3D hot-bendable glass ceramic, and preparation method therefor and use thereof

Abstract

The present disclosure belongs to the technical field of glass ceramic materials, and particularly relates to 3D hot-bendable glass ceramic, and a preparation method therefor and the use thereof. The present disclosure provides 3D hot-bendable glass ceramic, which comprises a petalite crystal phase, a lithium disilicate crystal phase and a quartz crystal phase. The total crystal phase content of the 3D hot-bendable glass ceramic is 40%-70%, wherein the sum of the content of the petalite crystal phase and the lithium disilicate crystal phase accounts for 50%-70% of the content of the total crystal phase, and the content of the quartz crystal phase accounts for 4%-10% of the content of the total crystal phase. In the present disclosure, by controlling the 3D hot-bendable glass ceramic to comprise a petalite crystal phase, a lithium disilicate crystal phase and a quartz crystal phase before hot bending, and controlling the proportion of each crystal phase to be within an appropriate range, the glass ceramic exhibits a pleasant white appearance, and it is ensured that same can be subjected to 3D hot bending forming at 810°C, so that the 3D glass ceramic can be prepared, and a three-dimensional product can be machined.

Description

3D hot bendable glass-ceramics and preparation method and application thereof

[0001] Cross-reference to Related Applications

[0002] The present disclosure claims priority to the Chinese patent application No. 202410417328.7, filed on April 08, 2024, entitled "3D hot bendable glass-ceramics and preparation method and application thereof", the entire content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure belongs to the technical field of glass-ceramics materials, in particular, relates to a 3D hot bendable glass-ceramics and a preparation method and application thereof. BACKGROUND

[0004] The shell of a portable terminal device, if composed of composite materials such as plastics and resins, has problems such as poor heat dissipation and easy scratching during use; if composed of ceramic materials, it has problems such as high density, poor impact resistance, and increased weight of the mobile phone.

[0005] Glass-ceramics can obtain rich and colorful colors through composition and process control, and exhibit a gorgeous appearance, thus becoming the best choice for portable electronic device cover materials in the market. However, the semi-transparent white glass made of glass-ceramics has problems such as large grain size, which leads to crack generation, high thermal expansion softening point, poor mechanical properties such as hot bending, dropping, and other properties, and inability to perform 3D forming. In addition, as a mobile phone back plate material, if the deformation amount of the glass-ceramics is large, the internal parts of the terminal are easily damaged.

[0006] In view of this, the present disclosure is proposed. SUMMARY

[0007] The present disclosure provides a 3D hot bendable glass-ceramics and a preparation method thereof to solve the above technical problems.

[0008] Specifically, the present disclosure provides the following technical solutions:

[0009] In a first aspect, the present disclosure provides a 3D hot bendable glass-ceramics, the crystal phase of the 3D hot bendable glass-ceramics includes 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 contents of the petalite crystal phase and the lithium disilicate crystal phase accounts for 50%-70% of the total crystal phase content, and the content of the quartz crystal phase accounts for 4%-10% of the total crystal phase content.

[0010] In a second aspect, the present disclosure provides a preparation method of the above-mentioned 3D hot bendable glass-ceramics, the preparation method includes the following steps:

[0011] Step 1: mixing raw materials for preparing glass, melting, and then cooling to obtain a base glass after annealing treatment;

[0012] Step 2: performing nucleation treatment on the base glass obtained in Step 1;

[0013] Step 3: performing crystallization treatment on the base glass after nucleation in Step 2 to obtain a 3D heat-bendable glass-ceramic.

[0014] In a third aspect, the present disclosure provides a 3D glass-ceramic prepared by performing a 3D heat-bending process on the 3D heat-bendable glass-ceramic or the 3D heat-bendable glass-ceramic prepared by the method described above.

[0015] In a fourth aspect, the present disclosure provides a 3D glass-ceramic product prepared by performing chemical strengthening treatment on the 3D glass-ceramic described above.

[0016] In a fifth aspect, the present disclosure provides an electronic device comprising the heat-bendable glass-ceramic or the heat-bendable glass-ceramic prepared by the method described above or the 3D glass-ceramic or the 3D glass-ceramic product described above; optionally, the electronic device comprises a mobile phone, a tablet computer, a notebook computer, a television, or a display device; optionally, the heat-bendable glass-ceramic or the 3D glass-ceramic is used as a housing or a part of a housing of the electronic device, or is used as a backboard or a part of a backboard of the electronic device.

[0017] In a sixth aspect, the 3D heat-bendable glass-ceramic or the 3D heat-bendable glass-ceramic prepared by the method described above or the 3D glass-ceramic or the 3D glass-ceramic product described above is used in an electronic device, optionally in a housing of the electronic device, or in a backboard of a mobile phone.

[0018] Advantages of the present disclosure:

[0019] The present disclosure controls the generation of quartz grains in the primary crystallization manner before heat bending of the 3D heat-bendable glass-ceramic, and the size and volume are controllable, so that the glass exhibits white color (white appearance according to L*a*b* values) and good mechanical properties, ensuring that it can be 3D heat-bent at 810℃, and 3D glass-ceramics and three-dimensional products can be prepared.

[0020] The present disclosure controls the crystal phase composition of the 3D heat-bendable glass-ceramic, so that it continues to crystallize during heat bending treatment, and the proportion of each crystal phase after heat bending treatment, especially the proportion of quartz crystal phase, is controlled in a suitable range, so that the prepared 3D glass-ceramic still has a white appearance, and has good mechanical properties and dimensional stability. BRIEF DESCRIPTION OF DRAWINGS

[0021] FIG. 1 is a thermal expansion coefficient curve of the white glass-ceramic of Example 3;

[0022] Figure 2 is a picture of the white glass-ceramic prepared in Example 3 after heat bending at 810°C;

[0023] Figure 3 is a picture of the white glass-ceramic prepared in Comparative Example 2 after heat bending at 810°C;

[0024] Figure 4 is a scanning electron microscope picture of the glass-ceramic of Example 3 before heat bending;

[0025] Figure 5 is a scanning electron microscope picture of the glass-ceramic of Example 3 after heat bending;

[0026] Figure 6 is a scanning electron microscope picture of the glass-ceramic of Comparative Example 2 before heat bending;

[0027] Figure 7 is a scanning electron microscope picture of the glass-ceramic of Comparative Example 5 before heat bending;

[0028] Figure 8 is a scanning electron microscope picture of the glass-ceramic of Comparative Example 5 after heat bending;

[0029] Figure 9 is an XRD pattern of the white glass-ceramic of Example 3 before and after heat bending;

[0030] Figure 10 is an XRD pattern of the white glass-ceramic of Comparative Example 2 before heat bending;

[0031] Figure 11 is an XRD pattern of the white glass-ceramic of Comparative Example 5 before and after heat bending. DETAILED DESCRIPTION

[0032] In the present disclosure, unless otherwise specified in a specific case, the numerical ranges listed herein include the upper and lower limit values, “above” and “below” include the end point values, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As referred to herein, “and / or” is inclusive, for example, “A; and / or B” means only A, or only B, or both A and B.

