WO2023279819A1 - 化学强化微晶玻璃及其制备方法与应用 - Google Patents

化学强化微晶玻璃及其制备方法与应用 Download PDF

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WO2023279819A1
WO2023279819A1 PCT/CN2022/090015 CN2022090015W WO2023279819A1 WO 2023279819 A1 WO2023279819 A1 WO 2023279819A1 CN 2022090015 W CN2022090015 W CN 2022090015W WO 2023279819 A1 WO2023279819 A1 WO 2023279819A1
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chemically strengthened
strengthened glass
glass
ceramic
ceramics
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PCT/CN2022/090015
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English (en)
French (fr)
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许文彬
陈秋群
赫明刚
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荣耀终端有限公司
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Priority to EP22773381.3A priority Critical patent/EP4137468A4/en
Priority to JP2022557822A priority patent/JP2023537168A/ja
Publication of WO2023279819A1 publication Critical patent/WO2023279819A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/035—Re-forming glass sheets by bending using a gas cushion or by changing gas pressure, e.g. by applying vacuum or blowing for supporting the glass while bending
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the application belongs to the technical field of glass products, and in particular relates to a chemically strengthened glass-ceramic and its preparation method and application.
  • Glass is widely used in daily life due to its own characteristics of transparency and high temperature resistance. For example, glass is widely used in protective devices, decoration and other fields. However, glass also has certain deficiencies, such as weak impact resistance and brittleness, which limit the application of glass in some fields.
  • the cover glass materials in the industry are developing from aluminum-silicon first-strength glass to lithium-aluminum-silicon second-strength glass.
  • the puncture resistance of the cover plate against rough ground is effectively improved.
  • the second-strongest glass in the industry is developing towards the direction of increasing deep stress, and has achieved a generation-by-generation improvement in sandpaper drop.
  • the main body of the second-strength glass is lithium-aluminosilicate glass.
  • the Young's modulus of lithium-aluminosilicate glass is generally ⁇ 80GPa, and the further improvement of its stress strength is limited by the compressive stress storage capacity of the matrix; excessive compressive stress introduces high internal tension. Stress, such as too high tensile stress, will cause the glass failure fragments to be too small ( ⁇ 3mm) or the cover glass to self-explode. Therefore, the improvement of the strength of the second-strength glass is limited by the strength of the body, and the improvement of the drop resistance performance is relatively limited.
  • the cover industry will introduce glass-ceramic as a new development direction of cover glass.
  • the nanocrystals inside the glass-ceramic can resist crack penetration, and the compressive stress introduced by ion exchange can resist crack propagation, which improves the drop resistance of the cover glass through dual effects (see Figure 1 for the mechanism). Therefore, the anti-drop performance on rough ground is qualitatively improved compared with the second-strength glass.
  • the main crystal phases are lithium petalite and lithium disilicate; the strengthening furnace water needs to actively introduce Li 2 O to control the concentration of Na salt on the surface to reduce the temperature at 85° The degree of sodium salt precipitation at 85° humidity.
  • This kind of crystal phase design uses K/Na and Na/Li secondary exchange to achieve strength improvement.
  • the characteristic of the glass-ceramic is that the crystallinity should be relatively high ( ⁇ 85wt%) in order to ensure the excellent optical properties of the original material (transmittance ⁇ 89.5%, absolute value of color difference b ⁇ 0.5, fog degree ⁇ 0.15%).
  • the purpose of this application is to overcome the above-mentioned deficiencies in the prior art, to provide a chemically strengthened glass-ceramic and its preparation method and its application, so as to solve the problem that the compressive stress of the existing aluminosilicate glass and chemically strengthened glass-ceramic is difficult to be further improved, Unsatisfactory technical problems such as anti-drop performance.
  • an aspect of the embodiment of the present application provides a chemically strengthened glass-ceramic.
  • the chemically strengthened glass-ceramic in the embodiment of the present application has a Na/Li exchange layer, and the depth Doc of the compressive stress layer of the chemically strengthened glass-ceramic is 0.15t-0.22t; the compressive stress intensity CS50 at the strengthening depth of the surface layer of the chemically strengthened glass-ceramic is 130+(20t-13) ⁇ 15MPa ⁇ 230+(20t-13) ⁇ 15MPa; and CS50 and Doc meet: CS50/(Doc-50) is 1.4 ⁇ 6, the unit is MPa/ ⁇ m; where, t is chemical strengthening The total thickness of the glass-ceramic.
  • the chemically strengthened glass-ceramics in the embodiment of the present application has a specific compressive stress layer depth, compressive stress intensity, and the relationship between the compressive stress layer depth and the compressive stress intensity, which endows the chemically strengthened glass-ceramic with relatively high compressive stress and stress intensity.
  • the anti-puncture ability of the chemically strengthened glass-ceramic in the embodiment of the present application is significantly improved on rough ground, and the drop height on rough ground is higher than that of the existing aluminosilicate glass and glass-ceramic.
  • the chemically strengthened glass-ceramic is extruded by a metal pressing rod with a round head of 10 mm in diameter until the average size of the longest side of the fragments is greater than or equal to 5 mm when broken.
  • the drop height of sandpaper for chemically strengthened glass-ceramic is ⁇ 1.5m.
  • no sodium salt precipitation occurs on the outer surface of the chemically strengthened glass-ceramic when stored at a temperature of 85° C./humidity of 85% for 72 hours.
  • the thickness of the chemically strengthened glass-ceramic is ⁇ 0.8mm
  • the average light transmittance of 400-940nm wavelength is ⁇ 89.5%
  • the single-point transmittance difference between 550nm and 400nm wavelength is less than 1%
  • chemically strengthened glass-ceramics has the above-mentioned relationship between compressive stress layer depth, compressive stress intensity and compressive stress layer depth and compressive stress intensity
  • chemically strengthened glass-ceramics has excellent resistance to rough ground puncture ability, and has High drop resistance, good heat and humidity stability, and good optical properties such as light transmission.
  • the main crystal phase of the plain glass-ceramics used to form chemically strengthened glass-ceramics is any one of lithium silicate or ⁇ -quartz solid solution, and the mass fraction of the total crystal phase contained is 35-75%, wherein The total content of secondary crystal phase is ⁇ 5%.
  • the Na/Li exchange layer contained in the chemically strengthened glass-ceramics can be effectively prevented from being adversely affected by Li, and the control of the CS50 range can be effectively realized, thereby Further improve the anti-puncture ability of chemically strengthened glass-ceramics on rough ground. At the same time, it can also improve the impact resistance of chemically strengthened glass-ceramics, and has high optical properties such as light transmission.
  • the plain glass-ceramics includes main components and nucleating agents; wherein, the main components include SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfy: SiO 2
  • the main components include SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfy: SiO 2
  • the nucleating agent includes TiO 2 , P 2 O 5 , ZrO 2 , And satisfy: the content of TiO 2 +P 2 O 5 +ZrO 2 is 2-8 mol%.
  • plain glass-ceramics endow plain glass-ceramics and chemically strengthened glass-ceramics with the above-mentioned main crystal phase types and crystal phase content, thereby improving the anti-puncture ability of chemically strengthened glass-ceramics on rough ground and improving the chemical strength of glass-ceramics. Strengthens the optical properties of glass-ceramics such as light transmission.
  • the plain glass-ceramic is prepared by melting casting method or calendering method.
  • the plain glass-ceramic undergoes the following two-step heat treatment:
  • the first step of heat treatment the temperature is 500-600°C, and the treatment time is 0.1-10h;
  • the second step of heat treatment the temperature is 640-800°C, and the treatment time is 0.1-10h.
  • the main crystal phase and its content of the crystallinity required for the formed glass-ceramic can be obtained, and the main crystal phase and the content of the crystal phase can be adjusted, thereby Achieve improved resistance to rough ground puncture and optical properties of chemically strengthened glass-ceramics.
  • the Young's modulus of the chemically strengthened glass-ceramic is ⁇ 95GPa. Based on the chemically strengthened glass-ceramic, the main crystal phase type and crystal phase content of the plain glass-ceramic endow the chemically strengthened glass-ceramic with a high Young's modulus, thereby endowing the chemically strengthened glass-ceramic with a capacity to accommodate greater compressive stress storage The space provides conditions for increasing the compressive stress of chemically strengthened glass-ceramics.
  • the surface layer of the chemically strengthened glass ceramics further has a K/Na exchange layer.
  • the introduction of the K/Na exchange layer (potassium layer) further improves the impact resistance of the chemically strengthened glass-ceramic, and at the same time helps to maintain the drop resistance of the chemically strengthened glass-ceramic on rough ground.
  • the thickness of the K/Na exchange layer is ⁇ 3 ⁇ m.
  • the thickness of the K/Na exchange layer (potassium layer)
  • the impact resistance and drop resistance of the chemically strengthened glass-ceramics can be further improved.
  • the thickness requirement of the K/Na exchange layer can be effectively reduced.
  • the chemically strengthened glass-ceramics is any one of 2D morphologically strengthened glass-ceramics, 2.5D morphologically strengthened glass-ceramics, and 3D morphologically strengthened glass-ceramics. Since the chemically strengthened glass-ceramic has the above-mentioned excellent anti-puncture ability on rough ground and optical properties, it can be any of 2D morphologically chemically strengthened glass-ceramic, 2.5D morphologically strengthened glass-ceramic, and 3D morphologically strengthened glass-ceramic , expanding the application range of chemically strengthened glass-ceramics, and improving the quality and performance stability of the corresponding products.
  • the color coordinates of the 2D morphologically strengthened glass-ceramics or/and 2.5D morphologically strengthened glass-ceramics b absolute value ⁇ 0.3, haze ⁇ 0.14.
  • the chemically strengthened glass-ceramic is chemically strengthened glass-ceramic in 3D form, and the bending angle of the long side thereof is 15-89°.
  • the absolute value of color coordinate b of the 3D morphologically strengthened glass-ceramics is ⁇ 0.4, and the haze is ⁇ 0.15.
  • chemically strengthened glass-ceramic When chemically strengthened glass-ceramic is used as a 3D form of chemically strengthened glass-ceramic, it still has excellent resistance to rough ground puncture and light transmission.
  • Another aspect of the embodiments of the present application provides a method for preparing chemically strengthened glass-ceramics in the above embodiments of the present application.
  • the preparation method of chemically strengthened glass-ceramics in the embodiment of the present application comprises the following steps:
  • the plain glass-ceramic to be chemically strengthened is chemically strengthened once in a sodium-containing salt bath to form a Na/Li exchange layer.
  • the preparation method of the chemically strengthened glass-ceramics of the present application carries out a chemical strengthening treatment to the plain glass-ceramics in a sodium-containing salt bath, so that a Na/Li exchange layer is formed in the surface layer of the plain glass-ceramics, and can pass through a chemical strengthening treatment.
  • Control can make the chemically strengthened glass-ceramics formed by chemical strengthening have the compressive stress layer depth and compressive stress intensity CS50 range and the relationship between the two, which endow the chemically strengthened glass-ceramics of the above application.
  • Strengthened glass-ceramic has relatively high compressive stress, the stress intensity has been greatly improved, it can resist crack propagation, and has excellent resistance to puncture on rough ground.
  • the chemical strengthening conditions of the preparation method of the chemically strengthened glass-ceramics of the present application are easy to control, so that the performance of the prepared chemically strengthened glass-ceramics is stable, the efficiency is high, and the production cost is reduced.
