, glass-ceramics exhibit better mechanical properties; compared to plastics, they offer superior heat resistance, resistance to aging, and scratch resistance; and compared to ceramics, they boast lower density and lighter weight. Furthermore, through compositional and process control, glass-ceramics can be produced in a wide variety of colors, resulting in vibrant and diverse appearances, making them an ideal choice for cover materials in portable electronic devices.

[0004] However, existing methods for preparing white cover glass, while capable of producing large-grain-size translucent glass from microcrystalline glass through secondary recrystallization, suffer from several drawbacks. These include excessively large grain sizes leading to cracking, a high thermal expansion softening point, deteriorated mechanical properties such as bending and drop resistance, and the inability to be 3D molded. Furthermore, as a back panel material for mobile phones, the deformation of the microcrystalline glass must be considered, as significant deformation can easily damage internal components. Therefore, there is a need in the art for microcrystalline glass materials that possess a pleasing white appearance, good mechanical properties and dimensional stability, and the ability to be 3D processed and molded. Summary of the Invention

[0005] To address the aforementioned problems, this application provides a 3D-bendable microcrystalline glass and its preparation method. This 3D-bendable microcrystalline glass is prepared through primary crystallization and has a pleasing white appearance, good mechanical properties and dimensional stability, and can be processed into three-dimensional products, exhibiting good processability.

[0006] Specifically, this application provides the following technical solution:

[0007] In a first aspect, this application provides a 3D heat-bendable microcrystalline glass, characterized in that the crystalline phase of the 3D heat-bendable microcrystalline glass includes a lithium feldspar crystalline phase, a lithium disilicate crystalline phase, and a quartz crystalline phase, wherein the total crystalline phase content of the 3D heat-bendable microcrystalline glass is 40-70%, wherein the sum of the contents of the lithium feldspar crystalline phase and the lithium disilicate crystalline phase accounts for 50-70% of the total crystalline phase content, and the content of the quartz crystalline phase accounts for 4-10% of the total crystalline phase content.

[0008] In some embodiments of this application, the quartz crystal phase in the 3D-bendable microcrystalline glass is β-quartz; and / or,

[0009] The 3D-bendable microcrystalline glass further includes a lithium silicate crystalline phase, preferably comprising 20-40% of the total crystalline phase content; and / or,

[0010] The crystalline phase of the 3D heat-bendable microcrystalline glass also includes a spodumene crystalline phase; preferably, the content of the spodumene crystalline phase accounts for 0-11% of the total crystalline phase content.

[0011] In some embodiments of this application, the grain size of the 3D-bendable microcrystalline glass is 20-40 nm;

[0012] And / or, the expansion softening point of the 3D heat-bendable microcrystalline glass is less than or equal to 810°C;

[0013] And / or, the 3D-bendable microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance of 30-50% at 550 nm;

[0014] And / or, the chromatic coordinates of the 3D heat-bendable microcrystalline glass in reflection mode are: L* is 70~82, a* is -4~2, b* is -12~5.

[0015] In some embodiments of this application, the composition, expressed as a molar percentage of oxides, comprises:

[0016] SiO2: 60-73%,

[0017] Al2O3: 4-6%,

[0018] P2O5: 0–2%,

[0019] ZrO2: 1-3%,

[0020] Na2O: 0.1-4%,

[0021] K2O: 0-1%,

[0022] Li2O: 14-23%,

[0023] CaO: 0–1.5% and

[0024] B2O3: 0.1–5%.

[0025] In some embodiments of this application, the composition, expressed as a molar percentage of oxides, comprises:

[0026] SiO2: 60-73%,

[0027] Al2O3: 4-6%,

[0028] P2O5: 0–2%,

[0029] ZrO2: 1-3%,

[0030] Na2O: 1-4%,

[0031] K2O: 0-1%,

[0032] Li2O: 14-23%,

[0033] CaO: 0–1.5% and

[0034] B2O3: 1-5%.

[0035] In some embodiments of this application, the 3D-bendable microcrystalline glass is prepared by nucleating and crystallizing a substrate glass.

[0036] Secondly, this application also provides a method for preparing the above-mentioned 3D-bendable microcrystalline glass, the preparation method comprising the following steps:

[0037] Step 1: Mix the raw materials for preparing glass, melt them, cool them, and then anneal them to obtain the substrate glass;

[0038] Step 2: Perform nucleation treatment on the substrate glass obtained in Step 1;

[0039] Step 3: The substrate glass nucleated in Step 2 is subjected to crystallization treatment to obtain the 3D heat-bendable microcrystalline glass.

[0040] In some embodiments of this application, in step 1 of the above preparation method, the melting temperature is 1350-1700°C, preferably 1400-1650°C, and more preferably cooled to 500-1000°C after melting.

[0041] In some embodiments of this application, in step 2 of the above preparation method, the nucleation treatment temperature is 520-590°C, and the nucleation treatment time is preferably 30-600 min; and / or,

[0042] In step 3, the crystallization treatment temperature is 640-750℃, and the crystallization treatment time is preferably 20-600 min.

[0043] Thirdly, the present invention also provides a 3D microcrystalline glass, which is prepared by subjecting the above-mentioned 3D heat-bendable microcrystalline glass or the 3D heat-bendable microcrystalline glass obtained by the above-mentioned preparation method to a 3D heat-bending process.

[0044] In some embodiments of this application, the 3D microcrystalline glass comprises a lithium feldspar crystal phase, a lithium disilicate crystal phase, and a quartz crystal phase, with a total crystal phase content of 60-90%. The sum of the contents of the lithium feldspar crystal phase and the lithium disilicate crystal phase accounts for 45-60% of the total crystal phase content, and the contents of the quartz crystal phase account for 15-22% of the total crystal phase content.

[0045] In some embodiments of this application, the quartz crystal phase is β-quartz.

[0046] And / or, the 3D glass-ceramic further includes a lithium silicate (Li2SiO3) crystal phase, preferably the content of the lithium silicate crystal phase accounts for 20-40% of the total crystal phase content;

[0047] And / or, the crystalline phase of the 3D microcrystalline glass further includes a spodumene crystalline phase; preferably, the content of the spodumene crystalline phase accounts for 0-15% of the total crystalline phase content.

[0048] In some embodiments of this application, the grain size of the 3D microcrystalline glass is 35-50 nm;

[0049] And / or, the 3D microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance of 15-35% at 550 nm;

[0050] And / or, the color coordinates of the 3D microcrystalline glass in the reflection mode are: L* is 70~81, a* is -2.60~0.00, and b* is -7~1;

[0051] And / or, the X-axis shrinkage of the 3D microcrystalline glass is less than or equal to 1%, preferably less than or equal to 0.5%; preferably, the Y-axis shrinkage of the 3D microcrystalline glass is less than or equal to 0.5%, preferably less than or equal to 0.35%;

[0052] And / or, the single-bar static compressive strength of the 3D microcrystalline glass is greater than 320N.

[0053] Fourthly, this application also provides a 3D microcrystalline glass product, which is obtained by chemically strengthening the aforementioned 3D microcrystalline glass.

[0054] Fifthly, this application also provides an electronic device comprising the above-described heat-bendable microcrystalline glass or the heat-bendable microcrystalline glass prepared by the above-described preparation method or the above-described 3D microcrystalline glass or the above-described 3D microcrystalline glass article; preferably, the electronic device includes a mobile phone, tablet computer, laptop computer, television set or display device; more preferably, the heat-bendable microcrystalline glass or the 3D microcrystalline glass is the outer shell or part of the outer shell of the electronic device, preferably the back panel or part of the back panel of the electronic device.