[0033] In a first aspect, the present disclosure provides a 3D heat-bendable glass-ceramic, the crystal phase of the 3D heat-bendable glass-ceramic comprising petalite (LiAlSi4O 10 ) crystal phase, lithium disilicate (Li2Si2O5) crystal phase and quartz crystal phase, the total crystal phase content of the 3D heat-bendable glass-ceramic being 40%-70%, wherein the sum of the content of the petalite crystal phase and the lithium disilicate crystal phase accounts for 50%-70% of the total crystal phase content, and the content of the quartz crystal phase accounts for 4%-10% of the total crystal phase content.

[0034] In some embodiments of the present disclosure, the total crystalline phase content of the 3D hot bendable glass-ceramics is 40-70%, or 45-60%. In some embodiments of the present disclosure, the total crystalline phase content of the 3D hot bendable glass-ceramics can be 40%, 42%, 43%, 45%, 48%, 50%, 55%, 60%, 65%, 68%, or 70%, or within a range between any two of the foregoing values.

[0035] In some embodiments of the present disclosure, the quartz crystalline phase is β-quartz. In some embodiments of the present disclosure, the content of the quartz crystalline phase in the 3D hot bendable glass-ceramics can account for 4-10%, 4-9%, 4-8%, 5-10%, 6-10%, or 7-10% of the total crystalline phase content. In some embodiments of the present disclosure, the content of the quartz crystalline phase can account for 4%, 5%, 6%, 7%, 8%, 9%, or 10% of the total crystalline phase content, or within a range between any two of the foregoing values. It should be understood that in specific embodiments, any of the foregoing ranges can be combined with any other range.

[0036] It should be noted that the A crystalline phase+B crystalline phase content ratio refers to the percentage of the sum of the crystalline phase content of the A crystalline phase+B crystalline phase to the total crystalline phase content of the glass-ceramics; the C crystalline phase content ratio refers to the percentage of the crystalline phase content of the C crystalline phase to the total crystalline phase content of the glass-ceramics; the D crystalline phase content ratio refers to the percentage of the crystalline phase content of the D crystalline phase to the total crystalline phase content of the glass-ceramics; and the E crystalline phase content ratio refers to the percentage of the crystalline phase content of the E crystalline phase to the total crystalline phase content of the glass-ceramics.

[0037] In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics further comprises a lithium silicate (Li2SiO3) crystalline phase. In some embodiments of the present disclosure, 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 the present disclosure, 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 within a range between any two of the foregoing values. It should be understood that in specific embodiments, any of the foregoing ranges can be combined with any other range.

[0038] In some embodiments of the disclosure, the total content of the eucryptite (LiAlSiO4) and the lithium disilicate (Li2Si2O5) crystal phases in the 3D hot bendable glass-ceramic can be 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 crystal phase content. In some embodiments of the disclosure, the total content of the eucryptite (LiAlSiO4) and the lithium disilicate (Li2Si2O5) crystal phases in the 3D hot bendable glass-ceramic can be 50%, 52%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 62%, 64%, 66%, 68%, or 70% of the total crystal phase content, or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range. 10 ) crystal phase and the lithium disilicate (Li2Si2O5) crystal phase can be 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 crystal phase content. In some embodiments of the disclosure, the total content of the eucryptite (LiAlSiO4) 10 ) crystal phase and the lithium disilicate (Li2Si2O5) crystal phase can be 50%, 52%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 62%, 64%, 66%, 68%, or 70% of the total crystal phase content, or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0039] In some embodiments of the disclosure, the 3D hot bendable glass-ceramic further comprises a spodumene (LiAlSi2O6) crystal phase. In some embodiments of the disclosure, the content of the spodumene crystal phase in the 3D hot bendable glass-ceramic can be 0-11%, 1-11%, 3-11%, 5-10%, 3-9%, or 6-9% of the total crystal phase content. In some embodiments of the disclosure, the content of the spodumene (LiAlSi2O6) crystal phase can be 0%, 1%, 2%, 3%, 5%, 8%, 10%, or 11% of the total crystal phase content; or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0040] In some embodiments of the disclosure, the average grain size of the 3D hot bendable glass-ceramic is 20-40 nm, optionally 25-38 nm. In some embodiments of the disclosure, the average grain size of the 3D hot bendable glass-ceramic 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 within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0041] In the present disclosure, the thickness t of the 3D heat-bendable glass-ceramic is not particularly limited, for example, it can be 0.4 mm to 2.0 mm; alternatively, it can be 0.4 mm to 1.0 mm. In some embodiments of the present disclosure, the thickness t of the 3D heat-bendable glass-ceramic 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.

[0042] In some embodiments of the present disclosure, the 3D heat-bendable glass-ceramic has an expansion softening point of less than or equal to 810°C; alternatively, it has an expansion softening point of 650°C to 810°C. In some embodiments of the present disclosure, the 3D heat-bendable glass-ceramic has an expansion softening point of 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 within 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.

[0043] In some embodiments of the present disclosure, the 3D heat-bendable glass-ceramic has a light transmittance at a wavelength of 550 nm of between 30% and 50% at a thickness of 0.60 mm. In some embodiments of the present disclosure, the 3D heat-bendable glass-ceramic has a light transmittance at a wavelength of 550 nm of 30%, 35%, 38%, 40%, 43%, 45%, 48%, or 50% at a thickness of 0.60 mm, or within 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.

[0044] In some embodiments of the present disclosure, the 3D heat-bendable glass-ceramic has color coordinates in reflection mode of L* being 70-82, a* being -4-2, and b* being -12.00-5.00; alternatively, the 3D heat-bendable glass-ceramic has color coordinates in reflection mode of L* being 72-82, a* being -3.62-4, and b* being -11.31-4.00; alternatively, the 3D heat-bendable glass-ceramic has color coordinates in reflection mode of L* being 74-80, a* being -3.00-3.00, and b* being -10.00-3.00.

[0045] In some embodiments of the present disclosure, the 3D heat-bendable glass-ceramic has a composition comprising, in mole percent on an oxide basis:

[0046] Si02: 60-73%, AI2O3: 4-6%, P205: 0-2%, Zr02: 1-3%, Na20: 0.1-4%, K20: 0-1%, Li20: 14-23%, CaO: 0-1.5%, and B203: 0.1-5%.

