WO2023206002A1 - Vitrocéramique, verre trempé, leur procédé de préparation et leur utilisation - Google Patents

Vitrocéramique, verre trempé, leur procédé de préparation et leur utilisation Download PDF

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WO2023206002A1
WO2023206002A1 PCT/CN2022/088998 CN2022088998W WO2023206002A1 WO 2023206002 A1 WO2023206002 A1 WO 2023206002A1 CN 2022088998 W CN2022088998 W CN 2022088998W WO 2023206002 A1 WO2023206002 A1 WO 2023206002A1
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glass
mass percentage
crystallized glass
exceeds
crystallized
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PCT/CN2022/088998
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English (en)
Chinese (zh)
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刘红刚
平文亮
肖子凡
王明忠
康庆伟
赵北玉
毛佳颖
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清远南玻节能新材料有限公司
咸宁南玻光电玻璃有限公司
中国南玻集团股份有限公司
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Priority to PCT/CN2022/088998 priority Critical patent/WO2023206002A1/fr
Publication of WO2023206002A1 publication Critical patent/WO2023206002A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/02—Tempering or quenching glass products using liquid
    • C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • This application relates to the technical field of glass products, specifically to a kind of crystallized glass, strengthened glass and their preparation methods and applications.
  • Crystallized glass also known as glass ceramics, is a material made by controlled precipitation of microcrystals as the base glass for certain specific glass systems. Its microcrystalline phase is evenly distributed in the glass phase. By heat treatment of traditional glass, a large number of tiny crystals are uniformly precipitated in the glass, forming a dense multi-phase complex of crystal phase and glass phase, thereby obtaining crystallized glass. With the help of the mechanical properties of the crystal material itself, the average hardness, flexural strength, fracture toughness and other mechanical properties of the glass can be improved.
  • the average visible light transmittance of the glass-ceramics is generally poor, making it difficult to achieve both high transmittance and good mechanical properties (especially high surface pressure). stress, stress depth, drop performance, ring crush strength and four-point bending strength).
  • a kind of crystallized glass the components of which include: in terms of mass percentage:
  • the ratio of the mass of the Na 2 O to the sum of the masses of the P 2 O 5 , the ZrO 2 and the TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass ceramics includes lithium disilicate and hectorite.
  • a method for preparing crystallized glass including the following steps:
  • the precursor glass is sequentially subjected to nucleation and crystallization treatments to prepare crystallized glass;
  • the components of the crystallized glass include, in terms of mass percentage:
  • the ratio of the mass of the Na 2 O to the sum of the masses of the P 2 O 5 , the ZrO 2 and the TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass ceramics includes lithium disilicate and hectorite.
  • a kind of strengthened glass which is obtained by chemically strengthening the crystallized glass
  • the components of the crystallized glass include, in terms of mass percentage:
  • the ratio of the mass of the Na 2 O to the sum of the masses of the P 2 O 5 , the ZrO 2 and the TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass ceramics includes lithium disilicate and hectorite.
  • a method for preparing strengthened glass including the following steps:
  • the first strengthening treatment perform the first strengthening treatment on the crystallized glass in a first molten salt; in terms of mass percentage, the first molten salt includes 30% to 100% sodium nitrate and 0 to 70% potassium nitrate;
  • Second strengthening treatment The crystallized glass that has undergone the first strengthening treatment is subjected to a second strengthening treatment in a second molten salt; in terms of mass percentage, the second molten salt includes 0 to 6% sodium nitrate. and 94% to 100% potassium nitrate;
  • the components of the crystallized glass include, in terms of mass percentage:
  • the ratio of the mass of the Na 2 O to the sum of the masses of the P 2 O 5 , the ZrO 2 and the TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass ceramics includes lithium disilicate and hectorite.
  • the strengthened glass is obtained from crystallized glass through chemical strengthening treatment
  • the components of the crystallized glass include, in terms of mass percentage:
  • the ratio of the mass of the Na 2 O to the sum of the masses of the P 2 O 5 , the ZrO 2 and the TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass ceramics includes lithium disilicate and hectorite.