  • the sodium-containing salt bath includes NaNO 3 or a mixed salt of NaNO 3 and KNO 3 , and in the mixed salt of NaNO 3 and KNO 3 , the content of NaNO 3 is ⁇ 50wt%.
  • the temperature of the first chemical strengthening treatment is 380-450° C.
  • the strengthening time is 0.5-6 hours.
  • the effect of chemical strengthening treatment on plain glass-ceramics is improved, and the depth of compressive stress layer and compressive stress intensity of chemically strengthened glass-ceramics formed are optimized CS50 range, thereby increasing the compressive stress of chemically strengthened glass-ceramic, improving its anti-puncture ability and light transmission performance on rough ground.
  • the first chemical strengthening treatment after the first chemical strengthening treatment, it also includes performing a second chemical strengthening treatment on the chemically strengthened glass-ceramics formed with the Na/Li exchange layer in a salt bath containing potassium to form a K/Na exchange layer.
  • a K/Na exchange layer is formed on the surface of the chemically strengthened glass-ceramics, thereby further improving the impact resistance and performance of the chemically strengthened glass-ceramics. Anti-drop performance on rough ground.
  • the potassium-containing salt bath includes KNO 3 or a mixed salt of NaNO 3 and KNO 3 ; in the mixed salt of NaNO 3 and KNO 3 , the content of KNO 3 is ⁇ 80wt%.
  • the temperature of the secondary chemical strengthening treatment is 380-450°C, and the strengthening time is 0.2-1h.
  • the effect of the secondary chemical strengthening treatment is improved, and the impact resistance and drop resistance of the chemically strengthened glass-ceramics are further improved.
  • the step of performing the following heat bending treatment on the plain glass-ceramics is also included:
  • the plain glass-ceramic is subjected to a single-stage heat bending treatment at 650-750° C. for 30-120 seconds to form a 3D plain glass-ceramic, wherein the pressure of the single-stage heat bending treatment is 0.1-0.9 MPa.
  • 3D plain glass-ceramics is formed by heat-bending the plain glass-ceramic, so that after the above-mentioned primary chemical strengthening treatment or further secondary chemical strengthening treatment, a 3D form of chemically strengthened glass-ceramic can be formed, and the 3D form of chemical strengthening can be guaranteed.
  • Glass-ceramic has high compressive stress and has excellent anti-puncture ability and light transmission performance on rough ground.
  • the electronic device in the embodiment of the present application includes a glass part, and the glass part is the chemically strengthened glass-ceramic in the above-mentioned application example or the chemically strengthened glass-ceramic prepared according to the preparation method of the chemically strengthened glass-ceramic in the above-mentioned application example.
  • the chemically strengthened glass-ceramic in the embodiment of the present application has the above-mentioned excellent resistance to rough ground puncture ability and optical performance or further has excellent impact resistance performance, therefore, the glass parts are endowed with excellent drop resistance and drop resistance, and high strength, thereby The electronic equipment of the embodiment of the present application is endowed with excellent drop resistance, drop resistance and impact resistance, and the quality and stability of the electronic equipment are high.
  • the glass component includes at least one of a display cover, a protection cover, and a protection screen.
  • the glass part has good light transmittance and strong protection, and is drop-resistant and drop-resistant, has high strength, and has good display or protection performance and is stable.
  • Figure 1 is a schematic diagram of the mechanism of glass-ceramic resistance to puncture
  • Fig. 2 is the stress curve diagram of existing aluminum-silicon one-strength glass, lithium-aluminum-silicate two-strength glass and chemically strengthened glass-ceramic of the present application embodiment;
  • Fig. 3 is a schematic flow chart of a method for preparing chemically strengthened glass-ceramics according to an embodiment of the present application.
  • At least one means one or more, and “multiple” means two or more.
  • At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • at least one item (unit) of a, b, or c or “at least one item (unit) of a, b, and c” can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
  • the term "and/or” describes the relationship between related objects, indicating that there may be three relationships, for example, A and/or B, which may mean: A exists alone, A and B exist simultaneously, and A and B exist independently. There is a case of B. Among them, A and B can be singular or plural.
  • the character "/" generally indicates that the contextual objects are an "or" relationship.
  • sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.
  • the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
  • the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
  • the mass described in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • first and second are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features.
  • first XX can also be called the second XX
  • second XX can also be called the first XX.
  • a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • Plain glass-ceramic glass-ceramic that has not been strengthened.
  • Chemically strengthened glass-ceramic It is chemically tempered glass-ceramic after high temperature ion exchange process. Large alkali metal ions replace small alkali metal ions in glass in high-temperature molten salt, resulting in a volume difference of exchanged ions, and a high-to-low compressive stress in the surface layer of plain glass, which hinders and delays the expansion of glass microcracks, and achieves an improvement.
  • the purpose of glass mechanical strength is used.
  • Depth of compressive stress layer Depth of compressive stress layer of chemically strengthened glass-ceramics.
  • Compressive stress value at a depth of 50 ⁇ m in the surface layer of chemically strengthened glass indicates the value of compressive stress at a depth of 50 ⁇ m in the surface layer of chemically strengthened glass-ceramics.
  • Na/Li exchange layer refers to the sodium-containing layer in which sodium ions of chemically strengthened glass-ceramics replace part of lithium ions.
  • K/Na exchange layer refers to the potassium-containing layer in which the potassium ions of the chemically strengthened glass-ceramics replace part of the sodium ions.
  • Sodium-lithium ion exchange During chemical strengthening, sodium ions in a salt bath replace lithium ions in the glass.
  • Potassium-sodium ion exchange During chemical strengthening, potassium ions in a salt bath replace sodium ions in the glass.
  • the embodiment of the present application provides a chemically strengthened glass-ceramic.
  • the chemically strengthened glass-ceramic in the embodiment of the present application has a Na/Li exchange layer and a compressive stress layer. It has been measured that the stress curve of the chemically strengthened glass-ceramic in the embodiment of the present application is shown in Figure 2, and its compressive stress layer depth and compressive stress intensity have at least the following 1 to 3 characteristics:
  • t in Formula 1-1 and Formula 1-2 is the total thickness of the chemically strengthened glass-ceramic, therefore, t is a positive number greater than 0, and the unit may be mm.
  • t is the total thickness of the chemically strengthened glass-ceramic in the embodiment of the present application, which is 0.3-0.8 mm.
  • the surface layer strengthening depth of 50 ⁇ m related to formula 1-2 refers to the direction from the surface of the chemically strengthened glass-ceramics to the inside, and the area with an internal depth of 50 ⁇ m.
  • the CS50 of the chemically strengthened glass-ceramics of the embodiment of the present application is too small, can cause the reduction such as the puncture ability of anti-rough ground of the chemically strengthened glass-ceramics, reliability is affected;
  • CS50 is too high, the chemical The broken fragments of strengthened glass-ceramics are too small.
  • the strengthening process generally adopts two strong processes: strengthening one uses pure NaNO 3 or NaNO 3 /KNO 3 mixed salt, the strengthening temperature is 380-450 °C, strengthening two uses pure KNO 3 or NaNO 3 /KNO 3 mixed salt), the strengthening Post-CS ⁇ 700MPa, strengthening depth of potassium layer Dol ⁇ 5 ⁇ m, CS50 ⁇ 130+(20t-13) ⁇ 15MPa, strengthening depth of compressive stress layer Doc ⁇ 0.18t.
  • the chemically strengthened glass-ceramic in the embodiment of the present application has the above-mentioned specific compressive stress layer depth, compressive stress intensity, and the relationship between the compressive stress layer depth and compressive stress intensity.
  • the chemically strengthened glass-ceramics in the embodiment of the present application has a relatively high compressive stress, and the stress intensity is greatly improved compared with the current aluminosilicate glass and glass-ceramic, and can resist Crack propagation.
  • the anti-puncture ability of the chemically strengthened glass-ceramic in the embodiment of the present application is significantly improved. Lifting, drop height on rough ground is higher than existing aluminosilicate glass and glass-ceramic.
  • the aluminum-silicon-strong glass curve (K/Na exchange) in Figure 2 is tested by the industry's general surface stress testing equipment FSM-6000LEUV, and the lithium-aluminum-silicon two-intensity curve (with K/Na and Na/Li exchange) is the industry's Surface stress testing equipment FSM-6000LEUV and Scattered Photoelastic Stress Instrument SLP2000 fitting test synthesis; the chemically strengthened glass-ceramic curve of this application is tested by SLP2000.
  • the chemically strengthened glass-ceramic when the chemically strengthened glass-ceramic is extruded by a 10 mm diameter round-headed metal pressure rod until it is broken, the average size of the longest side of the fragments is ⁇ 5 mm. Therefore, the internal tensile stress of the chemically strengthened glass-ceramics is appropriate, and the resistance to rough ground is strong, avoiding the risk of self-explosion.
  • the drop height of the sandpaper of the chemically strengthened glass-ceramic is ⁇ 1.5m. Reflects the excellent drop resistance of chemically strengthened glass-ceramics.
  • the sandpaper drop height data is tested under the scene of 180# sandpaper/200g load. Specifically, the chemically strengthened glass-ceramics of the application to be tested is faced down, and a standard 200g load is loaded on the other surface, with a fall of 0.5m , check the appearance every time it falls; if there is no problem, raise it by 0.1m, test directly until the glass breaks, and record the failure height.
  • the thickness of the chemically strengthened glass-ceramics is such that when the thickness is ⁇ 0.8mm, the average light transmittance at a wavelength of 400-940nm is ⁇ 89.5%, and the difference between the single point transmittance at a wavelength of 550nm and 400nm is ⁇ 1% , Absolute value of color coordinate b ⁇ 0.4, haze ⁇ 0.15. It embodies the optical properties such as the excellent light transmission of chemically strengthened glass-ceramics.
  • the chemically strengthened glass-ceramic has excellent compressive stress in addition to high compressive stress. It is resistant to puncture on rough ground and has high drop resistance, as shown in Table 1 below; it also has excellent heat and humidity stability, and good optical properties such as light transmission.
  • the main crystal phase of the plain glass-ceramics used to form the above-mentioned chemically strengthened glass-ceramics is any one of lithium silicate or ⁇ -quartz solid solution, and the mass fraction of the total crystal phase contained is 35-75%. Among them, the total content of secondary crystal phase is less than 5%.
  • the above-mentioned plain glass-ceramic includes a main composition and a nucleating agent; wherein, the main composition includes SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfies :
  • the content of SiO 2 +Al 2 O 3 +B 2 O 3 is 58-85mol%; the content of Li 2 O+Na 2 O+K 2 O is 10-32mol%;
  • the nucleating agent includes TiO 2 , P 2 O 5 , ZrO 2 , and satisfy: the content of TiO 2 +P 2 O 5 +ZrO 2 is 2-8 mol%.
  • plain glass-ceramics endow plain glass-ceramics and chemically strengthened glass-ceramics with the above-mentioned main crystal phase types and crystal phase content, thereby improving the anti-puncture ability of chemically strengthened glass-ceramics on rough ground and improving the chemical strength of glass-ceramics. Strengthens the optical properties of glass-ceramics such as light transmission.