[0047] Alternatively, in mole percent of oxides, the composition of the 3D hot-bent microcrystalline glass can contain:

[0048] Si02: 60-73%, AI2O3: 4-6%, P205: 0-2%, Zr02: 1-3%, Na20: 1-4%, K20: 0-1%, Li20: 14-23%, CaO: 0-1.5%, and B203: 1-5%.

[0049] Si02is an oxide that forms a glass network backbone, can stabilize the network structure of the glass and glass-ceramics, and can form lithium silicate, petalite, and quartz crystal phases in the lithium-aluminum-silicon system. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics include, in mole percent of oxides, from 60.00 mol% to 73.00 mol%, from 60.00 mol% to 72.00 mol%, from 60.00 mol% to 71.00 mol%, from 60.00 mol% to 70.00 mol%, from 60.00 mol% to 69.00 mol%, from 60.00 mol% to 68.00 mol%, from 60.00 mol% to 67.00 mol%, from 60.00 mol% to 66.00 mol%, from 60.00 mol% to 65.00 mol%, from 61.00 mol% to 73.00 mol%, from 62.00 mol% to 73.00 mol%, from 63.00 mol% to 73.00 mol%, from 64.00 mol% to 73.00 mol%, from 65.00 mol% to 73.00 mol%, from 66.00 mol% to 73.00 mol%, from 67.00 mol% to 73.00 mol%, from 68.00 mol% to 73.00 mol%, from 69.00 mol% to 73.00 mol%, or from 70.00 mol% to 73.00 mol% of Si02. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics include, in mole percent of oxides, 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 Si02, or a value of Si02within a range bounded by any two of the foregoing specific values. It should be appreciated that any of the foregoing ranges can be combined with any of the other ranges in specific embodiments.

[0050] Al2O3 can form a glass framework and is an indispensable component for forming petalite. In some embodiments of the disclosure, the 3D hot bendable glass-ceramics can include 4.00-6.00, 4.50-6.00, 5.00-6.00, 4.00-5.50, or 4.00-5.00 mol% Al2O3, in terms of mole percent of oxides. In some embodiments of the disclosure, the 3D hot bendable glass-ceramics can include 4.00, 4.10, 4.20, 4.50, 4.60, 4.70, 4.80, 5.00, 5.50, 5.70, 5.80, 5.90, or 6.00 mol% Al2O3, in terms of mole percent of oxides; or Al2O3 within a numerical range formed by any two of the foregoing specific numerical values as endpoints. It should be understood that in specific embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0051] P2O5 is a glass former oxide, which exists in the network structure as a phosphorus oxygen tetrahedron [PO4], can non-uniformly nucleate in the glass, promote crystal formation, and is beneficial to improving the uniformity of the glass-ceramics and the corrosion resistance and thermal resistance of the glass. In some embodiments of the disclosure, the 3D hot bendable glass-ceramics can include 0.00-2.00, 0.00-1.50, 0.00-1.00, 0.00-0.50, 0.50-2.00, 1.00-2.00, or 1.50-2.00 mol% P2O5, in terms of mole percent of oxides. In some embodiments of the disclosure, the 3D hot bendable glass-ceramics can include 0.20, 0.50, 0.80, 0.90, 1.00, 1.30, 1.50, or 2.00 mol% P2O5, in terms of mole percent of oxides; or P2O5 within a numerical range formed by any two of the foregoing specific numerical values as endpoints. It should be understood that in specific embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0052] Li2O is an essential component of the microcrystalline glass substrate of the present disclosure, which helps form petalite and lithium silicate crystalline phases, and is also essential for chemical strengthening, which is beneficial to improve the strength, melting and formability of the glass. In some embodiments of the present disclosure, the 3D hot bendable microcrystalline glass includes 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% Li2O, in terms of mole percent of oxides. In some embodiments of the present disclosure, the 3D hot bendable microcrystalline glass includes 14.00, 15.00, 16.00, 17.00, 18.00, 19.00, 20.00, 21.00, 22.00, 23.00, or 24.00 mol% Li2O, in terms of mole percent of oxides; or Li2O within a numerical range formed by any two of the above specific numerical values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range.

[0053] ZrO2can improve the viscosity, hardness, elastic modulus, refractive index, chemical stability of the glass, and reduce the thermal expansion coefficient of the glass. In some embodiments of the present disclosure, the 3D hot bendable microcrystalline glass includes 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, in terms of mole percent of oxides. In some embodiments of the present disclosure, the 3D hot bendable microcrystalline glass includes 0.50, 1.00, 1.50, 1.70, 1.8, 1.90, 2.00, 2.10, 2.20, 2.30, 2.40, 2.50, 2.60, 2.70, or 3.00 mol% ZrO2, in terms of mole percent of oxides; or ZrO2 within a numerical range formed by any two of the above specific numerical values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range.

[0054] Na2O is a glass network modifier oxide that can provide free oxygen to increase the SiO2 / O ratio in the glass structure, and can function to adjust grain size, among other things. In some embodiments of the disclosure, the 3D heat bendable glass-ceramic comprises 0.10-4.00, 0.50-4.00, 1.00-4.00, 1.50-4.00, 2.00-4.00, 3.00-4.00, 0.10-3.50, 0.10-3.00, 0.10-2.50, 0.10-2.00, 0.10-1.50, or 0.10-1.00 mol% Na2O, based on mole percent of oxides. In some embodiments of the disclosure, the 3D heat bendable glass-ceramic comprises 0.10, 0.20, 0.30, 1.00, 1.10, 1.50, 1.60, 1.90, 2.00, 2.50, 2.90, 3.00, 3.10, 3.50, 3.60, or 4.00 mol% Na2O, based on mole percent of oxides; or Na2O within a range having a minimum value selected from any two of the foregoing values, and a maximum value selected from any two of the foregoing values. It will be appreciated that in specific embodiments, any of the foregoing ranges can be combined with any other range.

[0055] K2O is a network modifier oxide that can help improve the low temperature melting and formability of the base glass. In some embodiments of the disclosure, the 3D heat bendable glass-ceramic comprises 0.00-1.00, 0.00-0.80, 0.00-0.50, 0.10-1.00, 0.20-1.00, or 0.50-1.00 mol% K2O, based on mole percent of oxides. In some embodiments of the disclosure, the 3D heat bendable glass-ceramic comprises 0.10, 0.20, 0.50, or 1.00 mol% K2O, based on mole percent of oxides; or K2O within a range having a minimum value selected from any two of the foregoing values, and a maximum value selected from any two of the foregoing values. It will be appreciated that in specific embodiments, any of the foregoing ranges can be combined with any other range.