  • An electronic product including a body and a protective glass embedded in the body, where the protective glass is tempered glass;
  • the strengthened glass is obtained from crystallized glass through chemical strengthening treatment
  • the components of the crystallized glass include, in terms of mass percentage:
  • the ratio of the mass of the Na 2 O to the sum of the masses of the P 2 O 5 , the ZrO 2 and the TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass ceramics includes lithium disilicate and hectorite.
  • Figure 1 is a flow chart of a method for preparing crystallized glass according to an embodiment of the present application
  • Figure 2 is a flow chart of a preparation method of tempered glass according to an embodiment of the present application
  • Figure 3 is the X-ray diffraction pattern (XRD) of the crystallized glass of Example 9;
  • Figure 4 is a graph showing the relationship between the ion exchange capacity CS*Dol-K and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) of the crystallized glass according to the embodiment of the present application.
  • One embodiment of the present application provides a crystallized glass, the components of which include, in terms of mass percentage:
  • the ratio of the mass of Na 2 O to the sum of the masses of P 2 O 5 , ZrO 2 and TiO 2 is 0.44 to 1.55;
  • the crystal phase of the glass-ceramics includes lithium disilicate and feldspar.
  • Li 2 Si 2 O 5 Glass-ceramics with lithium disilicate (Li 2 Si 2 O 5 ) as the main crystal phase are collectively called lithium disilicate glass-ceramics.
  • the Li 2 Si 2 O 5 crystal phase can prevent the further expansion of surface or internal microcracks or make the microcracks deflect and difficult to spread, thereby greatly improving the strength and mechanical properties of the glass-ceramics. Therefore, the lithium disilicate crystal phase can provide microcrystalline ceramics with high mechanical strength and fracture toughness, and can undergo ion exchange to obtain additional mechanical strength.
  • Illite is a monoclinic crystal that has a three-dimensional framework structure including a layered structure with folded Si 2 O 5 layers connected by Li and Al tetrahedra. Li is tetrahedrally coordinated with oxygen. Hectorite is a source of lithium and can be used as a low thermal expansion phase to improve the thermal shock resistance of glass-ceramics. Hectorite has a fine grain size that increases the visible light transmittance of glass-ceramics.
  • SiO2 is an oxide involved in glass forming and can be used to stabilize glass and glass-ceramic network structures. Regarding viscosity and mechanical properties, viscosity and mechanical properties are affected by the composition of the glass. In glasses and glass-ceramics, SiO 2 serves as the main glass-forming oxide for the base glass and can be used to stabilize the network structure of the glass and glass-ceramics. When the base glass is heat treated to nucleate crystallization into glass-ceramics, the concentration of SiO 2 should be high enough to form the lucite crystal phase. However, the melting temperature of high SiO glass is not ideal. Therefore, in the embodiment of the present application, the mass percentage of SiO 2 in the crystallized glass is 60.5% to 80%.
  • the mass percentage of SiO2 is 60.5%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78% or 80%. Further, the mass percentage of SiO 2 is 66.5% to 73.5%. Furthermore, the mass percentage of SiO 2 is 70.5% to 72.5%.
  • Al 2 O 3 also stabilizes the network and also provides improved mechanical properties and chemical durability. If the content of Al 2 O 3 is too high, the formation power of lithium disilicate can be reduced to the extent that the interlocking structure cannot be formed.
  • the melting temperature of Al 2 O 3 is relatively high. As a network intermediate, the amount of Al 2 O 3 can often be adjusted to control the viscosity. If the amount of Al2O3 is too high, it also usually increases the viscosity of the melt.
  • the Al 2 O 3 in the residual glass phase can enhance the Li-Na and Na-K ion exchange capabilities. Therefore, in the embodiment of the present application, the mass percentage of Al 2 O 3 is 3% to 18.5%.
  • the mass percentage of Al 2 O 3 is 3%, 5%, 8%, 10%, 12%, 14%, 15%, 16%, 18% or 18.5%. Further, the mass percentage of Al 2 O 3 is 6.5% to 8.5%. Furthermore, the mass percentage of Al 2 O 3 is 6.5% to 7.0% or 7.5% to 8.5%.