  • the above-mentioned plain glass-ceramic can be prepared by a melting casting method or a calendering method. In some embodiments, the above-mentioned plain glass-ceramics undergoes the following two-step heat treatment:
  • the first step of heat treatment the temperature is 500-600°C, and the treatment time is 0.1-10h;
  • the second step of heat treatment the temperature is 640-800°C, and the treatment time is 0.1-10h.
  • the main crystal phase and its content of the crystallinity required for the formed glass-ceramic can be obtained, and the main crystal phase and the content of the crystal phase can be adjusted, thereby Achieve improved resistance to rough ground puncture and optical properties of chemically strengthened glass-ceramics.
  • plain glass-ceramics Due to the main crystal phase type and crystal phase content of plain glass-ceramics, it has been tested that plain glass-ceramics also has excellent mechanical properties such as Young's modulus and optical properties such as light transmission properties.
  • the plain glass-ceramics when the thickness of the plain glass-ceramic is ⁇ 0.8mm, the average light transmittance at 400-940nm wavelength is ⁇ 89.5%, and the single-point transmittance difference between 550nm and 400nm wavelength is less than 1%, and the color coordinates b absolute value ⁇ 0.3, haze ⁇ 0.14.
  • the plain glass-ceramics By controlling the main crystal phase type and crystal phase content of the plain glass-ceramics, the plain glass-ceramics has good optical properties such as light transmission and stable optical properties.
  • the Young's modulus of the plain glass-ceramic is ⁇ 95GPa. Based on the main crystal phase type and crystal phase content of plain glass-ceramics, high Young's modulus is given to plain glass-ceramics, so as to give high Young's modulus to chemically strengthened glass-ceramics, such as chemically strengthened glass-ceramics with high Young's modulus
  • the Young's modulus of the chemically strengthened glass-ceramics is greater than or equal to 95GPa, thereby endowing the chemically strengthened glass-ceramics with a larger compressive stress storage space, which provides conditions for the improvement of the compressive stress of the chemically strengthened glass-ceramics.
  • plain glass-ceramics and chemically strengthened glass-ceramics are endowed with high impact resistance. If tested, chemically strengthened glass-ceramics is about 25-30GPa higher than the existing aluminosilicate glass, which effectively reduces the impact of chemically strengthened glass-ceramics on K /Na Exchange layer requirements and dependencies.
  • the surface layer of the chemically strengthened glass-ceramic in the above embodiments further has a K/Na exchange layer.
  • the K/Na exchange layer is further formed on the surface of the chemically strengthened glass-ceramic, that is, the potassium layer is added to the surface of the chemically strengthened glass-ceramic.
  • the chemically strengthened glass-ceramic having high resistance to rough ground it is further optimized. Improve the drop resistance of chemically strengthened glass-ceramics on rough ground, and further improve the impact resistance of chemically strengthened glass-ceramics.
  • the chemically strengthened glass-ceramics has a high Young's modulus, such as Young's modulus ⁇ 95GPa, the high Young's modulus supports better impact strength, effectively reducing the K/Na exchange layer rely.
  • Young's modulus ⁇ 95GPa the high Young's modulus supports better impact strength, effectively reducing the K/Na exchange layer rely.
  • the chemically strengthened glass-ceramic in the embodiment of the present application does not require a larger K/Na exchange layer.
  • the thickness of the K/Na exchange layer contained in the chemically strengthened glass-ceramics in the above embodiments is ⁇ 3 ⁇ m.
  • the thickness of the K/Na exchange layer (potassium layer)
  • the impact resistance and drop resistance of the chemically strengthened glass-ceramics can be further improved.
  • the thickness requirement of the K/Na exchange layer can be effectively reduced.
  • the chemically strengthened glass-ceramic has excellent anti-puncture ability on rough ground, anti-drop performance and optical properties such as light transmission, or further has high Young's modulus and impact resistance.
  • the chemically strengthened glass-ceramic in the embodiment of the present application may be any one of 2D morphologically chemically strengthened glass-ceramic, 2.5D morphologically strengthened glass-ceramic, and 3D morphologically strengthened glass-ceramic.
  • the chemically strengthened glass-ceramic has the above-mentioned excellent anti-puncture ability on rough ground and optical performance, which expands its application range and improves the quality and performance stability of corresponding products.
  • CS50 and Doc of the chemically strengthened glass-ceramics satisfy: CS50/(Doc- 50) is 1.4-6.
  • the average light transmittance at 400-940nm is ⁇ 89.5%
  • the single point transmittance difference between 550nm and 400nm wavelength is less than 1%
  • the chemically strengthened glass-ceramic when used as a 2D morphological chemically strengthened glass-ceramic or a 2.5D morphologically strengthened glass-ceramic, it has excellent anti-puncture ability and light transmittance on rough ground, which is comparable to the optical performance of plain glass-ceramic. In comparison, its optical properties such as light transmission remain stable.
  • the chemically strengthened glass-ceramics in each of the above embodiments is a 3D form of chemically strengthened glass-ceramics
  • the bending angle of the long side of the 3D form of chemically strengthened glass-ceramics is 15-89°.
  • the CS50, Doc, and the relationship between CS50 and Doc of the chemically strengthened glass-ceramics satisfy the characteristics shown in the above formulas 1-1 to 1-3, and still have excellent anti-puncture ability on rough ground. Has excellent impact resistance.
  • the embodiment of the present application provides a method for preparing chemically strengthened glass-ceramics in the above embodiment of the application.
  • the process flow of the preparation method of chemically strengthened glass-ceramics in the embodiment of the present application is shown in Figure 3, including the following steps:
  • S01 The plain glass-ceramic to be chemically strengthened is subjected to a chemical strengthening treatment in a sodium-containing salt bath to form a Na/Li exchange layer.
  • the sodium ions in the sodium-containing salt bath diffuse into the surface layer of the plain glass-ceramics under the action of heat, and exchange with the lithium ions in the surface layer of the plain glass-ceramics, that is, the sodium-lithium ion Exchange, so that Na/Li exchange layer is formed in plain glass-ceramic surface layer, and can pass through the control of chemical strengthening treatment, can make the chemically strengthened glass-ceramic that chemical strengthening forms have above text application embodiment chemically strengthened glass-ceramics as above
  • the depth of the compressive stress layer and the CS50 range of the compressive stress intensity shown in the formulas 1-1 to 1-3 and the relationship between the two endow the prepared chemically strengthened glass-ceramic with a relatively high compressive stress, and the stress intensity is obtained Larger lift, able to resist crack propagation, and has excellent resistance to puncture on rough ground.
  • the chemical strengthening conditions of the preparation method of the chemically strengthened glass-ceramics of the present application are easy to control, so that the
  • the sodium-containing salt bath includes NaNO 3 or a mixed salt of NaNO 3 and KNO 3 .
  • the sodium-containing salt bath is a mixed salt comprising NaNO 3 and KNO 3
  • the content of NaNO 3 is ⁇ 50 wt%.
  • the temperature of one chemical strengthening treatment is 380-450° C., and the strengthening time is 0.5-6 hours.
  • the effect of chemical strengthening treatment on plain glass-ceramics is improved, and the depth of compressive stress layer and compressive stress intensity of chemically strengthened glass-ceramics formed are optimized CS50 range, thereby increasing the compressive stress of chemically strengthened glass-ceramic, improving its anti-puncture ability and light transmission performance on rough ground.
  • the plain glass-ceramics to be chemically strengthened is the above-mentioned plain glass-ceramics of chemically strengthened glass-ceramics, if the main crystal phase is any one of lithium silicate or ⁇ -quartz solid solution, the total crystal phase contained The mass fraction is 35-75%, wherein the total content of secondary crystal phase is less than 5wt%.
  • the plain glass-ceramic in the specific embodiment includes main composition and nucleating agent; main composition includes SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfies: SiO 2 + The content of Al 2 O 3 +B 2 O 3 is 58-85mol%; the content of Li 2 O+Na 2 O+K 2 O is 10-32mol%; the nucleating agent includes TiO 2 , P 2 O 5 , ZrO 2 , and Satisfy: the content of TiO 2 +P 2 O 5 +ZrO 2 is 2-8 mol%.
  • the chemically strengthened glass-ceramics prepared is a 3D form chemically strengthened glass-ceramic
  • the plain glass-ceramics to be chemically strengthened is subjected to a chemical strengthening treatment in a sodium-containing salt bath
  • the plain glass-ceramic is also included.
  • the glass-ceramic is subjected to the following heat-bending steps:
  • the plain glass-ceramic is subjected to a single-stage heat bending treatment at 650-750° C. for 30-120 seconds to form a 3D plain glass-ceramic, wherein the pressure of the single-stage heat bending treatment is 0.1-0.9 MPa.
  • 3D plain glass-ceramics is formed by heat-bending the plain glass-ceramic, so that after the above-mentioned primary chemical strengthening treatment or further secondary chemical strengthening treatment, a 3D form of chemically strengthened glass-ceramic can be formed, and the 3D form of chemical strengthening can be guaranteed.
  • Glass-ceramic has high compressive stress and has excellent anti-puncture ability and light transmission performance on rough ground.
  • the bending angle of the long side of the 3D plain glass-ceramic is 15-89°. In some other specific embodiments, the absolute value of the change difference of the color coordinate b value of the 3D plain glass-ceramic is ⁇ 0.1.
  • the existing main crystal phases are microcrystals whose main crystal phases are lithium petalite and lithium disilicate
  • the hot bending temperature of the glass is >750°C, and the crystal phase size grows during the hot bending process, resulting in a sharp deterioration of the optical properties after 3D molding (absolute value of color difference b ⁇ 2, haze ⁇ 0.25%); it cannot meet the application of hot bending 3DCG cover plates.
  • the above-mentioned main crystal phase of the embodiment of the present application is any kind of plain glass-ceramic in lithium silicate or ⁇ -quartz solid solution.
  • the color coordinate b value of the glass changes before and after bending.
  • step S02 as shown in Figure 3 is also included: the chemically strengthened glass-ceramics formed with the Na/Li exchange layer is subjected to a secondary chemical strengthening treatment in a potassium-containing salt bath to form K/Na exchange layer.
  • the potassium ions in the potassium-containing salt bath diffuse into the surface layer of the chemically strengthened glass-ceramics under the action of heat, and exchange with the sodium ions in the Na/Li exchange layer, that is, carry out potassium- Sodium ion exchange forms a K/Na exchange layer in the surface layer of chemically strengthened glass-ceramics, thereby further improving the impact resistance and drop resistance of chemically strengthened glass-ceramics.
  • the potassium-containing salt bath includes KNO 3 or a mixed salt of NaNO 3 and KNO 3 ; when the potassium-containing salt bath is a mixed salt comprising NaNO 3 and KNO 3 , in the mixed salt of NaNO 3 and KNO 3 , KNO 3 content ⁇ 80wt%.
  • the temperature of the secondary chemical strengthening treatment is 380-450°C, and the strengthening time is 0.2-1h.
  • the chemically strengthened glass-ceramics prepared by the chemically strengthened glass-ceramics and its preparation method according to the above-mentioned embodiments of the present application are combined with the existing glass-ceramics, as mentioned in the background technology section, the main crystal phases are lithium petalite and lithium disilicate compared to glass-ceramics.