[0055] Sixthly, the application of the above-mentioned 3D heat-bendable microcrystalline glass or the 3D heat-bendable microcrystalline glass prepared by the above-mentioned preparation method or the above-mentioned 3D microcrystalline glass or the above-mentioned 3D microcrystalline glass articles in electronic devices is preferred to be used in the casing of electronic devices, and more preferably in the back panel of mobile phones.

[0056] The beneficial effects of this invention are:

[0057] 1. This application controls the formation of quartz grains in the microcrystalline glass that can be 3D hot-bent before hot bending, with controllable size and volume, so that the glass appears white (as can be seen from the L*a*b* value) and has good mechanical properties, ensuring that it can be 3D hot-bent at 810℃, and can prepare 3D microcrystalline glass and process it into three-dimensional products.

[0058] 2. This application controls the crystal phase composition of the 3D heat-bendable microcrystalline glass, allowing it to continue crystallizing during the heat-bending process, and controls the proportion of each crystal phase after the heat-bending process, especially the proportion of the quartz crystal phase, within a suitable range, thereby ensuring that the prepared 3D microcrystalline glass still has a white appearance and good mechanical properties and dimensional stability. Attached Figure Description

[0059] Figure 1 The graph shows the coefficient of thermal expansion of the white microcrystalline glass in Example 3.

[0060] Figure 2 The image shows the white microcrystalline glass prepared in Example 3 after being heat-bent at 810°C.

[0061] Figure 3 The image shows the white microcrystalline glass prepared in Comparative Example 2 after being heat-bent at 810℃.

[0062] Figure 4 This is a scanning electron microscope image of the glass-ceramic before hot bending in Example 3.

[0063] Figure 5 This is a scanning electron microscope image of the microcrystalline glass after hot bending in Example 3.

[0064] Figure 6This is a scanning electron microscope image of the microcrystalline glass before hot bending, as shown in Comparative Example 2.

[0065] Figure 7 This is a scanning electron microscope image of the microcrystalline glass before hot bending, as shown in Comparative Example 5.

[0066] Figure 8 This is a scanning electron microscope image of the microcrystalline glass after hot bending, as shown in Comparative Example 5.

[0067] Figure 9 The images show the XRD patterns of the white microcrystalline glass before and after hot bending in Example 3.

[0068] Figure 10 The image shows the XRD pattern of the white microcrystalline glass before hot bending, as shown in Comparative Example 2.

[0069] Figure 11 The XRD patterns of the white microcrystalline glass in Comparative Example 5 before and after hot bending are shown. Detailed Implementation

[0070] In this invention, unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits, and "above" and "below" include endpoint values ​​and all integers and fractions within that range, not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A; and / or B" means only A, or only B, or both A and B.

[0071] In a first aspect, this application provides a 3D heat-bendable microcrystalline glass, wherein the crystalline phase of the 3D heat-bendable microcrystalline glass includes lithium feldspar (LiAlSi4O). 10 The total crystalline phase content of the 3D heat-bendable microcrystalline glass is 40-70%, including lithium disilicate (Li2Si2O5) crystalline phase and quartz crystalline phase. The sum of the contents of the lithium feldspar crystalline phase and the lithium disilicate crystalline phase accounts for 50-70% of the total crystalline phase content, and the contents of the quartz crystalline phase account for 4-10% of the total crystalline phase content.

[0072] In some embodiments of this application, the total crystalline phase content of the 3D-bendable microcrystalline glass is 40-70%, preferably 45-60%. In some embodiments of this application, the total crystalline phase content of the 3D-bendable microcrystalline glass can be 40%, 42%, 43%, 45%, 48%, 50%, 55%, 60%, 65%, 68%, or 70%; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0073] In some embodiments of this application, the quartz crystal phase is β-quartz. In some embodiments of this application, the content of the quartz crystal phase in the 3D heat-bendable microcrystalline glass can account for 4-10%, 4-9%, 4-8%, 5-10%, 6-10%, or 7-10% of the total crystal phase content. In some embodiments of this application, the content of the quartz crystal phase can account for 4%, 5%, 6%, 7%, 8%, 9%, or 10% of the total crystal phase content, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0074] It should be noted that the A-phase + B-phase ratio mentioned in this application refers to the percentage of the sum of the A-phase + B-phase content in the total crystalline phase content of the glass-ceramic; the C-phase ratio is the percentage of the C-phase content in the total crystalline phase content of the glass-ceramic; the D-phase ratio is the percentage of the D-phase content in the total crystalline phase content of the glass-ceramic; and the E-phase ratio is the percentage of the E-phase content in the total crystalline phase content of the glass-ceramic.

[0075] In some embodiments of this application, the 3D-bendable microcrystalline glass further includes a lithium silicate (Li2SiO3) crystalline phase. In some embodiments of this application, the content of the lithium silicate (Li2SiO3) crystalline phase can account for 20-40%, 22-38%, 22-36%, 22-34%, 22-32%, 22-30%, 24-40%, 26-40%, 28-40%, or 30-40% of the total crystalline phase content. In some embodiments of this application, the content of the lithium silicate (Li2SiO3) crystalline phase can account for 20%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 34%, 36%, 38%, or 40% of the total crystalline phase content; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges.

[0076] In some embodiments of this application, the 3D-bendable microcrystalline glass is transparent to lithium feldspar (LiAlSi4O3). 10 The sum of the contents of the lithium disilicate (Li2Si2O5) and the lithium crystalline phase can account for 50-70%, 50-68%, 50-66%, 50-64%, 50-62%, 50-60%, 52-70%, 54-70%, 56-70%, 58-70%, or 60-70% of the total crystalline phase content. In some embodiments of this application, lithium feldspar (LiAlSi4O5) 10The sum of the contents of the crystalline phase and the lithium disilicate (Li2Si2O5) crystalline phase can account for 50%, 52%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 62%, 64%, 66%, 68%, or 70% of the total crystalline phase content, or fall within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0077] In some embodiments of this application, the crystalline phase of the 3D-bendable microcrystalline glass further includes a spodumene (LiAlSi2O6) crystalline phase. In some embodiments of this application, the content of the spodumene crystalline phase in the 3D-bendable microcrystalline glass can account for 0-11%, 1-11%, 3-11%, 5-10%, 3-9%, or 6-9% of the total crystalline phase content. In some embodiments of this application, the content of the spodumene (LiAlSi2O6) crystalline phase can account for 0%, 1%, 2%, 3%, 5%, 8%, 10%, or 11% of the total crystalline phase content; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0078] In some embodiments of this application, the average grain size of the 3D-bendable microcrystalline glass is 20-40 nm, preferably 25-38 nm. In some embodiments of this application, the average grain size of the 3D-bendable microcrystalline glass can be 20 nm, 23 nm, 25 nm, 27 nm, 28 nm, 30 nm, 32 nm, 34 nm, 35 nm, 37 nm, 38 nm, or 40 nm, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0079] In this application, the thickness t of the 3D-bendable microcrystalline glass is not particularly limited, for example, it can be 0.4 to 2.0 mm; preferably 0.4 to 1.0 mm. In some embodiments of this application, the thickness t of the 3D-bendable microcrystalline glass can be 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 2.0 mm, or a range formed by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0080] In some embodiments of this application, the expansion softening point of the 3D-bendable microcrystalline glass is less than or equal to 810°C; preferably 650°C-810°C. In some embodiments of this application, the expansion softening point of the 3D-bendable microcrystalline glass can be 650°C, 670°C, 690°C, 700°C, 720°C, 750°C, 770°C, 780°C, 790°C, 800°C, 805°C, or 810°C, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0081] In some embodiments of this application, the 3D-bendable microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance at a wavelength of 550 nm between 30% and 50%. In some embodiments of this application, the light transmittance of the 3D-bendable microcrystalline glass, with a thickness of 0.60 mm, at a wavelength of 550 nm can be 30%, 35%, 38%, 40%, 43%, 45%, 48%, or 50%, or fall within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0082] In some embodiments of this application, the chromaticity coordinates of the 3D-bendable microcrystalline glass in reflection mode are: L* is 70-82, a* is -4-2, and b* is -12.00-5.00; preferably, the chromaticity coordinates of the 3D-bendable microcrystalline glass in reflection mode are L* is 72-82, a* is -3.62-4, and b* is -11.31-4.00; more preferably, the chromaticity coordinates of the 3D-bendable microcrystalline glass in reflection mode are L* is 74-80, a* is -3.00-3.00, and b* is -10.00-3.00.