[0056] B2O3 can improve the physical and chemical properties of the glass, while reducing the melting point and viscosity of the glass, and increasing the transparency of the glass. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramic comprises 0.10-5.00, 0.50-5.00, 1.00-5.00, 1.50-5.00, 2.00-5.00, 2.50-5.00, 3.00-5.00, 0.10-4.50, 0.10-4.00, 0.10-3.50, 0.10-3.00, 0.10-2.50, or 0.10-2.00 mol% B2O3, in terms of mole percent of oxides. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramic comprises 0.10, 0.20, 0.30, 1.00, 1.50, 1.60, 1.90, 2.00, 2.50, 2.60, 2.90, 3.00, 3.50, 3.80, 3.90, or 4.00 mol% B2O3, in terms of mole percent of oxides; or B2O3 within a numerical range formed by any two of the above specific numerical values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range.

[0057] CaO can increase the chemical stability and mechanical strength of the glass, and can reduce the viscosity of the glass, improving the melting and forming properties of the glass. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramic comprises 0.00-1.50, 0.00-1.00, 0.00-0.50, 0.20-1.50, 0.5-1.50, or 1.00-1.50 mol% CaO, in terms of mole percent of oxides. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramic comprises 0.10, 0.30, 0.40, 0.50, 0.70, 0.80, 1.00, 1.10, 1.20, 1.30, or 1.50 mol% CaO, in terms of mole percent of oxides; or CaO within a numerical range formed by any two of the above specific numerical values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range.

[0058] In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics have a total crystalline phase content of 60-90% after 3D hot bending. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics are 3D hot bent at a temperature of 810°C.

[0059] The 3D hot bendable glass-ceramics can have a total crystalline phase content of 60%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 87%, 89%, or 90% after 3D hot bending, or within a range defined by any two of the foregoing specific numerical values as endpoints. It should be appreciated that any of the foregoing ranges can be combined with any of the other ranges in specific embodiments.

[0060] In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics have a total crystalline phase content of 60-90% after 3D hot bending. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics are 3D hot bent at a temperature of 810°C.

[0061] In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics further include lithium metasilicate (Li2SiO3) crystalline phase after 3D hot bending. In some embodiments of the present disclosure, the lithium metasilicate (Li2SiO3) crystalline phase can have a content of 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 the present disclosure, the lithium metasilicate (Li2SiO3) crystalline phase can have a content of 20%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 34%, 36%, 38%, or 40% of the total crystalline phase content; or within a range defined by any two of the foregoing specific numerical values as endpoints. It should be appreciated that any of the foregoing ranges can be combined with any of the other ranges in specific embodiments.

[0062] In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics after 3D hot bending further comprises a spodumene (LiAlSi2O6) crystalline phase. In some embodiments of the present disclosure, the content of the spodumene (LiAlSi2O6) crystalline phase can be 0%-15%, 1%-15%, 3%-15%, 5%-14%, 3%-10% or 6%-9% of the total crystalline phase content. In some embodiments of the present disclosure, the content of the spodumene (LiAlSi2O6) crystalline phase can be 0%, 2%, 3%, 5%, 8%, 10%, 12%, 14% or 15% of the total crystalline phase content; or within a range between any two of the above specific numerical values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range.

[0063] In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics after 3D hot bending has an average grain size of 35-50 nm, which can be 35-48 nm. In some embodiments of the present disclosure, the 3D hot bendable glass-ceramics after 3D hot bending can have an average grain size of 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 within a range between any two of the above specific numerical values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range.

[0064] In a second aspect, the present disclosure provides a method for preparing the 3D hot bendable glass-ceramics as described above, comprising the following steps:

[0065] Step 1: mixing and melting the raw material components for preparing the base glass, and then forming, cooling and annealing to obtain the base glass;

[0066] Step 2: subjecting the base glass obtained in step 1 to nucleation treatment and crystallization treatment to obtain the 3D hot bendable glass-ceramics.

[0067] In the preparation method of the present disclosure, in step 1, the raw material components for preparing the base glass further comprise a fining agent, which comprises one or more than two of NaCl, Na2SO4, SnO2, As2O3, Sb2O3, NaNO3, KNO3, CeO2 and (NH4)2SO4; and can be one or more than two of NaCl, SnO2, NaNO3 and CeO2.

[0068] In the preparation method of the present disclosure, in step 1, the melting temperature is 1350-1700°C, and the cooling temperature after melting can be 500-1000°C.

[0069] In the preparation method of the present disclosure, in step 2, the temperature of the nucleation treatment is 520-590°C, and the time of the nucleation treatment is optionally 30-600 min. In the preparation method of the present disclosure, in step 2, the temperature of the nucleation treatment can be 520°C, 540°C, 550°C, 560°C, 570°C, 580°C or 590°C, or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range. In the preparation method of the present disclosure, in step 2, the time of the nucleation treatment 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 within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0070] In some embodiments of the present disclosure, in step 3, the temperature of the crystallization treatment is 640-750°C, and the time of the crystallization treatment is optionally 20-600 min. In the preparation method of the present disclosure, in step 3, the temperature of the crystallization treatment can be 640°C, 680°C, 690°C, 700°C, 720°C, 740°C or 750°C, or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range. In the preparation method of the present disclosure, in step 3, the time of the crystallization treatment 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 within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0071] In a third aspect, the present disclosure provides a 3D heat-bendable glass-ceramic prepared by subjecting the 3D heat-bendable glass-ceramic as described above or the 3D heat-bendable glass-ceramic prepared by the preparation method of the 3D heat-bendable glass-ceramic as described above to a 3D heat-bending process.

[0072] In some embodiments of the present disclosure, the 3D glass-ceramics comprises petalite crystal phase, lithium disilicate crystal phase and quartz crystal phase, and the total crystal phase content is 60-90%, wherein the content of petalite crystal phase and lithium disilicate crystal phase is 45-60% of the total crystal phase content, and the content of quartz crystal phase is 15-22% of the total crystal phase content.

[0073] In some embodiments of the present disclosure, the total crystal phase content of the 3D glass-ceramics can be 60%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 87%, 89% or 90%, or 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.

[0074] In some embodiments of the present disclosure, the content of petalite (LiAlSi4O 10 ) crystal phase and lithium disilicate (Li2Si2O5) crystal phase in the 3D glass-ceramics can be 45-60%, 48-60%, 50-60%, 45-58%, 46-55%, 45-50% or 55-60% of the total crystal phase content. In some embodiments of the present disclosure, the content of petalite (LiAlSi4O 10 ) and lithium disilicate (Li2Si2O5) can be 45%, 48%, 50%, 52%, 54%, 55%, 56%, 57%, 58%, 59% or 60% of the total crystal phase content, or 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.