  • the existing glass-ceramic whose main crystal phase is lithium petalite and lithium disilicate (the material contains a variety of main crystal phases, which require high crystallinity to maintain excellent optical properties), ion exchange requires Greater potential energy, so a higher chemical strengthening temperature/longer chemical strengthening time is required; moreover, the glass-ceramic is sensitive to the Li concentration in the chemical strengthening furnace water, and the chemical strengthening process requires precise control of the Li concentration, and is limited by the Li Inhibition of Na/Li exchange during the chemical strengthening process, therefore, the CS50 of the chemically strengthened glass-ceramics formed by the chemical strengthening of the existing glass-ceramic is ⁇ 130+(20t-13) ⁇ 15MPa.
  • the chemically strengthened glass-ceramics in the embodiment of the present application especially the chemically strengthened glass-ceramics containing any one of the main crystal phase lithium silicate or ⁇ -quartz solid solution, has relatively low crystallinity, such as crystallinity ⁇ 75wt%;
  • the strengthening treatment process is not sensitive to Li; CS50, Doc and the relationship between CS50 and Doc of the chemically strengthened glass-ceramics obtained by chemical strengthening treatment meet the characteristics shown in the above formulas 1-1 to 1-3, especially the CS50 medium At 130+(20t-13) ⁇ 15MPa ⁇ 230+(20t-13) ⁇ 15MPa, so as to obtain better anti-puncture ability on rough ground.
  • the embodiment of the present application provides an electronic device.
  • the electronic device in the embodiment of the present application includes a glass component, which is the chemically strengthened glass-ceramic in the embodiment of the above application.
  • the chemically strengthened glass-ceramic in the embodiment of the present application has the above-mentioned excellent rough ground puncture resistance, optical performance and impact resistance, the glass part is endowed with excellent drop resistance and drop resistance, and has high strength.
  • the electronic equipment of the embodiment of the present application including the glass part also has excellent drop resistance, drop resistance and impact resistance, and the quality and working performance stability of the electronic equipment are high.
  • the glass part has good light transmittance, good display effect, and can also play a good protective role. At the same time, it is also anti-drop and drop-resistant and high-strength, and has good display or protective performance, so that the electronic equipment is stable.
  • the glass part can also be any one of 2D morphology chemically strengthened glass-ceramics, 2.5D morphology chemically strengthened glass-ceramics, and 3D morphology chemically strengthened glass-ceramics, which expands and strengthens the application range of chemically strengthened glass-ceramics, and Improve the quality and performance stability of the corresponding electronic equipment.
  • the electronic device includes at least one of a communication mobile terminal, an electronic watch, a bracelet, and a computer.
  • the glass components contained therein can be used as front and rear covers of the mobile phone. Because these electronic devices contain the glass component, these electronic devices have excellent drop resistance or further have excellent impact resistance and high strength, so that the performance of the electronic devices is stable.
  • This embodiment provides a 3D ⁇ -quartz solid solution chemically strengthened glass-ceramics and a chemically strengthened method thereof.
  • the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
  • the preparation method of chemically strengthened glass-ceramic comprises the following steps:
  • the prepared glass substrate is subjected to two-step heat treatment to obtain the desired crystal phase; the first heat treatment is 600°C, the treatment time is 0.1h, the second step heat treatment is 750-900°C, the treatment time is 0.1h, the obtained crystal
  • the main crystal phase is ⁇ -quartz solid solution, and the crystallinity obtained by XRD test is 35wt%;
  • step S3 After the 3D glass after hot bending in step S2 is polished with a 3D polishing brush (thickness 0.3 mm after polishing), it is chemically strengthened to form a 3D form of ⁇ -quartz solid solution chemically strengthened glass-ceramic; chemically strengthened The conditions are shown in Table 2.
  • This embodiment provides a 2.5D lithium silicate chemically strengthened glass-ceramic and its chemically strengthened method.
  • the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
  • the preparation method of chemically strengthened glass-ceramic comprises the following steps:
  • the prepared glass substrate is subjected to two-step heat treatment to obtain the required crystal phase; the first heat treatment is 500°C, the treatment time is 10h, the second step heat treatment is 640°C, the treatment time is 10h, and the main crystal phase of the obtained crystal is Lithium silicate, the crystallinity obtained by XRD test is 75wt%;
  • Cutting/grinding/computer numerical control Computer numerical control, CNC processing/polishing the lithium silicate glass-ceramics prepared in step S1 into a 0.65mm2.5D form carrier;
  • step S3 Polish the concave-convex surface of the 2.5D plain glass-ceramics in step S2, and then perform chemical strengthening treatment to form 2.5D lithium silicate chemically strengthened glass-ceramics, the thickness of the finished product is 0.6mm, and the chemical strengthening conditions are shown in Table 2 shown.
  • This embodiment provides a 3D lithium silicate chemically strengthened glass-ceramic and a chemically strengthened method thereof.
  • the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
  • the preparation method of chemically strengthened glass-ceramic comprises the following steps:
  • the prepared glass matrix is subjected to two-step heat treatment to obtain the required crystal phase; the first heat treatment is 550°C, the treatment time is 6h, the second step heat treatment is 800°C, and the treatment time is 2h, the main crystal phase of the obtained crystal is Lithium silicate, the crystallinity obtained by XRD test is 65wt%;
  • the lithium silicate glass-ceramics prepared in step S1 is cut/grinded/polished into a 0.7mm-thick glass original sheet; then it is bent into a 3D shape with a 3D graphite mold, and the highest bending temperature is 750°C.
  • the compressive stress is 0.1MPa, and the single-station bending time is 120s;
  • step S3 Use a 3D polishing brush to polish the concave-convex surface of the plain glass-ceramic in step S2, and then perform chemical strengthening treatment to form a 3D lithium silicate chemically strengthened glass-ceramic.
  • the thickness of the finished product is 0.65 mm.
  • the chemical strengthening conditions are shown in Table 2. .
  • This embodiment provides a 2.5D lithium silicate chemically strengthened glass-ceramic and its chemically strengthened method.
  • the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
  • the preparation method of chemically strengthened glass-ceramic comprises the following steps:
  • the prepared glass substrate is subjected to two-step heat treatment to obtain the desired crystal phase; the first heat treatment is at 550° C. for 6 hours, and the second step is 800° C. for 2 hours.
  • the main crystal phase of the obtained crystal is lithium silicate, and the crystallinity obtained by XRD test is 65wt%;
  • step S3 Perform chemical strengthening treatment on the 2.5D plain glass-ceramic in step S2, and the strengthening conditions of chemical strengthening are shown in Table 1.
  • the depth Doc of the compressive stress layer of the chemically strengthened glass-ceramics in each embodiment is consistent with the thickness of the chemically strengthened glass-ceramics in the range of 0.15t to 0.22t;
  • the thickness of CS50 and chemically strengthened glass-ceramics conforms to 130+(20t-13) ⁇ 15MPa ⁇ 230+(20t-13) ⁇ 15MPa;
  • CS50 and Doc meet:
  • CS50/(Doc-50) is 1 ⁇ 7.5, and It has high resistance to puncture on rough ground, excellent optical properties such as light transmission, and good heat and humidity stability.
  • the shape and thickness of the aluminum-silicon one-strength glass, the lithium-aluminum-silicate two-strength glass and the chemically strengthened glass-ceramic in the embodiment of the present application are the same.
  • the test results are shown in Table 2:
  • the CS50 and sandpaper surface slump height of the chemically strengthened glass-ceramic in the embodiment of the present application are significantly higher than the CS50 and the sandpaper surface slump height of the existing aluminum-silicon first-strength glass and lithium-aluminum-silicate second-strength glass. Therefore, the present application EXAMPLES
  • the chemically strengthened glass-ceramic has significantly improved resistance to rough ground puncture. Therefore, the chemically strengthened glass-ceramic provided by the embodiment of the present application is used in electronic products, such as front and rear covers of mobile phones, specifically 2D cover, 2.5D cover, 3D cover, etc.
  • the anti-drop performance of the product endows the corresponding electronic products with excellent anti-drop performance, and can also improve the impact resistance of electronic products such as mobile phones, thereby making the performance of electronic products stable.