[0083] In some embodiments of this application, the composition of the 3D-bendable microcrystalline glass, based on the molar percentage of oxides, comprises:

[0084] SiO2: 60-73%,

[0085] Al2O3: 4-6%,

[0086] P2O5: 0–2%,

[0087] ZrO2: 1-3%,

[0088] Na2O: 0.1-4%,

[0089] K2O: 0-1%,

[0090] Li2O: 14-23%,

[0091] CaO: 0–1.5% and

[0092] B2O3: 0.1–5%.

[0093] Preferably, the composition of the 3D-bendable microcrystalline glass, based on the molar percentage of oxides, contains:

[0094] SiO2: 60-73%,

[0095] Al2O3: 4-6%,

[0096] P2O5: 0–2%,

[0097] ZrO2: 1-3%,

[0098] Na2O: 1-4%,

[0099] K2O: 0-1%,

[0100] Li2O: 14-23%,

[0101] CaO: 0–1.5% and

[0102] B2O3: 1-5%.

[0103] SiO2 is an oxide that forms the network framework of glass, stabilizing the network structure of glass and glass-ceramics. In lithium aluminum silicon systems, it is used to form crystalline phases such as lithium silicate, litharge, and quartz. In some embodiments of this application, the 3D heat-bendable glass-ceramics, based on the molar percentage of oxides, comprises 60.00–73.00 mol%, 60.00–72.00 mol%, 60.00–71.00 mol%, 60.00–70.00 mol%, 60.00–69.00 mol%, 60.00–68.00 mol%, 60.00–67.00 mol%, 60.00–66.00 mol%, and 60.00–66.00 mol%. 5.00 mol%, 61.00–73.00 mol%, 62.00–73.00 mol%, 63.00–73.00 mol%, 64.00–73.00 mol%, 65.00–73.00 mol%, 66.00–73.00 mol%, 67.00–73.00 mol%, 68.00–73.00 mol%, 69.00–73.00 mol%, or 70.00–73.00 mol% of SiO2. In some embodiments of this application, the 3D-bendable glass-ceramic comprises, by molar percentage of oxide, 60.00 mol%, 61.00 mol%, 62.00 mol%, 63.00 mol%, 64.00 mol%, 65.00 mol%, 66.00 mol%, 67.00 mol%, 68.00 mol%, 69.00 mol%, 70.00 mol%, 71.00 mol%, 72.00 mol%, or 73.00 mol% of SiO2, or SiO2 falling within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0104] Al₂O₃ is used to form the glass framework and is an indispensable component for the formation of lithopelite. In some embodiments of this application, the 3D-bendable glass-ceramic comprises 4.00–6.00 mol%, 4.50–6.00 mol%, 5.00–6.00 mol%, 4.00–5.50 mol%, or 4.00–5.00 mol% of Al₂O₃, based on the molar percentage of oxides. In some embodiments of the present invention, the 3D-bendable glass-ceramic comprises 4.00 mol%, 4.10 mol%, 4.20 mol%, 4.50 mol%, 4.60 mol%, 4.70 mol%, 4.80 mol%, 5.00 mol%, 5.50 mol%, 5.70 mol%, 5.80 mol%, 5.90 mol%, or 6.00 mol% of Al₂O₃, based on the molar percentage of oxides; or Al₂O₃ within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges.

[0105] P2O5 is a glass-forming oxide that exists as phosphorus-oxygen tetrahedra [PO4] in a network structure. It can undergo heterogeneous nucleation in glass, promoting crystal formation and improving the uniformity of the glass-ceramic, thus enhancing its corrosion resistance and heat resistance. In some embodiments of this application, the 3D-bendable glass-ceramic comprises 0.00–2.00 mol%, 0.00–1.50 mol%, 0.00–1.00 mol%, 0.00–0.50 mol%, 0.50–2.00 mol%, 1.00–2.00 mol%, or 1.50–2.00 mol% of P2O5, based on the molar percentage of the oxide. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises, by molar percentage of oxide, 0.20 mol%, 0.50 mol%, 0.80 mol%, 0.90 mol%, 1.00 mol%, 1.30 mol%, 1.50 mol%, or 2.00 mol% of P2O5; or P2O5 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0106] Li₂O is an essential component of the microcrystalline glass substrate of this invention, contributing to the formation of lithium feldspar and lithium silicate crystalline phases. It is also a necessary component for chemical strengthening, improving strength, melt permeability, and formability of the glass. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises, by molar percentage of oxide, 14.00–23.00 mol%, 14.00–22.00 mol%, 14.00–21.00 mol%, 14.00–20.00 mol%, 14.00–19.00 mol%, 15.00–23.00 mol%, 16.00–23.00 mol%, 17.00–23.00 mol%, 18.00–23.00 mol%, 19.00–23.00 mol%, or 20.00–23.00 mol% of Li₂O. In some embodiments of this application, the 3D-bendable glass-ceramic comprises, by mole percentage of oxide, 14.00 mol%, 15.00 mol%, 16.00 mol%, 17.00 mol%, 18.00 mol%, 19.00 mol%, 20.00 mol%, 21.00 mol%, 22.00 mol%, 23.00 mol%, or 24.00 mol% of Li₂O; or Li₂O within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0107] ZrO2 can improve the viscosity, hardness, elastic modulus, refractive index, and chemical stability of glass, and reduce the coefficient of thermal expansion of glass. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises 1.00–3.00 mol%, 1.50–3.00 mol%, 2.00–3.00 mol%, 1.00–2.50 mol%, or 1.00–2.00 mol% ZrO2, based on the molar percentage of oxides. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises, by molar percentage of oxide, 0.50 mol%, 1.00 mol%, 1.50 mol%, 1.70 mol%, 1.8 mol%, 1.90 mol%, 2.00 mol%, 2.10 mol%, 2.20 mol%, 2.30 mol%, 2.40 mol%, 2.50 mol%, 2.60 mol%, 2.70 mol%, or 3.00 mol% ZrO2; or ZrO2 falling within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0108] Na₂O is an oxide on the outer layer of the glass network, which can provide free oxygen to increase the oxygen-silicon ratio in the glass structure, thereby regulating grain size. In some embodiments of this application, the 3D heat-bendable microcrystalline glass comprises 0.10–4.00 mol%, 0.50–4.00 mol%, 1.00–4.00 mol%, 1.50–4.00 mol%, 2.00–4.00 mol%, 3.00–4.00 mol%, 0.10–3.50 mol%, 0.10–3.00 mol%, 0.10–2.50 mol%, 0.10–2.00 mol%, 0.10–1.50 mol%, or 0.10–1.00 mol% Na₂O, based on the molar percentage of the oxide. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises, by mole percentage of oxide, 0.10 mol%, 0.20 mol%, 0.30 mol%, 1.00 mol%, 1.10 mol%, 1.50 mol%, 1.60 mol%, 1.90 mol%, 2.00 mol%, 2.50 mol%, 2.90 mol%, 3.00 mol%, 3.10 mol%, 3.50 mol%, 3.60 mol%, or 4.00 mol% of Na₂O; or Na₂O within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0109] K2O is a network-external oxide, and its addition helps improve the low-temperature melting and formability of the substrate glass. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises 0.00–1.00 mol%, 0.00–0.80 mol%, 0.00–0.50 mol%, 0.10–1.00 mol%, 0.20–1.00 mol%, or 0.50–1.00 mol% of K2O, based on the molar percentage of oxide. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises 0.10 mol%, 0.20 mol%, 0.50 mol%, or 1.00 mol% of K2O, based on the molar percentage of oxide; or K2O within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0110] B2O3 can improve the physical and chemical properties of glass, while lowering its melting point and viscosity, and increasing its transparency. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises, by molar percentage of oxide, 0.10–5.00 mol%, 0.50–5.00 mol%, 1.00–5.00 mol%, 1.50–5.00 mol%, 2.00–5.00 mol%, 2.50–5.00 mol%, 3.00–5.00 mol%, 0.10–4.50 mol%, 0.10–4.00 mol%, 0.10–3.50 mol%, 0.10–3.00 mol%, 0.10–2.50 mol%, or 0.10–2.00 mol% of B2O3. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises, by molar percentage of oxide, 0.10 mol%, 0.20 mol%, 0.30 mol%, 1.00 mol%, 1.50 mol%, 1.60 mol%, 1.90 mol%, 2.00 mol%, 2.50 mol%, 2.60 mol%, 2.90 mol%, 3.00 mol%, 3.50 mol%, 3.80 mol%, 3.90 mol%, or 4.00 mol% of B2O3; or B2O3 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0111] CaO can increase the chemical stability and mechanical strength of glass, reduce its viscosity, and improve its meltability and formability. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises 0.00–1.50 mol%, 0.00–1.00 mol%, 0.00–0.50 mol%, 0.20–1.50 mol%, 0.5–1.50 mol%, or 1.00–1.50 mol% of CaO, based on the molar percentage of oxides. In some embodiments of this application, the 3D-bendable microcrystalline glass comprises 0.10 mol%, 0.30 mol%, 0.40 mol%, 0.50 mol%, 0.70 mol%, 0.80 mol%, 1.00 mol%, 1.10 mol%, 1.20 mol%, 1.30 mol%, or 1.50 mol% of CaO, based on the molar percentage of oxides; or CaO within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges.