[0075] In some embodiments of the present disclosure, the quartz crystal phase is β-quartz. In some embodiments of the present disclosure, the content of quartz crystal phase in the 3D glass-ceramics can be 15-22%, 15-20%, 15-18%, 16-22% or 16-20% of the total crystal phase content. In some embodiments of the present disclosure, the content of quartz crystal phase can be 15%, 16%, 17%, 18%, 19%, 20% or 22% of the total crystal phase content, or 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.

[0076] In some embodiments of the present disclosure, the 3D glass-ceramics further comprise lithium metasilicate (Li2SiO3) crystalline phase. In some embodiments of the present disclosure, the lithium metasilicate (Li2SiO3) crystalline phase can have a content of 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 the present disclosure, the lithium metasilicate (Li2SiO3) crystalline phase can have a content of 20%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 34%, 36%, 38%, or 40% of the total crystalline phase content; or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0077] In some embodiments of the present disclosure, the 3D glass-ceramics further comprise spodumene (LiAlSi2O6) crystalline phase. In some embodiments of the present disclosure, the spodumene (LiAlSi2O6) crystalline phase can have a content of 0-15%, 1-15%, 3-15%, 5-14%, 3-10%, or 6-9% of the total crystalline phase content. In some embodiments of the present disclosure, the spodumene (LiAlSi2O6) crystalline phase can have a content of 0%, 2%, 3%, 5%, 8%, 10%, 12%, 14%, or 15% of the total crystalline phase content; or within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0078] In some embodiments of the present disclosure, the 3D glass-ceramics have an average crystalline grain size of 35-50 nm, optionally 35-47 nm. In some embodiments of the present disclosure, the 3D glass-ceramics can have an average crystalline grain size of 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 within a range between any two of the above-mentioned specific values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range.

[0079] In the present disclosure, the thickness t of the 3D glass-ceramics is not particularly limited, for example, it can be 0.4 mm-2.0 mm; alternatively, it can be 0.4 mm-1.0 mm. In some embodiments of the present disclosure, the thickness t of the 3D glass-ceramics 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 end points. 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 the present disclosure, the light transmittance of the 3D glass-ceramics at a wavelength of 550 nm is between 15%-35% at a thickness of 0.60 mm. In some embodiments of the present disclosure, the light transmittance of the 3D glass-ceramics at a wavelength of 550 nm can be 15%, 17%, 19%, 20%, 23%, 25%, 28%, 30%, 32%, 33%, or 35%, or within a numerical range formed by any two of the above values as end points. 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 the present disclosure, the color coordinates of the 3D glass-ceramics in reflection mode are: L* is 70-81, a* is -2.60-0.00, and b* is -7-1; alternatively, the color coordinates of the 3D glass-ceramics in reflection mode are: L* is 72-81, a* is -2.21-0, and b* is -6.60-1; alternatively, the color coordinates of the 3D glass-ceramics in reflection mode are: L* is 74-81, a* is -2.00-0, and b* is -6.00-1.

[0082] In some embodiments of the present disclosure, the X-axis shrinkage of the 3D glass-ceramics is less than or equal to 1%, alternatively, less than or equal to 0.5%, alternatively, less than or equal to 0.49%.

[0083] In some embodiments of the present disclosure, the Y-axis shrinkage of the 3D glass-ceramics is less than or equal to 0.5%, alternatively, less than or equal to 0.35%, alternatively, less than or equal to 0.30%, alternatively, less than or equal to 0.25%.

[0084] In a fourth aspect, the present disclosure provides a method for preparing the 3D glass-ceramics as described above, comprising the following steps: preparing the 3D glass-ceramics by subjecting the 3D heat-bendable glass-ceramics to 3D heat bending treatment.

[0085] In the method for preparing the 3D glass-ceramics of the present disclosure, the heat bending treatment is accompanied by a continuous crystallization process. Alternatively, the temperature of the heat bending treatment is 810°C.

[0086] In a fifth aspect, the present disclosure also provides a 3D glass-ceramic article, which is obtained by chemically strengthening the 3D glass-ceramic as described above.

[0087] The present disclosure does not limit the conditions for chemical strengthening, as long as the conditions are common in the art and can achieve the performance of the present disclosure.

[0088] In a sixth aspect, the present disclosure also provides the use of the 3D heat-bendable glass-ceramic or the 3D glass-ceramic or the 3D glass-ceramic article as described above in an electronic device, which can be optionally in the housing of the electronic device.

[0089] In some embodiments of the present disclosure, the electronic device includes one or more of a mobile phone, a tablet computer, a notebook computer, a television, and a display device.

[0090] Terminology:

[0091] Base glass: a glass that has not been subjected to nucleation treatment, crystallization treatment, and strengthening treatment.

[0092] Glass-ceramic: also known as glass ceramic, is a kind of solid composite material containing both glass phase and crystal phase (microcrystalline phase, crystalline phase) prepared by targeted and controlled crystallization of base glass.

[0093] Nucleation: the growth of small crystal nuclei from nucleating substances in glass through heat treatment.

[0094] Crystallization: the growth of certain crystals in glass based on crystal nuclei through heat treatment.

[0095] Opacification: refers to the complete loss of the transparent properties of glass-ceramic / glass ceramic due to large crystals or phase separation, and the inability to see any picture on the back through the glass.

[0096] Crystallinity: refers to the percentage of the total mass of crystal phase / crystals in glass-ceramic to the mass of glass-ceramic, i.e., the total content of crystal phase in glass-ceramic.

[0097] L value: represents the specular reflection light (SCI) L value, which indicates the brightness of the material. A positive L value indicates a white bias, and a negative L value indicates a black bias.

[0098] a value: represents the specular reflection light a value, which indicates the red-green value of the material. A positive a value indicates a red bias, and a negative a value indicates a green bias.

[0099] b value: represents the yellow-blue value of the material. The transmission light is used to test the b value, which increases: the optical b value in the present disclosure is the transmission light b value. A positive optical b value indicates a blue bias.

[0100] Expansion softening point: the temperature at which the glass softens. It refers primarily to the temperature at which the glass begins to soften.

[0101] Deformation amount: the deformation amount refers to the amount of deformation of the glass. An object is said to "deform" when it changes shape under an external force.

[0102] Primary recrystallization: the process is essentially the nucleation and growth of new strain-free grains.

[0103] Secondary recrystallization: refers to the abnormal growth of secondary grains on the basis of the grains after primary recrystallization. Strictly speaking, it is a grain growth process under special conditions, not a primary recrystallization process.