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Abstract

一种化学强化微晶玻璃及其制备方法与应用，化学强化微晶玻璃具有Na/Li交换层，压应力层深度与化学强化微晶玻璃总厚度t满足：0.15t～0.22t；而且在化学强化微晶玻璃表层强化深度50μm处的压应力强度CS50为：130+(20t-13)×15MPa～230+(20t-13)×15MPa，CS50/(Doc-50)等于1.4～6；该化学强化微晶玻璃的制备方法包括化学强化处理；化学强化微晶玻璃应用于电子设备，具有较强的抗粗糙地面的刺破能力。

Description

化学强化微晶玻璃及其制备方法与应用
本申请要求于2021年07月08日提交国家知识产权局、申请号为202110774451.0、申请名称为“化学强化微晶玻璃及其制备方法与应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于玻璃制品技术领域，具体涉及一种化学强化微晶玻璃及其制备方法与应用。
背景技术
玻璃由于其本身具有透明性、耐高温等特点，因此，玻璃在日常生活中得到了广泛的应用。比如，玻璃在保护装置、装潢等领域得到了广泛的应用。但是玻璃也存在一定的不足，如存在抗冲击性不强，易碎等缺陷，从而限制了玻璃在一些领域的应用。
随着电子产品的普及，对玻璃材料的要求越来越高。如目前智能手机上的屏幕保护材料巨大多数为化学强化玻璃材料。而且随着电子产品的发展，电子产品的后盖材料也逐渐被玻璃等材料取代。
目前业界盖板玻璃材料从铝硅一强玻璃向锂铝硅二强玻璃发展。随着化学强化程度的提高，盖板抗粗糙地面的刺破能力得到有效提升。业界的二强玻璃从2016年到2021年的迭代方向朝着提升深层应力方向发展，获得砂纸跌落的逐代提升。
但是在实际应用中发现目前业界铝硅玻璃如盖板玻璃材料存在如下不足：
二强玻璃本体采用锂铝硅玻璃，锂铝硅玻璃的杨氏模量一般为～80GPa，其应力强度的进一步提升受限于基质的压应力存储能力；过大的压应力引入高的内部张应力，如张应力过高，会导致玻璃失效碎片过小(<3mm)或者盖板玻璃自爆。因此二强玻璃对强度的提升受限于本体强度，抗跌落性能的提升较为有限。
2020年起，盖板行业推出微晶玻璃，作为一个盖板玻璃新的发展方向。微晶玻璃内部的纳米晶能够抵抗裂纹刺穿，以及离子交换引入的压应力能够抵抗裂纹扩展，通过双重作用提高盖板玻璃的抗跌能力(机理见图1)。因此抗粗糙地面的跌落性能相对二强玻璃有着质的提高。
如在公开的一份微晶玻璃，其主晶相为透锂长石和二硅酸锂；其强化炉水需要主动引入Li 2O，用于控制表面Na盐浓度，用以降低在85°温度/85°湿度下钠盐析出程度。该种晶相设计，利用K/Na及Na/Li二次交换，实现强度提升。但是在研究中发现，该微晶玻璃特点是需要结晶度要做得比较高(≥85wt％)，才能保障原材优秀的光学性能(透过率≥89.5％，色差b绝对值≤0.5，雾度≤0.15％)。然而该类微晶玻璃在3D热弯成型过程中，晶相易受热影响致使光学性能恶化；以及微晶玻璃离子交换受晶相影响，需要更长的交换路径，因此化学强化较难获得较高的压应力，抗跌落性能的提高依然不理想。
发明内容
本申请的目的在于克服现有技术的所述不足，提供一种化学强化微晶玻璃及其制备方法及其应用，以解决现有铝硅玻璃和化学强化微晶玻璃存在压应力难以进一步提 高、抗跌落性能等不理想的技术问题。
为了实现上述申请目的，本申请实施例的一方面，提供了一种化学强化微晶玻璃。本申请实施例化学强化微晶玻璃具有Na/Li交换层，化学强化微晶玻璃的压应力层深度Doc为0.15t～0.22t；化学强化微晶玻璃表层强化深度50μm处的压应力强度CS50为130+(20t-13)×15MPa～230+(20t-13)×15MPa；且CS50与Doc满足：CS50/(Doc-50)为1.4～6，单位为MPa/μm；其中，t为化学强化微晶玻璃的总厚度。
本申请实施例化学强化微晶玻璃具有特定的压应力层深度、压应力强度以及压应力层深度与压应力强度两者之间的关系，赋予化学强化微晶玻璃相对高的压应力，应力强度相对于当前的铝硅玻璃和微晶玻璃有较大提升，能够抵抗裂纹扩展。因此，本申请实施例化学强化微晶玻璃的抗粗糙地面的刺破能力得到显著提升，在粗糙地面的跌落高度高于现有的铝硅玻璃和微晶玻璃。
可选地，采用10mm直径圆头金属压杆挤压化学强化微晶玻璃至破碎时，碎片最长边平均尺寸≥5mm。
可选地，厚度为0.6mm时，化学强化微晶玻璃的砂纸跌落高度≥1.5m。
可选地，在温度85℃/湿度85％环境保存72h，化学强化微晶玻璃的外表面不出现钠盐析出。
可选地，化学强化微晶玻璃在厚度≤0.8mm厚度时，400-940nm波长的光平均透过率≥89.5％，且550nm与400nm波长时的单点透过率差<1％，色坐标b绝对值≤0.4，雾度≤0.15％。
基于化学强化微晶玻璃具有上述压应力层深度、压应力强度以及压应力层深度与压应力强度两者之间的关系，化学强化微晶玻璃除了具有优异的抗粗糙地面的刺破能力，具有高的抗跌落高度，热湿稳定性好，而且透光性等光学性好。
可选地，用于形成化学强化微晶玻璃的素微晶玻璃的主晶相为硅酸锂或β-石英固溶体中的任一种，所含总晶相质量分数为35～75％，其中次晶相总含量<5％。通过对素微晶玻璃的主晶相种类和晶相含量进行控制，能够有效使得化学强化微晶玻璃所含的Na/Li交换层不受Li的不利影响，能够有效实现CS50范围的控制，从而进一步提高化学强化微晶玻璃的抗粗糙地面刺破能力。同时还能够提高化学强化微晶玻璃的抗冲击性能，并具有高的如透光性等光学性能。
进一步地，素微晶玻璃包括主要组成和成核剂；其中，主要组成包括SiO 2、Al 2O 3、B 2O 3、Li 2O、Na 2O、K 2O，且满足：SiO 2+Al 2O 3+B 2O 3含量为58～85mol％；Li 2O+Na 2O+K 2O含量为10～32mol％；成核剂包括TiO 2、P 2O 5、ZrO 2，且满足：TiO 2+P 2O 5+ZrO 2含量为2～8mol％。素微晶玻璃的该些组分，赋予素微晶玻璃和化学强化微晶玻璃具有上述的主晶相种类和晶相含量，从而提高化学强化微晶玻璃的抗粗糙地面刺破能力和提高化学强化微晶玻璃的如透光性等光学性能。
进一步地，素微晶玻璃采用熔融浇筑法或者压延法制备形成。
进一步地，素微晶玻璃经过如下两步热处理：
第一步热处理：温度为500-600℃，处理时间为0.1-10h；
第二步热处理：温度为640-800℃，处理时间为0.1-10h。
通过对素微晶玻璃的制备方法或进一步采用该两步热处理，使得形成的获得素微 晶玻璃所需的结晶度的主晶相及其含量，并能够调节主晶相及晶相含量，从而实现提高化学强化微晶玻璃的抗粗糙地面刺破能力和光学性能。
进一步地，化学强化微晶玻璃的杨氏模量≥95GPa。基于化学强化微晶玻璃的素微晶玻璃具有的主晶相种类和晶相含量，赋予化学强化微晶玻璃高的杨氏模量，从而赋予化学强化微晶玻璃具有容纳更大的压应力存储空间，为化学强化微晶玻璃的压应力的提高提供了条件。
可选地，化学强化微晶玻璃的表层还具有K/Na交换层。通过K/Na交换层(钾层)的引入进一步提高化学强化微晶玻璃抗冲击性能，同时有助于维持化学强化微晶玻璃的抗粗糙地面跌落性能。
进一步地，K/Na交换层的厚度≤3μm。通过对K/Na交换层(钾层)厚度的控制，能够进一步提高化学强化微晶玻璃抗冲击性能和抗粗糙地面跌落性能。并在上述压应力层深度、压应力强度以及压应力层深度与压应力强度两者之间的关系的基础上，能够有效降低K/Na交换层的厚度要求。
可选地，化学强化微晶玻璃为2D形态强化微晶玻璃、2.5D形态化学强化微晶玻璃、3D形态化学强化微晶玻璃中的任一种。由于化学强化微晶玻璃具有上述优异的抗粗糙地面刺破能力和光学性能，其可以是2D形态化学强化微晶玻璃、2.5D形态化学强化微晶玻璃、3D形态化学强化微晶玻璃任一种，扩展了化学强化微晶玻璃的应用范围，并提高相应产品的质量和性能的稳定性。
进一步地，当化学强化微晶玻璃为2D形态化学强化微晶玻璃或/和2.5D形态化学强化微晶玻璃，2D形态化学强化微晶玻璃或/和2.5D形态化学强化微晶玻璃的色坐标b绝对值≤0.3，雾度≤0.14。
化学强化微晶玻璃作为2D形态化学强化微晶玻璃或2.5D形态化学强化微晶玻璃时，其具有优异的抗粗糙地面刺破能力和透光性。
进一步地，化学强化微晶玻璃为3D形态化学强化微晶玻璃，其长边折弯角度为15～89°。
进一步地，3D形态化学强化微晶玻璃色坐标b绝对值≤0.4，雾度≤0.15。
化学强化微晶玻璃作为3D形态化学强化微晶玻璃时，依然具有优异的抗粗糙地面刺破能力和透光性。
本申请实施例的另一方面，提供了上述本申请实施例化学强化微晶玻璃的制备方法。本申请实施例化学强化微晶玻璃的制备方法包括如下步骤：
将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理，形成Na/Li交换层。
本申请化学强化微晶玻璃的制备方法于含钠盐浴中对素微晶玻璃进行一次化学强化处理，使得在素微晶玻璃表层中形成Na/Li交换层，并能够通过一次化学强化处理的控制，能够使得化学强化形成的化学强化微晶玻璃具有上文本申请实施例化学强化微晶玻璃所具有的压应力层深度和压应力强度CS50范围以及两者之间的关系，从而赋予制备的化学强化微晶玻璃具有相对高的压应力，应力强度得到了较大提升，能够抵抗裂纹扩展，具有优异的抗粗糙地面的刺破能力。另外，本申请化学强化微晶玻璃的制备方法化学强化条件易控，使得制备的化学强化微晶玻璃性能稳定，效率高，降 低了制备成本。
可选地，含钠盐浴包括NaNO 3或NaNO 3与KNO 3的混合盐，在NaNO 3与KNO 3的混合盐混合盐中，NaNO 3含量≥50wt％。
可选地，一次化学强化处理的温度380-450℃，强化时间0.5-6h。
通过对含钠盐浴的种类和NaNO 3的含量以及一次化学强化处理控制，提高对素微晶玻璃的化学强化处理效果，优化形成的化学强化微晶玻璃的压应力层深度和压应力强度CS50范围，从而提高化学强化微晶玻璃压应力，提高其抗粗糙地面的刺破能力和透光性能。
可选地，在一次化学强化处理之后，还包括对形成有Na/Li交换层的化学强化微晶玻璃于含钾盐浴中进行二次化学强化处理，形成K/Na交换层。通过进一步对经一次化学强化处理形成的化学强化微晶玻璃进行二次化学强化处理，在形成的化学强化微晶玻璃表层形成K/Na交换层，从而进一步提高化学强化微晶玻璃抗冲击性能和抗粗糙地面跌落性能。
进一步地，含钾盐浴包括KNO 3或NaNO 3与KNO 3的混合盐；在NaNO 3与KNO 3的混合盐中，KNO 3含量≥80wt％。
进一步地，二次化学强化处理的温度380-450℃，强化时间0.2-1h。
通过对含钾盐浴的种类和KNO 3的含量以及二次化学强化处理控制，提高二次化学强化处理的效果，进一步提高化学强化微晶玻璃的抗冲击性能和抗粗糙地面跌落性能。