[0112] In some embodiments of this application, the 3D-bendable microcrystalline glass undergoes a continued crystallization process while being 3D-bent, resulting in a total crystalline phase content of 60-90% after 3D bending. In some embodiments of this application, the 3D-bendable microcrystalline glass is subjected to a 3D-bending temperature of 810°C.

[0113] After 3D hot bending, the total crystalline phase content of the 3D-bendable microcrystalline glass can be 60%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 87%, 89%, or 90%, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0114] In some embodiments of this application, after 3D hot bending, the sum of the contents of the lithium feldspar crystal phase and the lithium disilicate crystal phase in the 3D-bendable microcrystalline glass accounts for 45-60% of the total crystal phase content, and the content of the quartz crystal phase accounts for 15-22% of the total crystal phase content; preferably, after 3D hot bending, the sum of the contents of the lithium feldspar crystal phase and the lithium disilicate crystal phase in the 3D-bendable microcrystalline glass accounts for 45-55% of the total crystal phase content, and the content of the quartz crystal phase accounts for 15-20% of the total crystal phase content.

[0115] In some embodiments of this application, the 3D-bendable microcrystalline glass further includes a lithium silicate (Li2SiO3) crystalline phase after 3D hot bending. In some embodiments of this application, the content of the lithium silicate (Li2SiO3) crystalline phase can account for 20-40%, 22-38%, 22-36%, 22-34%, 22-32%, 22-30%, 24-40%, 26-40%, 28-40%, or 30-40% of the total crystalline phase content. In some embodiments of this application, the content of the lithium silicate (Li2SiO3) crystalline phase can account for 20%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 34%, 36%, 38%, or 40% of the total crystalline phase content; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges.

[0116] In some embodiments of this application, the 3D-bendable microcrystalline glass further includes a spodumene (LiAlSi2O6) crystalline phase after 3D hot bending. In some embodiments of this application, the content of the spodumene (LiAlSi2O6) crystalline phase can account for 0-15%, 1-15%, 3-15%, 5-14%, 3-10%, or 6-9% of the total crystalline phase content. In some embodiments of this application, the content of the spodumene (LiAlSi2O6) crystalline phase can account for 0%, 2%, 3%, 5%, 8%, 10%, 12%, 14%, or 15% of the total crystalline phase content; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0117] In some embodiments of this application, the average grain size of the 3D-bendable microcrystalline glass after 3D hot bending is 35-50 nm, preferably 35-48 nm. In some embodiments of this application, the average grain size of the 3D-bendable microcrystalline glass after 3D hot bending can be 35 nm, 37 nm, 38 nm, 40 nm, 42 nm, 43 nm, 44 nm, 45 nm, 46 nm, 47 nm, 48 nm, 49 nm, or 50 nm, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0118] Secondly, this application provides a method for preparing the 3D heat-bendable microcrystalline glass as described above, comprising the following steps:

[0119] Step 1: Mix and melt the various raw material components for preparing the substrate glass, and after forming, cool and anneal to obtain the substrate glass;

[0120] Step 2: The substrate glass obtained in Step 1 is subjected to nucleation and crystallization treatments to obtain 3D heat-bent microcrystalline glass.

[0121] In the preparation method of this application, in step 1, the raw material components for preparing the substrate glass also include a clarifying agent, which includes one or more of NaCl, Na2SO4, SnO2, As2O3, Sb2O3, NaNO3, KNO3, CeO2 and (NH4)2SO4; preferably one or more of NaCl, SnO2, NaNO3 and CeO2.

[0122] In the preparation method of this application, in step 1, the melting temperature is 1350-1700℃, preferably 1400-1650℃, and more preferably cooled to 500-1000℃ after melting.

[0123] In the preparation method of this application, in step 2, the nucleation treatment temperature is 520-590℃, and preferably, the nucleation treatment time is 30-600 min. In the preparation method of this application, in step 2, the nucleation treatment temperature can be 520℃, 540℃, 550℃, 560℃, 570℃, 580℃, or 590℃, or fall within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range. In the preparation method of this application, in step 2, the nucleation treatment time can be 30 min, 60 min, 90 min, 100 min, 120 min, 150 min, 180 min, 200 min, 250 min, 280 min, 300 min, 350 min, 380 min, 400 min, 450 min, 480 min, 500 min, 550 min, 580 min, or 600 min, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0124] In some embodiments of this application, in step 3, the crystallization treatment temperature is 640-750°C, and preferably, the crystallization treatment time is 20-600 min. In the preparation method of this application, in step 3, the crystallization treatment temperature can be 640°C, 680°C, 690°C, 700°C, 720°C, 740°C, or 750°C, or a value range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range. In the preparation method of this application, in step 3, the crystallization treatment time can be 20 min, 60 min, 90 min, 100 min, 120 min, 150 min, 180 min, 200 min, 250 min, 280 min, 300 min, 350 min, 380 min, 400 min, 450 min, 480 min, 500 min, 550 min, 580 min, or 600 min, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0125] Thirdly, this application provides a 3D microcrystalline glass, which is prepared by a 3D hot bending process from the 3D hot bending microcrystalline glass as described above or the 3D hot bending microcrystalline glass prepared by the preparation method of the 3D hot bending microcrystalline glass as described above.