[0104] The glass of the present disclosure is tested by the following method:

[0105] Differential scanning calorimetry (DSC) test

[0106] The instrument used is Mettler Toledo TGA / DSC 3+ simultaneous thermal analyzer, and the test is performed according to JY / T 0589.5-202. The standard substance used for testing is α-Al2O3 powder, and the container for placing the sample is a platinum crucible. The instrument is placed in an environment with a temperature of 24°C and an air humidity of 40%. The glass is ground and sieved through a 200-mesh sieve to obtain the sample to be tested. About 20 mg of the sample is weighed and heated from room temperature to 900°C at a heating rate of 10°C / min under a nitrogen protective atmosphere to obtain the DSC curve of the sample.

[0107] Test of total crystalline phase content and content of each specific crystalline phase

[0108] The glass-ceramic sample is crushed and ground into a sample with a particle size of less than 75 μm. The glass-ceramic sample is tested using an X-ray diffractometer to obtain an XRD diffraction peak curve. Then, the X-ray diffractometer (Shimadzu XRD-6100) test result file (RAW format) X-ray diffraction data Rietveld refinement software (such as Jade, Maud, High score) is used for fitting and calculation 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 the present disclosure is Shimadzu XRD-6100. The incident angle range used for testing is 2θ = 10-50, the scanning speed is 3° / min, the working voltage is 40 kV, and the working current is 30 mA.

[0109] Test of average grain size

[0110] The average grain size of the sample can be calculated according to the Scherrer formula D = Kλ / (βcosθ) using the data obtained from the XRD test. Wherein, λ is the X-ray wavelength, λ = 0.154056 nm, β is the half-height width of the diffraction peak, K = 0.89, and θ is the Bragg diffraction angle. Specifically, the RAW file (diffraction pattern) output by the XRD instrument is curve-fitted in the Jade software, and the Jade outputs a fitting report. According to the angle 2θ value and the Peak FWHM value (half-height width of the diffraction peak) corresponding to each diffraction peak in the fitting report, and the Peak FWHM value is converted to radian: β = (FWHM / 180*3.14), the grain size of each diffraction peak is calculated by the Scherrer formula D = Kλ / (βcosθ), and the average grain size is obtained by taking the average value.

[0111] Thickness test

[0112] Determined by a laser thickness tester.

[0113] CIE L*a*b* parameter test

[0114] The present disclosure adopts Konica Minolta's spectrophotometer CM-3600A test, and is connected to Spectra Magic NX spectral analysis software. The test results are converted into CIELAB color space coordinates (L*; a*; and b*) in reflection mode based on D65 light source and 10-degree standard observation angle, and the measurement area is LAV (25.4 mm).

[0115] Five pieces of glass under the same conditions were tested respectively, and the average value of each test result was taken as the L* value, a* value and b* value of the glass-ceramic.

[0116] Light transmittance test

[0117] The light transmittance of the glass at a wavelength of 550 nm was tested using a Shimadzu UV-2000 ultraviolet-visible spectrophotometer. Five pieces of glass under the same conditions were tested respectively, and the average value of each test result was taken as the light transmittance of the glass measured at a wavelength of 550 nm.

[0118] Single-rod static pressure test

[0119] The glass sample to be tested was placed on the bottom ring of a tensile testing machine (LT-850A), the test software was started, and the moving speed of the extrusion rod (rod diameter 8 mm, indenter arc radius 10 mm) was set to 50 mm / min. Click to start the test, and the extrusion rod 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.

[0120] The test software will automatically read the force (N) when the glass sample breaks as the test result.

[0121] Take 10 pieces of glass samples under the same conditions for testing, take the average value of the test results as the average single rod static pressure strength of the glass sample to be tested.

[0122] Test of glass dilatant softening point

[0123] The sample is made into a cylinder with a diameter of 5.5 mm and a length of 20 mm, and the sample is tested using a thermal dilatometer LINSEIS L75VD1000, the test temperature is room temperature~900℃, the heating rate is 10℃ / min;

[0124] After the test is completed, the thermal expansion coefficient test curve is output, and when the curve starts to rise and then fall with temperature, the corresponding inflection point temperature is the thermal expansion softening point temperature of the sample.

[0125] The present disclosure will be described in detail below through examples and comparative examples.

[0126] Example 1

[0127] (1) According to the formula of Example 1 in Table 1, each raw material component is accurately weighed in proportion and mixed to obtain a mixture, and the total weight of each raw material component is 1000g; the mixture is placed in a platinum crucible and heated to 1650℃ in a high-temperature smelting furnace for melting, the melting time is 6h, after the bubbles are removed, the glass liquid is poured into a mold for cooling and forming, and after cooling to 900℃, it is placed in a 500℃ annealing furnace for annealing for 24 hours, and then cooled to room temperature with the furnace, to obtain the base glass.

[0128] (2) The base glass obtained in step (1) is heated to a nucleation temperature at a heating rate of 10℃ / min for nucleation treatment; then heated to a crystallization temperature at a heating rate of 10℃ / min for crystallization treatment; to obtain a glass brick. The nucleation temperature, nucleation treatment time, crystallization temperature, and crystallization treatment time are shown in Table 1, respectively.

[0129] (3) The glass brick obtained in step (2) is cut and polished to obtain a 3D heat-bendable microcrystalline glass with a size of 50mm×50mm×0.60mm.

[0130] The 3D heat-bendable microcrystalline glass obtained above is tested for performance, and the results are shown in Tables 2-3.

[0131] (4) The 3D heat-bendable glass-ceramics prepared in step (3) are placed in a 3D heat-bender for heat-bending treatment, and the heat-bending treatment process comprises three preheating stations, three hot-pressing stations and three cooling stations; the temperatures of the three preheating stations are set to 590℃, 680℃ and 810℃ respectively in sequence, the temperatures and pressures of the three hot-pressing stations are set to 810℃ / 0.40MPa, 810℃ / 0.40MPa and 810℃ / 0.20MPa respectively in sequence, and the temperatures of the three cooling stations are set to 810℃, 650℃ and 600℃ respectively in sequence; the residence time of each station is 90s; and the final 3D glass-ceramics is obtained.

[0132] The 3D glass-ceramics obtained above is subjected to performance testing, and the result data are shown in Tables 4-5.

[0133] Examples 2-9 and Comparative Examples 1-4 are operated under the same conditions as Example 1, except that the raw material compositions for preparing the base glass and the nucleation and crystallization conditions shown in Tables 1 and 2 are used.

[0134] The 3D glass-ceramics prepared in Examples 1-9 is subjected to chemical strengthening to obtain 3D glass-ceramic products, and the specific strengthening process is shown in Table 6.