可选地，在将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理之前，还包括将素微晶玻璃进行如下热弯处理的步骤：
将素微晶玻璃于650～750℃下进行单段热弯处理30～120s，形成3D素微晶玻璃，其中，单段热弯处理的压力为0.1～0.9MPa。
通过对素微晶玻璃进行热弯处理形成3D素微晶玻璃，从而经上述一次化学强化处理或进一步经二次化学强化处理后，能够形成3D形态化学强化微晶玻璃，并保证3D形态化学强化微晶玻璃具有高的压应力和具有优异的抗粗糙地面的刺破能力和透光性能。
本申请实施例的另一方面，提供了电子设备。本申请实施例电子设备包括玻璃部件，玻璃部件为上文本申请实施例化学强化微晶玻璃或根据上文本申请实施例化学强化微晶玻璃的制备方法制备的化学强化微晶玻璃。由于本申请实施例化学强化微晶玻璃具有上述优异的抗粗糙地面刺破能力和光学性能或进一步具有优异的抗冲击性能，因此，赋予玻璃部件优异的抗跌和抗摔性，而且强度高，从而赋予本申请实施例电子设备优异的抗跌和抗摔性以及抗冲击性，电子设备质量和工作性能稳定性高。
进一步地，玻璃部件包括显示盖板、保护盖板、保护屏中的至少一种。该玻璃部件透光性好和保护力度强，而且抗跌和抗摔，同时具有高强度，其显示或保护性能好，且稳定。
附图说明
图1为微晶玻璃抵抗刺破机理示意图；
图2为现有铝硅一强玻璃、锂铝硅二强玻璃和本发申请实施例化学强化微晶玻璃 进行应力曲线图；
图3为本申请实施例化学强化微晶玻璃的制备方法工艺流程示意图。
具体实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
在本申请的描述中，需要理解的是，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
在本申请实施例中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中所述的质量可以是μg、mg、g、kg等化工领域公知的质量单位。
术语“第一”、“第二”仅用于描述目的，用来将目的如物质彼此区分开，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本申请实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
下文相关专用名称的解释：
素微晶玻璃：未被强化处理的微晶玻璃。
化学强化微晶玻璃：是经过高温离子交换工艺处理后的化学钢化微晶玻璃。在高温熔盐中大碱金属离子取代玻璃中的小碱金属离子从而产生交换离子体积差，在素玻璃的表层中产生由高到低的压应力，阻碍和延缓玻璃微裂纹的扩展，达到提高玻璃机 械强度的目的。
压应力层深度(Doc)：化学强化微晶玻璃的压应力层深度。
化学强化玻璃表层50μm深度处的压应力值(CS50)：表示化学强化微晶玻璃表层中50μm深度处的压应力值。
Na/Li交换层：是指化学强化微晶玻璃的钠离子替代部分锂离子的含钠层。
K/Na交换层：是指化学强化微晶玻璃的钾离子替代部分钠离子的含钾层。
钠-锂离子交换：化学强化中，盐浴中的钠离子取代玻璃中的锂离子。
钾-钠离子交换：化学强化中，盐浴中的钾离子取代玻璃中的钠离子。
一方面，本申请实施例提供了一种化学强化微晶玻璃。本申请实施例化学强化微晶玻璃具有Na/Li交换层，且具有压应力层。经测得，本申请实施例化学强化微晶玻璃的应力曲线如图2所示，其压应力层深度和压应力强度至少具有如下1至3点特征：
1.化学强化微晶玻璃的压应力层深度Doc与化学强化微晶玻璃的总厚度满足如下式1-1所示关系：
Doc＝0.15t～0.22t(1-1)。
2.化学强化微晶玻璃表层压应力强度满足如下式1-2所示关系：
化学强化微晶玻璃表层强化深度50μm处的压应力强度CS50满足如下式1-2所示关系：
CS50＝130+(20t-13)×15MPa～230+(20t-13)×15MPa；(1-2)。
3.化学强化微晶玻璃表层压应力强度与压应力层深度Doc之间的关系满足如下式1-3所示关系：
CS50/(Doc-50)＝1.4～6，单位为MPa/μm；(1-3)。
其中，式1-1和式1-2中的t为化学强化微晶玻璃的总厚度，因此，t为大于0的正数，单位可以是mm。实施例中，t也即是本申请实施例化学强化微晶玻璃的总厚度为0.3～0.8mm。
与式1-2相关的表层强化深度50μm处是指化学强化微晶玻璃表面至内部方向，其内部深度50μm区域。在实验过程中发现，本申请实施例化学强化微晶玻璃的CS50过小时，会导致化学强化微晶玻璃的如抗粗糙地面的刺破能力等降低，可靠性受影响；CS50过高时，化学强化微晶玻璃的破裂碎片过小。
另外，由图2中所示的现有铝硅一强玻璃(主要成分含SiO 2+Al 2O 3+B 2O 3+P 2O 5＝75～85mol％，Na 2O+K 2O＝10～16mol％，不含Li 2O；其强化工艺一般采用纯KNO 3在380-460℃强化1～10h)，其强化后CS≥700MPa，CS50≈0；强化层深度(K/Na)交换层深度0.04-0.09t。现有锂铝硅二强玻璃(主要成分含SiO 2+Al 2O 3+B 2O 3+P 2O 5＝75～85mol％，Li 2O+Na 2O+K 2O＝10～20mol％。强化工艺一般采用二强工艺：强化一采用纯NaNO 3或NaNO 3/KNO 3混盐，强化温度380-450℃，强化二采用纯KNO 3或NaNO 3/KNO 3混盐)，其强化后CS≥700MPa，钾层强化深度Dol≥5μm，CS50＜130+(20t-13)×15MPa，压应力层强化深度Doc≥0.18t。
基于上文所述的由于本申请实施例化学强化微晶玻璃具有上述特定的压应力层深度、压应力强度以及压应力层深度与压应力强度两者之间的关系，因此，与现有铝硅一强玻璃、锂铝硅二强玻璃相比，本申请实施例化学强化微晶玻璃具有相对高的压应 力，应力强度相对于当前的铝硅玻璃和微晶玻璃有较大提升，能够抵抗裂纹扩展。与当前生活场景常见强化玻璃(如当前手机在生活场景常见失效的粗糙地面刺破深度一般为40～70μm)相比，本申请实施例化学强化微晶玻璃的抗粗糙地面的刺破能力得到显著提升，在粗糙地面的跌落高度高于现有的铝硅玻璃和微晶玻璃。其中，图2中的铝硅一强玻璃曲线(K/Na交换)为业界通用表面应力测试设备FSM-6000LEUV测试，锂铝硅二强曲线(同时具备K/Na，Na/Li交换)为业界表面应力测试设备FSM-6000LEUV及散乱光光弹性应力仪SLP2000拟合测试合成；本申请化学强化微晶玻璃曲线采用SLP2000测试。
进一步测得，本申请实施例化学强化微晶玻璃还具有如下的相关机械性能和光学等性能：
实施例中，采用10mm直径圆头金属压杆挤压化学强化微晶玻璃至破碎时，碎片最长边平均尺寸≥5mm。因此，化学强化微晶玻璃内部张应力适当，抗粗糙地面的刺破能力强，避免了自爆的风险。
实施例中，厚度为0.6mm时，化学强化微晶玻璃的砂纸跌落高度≥1.5m。体现了化学强化微晶玻璃优异的抗跌落性能。该砂纸跌落高度数据是在180#砂纸/200g载重场景下进行测试，具体是将待测的本申请化学强化微晶玻璃平面朝下，并在另表面负载标准的200g负载物，0.5m起跌，每跌一次检查外观；；没问题的话，提升0.1m，直接测试到玻璃破裂为止，记录失效高度。
实施例中，在温度85℃/湿度85％的环境保存72h，化学强化微晶玻璃的外表面不出现钠盐析出，体现了化学强化微晶玻璃优异的热湿稳定性。
实施例中，化学强化微晶玻璃的厚度为在厚度≤0.8mm时，在400-940nm波长的光平均透过率≥89.5％，且550nm与400nm波长时的单点透过率差<1％，色坐标b绝对值≤0.4，雾度≤0.15。体现了化学强化微晶玻璃优异的透光性等光学性能。
因此，基于化学强化微晶玻璃具有上述压应力层深度、压应力强度以及压应力层深度与压应力强度两者之间的关系，化学强化微晶玻璃除了具有高的压应力强度，具有优异的抗粗糙地面的刺破能力，具有高的抗跌落高度，如下文表1中所示；还具有优异的热湿稳定性好，而且透光性等光学性好。
实施例中，用于形成上述化学强化微晶玻璃的素微晶玻璃的主晶相为硅酸锂或β-石英固溶体中的任一种，所含总晶相质量分数为35～75％，其中次晶相总含量<5％。通过对素微晶玻璃的主晶相种类和晶相含量进行控制，能够有效使得化学强化微晶玻璃所含的Na/Li交换层不受Li的不利影响，能够有效实现CS50范围的控制，从而进一步提高化学强化微晶玻璃的抗粗糙地面刺破能力。同时还能够提高化学强化微晶玻璃的如透光性等光学性能。
一些实施例中，上述素微晶玻璃包括主要组成和成核剂；其中，主要组成包括SiO 2、Al 2O 3、B 2O 3、Li 2O、Na 2O、K 2O，且满足：SiO 2+Al 2O 3+B 2O 3含量为58～85mol％；Li 2O+Na 2O+K 2O含量为10～32mol％；成核剂包括TiO 2、P 2O 5、ZrO 2，且满足：TiO 2+P 2O 5+ZrO 2含量为2～8mol％。素微晶玻璃的该些组分，赋予素微晶玻璃和化学强化微晶玻璃具有上述的主晶相种类和晶相含量，从而提高化学强化微晶玻璃的抗粗糙地面刺破能力和提高化学强化微晶玻璃的如透光性等光学性能。
实施例中，上述素微晶玻璃可以采用熔融浇筑法或者压延法制备形成。一些实施例中，上述素微晶玻璃经过如下两步热处理：
第一步热处理：温度为500-600℃，处理时间为0.1-10h；
第二步热处理：温度为640-800℃，处理时间为0.1-10h。
通过对素微晶玻璃的制备方法或进一步采用该两步热处理，使得形成的获得素微晶玻璃所需的结晶度的主晶相及其含量，并能够调节主晶相及晶相含量，从而实现提高化学强化微晶玻璃的抗粗糙地面刺破能力和光学性能。
由于素微晶玻璃具有的主晶相种类和晶相含量，经检测，素微晶玻璃还具有优异的杨氏模量等机械性能和透光性能等光学性能。
如实施例中，素微晶玻璃厚度为厚度≤0.8mm时，在400-940nm波长的光平均透过率≥89.5％，且550nm与400nm波长的单点透过率差<1％，色坐标b绝对值≤0.3，雾度≤0.14。通过对素微晶玻璃主晶相种类和晶相含量进行控制，使得素微晶玻璃具有良好的如透光性等光学性能，且光学性能稳定。
实施例中，素微晶玻璃的杨氏模量≥95GPa。基于素微晶玻璃具有的主晶相种类和晶相含量，赋予素微晶玻璃高的杨氏模量，以此赋予化学强化微晶玻璃高的杨氏模量，如化学强化微晶玻璃高的杨氏模量≥95GPa，从而赋予化学强化微晶玻璃具有容纳更大的压应力存储空间，为化学强化微晶玻璃的压应力的提高提供了条件。而且赋予素微晶玻璃和化学强化微晶玻璃高的抗冲击性能，如经检测，化学强化微晶玻璃相对于现有铝硅玻璃约提高25～30GPa，有效降低了化学强化微晶玻璃对K/Na交换层的要求和依赖。
实施例中，上述各实施例中化学强化微晶玻璃的表层还具有K/Na交换层。在化学强化微晶玻璃的表层进一步形成K/Na交换层也即是在化学强化微晶玻璃表层增加钾层，在化学强化微晶玻璃具有高抗粗糙地面的刺破能力的基础上，进一步优化提高化学强化微晶玻璃的抗粗糙地面跌落性能，并进一步提高化学强化微晶玻璃的抗冲击性能。