[0126] In some embodiments of this application, the 3D microcrystalline glass comprises a lithium feldspar crystal phase, a lithium disilicate crystal phase, and a quartz crystal phase, with a total crystal phase content of 60-90%. The sum of the contents of the lithium feldspar crystal phase and the lithium disilicate crystal phase accounts for 45-60% of the total crystal phase content, and the contents of the quartz crystal phase account for 15-22% of the total crystal phase content.

[0127] In some embodiments of this application, the total crystalline phase content of the 3D microcrystalline glass can be 60%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 87%, 89%, or 90%, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0128] In some embodiments of this application, the 3D microcrystalline glass is transparent with lithium feldspar (LiAlSi4O3). 10 The sum of the contents of the lithium disilicate (Li2Si2O5) and the lithium disilicate (Li2Si2O5) crystalline phases can account for 45-60%, 48-60%, 50-60%, 45-58%, 46-55%, 45-50%, or 55-60% of the total crystalline phase content. In some embodiments of this application, lithium disilicate (LiAlSi4O5) 10 The sum of the contents of lithium disilicate (Li₂Si₂O₅) and lithium disilicate (Li₂Si₂O₅) can account for 45%, 48%, 50%, 52%, 54%, 55%, 56%, 57%, 58%, 59%, or 60% of the total crystalline phase content, or fall within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0129] In some embodiments of this application, the quartz crystal phase is β-quartz. In some embodiments of this application, the content of the quartz crystal phase in the 3D microcrystalline glass can account for 15-22%, 15-20%, 15-18%, 16-22%, or 16-20% of the total crystal phase content. In some embodiments of this application, the content of the quartz crystal phase can account for 15%, 16%, 17%, 18%, 19%, 20%, or 22% of the total crystal phase content, or fall within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0130] In some embodiments of this application, the 3D microcrystalline glass further includes a lithium silicate (Li2SiO3) crystalline phase. In some embodiments of this application, the content of the lithium silicate (Li2SiO3) crystalline phase may account for 20-40%, 22-38%, 22-36%, 22-34%, 22-32%, 22-30%, 24-40%, 26-40%, 28-40%, or 30-40% of the total crystalline phase content. In some embodiments of this application, the content of the lithium silicate (Li2SiO3) crystalline phase may account for 20%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 34%, 36%, 38%, or 40% of the total crystalline phase content; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges.

[0131] In some embodiments of this application, the 3D microcrystalline glass further includes a spodumene (LiAlSi2O6) crystalline phase. In some embodiments of this application, the content of the spodumene (LiAlSi2O6) crystalline phase can account for 0-15%, 1-15%, 3-15%, 5-14%, 3-10%, or 6-9% of the total crystalline phase content. In some embodiments of this application, the content of the spodumene (LiAlSi2O6) crystalline phase can account for 0%, 2%, 3%, 5%, 8%, 10%, 12%, 14%, or 15% of the total crystalline phase content; or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0132] In some embodiments of this application, the average grain size of the 3D glass-ceramic is 35-50 nm, preferably 35-47 nm. In some embodiments of this application, the average grain size of the 3D glass-ceramic can be 35 nm, 37 nm, 38 nm, 40 nm, 42 nm, 43 nm, 44 nm, 45 nm, 46 nm, 47 nm, 48 nm, 49 nm, or 50 nm, or fall within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0133] In this application, the thickness t of the 3D microcrystalline glass is not particularly limited, for example, it can be 0.4 to 2.0 mm; preferably 0.4 to 1.0 mm. In some embodiments of this application, the thickness t of the 3D microcrystalline glass can be 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 2.0 mm, or a range formed by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0134] In some embodiments of this application, the 3D microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance at a wavelength of 550 nm between 15% and 35%. In some embodiments of this application, the light transmittance of the 3D microcrystalline glass, with a thickness of 0.60 mm, at a wavelength of 550 nm can be 15%, 17%, 19%, 20%, 23%, 25%, 28%, 30%, 32%, 33%, or 35%, or fall within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0135] In some embodiments of this application, the chromaticity coordinates of the 3D microcrystalline glass in reflection mode are: L* is 70-81, a* is -2.60-0.00, and b* is -7-1; preferably, the chromaticity coordinates of the 3D microcrystalline glass in reflection mode are: L* is 72-81, a* is -2.21-0, and b* is -6.60-1; more preferably, the chromaticity coordinates of the 3D microcrystalline glass in reflection mode are: L* is 74-81, a* is -2.00-0, and b* is -6.00-1.

[0136] In some embodiments of this application, the X-axis shrinkage of the 3D microcrystalline glass is less than or equal to 1%, preferably less than or equal to 0.5%, and more preferably less than or equal to 0.49%.

[0137] In some embodiments of this application, the Y-axis shrinkage of the 3D microcrystalline glass is less than or equal to 0.5%, preferably less than or equal to 0.35%, more preferably less than or equal to 0.30%, and even more preferably less than or equal to 0.25%.

[0138] Fourthly, this application provides a method for preparing 3D microcrystalline glass as described above, comprising the following steps: preparing 3D microcrystalline glass by subjecting 3D heat-bending microcrystalline glass to 3D heat-bending treatment.

[0139] In the preparation method of the 3D microcrystalline glass of this application, the hot bending process is accompanied by a continued crystallization process. Preferably, the hot bending temperature is 810°C.

[0140] Fifthly, this application also provides a 3D microcrystalline glass article, which is obtained by chemical strengthening treatment of the 3D microcrystalline glass as described above.

[0141] This application does not restrict the conditions for chemical forging; any chemical forging conditions common in the field that can achieve the performance of this application are acceptable.

[0142] Sixthly, this application also provides the application of the 3D heat-bendable microcrystalline glass or 3D microcrystalline glass or 3D microcrystalline glass articles as described above in electronic devices, preferably in the housing of electronic devices.

[0143] In some embodiments of this application, the electronic device includes one or more of a mobile phone, tablet computer, laptop computer, television set, and display device.

[0144] Terminology Explanation:

[0145] Substrate glass: Glass that has not undergone nucleation, crystallization, or strengthening treatments.

[0146] Glass-ceramics, also known as glass-ceramics, are a type of solid composite material that contains both glass phase and crystalline phase (microcrystalline phase, crystalline phase) through the targeted and controlled crystallization of a substrate glass.

[0147] Nucleation: The process of growing small crystal nuclei from nucleating material in glass through heat treatment.

[0148] Crystallization: Glass grows into a certain crystal based on crystal nuclei through heat treatment.

[0149] Devitrification: This refers to the complete loss of the transparent properties of glass due to the large size or phase separation of crystals in the microcrystalline glass / glass ceramic, making it impossible to see any image on the back of the glass.

[0150] Crystallinity: refers to the percentage of the total mass of crystalline phases / crystals in glass-ceramics, which is also the total content of crystalline phases in glass-ceramics.

[0151] L-value: Represents the specular reflection (SCI) value, indicating the brightness of the material. A positive L-value indicates a whiter appearance, while a negative L-value indicates a darker appearance.

[0152] a-value: Represents the a-value of specular reflection, and indicates the red-green value of the material. A positive a-value indicates that the material is reddish, and a negative a-value indicates that the material is greenish.

[0153] b-value: Used to characterize the yellow-blue value of a material. When measuring the b-value using transmitted light, the optical b-value in this invention is added: the optical b-value is the transmitted light b-value, and a positive optical b-value indicates that the material has a bluish tint.

[0154] Expansion softening point: The temperature at which glass softens. It mainly refers to the temperature at which glass begins to soften.