[0135] Table 1 Base glass of Examples 1-9 and Comparative Examples 1-4

[0136] Table 2 3D heat-bendable glass-ceramics of Examples 1-9 and Comparative Examples 1-4

[0137] wherein: A represents LiAlSi4O 10 ; B represents Li2Si2O5; C represents Li2SiO3; D represents β-quartz; and E represents LiAlSi2O6.

[0138] Table 3 Performance parameters of the 3D heat-bendable glass-ceramics of Examples 1-9 and Comparative Examples 1-4

[0139] Table 4 3D glass-ceramics after heat-bending and its performance parameters

[0140] wherein: A represents LiAlSi4O 10 ; B represents Li2Si2O5; C represents Li2SiO3; D represents β-quartz; and E represents LiAlSi2O6.

[0141] Table 5 Performance parameters of the 3D glass-ceramics after heat-bending

[0142] Table 6 Strengthening process conditions and properties of 3D microcrystalline glass of Examples 1-9

[0143] The thermal expansion coefficient curve of the white microcrystalline glass of Example 3 is shown in Figure 1. As can be seen from the thermal expansion coefficient curve of Figure 1, the expansion softening point of the white microcrystalline glass prepared in Example 3 is 676°C.

[0144] The picture of the white microcrystalline glass prepared in Example 3 after heat bending at 810°C is shown in Figure 2, and the picture of the microcrystalline glass prepared in Comparative Example 2 after heat bending at 810°C is shown in Figure 3. As can be seen from Figures 2 and 3, the 3D curved microcrystalline glass prepared in Example 3 has uniform color and is more pleasing to the eye.

[0145] The scanning electron microscope picture of the white microcrystalline glass prepared in Example 3 before heat bending is shown in Figure 4, and the scanning electron microscope picture of the white microcrystalline glass after heat bending at 810°C is shown in Figure 5. As can be seen from Figures 4 and 5, the grain size of the white microcrystalline glass prepared in Example 3 by the primary crystallization method becomes larger after heat bending at 810°C.

[0146] The scanning electron microscope picture of the white microcrystalline glass prepared in Comparative Example 2 before heat bending is shown in Figure 6. As can be seen from the figure, the grain size of the white microcrystalline glass prepared in Comparative Example 2 by the secondary crystallization method is relatively large.

[0147] The scanning electron microscope picture of the white microcrystalline glass prepared in Comparative Example 5 before heat bending is shown in Figure 7. As can be seen from the figure, the grain size of the white microcrystalline glass prepared in Comparative Example 5 is relatively small.

[0148] The scanning electron microscope picture of the white microcrystalline glass prepared in Comparative Example 5 after heat bending is shown in Figure 8. As can be seen from the figure, the grain size of the white microcrystalline glass prepared in Comparative Example 5 becomes slightly larger after heat bending at 810°C, and the glass is still transparent.

[0149] The XRD patterns of the white microcrystalline glass of Example 3 before and after heat bending are shown in Figure 9. As can be seen from Figure 9, the white microcrystalline glass of Example 3 before heat bending contains crystal phases of petalite, lithium disilicate, lithium silicate and quartz, and the white microcrystalline glass of Example 3 after heat bending has more spodumene crystal phase.

[0150] The XRD pattern of the white microcrystalline glass prepared in Comparative Example 2 before heat bending is shown in Figure 10, which contains crystal phases of petalite, lithium disilicate, lithium silicate, quartz and spodumene.

[0151] The XRD patterns of the white microcrystalline glass of Comparative Example 5 before and after heat bending are shown in Figure 11. As can be seen from Figure 11, the transparent microcrystalline glass of Comparative Example 5 only contains petalite and lithium disilicate crystal phases before and after heat bending.

[0152] As shown in Tables 2-4, the crystal phases of the 3D hot bendable glass-ceramics prepared in Examples 1-9 are all eucryptite, lithium disilicate and quartz, and the sum of the contents of eucryptite and lithium disilicate accounts for 45%-70% of the content of the crystal phases, the content of the quartz crystal phase accounts for 4%-10% of the content of the crystal phases, and the dilatometric softening point ranges from 600°C to 800°C. Therefore, the glass-ceramics prepared in Examples 1-9 can be 3D hot bent at 810°C.

[0153] The white glass containing quartz crystal phase prepared by the primary crystallization method in Examples 1-9 contains 50%-70% of the sum of the contents of eucryptite and lithium disilicate and 4%-10% of the content of the quartz crystal phase in the total content of the crystal phases, and the average crystal size ranges from 20 nm to 32 nm. When the thickness is 0.60 mm, L* is 70-82, a* is -4-2, and b* is -12-5, and the white appearance is pleasing to the eye. After the heat bending treatment, the sum of the contents of eucryptite and lithium disilicate accounts for 45%-60% of the total content of the crystal phases, the quartz crystal phase accounts for 15%-22%, the average crystal size ranges from 35 nm to 50 nm, and when the thickness is 0.60 mm, L* is 70-81, a* is -2.60-0.00, and b* is -7-1. The white appearance is also pleasing to the eye.

[0154] In Comparative Examples 1-3, the white glass prepared by the secondary recrystallization method contains 60%-70% of the sum of the contents of eucryptite and lithium disilicate in the total content of the crystal phases, but the content of the quartz crystal phase is much more than 10%, so that the dilatometric softening point of the prepared glass-ceramics is higher than 810°C, and the glass-ceramics cannot be 3D hot bent at 810°C.

[0155] In Comparative Example 4, the sum of the contents of eucryptite and lithium disilicate accounts for 96.5% of the content of the crystal phases, and the content of the quartz crystal phase is only 3.50%, so that the dilatometric softening point is also much higher than 810°C, and the glass-ceramics cannot be 3D hot bent at 810°C.

[0156] In Comparative Example 5, the sum of the contents of eucryptite and lithium disilicate accounts for 100% of the content of the crystal phases, and the content of the quartz crystal phase is 0.00%, the dilatometric softening point is less than 810°C, and the glass-ceramics can be 3D hot bent at 810°C, but the glass appears non-white before and after the heat bending.

[0157] As shown in Tables 4-5, the 3D glass-ceramics prepared in the examples of the present disclosure have a pleasing white appearance (known from the L*a*b* values), and the X-axis shrinkage is less than or equal to 0.5%, and the Y-axis shrinkage is less than or equal to 0.35%, which shows good dimensional stability.

[0158] As shown in Table 6, the 3D microcrystalline glass prepared by the embodiment of the present disclosure can obtain excellent mechanical properties with a single rod static pressure strength greater than 320N after chemical strengthening.