而且基于本申请实施例化学强化微晶玻璃具有高杨氏模量，如杨氏模量≥95GPa，该高的杨氏模量支撑较好的抗冲击强度，有效降低了K/Na交换层的依赖。如图2所示应力曲线，相对于现有铝硅一强玻璃曲线，本申请实施例化学强化微晶玻璃不需要较大的K/Na交换层。如实施例中，上述各实施例中化学强化微晶玻璃所含的K/Na交换层的厚度≤3μm。通过对K/Na交换层(钾层)厚度的控制，能够进一步提高化学强化微晶玻璃抗冲击性能和抗粗糙地面跌落性能。并在上述压应力层深度、压应力强度以及压应力层深度与压应力强度两者之间的关系的基础上，能够有效降低K/Na交换层的厚度要求。
基于上述各实施例化学强化微晶玻璃具有优异的抗粗糙地面的刺破能力，抗跌落性能和透光等光学性能，或进一步具有高的杨氏模量、抗冲击性能。本申请实施例化学强化微晶玻璃可以是2D形态化学强化微晶玻璃、2.5D形态化学强化微晶玻璃、3D形态化学强化微晶玻璃中的任一种。化学强化微晶玻璃具有的上述优异的抗粗糙地面刺破能力和光学性能，扩展了其应用范围，并提高相应产品的质量和性能的稳定性。
当上述各实施例化学强化微晶玻璃为2D形态化学强化微晶玻璃或2.5D形态化学 强化微晶玻璃时，实施例中，该化学强化微晶玻璃的CS50与Doc满足：CS50/(Doc-50)为1.4～6。
另些实施例中，该化学强化微晶玻璃在厚度≤0.8mm时，在400-940nm时的光平均透过率≥89.5％，且550nm与400nm波长时的单点透过率差<1％，色坐标b绝对值≤0.3，雾度≤0.14。
因此，该化学强化微晶玻璃作为2D形态化学强化微晶玻璃或2.5D形态化学强化微晶玻璃时，其具有优异的抗粗糙地面刺破能力和透光性，与素微晶玻璃的光学性能相比，且其如透光性等光学性能保持稳定。
当上述各实施例化学强化微晶玻璃为3D形态化学强化微晶玻璃时，实施例中，该3D形态化学强化微晶玻璃长边折弯角度为15～89°。而且，其化学强化微晶玻璃的CS50、Doc以及CS50与Doc之间的关系满足上文式1-1至1-3所示特性，具有依然具有优异的抗粗糙地面刺破能力，当然同时依然具有优异的抗冲击性能。测得其光学特性为如上述400-940nm时的光平均透过率≥89.5％，且550nm与400nm波长时的单点透过率差<1％，色坐标b绝对值≤0.4，雾度≤0.15。虽然与其素微晶玻璃的光学性能相比，略有差异，但是差异不明显，因此，上述各实施例化学强化微晶玻璃为3D形态化学强化微晶玻璃时，其依然具有优异的如透光性等光学性能保持稳定。
另一方面，本申请实施例的提供了上文本申请实施例化学强化微晶玻璃的制备方法。本申请实施例化学强化微晶玻璃的制备方法工艺流程如图3所示，包括如下步骤：
S01：将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理，形成Na/Li交换层。
在一次化学强化处理过程中，含钠盐浴中的钠离子在热力作用下向素微晶玻璃表层中扩散，并与素微晶玻璃表层中的锂离子交换，也即是进行钠-锂离子交换，使得在素微晶玻璃表层中形成Na/Li交换层，并能够通过一次化学强化处理的控制，能够使得化学强化形成的化学强化微晶玻璃具有上文本申请实施例化学强化微晶玻璃如上文式1-1至1-3所示的压应力层深度和压应力强度CS50范围以及两者之间的关系，从而赋予制备的化学强化微晶玻璃具有相对高的压应力，应力强度得到了较大提升，能够抵抗裂纹扩展，具有优异的抗粗糙地面的刺破能力。另外，本申请化学强化微晶玻璃的制备方法化学强化条件易控，使得制备的化学强化微晶玻璃性能稳定，效率高，降低了制备成本。
实施例中，含钠盐浴包括NaNO 3或NaNO 3与KNO 3的混合盐。当含钠盐浴为包括NaNO 3与KNO 3的混合盐时，在NaNO 3与KNO 3的混合盐混合盐中，NaNO 3含量≥50wt％。实施例中，一次化学强化处理的温度380-450℃，强化时间0.5-6h。通过对含钠盐浴的种类和NaNO 3的含量以及一次化学强化处理控制，提高对素微晶玻璃的化学强化处理效果，优化形成的化学强化微晶玻璃的压应力层深度和压应力强度CS50范围，从而提高化学强化微晶玻璃压应力，提高其抗粗糙地面的刺破能力和透光性能。
另外，该待化学强化处理的素微晶玻璃为上文化学强化微晶玻璃的素微晶玻璃，如主晶相为硅酸锂或β-石英固溶体中的任一种，所含总晶相质量分数为35～75％，其中次晶相总含量<5wt％。具体实施例中素微晶玻璃包括主要组成和成核剂；主要组成包括SiO 2、Al 2O 3、B 2O 3、Li 2O、Na 2O、K 2O，且满足：SiO 2+Al 2O 3+B 2O 3含量为58～85mol％； Li 2O+Na 2O+K 2O含量为10～32mol％；成核剂包括TiO 2、P 2O 5、ZrO 2，且满足：TiO 2+P 2O 5+ZrO 2含量为2～8mol％。
实施例中，当制备的化学强化微晶玻璃为3D形态化学强化微晶玻璃时，在将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理之前，还包括将素微晶玻璃进行如下热弯处理的步骤：
将素微晶玻璃于650～750℃下进行单段热弯处理30～120s，形成3D素微晶玻璃，其中，单段热弯处理的压力为0.1～0.9MPa。
通过对素微晶玻璃进行热弯处理形成3D素微晶玻璃，从而经上述一次化学强化处理或进一步经二次化学强化处理后，能够形成3D形态化学强化微晶玻璃，并保证3D形态化学强化微晶玻璃具有高的压应力和具有优异的抗粗糙地面的刺破能力和透光性能。
具体实施例中，3D素微晶玻璃的长边折弯角度为15～89°。另些具体实施例中，3D素微晶玻璃的色坐标b值变化差异绝对值≤0.1。通过对上述热弯处理条件的控制，制备的3D素微晶玻璃具有所需的长边折弯角度，而且光学性能稳定。
与现有微晶玻璃如背景技术部分中提到的主晶相为透锂长石和二硅酸锂的微晶玻璃相比，现有主晶相为透锂长石和二硅酸锂的微晶玻璃的热弯温度＞750℃，热弯过程晶相尺寸长大，导致3D成型后光学性能急剧恶化(色差b绝对值≥2，雾度≥0.25％)；无法满足热弯3DCG盖板应用。而本申请实施例的上述主晶相为硅酸锂或β-石英固溶体中的任一种素微晶玻璃采用上述的最高热弯温度650～750℃，热弯前后，玻璃色坐标b值变化差异绝对值≤0.1，色坐标b绝对值≤0.4，雾度≤0.14；满足3D热弯3DCG盖板应用。
实施例中，在上述一次化学强化处理之后，还包括如图3中的步骤S02：对形成有Na/Li交换层的化学强化微晶玻璃于含钾盐浴中进行二次化学强化处理，形成K/Na交换层。
在二次化学强化处理过程中，含钾盐浴中的钾离子在热力作用下向化学强化微晶玻璃表层中扩散，并与Na/Li交换层中的钠离子交换，也即是进行钾-钠离子交换，在化学强化微晶玻璃表层中形成K/Na交换层，从而进一步提高化学强化微晶玻璃抗冲击性能和抗粗糙地面跌落性能。
实施例中，含钾盐浴包括KNO 3或NaNO 3与KNO 3的混合盐；当含钾盐浴为包括NaNO 3与KNO 3的混合盐时，在NaNO 3与KNO 3的混合盐中，KNO 3含量≥80wt％。实施例中，二次化学强化处理的温度380-450℃，强化时间0.2-1h。通过对含钾盐浴的种类和KNO 3的含量以及二次化学强化处理控制，提高二次化学强化处理的效果，进一步提高化学强化微晶玻璃的抗冲击性能和抗粗糙地面跌落性能。
另外，将上述本申请实施例化学强化微晶玻璃及其制备方法制备的化学强化微晶玻璃与现有微晶玻璃如背景技术部分中提到的主晶相为透锂长石和二硅酸锂的微晶玻璃相比。由于现有主晶相为透锂长石和二硅酸锂的微晶玻璃的结晶度较高(该材料含多种主晶相，需要较高的结晶度维持优秀的光学性能)，离子交换需要更大的势能，因此需要更高的化学强化温度/更长的化学强化时间；而且该微晶玻璃对化学强化炉水中的Li浓度敏感，化学强化过程需要精确控制Li浓度，且受限于Li在化学强化过程 中对Na/Li交换的抑制，因此，现有的该微晶玻璃化学强化形成的化学强化微晶玻璃的CS50<130+(20t-13)×15MPa。而本申请实施例化学强化微晶玻璃特别是含有主晶相硅酸锂或β-石英固溶体中的任一种的化学强化微晶玻璃，其结晶度相对低，如结晶度≤75wt％；化学强化处理过程对Li不敏感；通过化学强化处理获得的化学强化微晶玻璃的CS50、Doc以及CS50与Doc之间的关系满足上文式1-1至1-3所示特性，特别是CS50介于130+(20t-13)×15MPa～230+(20t-13)×15MPa，从而获得更优秀的抗粗糙地面刺破能力。
再一方面，基于上文化学强化微晶玻璃及其制备方法，本申请实施例提供了电子设备。本申请实施例电子设备包括玻璃部件，玻璃部件为上文本申请实施例化学强化微晶玻璃。这样，由于本申请实施例化学强化微晶玻璃具有上文所述优异的抗粗糙地面刺破能力和光学性能以及抗冲击性能，从而赋予该玻璃部件具有优异的抗跌和抗摔性，强度高，那么使得包括有该玻璃部件的本申请实施例电子设备也具有优异的抗跌和抗摔性以及抗冲击性，电子设备质量和工作性能稳定性高。
实施例中，电子设备所含的显示盖板、保护盖板、保护屏中的至少一种。该玻璃部件透光性好，显示效果，而且还能够起到良好的保护作用，同时还抗跌和抗摔以及高强度，其显示或保护性能好，使得电子设备稳定。该玻璃部件还可以是2D形态化学强化微晶玻璃、2.5D形态化学强化微晶玻璃、3D形态化学强化微晶玻璃中的任一种，扩展并增强了化学强化微晶玻璃的应用范围，并提高相应电子设备的质量和性能的稳定性。
实施例中，电子设备包括通信移动终端、电子手表、手环、电脑中的至少一种。具体实施例中，当电子设备为通信移动终端如手机时，其所含的玻璃部件可以作为手机的前后盖板。由于该些电子设备含有该玻璃部件，因此，该些电子设备具有优异的抗跌落性能或进一步具有优异的抗冲击性，强度高，从而使得电子设备性能稳定。
以下结合具体实施例对上述化学强化微晶玻璃及其制备方法进行详细阐述。
实施例1
本实施例提供一种3D形态β-石英固溶体化学强化微晶玻璃及其化学强化方法。化学强化微晶玻璃的相关性能及其化学强化方法的相关工艺参数分别如下表2中所述。
其中，化学强化微晶玻璃制备方法包括如下步骤：
S1：素微晶玻璃及其制备：
(1)采用熔融浇筑法制备玻璃基体，其成分组成为SiO 2+Al 2O 3+B 2O 3＝85mol％；Li 2O+Na 2O+K 2O＝10mol％；成核剂TiO 2+P 2O 5+ZrO 2＝2mol％，其他成分为MgO；
(2)将制备的玻璃基体通过两步热处理获得所需晶相；第一步热处理为600℃，处理时间0.1h，第二步热处理为750～900℃，处理时间0.1h，所获得的晶体主晶相为β-石英固溶体，采用XRD测试获得的结晶度为35wt％；
S2：3D素微晶玻璃及其制备：
将步骤S1中制备得到的β-石英固溶体微晶玻璃经切割/研磨/抛光成0.35mm厚度玻璃原片；再采用3D石墨模具热弯成3D造型，其中最高热弯温度为650℃，热弯压应力为0.9MPa，单站热弯时间30s；