[0155] Deformation: Deformation refers to the amount of deformation that occurs in glass. Any change in shape caused by an external force is called "deformation".

[0156] Primary recrystallization: In essence, it is the process of nucleation and growth of new strain-free grains.

[0157] Secondary recrystallization refers to the abnormal growth of secondary grains based on the grains after primary recrystallization. Strictly speaking, it is a grain growth process under special conditions, not a primary recrystallization process.

[0158] The glass of this invention is tested using the following methods:

[0159] Differential Scanning Calorimetry (DSC) Test

[0160] The instrument used was a Mettler Toledo TGA / DSC 3+ simultaneous thermal analyzer, and the tests were conducted according to JY / T0589.5-202. The standard used was α-Al2O3 powder, and the sample was placed in a platinum crucible. The ambient temperature of the instrument was 24℃, and the air humidity was 40%. After grinding the glass and passing it through a 200-mesh sieve, the sample to be tested was obtained. Approximately 20 mg of the sample was weighed and heated from room temperature to 900℃ at a heating rate of 10℃ / min under a nitrogen protective atmosphere to obtain the DSC curve of the sample.

[0161] Testing of total crystalline phase content and the content of each specific crystalline phase.

[0162] The glass-ceramic sample was crushed and ground into particles smaller than 75 μm. The sample was then tested using an X-ray diffractometer to obtain the XRD diffraction peak curve. The X-ray diffraction data (RAW format) from the Shimadzu XRD-6100 X-ray diffraction instrument was then fitted and calculated using Rietveld refining software (such as Jade, Maud, or High score) to obtain the total crystalline phase content and the content of each specific crystalline phase in the glass-ceramic sample. The X-ray diffractometer used in this application was a Shimadzu XRD-6100, with an incident angle range of 2θ = 10–50°, a scanning speed of 3° / min, an operating voltage of 40 kV, and an operating current of 30 mA.

[0163] Test of average grain size

[0164] Using the XRD test results, the average grain size of the sample can be calculated according to the Scherrer formula D = Kλ / (βcosθ). Here, λ is the X-ray wavelength (λ = 0.154056 nm), β is the full width at half maximum (FWHM) of the diffraction peak (K = 0.89), and θ is the Bragg diffraction angle. Specifically, the RAW file (diffraction pattern) output from the XRD instrument is curve-fitted in Jade software. Jade outputs a fitting report. Based on the angle 2θ and PeakFWHM value (FWHM value) corresponding to each diffraction peak in the fitting report, and converting the PeakFWHM value to radians: β = (FWHM / 180 × 3.14), the grain size of each diffraction peak is calculated using the Scherrer formula D = Kλ / (βcosθ), and the average value is taken to obtain the average grain size.

[0165] Thickness test

[0166] Determined by laser thickness gauge testing.

[0167] CIE L*a*b* parameter test

[0168] This invention uses a Konica Minolta CM-3600A spectrophotometer from Japan for testing, and connects it to SpectraMagicNX spectral analysis software. Based on a D65 light source and a 10-degree standard observation angle, the test results are converted into CIELAB color space coordinates (L*; a*; and b*) in reflection mode, with the measurement area being LAV (25.4 mm).

[0169] Five pieces of glass under the same conditions were tested, and the average value of each test result was taken as the L* value, a* value and b* value of the glass-ceramic.

[0170] Light transmittance test

[0171] The light transmittance of glass at a wavelength of 550 nm was tested using a Shimadzu UV-2000 UV-Vis spectrophotometer. Five pieces of glass under the same conditions were tested, and the average value of the test results was taken as the light transmittance of the glass at a wavelength of 550 nm.

[0172] Single rod static pressure test

[0173] Place the glass sample to be tested on the bottom ring of the tensile testing machine (LT-850A), start the testing software, and set the moving speed of the extrusion bar (8mm diameter, 10mm radius of the indenter) to 50mm / min. Click "Start Test". The extrusion bar will apply force to the center of the glass sample to be tested at the set moving speed until the glass sample cracks and breaks.

[0174] The testing software will automatically read the force (N) when the glass sample breaks as the test result.

[0175] Ten glass samples under the same conditions were tested, and the average value of the test results was taken as the average single-bar static compressive strength of the glass sample to be tested.

[0176] Test of glass expansion softening point

[0177] The sample was made into a cylinder with a diameter of 5.5 mm and a length of 20 mm. The sample was tested using a LINSEIS L75VD1000 thermal expansion meter. The test temperature ranged from room temperature to 900℃, and the heating rate was 10℃ / min. After the test, the thermal expansion coefficient test curve was output. The inflection point temperature at which the curve first rises and then falls with the temperature is the thermal expansion softening point temperature of the sample.

[0178] The present invention will be described in detail below through examples and comparative examples.

[0179] Example 1

[0180] (1) According to the formula of Example 1 in Table 1, each raw material component is accurately weighed according to the proportion and thoroughly mixed to obtain a mixture. The total weight of each raw material component is 1000g. The mixture is placed in a platinum crucible and heated to 1650°C in a high-temperature melting furnace for 6 hours. After removing the bubbles, the glass liquid is poured into a mold for cooling and shaping. After cooling to 900°C, it is placed in a 500°C annealing furnace for 24 hours. Then, it is cooled to room temperature with the furnace to obtain the substrate glass.

[0181] (2) The substrate glass obtained in step (1) is heated to the nucleation temperature at a heating rate of 10℃ / min for nucleation treatment; then heated to the crystallization temperature at a heating rate of 10℃ / min for crystallization treatment; glass brick is obtained. The nucleation temperature, nucleation treatment time, crystallization temperature and crystallization treatment time are shown in Table 1.

[0182] (3) After cutting and polishing the glass brick obtained in step (2), a 3D heat-bent microcrystalline glass with a size of 50mm×50mm×0.60mm is obtained.

[0183] The performance of the 3D heat-bent microcrystalline glass obtained above was tested, and the results are shown in Table 2-3.

[0184] (4) The 3D heat-bending microcrystalline glass obtained in step (3) is placed in a 3D heat-bending machine for heat bending treatment. The heat bending treatment process includes 3 preheating stations, 3 hot pressing stations and 3 cooling stations. The temperatures of the 3 preheating stations are set to 590℃, 680℃ and 810℃ respectively. The temperatures and pressures of the 3 hot pressing stations are set to 810℃ / 0.40MPa, 810℃ / 0.40MPa and 810℃ / 0.20MPa respectively. The temperatures of the 3 cooling stations are set to 810℃, 650℃ and 600℃ respectively. The dwell time of each station is 90s. The final 3D microcrystalline glass is obtained.

[0185] The performance of the 3D microcrystalline glass obtained above was tested, and the results are shown in Table 4-5.

[0186] Examples 2-9 and Comparative Examples 1-5 were operated under the same conditions as in Example 1, except that the raw material composition for preparing the substrate glass is shown in Table 1 and the nucleation and crystallization conditions are shown in Table 2.

[0187] The 3D microcrystalline glass prepared in Examples 1-9 was chemically strengthened to obtain 3D microcrystalline glass products. The specific strengthening process is shown in Table 6.

[0188] Table 1. Substrate Glass of Examples 1-9 and Comparative Examples 1-4

[0189]

[0190] Table 2. 3D-bendable microcrystalline glass of Examples 1-9 and Comparative Examples 1-5

[0191]

[0192] Where: A represents LiAlSi4O 10 B represents Li2Si2O5; C represents Li2SiO3; D represents β-quartz; E represents LiAlSi2O6.

[0193] Table 3 Performance parameters of the 3D-bendable microcrystalline glass in Examples 1-9 and Comparative Examples 1-5

[0194]

[0195]

[0196] Table 4. 3D microcrystalline glass after hot bending and its performance parameters

[0197]

[0198] Where: A represents LiAlSi4O 10B represents Li2Si2O5; C represents Li2SiO3; D represents β-quartz; E represents LiAlSi2O6.