[0159] Finally, it should be pointed out that the above optional embodiments are only used to illustrate the technical solutions of the present disclosure and are not limiting. Although the present disclosure has been described in detail through the above optional embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present disclosure. Industrial applicability

[0160] In summary, the 3D hot-bendable microcrystalline glass provided by the present disclosure has controllable size and volume, has a pleasing white appearance, good mechanical properties, size stability, and three-dimensional processability, and is easy to industrialize and popularize.

Claims

1. A 3D heat-bendable glass-ceramic, characterized in that: The crystalline phases of the 3D heat-bendable microcrystalline glass include petalite crystalline phase, lithium disilicate crystalline phase and quartz crystalline phase. The total crystalline phase content of the 3D heat-bendable microcrystalline glass is 40%-70%, of which the sum of the petalite crystalline phase and the lithium disilicate crystalline phase accounts for 50%-70% of the total crystalline phase content, and the content of the quartz crystal phase accounts for 4%-10% of the total crystalline phase content.

2. The 3D heat-bendable glass-ceramic according to claim 1, characterized in that: The quartz crystal phase is β-quartz; And / or, the 3D heat-bendable glass-ceramics further comprises lithium silicate, and preferably the content of the lithium silicate crystal phase accounts for 20%-40% of the total crystal phase content; And / or, the crystal phase of the 3D heat-bendable glass-ceramics further includes a spodumene crystal phase, and preferably, the content of the spodumene crystal phase can account for 0%-11% of the total crystal phase content.

3. The 3D heat-bendable glass-ceramic according to claim 1 or 2, characterized in that: The grain size of the 3D heat-bendable glass-ceramics is 20nm-40nm; And / or, the expansion softening point of the 3D heat-bendable glass-ceramics is less than or equal to 810° C.; And / or, when the 3D heat-bendable glass-ceramics has a thickness of 0.60 mm, a light transmittance at 550 nm of between 30% and 50%; And / or, the color coordinates of the 3D heat-bendable micro-ceramic glass in reflection mode are: L* is 70-82, a* is -4-2, and b* is -12-5.

4. The 3D heat-bendable glass-ceramic according to any one of claims 1 to 3, characterized in that: The composition thereof, expressed in terms of the content expressed as a molar percentage of oxides, comprises: 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%.

5. The 3D heat-bendable glass-ceramic according to claim 4, characterized in that: The composition thereof, expressed in terms of the content expressed as a molar percentage of oxides, comprises: 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%.

6. The 3D heat-bendable glass-ceramic according to any one of claims 1 to 5, characterized in that: The 3D heat-bendable microcrystalline glass is produced by subjecting substrate glass to nucleation and crystallization treatments.

7. The method for preparing 3D heat-bendable glass-ceramics according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: Step 1: Mix the raw materials for preparing glass, melt them, cool them and perform annealing treatment to obtain the base glass; Step 2: performing a nucleation treatment on the substrate glass obtained in step 1; Step 3: The substrate glass after the nucleation in the above step 2 is crystallized to obtain the microcrystalline glass that can be 3D hot-bent.

8. The preparation method according to claim 7, characterized in that In step 1, the melting temperature is 1350°C-1700°C, and / or the temperature is cooled to 500°C-1000°C after melting.

9. The preparation method according to claim 8, characterized in that In step 1, the melting temperature is 1400°C-1650°C.

10. The preparation method according to any one of claims 7 to 9, characterized in that: In step 2, the temperature of the nucleation treatment is 520° C.-590° C., and / or the nucleation treatment time is 30 min-600 min; And / or, in step 3, the temperature of the crystallization treatment is 640° C.-750° C., and / or the crystallization treatment time is 20 min-600 min.

11. A 3D glass-ceramic, characterized in that: The 3D heat-bendable glass-ceramic according to any one of claims 1 to 6 or the 3D heat-bendable glass-ceramic obtained by the preparation method according to any one of claims 7 to 10 is prepared by a 3D heat-bending process.

12. The 3D glass-ceramics according to claim 11, characterized in that: The 3D microcrystalline glass includes a petalite crystal phase, a lithium disilicate crystal phase and a quartz crystal phase, and its total crystal phase content is 60%-90%, wherein the sum of the content of the petalite 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.

13. The 3D glass-ceramics according to claim 12, characterized in that: The quartz crystal phase is β-quartz, And / or, the 3D glass-ceramics further comprises lithium silicate (Li2SiO3), and preferably the content of the lithium silicate crystal phase accounts for 20%-40% of the total crystal phase content; And / or, the crystal phase of the 3D glass-ceramics further includes a spodumene crystal phase, and preferably, the content of the spodumene crystal phase can account for 0%-15% of the total crystal phase content.

14. The 3D glass-ceramics according to any one of claims 11 to 13, characterized in that: The grain size of the 3D glass-ceramics is 35nm-50nm; And / or, when the 3D glass-ceramics has a thickness of 0.60 mm, a light transmittance at 550 nm of between 15% and 35%; And / or, the color coordinates of the 3D glass-ceramics in 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 glass-ceramics is less than or equal to 1%; And / or, the Y-axis shrinkage of the 3D glass-ceramics is less than or equal to 0.5%; And / or, the single-rod static pressure strength of the 3D microcrystalline glass is greater than 320N.

15. The 3D glass-ceramics according to claim 14, characterized in that: The X-axis shrinkage of the 3D glass-ceramics is less than or equal to 0.5%.

16. The 3D glass-ceramics according to claim 14, characterized in that: The Y-axis shrinkage of the 3D glass-ceramics is less than or equal to 0.35%.

17. A 3D glass-ceramic product, characterized in that: The 3D glass-ceramics is obtained by subjecting the 3D glass-ceramics according to any one of claims 11 to 16 to chemical strengthening treatment.

18. An electronic device comprising the bendable glass-ceramic according to any one of claims 1 to 6, or the bendable glass-ceramic produced by the preparation method according to any one of claims 7 to 10, or the 3D glass-ceramic according to any one of claims 11 to 14, or the 3D glass-ceramic product according to claim 17; and / or, the electronic device is a mobile phone, a tablet computer, a laptop computer, a television, or a display device; And / or, the heat-bendable glass-ceramic or the 3D glass-ceramic is the housing of the electronic device or a part of the housing.

19. The electronic device according to claim 18, wherein: The heat-bendable glass-ceramic or the 3D glass-ceramic is a back panel or a part of a back panel of an electronic device.

20. Use of the heat-bendable glass-ceramic according to any one of claims 1 to 6, or the heat-bendable glass-ceramic prepared by the preparation method according to any one of claims 7 to 10, or the 3D glass-ceramic according to any one of claims 11 to 14, or the 3D glass-ceramic product according to claim 17 in electronic devices, preferably in the housing of electronic devices, more preferably in the back panel of mobile phones.

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