  • Li 2 O contributes to the formation of lithium feldspar and lithium silicate crystal phases.
  • the mass percentage of Li 2 O is 5% to 15%.
  • the mass percentage of Li 2 O is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.
  • the mass percentage of Li 2 O is 7% to 11%.
  • the mass percentage of Li 2 O is 9.5% to 11%.
  • Na 2 O can control the residual glass phase of the glass, and Na 2 O is beneficial to enhancing the chemical strengthening ability of the base glass and glass-ceramics.
  • the mass percentage of Na 2 O is 2% to 9%.
  • the mass percentage of Na 2 O is 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.
  • the mass percentage of Na 2 O is 3% to 8%.
  • the mass percentage of Na 2 O is 3.5% to 8%.
  • the mass percentage of K 2 O is 0 to 2%.
  • the mass percentage of K 2 O is 0, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5% or 2%. Further, the mass percentage of K 2 O is 0 to 1%.
  • P 2 O 5 can be used as a nucleating agent to promote bulk nucleation. If the P 2 O 5 concentration is too low, the base glass will not crystallize, or only surface crystallization will form at a higher temperature, which is not conducive to the control of the crystallization process; but if the P 2 O 5 concentration is too high, the base glass will not crystallize during the formation process. It will be difficult to control devitrification when cooling. Therefore, in the embodiment of the present application, the mass percentage of P 2 O 5 is 1% to 7%. Alternatively, the mass percentage of P 2 O 5 is 1%, 2%, 3%, 4%, 5%, 6% or 7%. Further, the mass percentage of P 2 O 5 is 1% to 2%.
  • ZrO 2 can improve the stability of the Li 2 O-Al 2 O 3 -SiO 2 glass system by significantly reducing the glass devitrification during the formation process and lowering the liquidus temperature.
  • transparent glass can be formed because the high field strength of ZrO 2 can attract part of the network external oxides, and the solubility of ZrO 2 in the glass body is low and it is easy to precipitate during heat treatment.
  • ZrO 2 agglomerates, together with Li 3 PO 4 , become glass crystal nuclei.
  • adding ZrO 2 can also help reduce the size of feldspar crystal grains, which helps to form transparent glass-ceramics.
  • the melting temperature of ZrO 2 is extremely high, and its solubility in the glass system is limited. The content is too high, resulting in a very high melting temperature of the basic glass, making it difficult to form a uniform glass body, and it is easy to precipitate impurity crystal phases such as ZrO 2 , resulting in glass devitrification. Therefore, in the embodiment of the present application, the mass percentage of ZrO 2 is 2% to 8%. Alternatively, the mass percentage of ZrO2 is 2%, 3%, 4%, 5%, 6%, 7% or 8%. Further, the mass percentage of ZrO 2 is 3% to 5%.
  • TiO 2 has a similar effect to ZrO 2 and can form fine crystal nuclei in the glass. Too much will cause the base glass to turn yellow. Therefore, in the embodiment of the present application, the mass percentage of TiO 2 is 0 to 2%. Alternatively, the mass percentage of TiO2 is 0, 0.2%, 0.5%, 0.8%, 1%, 1.5% or 2%. Further, the mass percentage of TiO 2 is 0 to 1%.
  • the components of the above-mentioned glass-ceramics include specific contents of SiO 2 , Al 2 O 3 , Li 2 O, P 2 O 5 , ZrO 2 , Na 2 O, K 2 O and TiO 2 , and the mass of Na 2 O is The ratio of the sum of the masses of P 2 O 5 , ZrO 2 and TiO 2 is 0.44 to 1.55; the crystal phase of the glass-ceramics includes lithium disilicate and feldspar.
  • the above-mentioned glass-ceramics have both high transmittance and good mechanical properties.
  • the above-mentioned glass-ceramics After chemical strengthening, the above-mentioned glass-ceramics have both high surface stress and large deep stress depth, as well as high hardness and strong impact resistance.
  • the ratio of the mass of Na 2 O to the sum of the masses of P 2 O 5 , ZrO 2 and TiO 2 is 0.8 to 0.155.