S3：将步骤S2中热弯后的3D玻璃采用3D抛光毛刷抛光凹凸面后(抛光完后厚 度0.3mm)进行化学强化处理，形成3D形态β-石英固溶体化学强化微晶玻璃；化学强化强化条件见表2所示。
实施例2
本实施例提供一种2.5D形态硅酸锂化学强化微晶玻璃及其化学强化方法。化学强化微晶玻璃的相关性能及其化学强化方法的相关工艺参数分别如下表2中所述。
其中，化学强化微晶玻璃制备方法包括如下步骤：
S1：素微晶玻璃及其制备：
(1)采用熔融浇筑法制备玻璃基体，其成分组成为SiO 2+Al 2O 3+B 2O 3＝58mol％；Li 2O+Na 2O+K 2O＝32mol％；成核剂TiO 2+P 2O 5+ZrO 2＝8mol％，其他成分为2％MgO；
(2)将制备的玻璃基体通过两步热处理获得所需晶相；第一步热处理为500℃，处理时间10h，第二步热处理为640℃，处理时间10h，所获的晶体主晶相为硅酸锂，采用XRD测试获得的结晶度为75wt％；
S2：2.5D素微晶玻璃及其制备：
将步骤S1中制备得到的硅酸锂素微晶玻璃经切割/研磨/计算机数字控制机床(Computer numerical control，CNC)加工/抛光成0.65mm2.5D形态载体；
S3：将步骤S2中2.5D素微晶玻璃进行抛光毛刷抛光凹凸面后进行化学强化处理，形成2.5D形态硅酸锂化学强化微晶玻璃，成品厚度0.6mm，化学强化强化条件见表2所示。
实施例3
本实施例提供一种3D形态硅酸锂化学强化微晶玻璃及其化学强化方法。化学强化微晶玻璃的相关性能及其化学强化方法的相关工艺参数分别如下表2中所述。
其中，化学强化微晶玻璃制备方法包括如下步骤：
S1：素微晶玻璃及其制备：
(1)采用熔融浇筑法制备玻璃基体，其成分组成为SiO 2+Al 2O 3+B 2O 3＝65mol％；Li 2O+Na 2O+K 2O＝30mol％；成核剂TiO 2+P 2O 5+ZrO 2＝5mol％；
(2)将制备的玻璃基体通过两步热处理获得所需晶相；第一步热处理为550℃，处理时间6h，第二步热处理为800℃，处理时间2h，所获得的晶体主晶相为硅酸锂，采用XRD测试获得的结晶度为65wt％；
S2：3D素微晶玻璃及其制备：
将步骤S1中制备得到的硅酸锂素微晶玻璃经切割/研磨/抛光成0.7mm厚度玻璃原片；再采用3D石墨模具热弯成3D造型，其中最高热弯温度为750℃，热弯压应力为0.1MPa，单站热弯时间120s；
S3：将步骤S2中素微晶玻璃采用3D抛光毛刷抛光凹凸面后进行化学强化处理，形成3D形态硅酸锂化学强化微晶玻璃，成品厚度0.65mm，化学强化强化条件见表2所示。
实施例4
本实施例提供一种2.5D形态硅酸锂化学强化微晶玻璃及其化学强化方法。化学强化微晶玻璃的相关性能及其化学强化方法的相关工艺参数分别如下表2中所述。
其中，化学强化微晶玻璃制备方法包括如下步骤：
S1：素微晶玻璃及其制备：
(1)采用熔融浇筑法制备玻璃基体，其成分组成为SiO 2+Al 2O 3+B 2O 3＝65mol％；Li 2O+Na 2O+K 2O＝30mol％；成核剂TiO 2+P 2O 5+ZrO 2＝5mol％；
(2)将制备的玻璃基体通过两步热处理获得所需晶相；第一步热处理为550℃，处理时间6h，第二步热处理为800℃，处理时间2h。所获得的晶体主晶相为硅酸锂，采用XRD测试获得的结晶度为65wt％；
S2：2.5D素微晶玻璃及其制备：
将步骤S1中制备得到的硅酸锂素微晶玻璃经切割/研磨/抛光成1mm厚度2.5D形态玻璃原片；
S3：将步骤S2中2.5D素微晶玻璃进行化学强化处理，化学强化强化条件见表1所示。
化学强化微晶玻璃相关性能测试：
将上述实施例1至实施例4分别进行如下表2中的相关性能测试，测试方法如下，测试结果如下表1所示：
表1
Figure PCTCN2022090015-appb-000001
Figure PCTCN2022090015-appb-000002
由表1可知，各实施例中化学强化微晶玻璃的压应力层深度Doc与化学强化微晶玻璃的厚度符合0.15t～0.22t；各化学强化微晶玻璃表层强化深度50μm处的压应力强度CS50与化学强化微晶玻璃的厚度符合130+(20t-13)×15MPa～230+(20t-13)×15MPa；CS50与Doc满足：CS50/(Doc-50)为1～7.5的关系，而且具有高的抗粗糙地面的刺破能力，透光性等光学性优异，且热湿稳定性好。
进一步以业界现有0.6mm厚度的铝硅一强玻璃(K/Na交换)和0.6mm厚度的锂铝硅二强玻璃(同时具备K/Na，Na/Li交换)为对比例，与上述实施例3中相同素微晶玻璃和相同化学强化处理获得的化学强化微晶玻璃分别进行CS50(MPa)和于180#砂纸面跌高度测试。其中，铝硅一强玻璃、锂铝硅二强玻璃和本申请实施例化学强化微晶玻璃的形态及厚度相同。测试结果如表2中所示：
表2
Figure PCTCN2022090015-appb-000003
由表2可知，本申请实施例化学强化微晶玻璃的CS50和砂纸面跌高度显著高于现有铝硅一强玻璃和锂铝硅二强玻璃的CS50和砂纸面跌高度，因此，本申请实施例化学强化微晶玻璃的抗粗糙地面刺破能力得到了显著提高。因此，将本申请实施例提供的化学强化微晶玻璃用于电子产品中，如作为手机的前后盖板，具体可以是2D盖板、2.5D盖板、3D盖板等，从而提高手机等电子产品的抗跌落性能，赋予相应电子产品优异的抗摔，而且还能够提高手机等电子产品抗冲击性，从而使得电子产品性能稳定。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。

Claims (17)

  1. 一种化学强化微晶玻璃，其特征在于：具有Na/Li交换层，所述化学强化微晶玻璃的压应力层深度Doc为0.15t～0.22t；
    所述化学强化微晶玻璃表层强化深度50μm处的压应力强度CS50为130+(20t-13)×15MPa～230+(20t-13)×15MPa；
    且所述CS50与所述Doc满足：CS50/(Doc-50)为1.4～6，单位为MPa/μm；
    其中，t为所述化学强化微晶玻璃的总厚度。
  2. 根据权利要求1所述的化学强化微晶玻璃，其特征在于：采用10mm直径圆头金属压杆挤压所述化学强化微晶玻璃至破碎时，碎片最长边平均尺寸≥5mm；和/或
    厚度为0.6mm时，所述化学强化微晶玻璃的砂纸跌落高度≥1.5m；和/或
    在温度85℃/湿度85％环境保存72h，所述化学强化微晶玻璃的外表面不出现钠盐析出；和/或
    所述化学强化微晶玻璃在厚度≤0.8mm时，在400-940nm波长的光平均透过率≥89.5％，且550nm与400nm波长时的单点透过率差<1％，色坐标b绝对值≤0.4，雾度≤0.15％。
  3. 根据权利要求1-2任一项所述的化学强化微晶玻璃，其特征在于：用于形成所述化学强化微晶玻璃的素微晶玻璃的主晶相为硅酸锂或β-石英固溶体中的任一种，所含总晶相质量分数为35～75％，其中次晶相总含量<5％。
  4. 根据权利要求3所述的化学强化微晶玻璃，其特征在于：所述素微晶玻璃包括主要组成和成核剂；
    所述主要组成包括SiO 2、Al 2O 3、B 2O 3、Li 2O、Na 2O、K 2O，且满足：SiO 2+Al 2O 3+B 2O 3含量为58～85mol％；Li 2O+Na 2O+K 2O含量为10～32mol％；
    所述成核剂包括TiO 2、P 2O 5、ZrO 2，且满足：TiO 2+P 2O 5+ZrO 2含量为2～8mol％。
  5. 根据权利要求3所述的化学强化微晶玻璃，其特征在于：所述素微晶玻璃采用熔融浇筑法或者压延法制备形成；和/或
    所述素微晶玻璃经过如下两步热处理：
    第一步热处理：温度为500-600℃，处理时间为0.1-10h；
    第二步热处理：温度为640-800℃，处理时间为0.1-10h。
  6. 根据权利要求3所述的化学强化微晶玻璃，其特征在于：所述化学强化微晶玻璃的杨氏模量≥95GPa。
  7. 根据权利要求3所述的化学强化微晶玻璃，其特征在于：所述化学强化微晶玻璃的表层还具有K/Na交换层。
  8. 根据权利要求7所述的化学强化微晶玻璃，其特征在于：所述K/Na交换层的厚度≤3μm。
  9. 根据权利要求1、2、4-8任一项所述的化学强化微晶玻璃，其特征在于：所述化学强化微晶玻璃为2D形态化学强化微晶玻璃、2.5D形态化学强化微晶玻璃、3D形态化学强化微晶玻璃中的任一种。
  10. 根据权利要求9所述的化学强化微晶玻璃，其特征在于：所述化学强化微晶 玻璃为2D形态化学强化微晶玻璃或/和2.5D形态化学强化微晶玻璃，所述2D形态化学强化微晶玻璃或/和2.5D形态化学强化微晶玻璃的色坐标b绝对值≤0.3，雾度≤0.14。
  11. 根据权利要求9所述的化学强化微晶玻璃，其特征在于：所述化学强化微晶玻璃为所述3D形态化学强化微晶玻璃，其长边折弯角度为15～89°；和/或
    所述3D形态化学强化微晶玻璃的色坐标b绝对值≤0.4，雾度≤0.15。
  12. 一种化学强化微晶玻璃的制备方法，包括如下步骤：
    将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理，形成Na/Li交换层。
  13. 根据权利要求12所述的制备方法，其特征在于：所述含钠盐浴包括NaNO 3或NaNO 3与KNO 3的混合盐，在所述NaNO 3与KNO 3的混合盐混合盐中，所述NaNO 3含量≥50wt％；和/或
    所述一次化学强化处理的温度380-450℃，强化时间0.5-6h。
  14. 根据权利要求12或13所述的制备方法，其特征在于：在所述一次化学强化处理之后，还包括对形成有所述Na/Li交换层的化学强化微晶玻璃于含钾盐浴中进行二次化学强化处理，形成K/Na交换层。
  15. 根据权利要求14所述的制备方法，其特征在于：所述含钾盐浴包括KNO 3或NaNO 3与KNO 3的混合盐；在所述NaNO 3与KNO 3的混合盐中，所述KNO 3含量≥80wt％；和/或
    所述二次化学强化处理的温度380-450℃，强化时间0.2-1h。
  16. 根据权利要求12所述的制备方法，其特征在于：在所述将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理之前，还包括将所述素微晶玻璃进行如下热弯处理的步骤：
    将所述素微晶玻璃于650～750℃下进行单段热弯处理30～120s，形成3D素微晶玻璃，其中，所述单段热弯处理的压力为0.1～0.9MPa。
  17. 一种电子设备，其特征在于：包括玻璃部件，所述玻璃部件为权利要求1-11任一所述的化学强化微晶玻璃或根据权利要求12-16任一所述的制备方法制备的化学强化微晶玻璃。
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