[0199] Table 5 Performance parameters of 3D microcrystalline glass after hot bending

[0200]

[0201] Table 6. Strengthening process conditions and properties of 3D microcrystalline glass in Examples 1-9

[0202]

[0203] The thermal expansion coefficient curve of the white microcrystalline glass in Example 3 is shown in the figure below. Figure 1 As shown, by Figure 1 The thermal expansion coefficient curve shows that the expansion softening point of the white microcrystalline glass prepared in Example 3 is 676℃.

[0204] The image of the white microcrystalline glass prepared in Example 3 after being hot-bent at 810°C is shown below. Figure 2 As shown, the image of the microcrystalline glass prepared in Comparative Example 2 after being hot-bent at 810℃ is as follows. Figure 3 As shown, by Figure 2 and 3 It can be seen that the 3D curved microcrystalline glass prepared in Example 3 has a uniform color and is more pleasing to the eye.

[0205] Scanning electron microscope (SEM) image of the white microcrystalline glass prepared in Example 3 before hot bending is shown below. Figure 4 As shown, the scanning electron microscope image of the prepared white microcrystalline glass after hot bending at 810℃ is as follows. Figure 5 As shown. By Figure 4 and 5 It can be seen that the white microcrystalline glass prepared by the primary crystallization method in Example 3 has a larger grain size after hot bending at 810°C.

[0206] The scanning electron microscope image of the white microcrystalline glass prepared in Comparative Example 2 before hot bending is shown below. Figure 6 As shown in the figure, the white microcrystalline glass prepared by secondary crystallization in Comparative Example 2 has a larger grain size.

[0207] The scanning electron microscope image of the white microcrystalline glass prepared in Comparative Example 5 before hot bending is shown below. Figure 7 As shown in the figure, the white microcrystalline glass prepared in Comparative Example 5 has a smaller grain size.

[0208] Scanning electron microscope image of the white microcrystalline glass prepared in Comparative Example 5 after hot bending is shown below. Figure 8 As shown in the figure, the white microcrystalline glass prepared in Comparative Example 5 exhibits a slightly larger grain size after hot bending at 810℃, while remaining transparent.

[0209] The XRD patterns of the white microcrystalline glass before and after hot bending in Example 3 are as follows: Figure 9 As shown, by Figure 9 It can be seen that the white microcrystalline glass of Example 3 contained crystalline phases of lithium feldspar, lithium disilicate, lithium silicate and quartz before hot bending, and the white microcrystalline glass of Example 3 had an additional spodumene crystalline phase after hot bending.

[0210] The XRD pattern of the white glass-ceramic prepared in Comparative Example 2 before hot bending is shown in the figure. Figure 10 As shown, it contains crystalline phases of lithium feldspar, lithium disilicate, lithium silicate, quartz, and spodumene.

[0211] The XRD patterns of the white glass-ceramic in Comparative Example 5 before and after hot bending are as follows: Figure 11 As shown, by Figure 11 It can be seen that the transparent microcrystalline glass of Comparative Example 5 contains only lithium feldspar and lithium disilicate crystalline phases before and after hot bending.

[0212] As shown in Tables 2-4, the crystalline phases of the 3D-bendable microcrystalline glass prepared in Examples 1-9 are all lithium feldspar, lithium disilicate, and quartz. The sum of the contents of lithium feldspar and lithium disilicate accounts for 45-70% of the crystalline phase content, and the content of quartz accounts for 4-10% of the crystalline phase content. The expansion and softening point ranges from 600 to 800°C. Therefore, the microcrystalline glass prepared in Examples 1-9 can be 3D-bent at 810°C.

[0213] The 3D-bendable microcrystalline glass prepared in Examples 1-9 was used to prepare white glass containing a quartz crystal phase through primary crystallization. The sum of the contents of petalite and lithium disilicate accounted for 50-70% of the total crystalline phase content, and the quartz crystal phase accounted for 4-10% of the total crystalline phase content. The average crystal size ranged from 20 to 32 nm. At 0.60 mm, L* was 70-82, a* was -4-2, and b* was -12-5, exhibiting a pleasing white appearance. After hot bending treatment, the sum of the contents of petalite and lithium disilicate accounted for 45-60% of the total crystalline phase content, and the quartz crystal phase accounted for 15-22%. The average crystal size ranged from 35-50 nm. At 0.60 mm, L* was 70-81, a* was -2.60-0.00, and b* was -7-1, also exhibiting a pleasing white appearance.

[0214] In Comparative Examples 1-3, the white glass prepared by secondary recrystallization contained 60-70% lithium feldspar and lithium disilicate in total crystalline phase, but the quartz phase accounted for far more than 10%, which resulted in the thermal expansion softening point of the prepared microcrystalline glass being above 810℃, making it impossible to perform 3D hot bending at 810℃.

[0215] In Comparative Example 4, the combined content of lithium feldspar and lithium disilicate accounted for 96.5% of the crystalline phase content, while the quartz crystalline phase accounted for only 3.50%, resulting in a thermal expansion softening point much higher than 810℃, making 3D hot bending molding impossible at 810℃.

[0216] In Comparative Example 5, the sum of the contents of lithium feldspar and lithium disilicate accounted for 100% of the crystalline phase content, while the quartz crystalline phase accounted for 0.00%. The thermal expansion softening point was less than 810℃, and it could be 3D hot-bent at 810℃. However, the glass was not white before and after hot bending.

[0217] As shown in Tables 4-5, the 3D microcrystalline glass prepared in the embodiments of this application exhibits a pleasing white appearance (as can be seen from the L*a*b* values), and its shrinkage on the X-axis is less than or equal to 0.5%, and its shrinkage on the Y-axis is less than or equal to 0.35%, demonstrating good dimensional stability.

[0218] As shown in Table 6, the 3D microcrystalline glass prepared in the embodiments of this application can still obtain excellent mechanical properties with a single bar static compressive strength greater than 320N after chemical strengthening.

[0219] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. A 3D-bendable microcrystalline glass, characterized in that, The crystalline phases of the 3D-bendable microcrystalline glass include lithium feldspar, lithium disilicate, quartz, and Li₂SiO₃. The total crystalline phase content of the 3D-bendable microcrystalline glass is 40-70%, wherein the sum of the contents of lithium feldspar and lithium disilicate accounts for 50-70% of the total crystalline phase content, the quartz phase accounts for 4-10% of the total crystalline phase content, and the Li₂SiO₃ phase accounts for 20-40% of the total crystalline phase content. The color coordinates of the 3D heat-bendable microcrystalline glass in reflection mode are: L* is 70~82, a* is -4~2, and b* is -12~5.

2. The 3D-bendable microcrystalline glass according to claim 1, characterized in that, The quartz crystal phase is β-quartz; and / or, The crystalline phase of the 3D-bendable microcrystalline glass also includes the spodumene crystalline phase.

3. The 3D-bendable microcrystalline glass according to claim 2, characterized in that, The content of the spodumene crystal phase accounts for 0-11% of the total crystal phase content.

4. The 3D-bendable microcrystalline glass according to claim 1, characterized in that, The grain size of the 3D-bendable microcrystalline glass is 20-40 nm. And / or, the expansion softening point of the 3D heat-bendable microcrystalline glass is less than or equal to 810°C; And / or, the 3D-bendable microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance of 30-50% at 550 nm.