  • the ratio of the mass of Na 2 O to the sum of the masses of P 2 O 5 , ZrO 2 and TiO 2 in the range of 0.8 to 1.55, the surface stress and deep stress depth of the chemically strengthened glass-ceramics can be further improved. Crystal glass has good mechanical properties.
  • the particle size (grain size) of the crystal phase of the glass-ceramics is 25 nm to 80 nm. Furthermore, the particle size of the crystal phase of the glass-ceramics is 28 nm to 79 nm.
  • the crystal grain size of the above-mentioned crystallized glass is smaller, so the average transmittance of the obtained crystallized glass is higher.
  • the crystal phase of the glass ceramics further includes at least one of lithium metasilicate and lithium phosphate.
  • the crystal form of lithium metasilicate is nanometer-sized and uniformly spherical. It is the precursor of the lithium disilicate crystal phase.
  • the glass-ceramic matrix often retains some lithium metasilicate Li 2 SiO 3 due to incomplete reaction. Due to the structural characteristics of lithium metasilicate, the hardness of glass ceramics containing lithium metasilicate is lower, which is beneficial to the cold working process to reduce wear and tear. Tool loss, processing time and product defects are reduced, and the yield rate is increased. And microcracks caused by processing or grinding, during the secondary crystallization process, that is, the process in which the main crystal phase in the ceramic changes from spherical lithium metasilicate to lath-shaped lithium disilicate (700°C ⁇ 800°C) , it is easy to recover or seal due to crystalline transformation and crystal growth.
  • the chemical resistance of lithium metasilicate crystal is about 1/20 to 1/50 of that of glass, and it is very easy to be eroded by alkaline cleaning agents or acidic cleaning agents during the cleaning process, or eroded by sweat during daily use, thus causing Point-like defects are left on the surface of the glass-ceramics, which may even reduce the strength of the glass-ceramics products. Therefore, the present invention contains as little or no lithium metasilicate as possible.
  • Phosphate crystal phases such as lithium phosphate or aluminum phosphate are by-products of the lithium aluminosilicate glass system using composite nucleating agents such as P 2 O 5 and ZrO 2 or TiO 2 , which are produced through the aggregation of high field strength ions P/Zr/Ti.
  • a nanometer-sized differential phase (rich in P, rich in Ti or rich in Zr, or called phosphate, titanate or zirconate micronucleus) is formed in the glass matrix, which provides conditions for the growth of the lithium metasilicate crystal phase. Conditions are the key to the formation of glass-ceramics. Generally, they still exist as glass structural units before 700°C.
  • the crystallized glass further includes no more than 3% MgO by mass percentage.
  • the mass percentage of MgO is 0, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, in terms of mass percentage, the content of MgO does not exceed 2%, 1.5%, 1% or 0.5%.
  • the crystallized glass further includes no more than 3% CaO by mass percentage.
  • the mass percentage of CaO is 0, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, in terms of mass percentage, the content of CaO does not exceed 2%, 1.5%, 1% or 0.5%.
  • the crystallized glass further includes no more than 2% SrO by mass percentage.
  • the mass percentage of SrO is 0, 0.5%, 1%, 1.5% or 2%. Further, in terms of mass percentage, the content of SrO does not exceed 1.5%, 1% or 0.5%.
  • the crystallized glass further includes no more than 3% ZnO in terms of mass percentage.
  • the mass percentage of ZnO is 0, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, in terms of mass percentage, the content of ZnO does not exceed 2%, 1.5%, 1% or 0.5%.
  • B 2 O 3 helps provide a base glass with a low melting temperature.
  • adding B 2 O 3 to the base glass can promote the phase separation, nucleation and crystallization of the base glass, shorten the crystallization time of the base glass, especially the precipitation of the feldspar crystal phase, and the glass-ceramics simultaneously precipitate lithium disilicate and Hectorite helps to achieve an interlocking crystal microstructure and also improves the damage resistance of glass ceramics.