5. The 3D-bendable microcrystalline glass according to claim 2, characterized in that, The grain size of the 3D-bendable microcrystalline glass is 20-40 nm. And / or, the expansion softening point of the 3D heat-bendable microcrystalline glass is less than or equal to 810°C; And / or, the 3D-bendable microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance of 30-50% at 550 nm.

6. The 3D-bendable microcrystalline glass according to claim 3, characterized in that, The grain size of the 3D-bendable microcrystalline glass is 20-40 nm. And / or, the expansion softening point of the 3D heat-bendable microcrystalline glass is less than or equal to 810°C; And / or, the 3D-bendable microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance of 30-50% at 550 nm.

7. The 3D-bendable microcrystalline glass according to any one of claims 1-6, characterized in that, The composition, expressed as a molar percentage of oxides, contains: SiO2: 60~73%, Al2O3: 4~6%, P2O5: 0~2%, ZrO2: 1~3%, Na2O: 0.1~4%, K2O: 0~1%, Li2O: 14~23%, CaO: 0~1.5% and B2O3: 0.1~5%.

8. The 3D-bendable microcrystalline glass according to claim 7, characterized in that, The composition, expressed as a molar percentage of oxides, contains: SiO2: 60~73%, Al2O3: 4~6%, P2O5: 0~2%, ZrO2: 1~3%, Na2O: 1~4%, K2O: 0~1%, Li2O: 14~23%, CaO: 0~1.5% and B2O3: 1~5%.

9. The 3D-bendable microcrystalline glass according to any one of claims 1-6, characterized in that, The 3D-bendable microcrystalline glass is made by nucleating and crystallizing a substrate glass.

10. The 3D-bendable microcrystalline glass according to claim 7, characterized in that, The 3D-bendable microcrystalline glass is made by nucleating and crystallizing a substrate glass.

11. The 3D-bendable microcrystalline glass according to claim 8, characterized in that, The 3D-bendable microcrystalline glass is made by nucleating and crystallizing a substrate glass.

12. The method for preparing the 3D-bendable microcrystalline glass according to any one of claims 1-11, characterized in that, The preparation method includes the following steps: Step 1: Mix the raw materials for preparing glass, melt them, cool them, and then anneal them to obtain the substrate glass; Step 2: Perform nucleation treatment on the substrate glass obtained in Step 1; Step 3: The substrate glass nucleated in Step 2 is subjected to crystallization treatment to obtain the 3D heat-bendable microcrystalline glass.

13. The method for preparing 3D-bendable microcrystalline glass according to claim 12, characterized in that, In step 1, the melting temperature is 1350-1700℃.

14. The method for preparing 3D-bendable microcrystalline glass according to claim 12, characterized in that, In step 1, the melting temperature is 1400-1650℃.

15. The method for preparing 3D-bendable microcrystalline glass according to claim 12, characterized in that, In step 1, the material is melted and then cooled to 500-1000°C.

16. The method for preparing 3D-bendable microcrystalline glass according to claim 13, characterized in that, In step 1, the material is melted and then cooled to 500-1000°C.

17. The method for preparing 3D-bendable microcrystalline glass according to any one of claims 12-16, characterized in that, In step 2, the nucleation treatment is performed at a temperature of 520-590°C; and / or, In step 3, the temperature of the crystallization treatment is 640-750℃.

18. The method for preparing 3D-bendable microcrystalline glass according to claim 17, characterized in that, In step 2, the nucleation process takes 30-600 min; and / or, In step 3, the crystallization treatment time is 20-600 min.

19. A 3D microcrystalline glass, characterized in that, It is prepared by a 3D hot bending process using the 3D hot bending process of the 3D hot bending microcrystalline glass prepared by any one of the methods of claims 1-11 or any one of claims 12-18.

20. The 3D microcrystalline glass according to claim 19, characterized in that, The 3D microcrystalline glass comprises a lithium feldspar crystal phase, a lithium disilicate crystal phase, and a quartz crystal phase, with a total crystal phase content of 60-90%. Among them, the combined content of the lithium feldspar crystal phase and the lithium disilicate crystal phase accounts for 45-60% of the total crystal phase content, and the content of the quartz crystal phase accounts for 15-22% of the total crystal phase content.

21. The 3D microcrystalline glass according to claim 20, characterized in that, The quartz crystal phase is β-quartz. And / or, 3D glass-ceramics also include the Li2SiO3 crystalline phase; And / or, the crystal phase of the 3D microcrystalline glass may also include a spodumene crystal phase.

22. The 3D microcrystalline glass according to claim 21, characterized in that, The content of the Li2SiO3 crystal phase accounts for 20-40% of the total crystal phase content; and / or, the content of the spodumene crystal phase accounts for 0-15% of the total crystal phase content.

23. The 3D microcrystalline glass according to any one of claims 19-22, characterized in that, The grain size of the 3D microcrystalline glass is 35-50nm; And / or, the 3D microcrystalline glass, with a thickness of 0.60 mm, has a light transmittance of 15-35% at 550 nm; And / or, the color coordinates of the 3D microcrystalline glass in the reflection mode are: L* is 70~81, a* is -2.60~0.00, and b* is -7~1; And / or, the X-axis shrinkage of the 3D microcrystalline glass is less than or equal to 1%; And / or, the single-bar static compressive strength of the 3D microcrystalline glass is greater than 320N.

24. The 3D microcrystalline glass according to claim 23, characterized in that, The X-axis shrinkage of the 3D microcrystalline glass is less than or equal to 0.5%.

25. The 3D microcrystalline glass according to claim 23, characterized in that, The Y-axis shrinkage of the 3D microcrystalline glass is less than or equal to 0.5%.

26. The 3D microcrystalline glass according to claim 23, characterized in that, The Y-axis shrinkage of the 3D microcrystalline glass is less than or equal to 0.35%.

27. A 3D microcrystalline glass product, characterized in that, It is obtained by chemically strengthening the 3D microcrystalline glass according to any one of claims 19-26.

28. An electronic device comprising the 3D heat-bendable microcrystalline glass according to any one of claims 1-11, or the heat-bendable microcrystalline glass prepared by the method of preparing the 3D heat-bendable microcrystalline glass according to any one of claims 12-18, or the 3D microcrystalline glass according to any one of claims 19-26, or the 3D microcrystalline glass article according to claim 27.

29. The electronic device according to claim 28, wherein, The electronic device is a mobile phone, tablet computer, laptop computer, or television.

30. The electronic device according to claim 28, wherein, The electronic device is a display device.

31. The electronic device according to any one of claims 28-30, wherein, The 3D heat-bendable microcrystalline glass or the 3D microcrystalline glass is the housing or part of the housing of the electronic device.

32. The electronic device according to any one of claims 28-30, wherein, The 3D heat-bendable microcrystalline glass, or the 3D microcrystalline glass, is a back panel or part of a back panel of an electronic device.

33. The application of the 3D heat-bendable microcrystalline glass according to any one of claims 1-11, or the 3D heat-bendable microcrystalline glass according to any one of claims 12-18, or the 3D microcrystalline glass according to any one of claims 19-26, or the 3D microcrystalline glass article according to claim 27, in electronic devices.

34. The use of the 3D heat-bendable microcrystalline glass according to any one of claims 1-11, or the 3D heat-bendable microcrystalline glass according to any one of claims 12-18, or the 3D microcrystalline glass according to any one of claims 19-26, or the 3D microcrystalline glass article according to claim 27, in the housing of electronic devices.

35. The application of the 3D heat-bendable microcrystalline glass according to any one of claims 1-11, or the 3D heat-bendable microcrystalline glass according to any one of claims 12-18, or the 3D microcrystalline glass according to any one of claims 19-26, or the 3D microcrystalline glass article according to claim 27, in the back panel of a mobile phone.

Images