  • the boron in the residual glass is not charge balanced by an alkali oxide or a divalent cationic oxide, the boron will be in a triangular-coordinated state (or triple-coordinated boron), passing through the [BO 3 ] triangle and [BO 4 ]
  • the conversion of tetrahedrons adjusts the oxygen-to-silicon ratio of the base glass, which opens the structure of the glass and reduces the brittleness of the glass.
  • it and other residual glass components act as lubricants and isolation phases between crystal phases to prevent crystallization.
  • the secondary growth of the phase leads to the growth of the crystal phase and the loss of clarity or strength of the glass.
  • the crystallized glass further includes 0 to 3% B 2 O 3 in terms of mass percentage.
  • the mass percentage of B 2 O 3 is 0, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, in terms of mass percentage, the content of B 2 O 3 does not exceed 2%, 1.5%, 1% or 0.5%.
  • the components of the glass-ceramics include: SiO 2 66.5% to 73.5%, Al 2 O 3 3% to 18.5%, Li 2 O 5% to 15%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3% , ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the crystallized glass include: SiO 2 66.5% ⁇ 73.5%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 5% ⁇ 15%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 66.5% ⁇ 73.5%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 66.5% ⁇ 73.5%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 66.5% ⁇ 73.5%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 2% ⁇ 8%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 66.5% ⁇ 73.5%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% to 80%, Al 2 O 3 6.5% to 8.5%, Li 2 O 5% to 15%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3% , ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 2% ⁇ 8%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 6.5% ⁇ 8.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% to 80%, Al 2 O 3 3% to 18.5%, Li 2 O 7% to 11%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3% , ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 3% ⁇ 18.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 3% ⁇ 18.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 2% ⁇ 8%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the glass-ceramics include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 3% ⁇ 18.5%, Li 2 O 7% ⁇ 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the crystallized glass include: SiO 2 60.5% to 80%, Al 2 O 3 3% to 18.5%, Li 2 O 5% to 15%, P 2 O 5 1% ⁇ 2%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the crystallized glass include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 3% ⁇ 18.5%, Li 2 O 5% ⁇ 15%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the crystallized glass include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 3% ⁇ 18.5%, Li 2 O 5% ⁇ 15%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3%, ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%.
  • the components of the crystallized glass include: SiO 2 60.5% ⁇ 80%, Al 2 O 3 3% ⁇ 18.5%, Li 2 O 5% ⁇ 15%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 2%, CaO 0 ⁇ 2%, ZnO 0 ⁇ 2%, SrO 0 ⁇ 1% and B 2 O 3 0 ⁇ 3%.
  • the components of the crystallized glass include: SiO 2 60.5% to 80%, Al 2 O 3 3% to 18.5%, Li 2 O 5% to 15%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 0.5%, MgO 0 ⁇ 1.5% and B 2 O 3 0 ⁇ 1.5%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.44 to 1.50, and the crystal phase includes lithium feldspar and lithium disilicate.
  • the components of the crystallized glass include: SiO 2 66.5% to 73.5%, Al 2 O 3 6.5% to 7%, Li 2 O 9.5% to 10.5%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3.5% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3% , ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.5 ⁇ 1.33.
  • the crystal phase includes lithium-transmissive long stone and lithium disilicate.
  • the components of the glass-ceramics include: SiO 2 70.5% to 72.5%, Al 2 O 3 7.5% to 8.5%, Li 2 O 7% to 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 1%, MgO 0 ⁇ 1% and B 2 O 3 0 ⁇ 1%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.44 to 1.33, and the crystal phase includes lithium feldspar and lithium disilicate.
  • the average transmittance (380nm-780nm) of the crystallized glass is not less than 83%. Further, the average transmittance of the crystallized glass is not less than 87% or 89%.
  • the above-mentioned crystallized glass has a high average transmittance and good mechanical strength, so it is suitable for preparing cover glass for electronic products.
  • the crystallized glass has a haze of less than 2.7%. Further, the haze of the crystallized glass is less than 2.0% or 1.0%. The haze of the above-mentioned crystallized glass is less than 2.7% or lower, and it is transparent or translucent.
  • the components of the crystallized glass include: SiO 2 60.5% to 80%, Al 2 O 3 3% to 18.5%, Li 2 O 5% to 15%, P 2 O 5 1% ⁇ 7%, ZrO 2 2% ⁇ 8%, Na 2 O 2% ⁇ 9%, K 2 O 0 ⁇ 0.5%, MgO 0 ⁇ 1.5% and B 2 O 3 0 ⁇ 1.5%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.44 to 1.50, and the crystal phase includes lithium feldspar and lithium disilicate.
  • the grain size of crystallized glass is 28nm ⁇ 79nm, the average transmittance is greater than 83.8%, and the haze is less than 2.65%.
  • the surface stress value of glass-ceramics exceeds 623MPa
  • the surface stress depth Dol-K exceeds 9.2 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 61MPa
  • the deep stress depth Dol-Na exceeds 132 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 746kgf/mm 2
  • the four-point bending strength exceeds 717MPa
  • the falling ball impact energy exceeds 0.39J
  • the ring pressure strength exceeds 1000N.
  • the components of the crystallized glass include: SiO 2 66.5% to 73.5%, Al 2 O 3 6.5% to 7%, Li 2 O 9.5% to 10.5%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3.5% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2%, MgO 0 ⁇ 3%, CaO 0 ⁇ 3% , ZnO 0 ⁇ 3%, SrO 0 ⁇ 2% and B 2 O 3 0 ⁇ 3%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.5 ⁇ 1.33.
  • the crystal phase includes lithium-transmissive long stone and lithium disilicate.
  • the grain size of crystallized glass is 26nm ⁇ 65nm, the average transmittance is greater than 84.6%, and the haze is less than 2.17%.
  • the surface stress value of crystallized glass exceeds 693MPa
  • the surface stress depth Dol-K exceeds 12.1 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 83.6MPa
  • the deep stress depth Dol-Na exceeds 133.2 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 762kgf/mm 2
  • the four-point bending strength exceeds 785MPa
  • the falling ball impact energy exceeds 0.42J
  • the ring pressure strength exceeds 1040N.
  • the components of the glass-ceramics include: SiO 2 70.5% to 72.5%, Al 2 O 3 7.5% to 8.5%, Li 2 O 7% to 11%, P 2 O 5 1% ⁇ 2%, ZrO 2 3% ⁇ 5%, Na 2 O 3% ⁇ 8%, K 2 O 0 ⁇ 1%, MgO 0 ⁇ 1% and B 2 O 3 0 ⁇ 1%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.44 to 1.33, and the crystal phase includes lithium feldspar and lithium disilicate.
  • the grain size of crystallized glass is 29nm ⁇ 71nm, the average transmittance is greater than 89.1%, and the haze is less than 0.38%.
  • the surface stress value of glass-ceramics exceeds 693MPa
  • the surface stress depth Dol-K exceeds 10.4 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 78.5MPa
  • the deep stress depth Dol-Na exceeds 138.9 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 759kgf/mm 2
  • the four-point bending strength exceeds 803MPa
  • the falling ball impact energy exceeds 0.46J
  • the ring pressure strength exceeds 1040N.
  • FIG. 1 another embodiment of the present application also provides the above-mentioned preparation method of crystallized glass, including the following steps S110 to S130.
  • Step S110 Melt raw materials into clear glass liquid.
  • the melting temperature is 1400°C to 1600°C.
  • the melting time is 6h ⁇ 8h.
  • Step S120 Shape the clear glass liquid to prepare precursor glass.
  • the forming process is selected from one of the float forming process, the overflow down-drawing method, the upward drawing method, the flat drawing method and the rolling method.
  • Step S130 Nucleate and crystallize the precursor glass in sequence to prepare crystallized glass.
  • the temperature of the nucleation treatment is 500°C to 640°C; the time of the nucleation treatment is 6h to 24h.
  • step S130 the temperature of the crystallization treatment is 680°C to 740°C; the time of the crystallization treatment is 1h to 18h.
  • a step of annealing the precursor glass is also included before step S130.
  • the annealing treatment time is 2h to 4h.
  • Another embodiment of the present application also provides a strengthened glass, which is obtained by chemically strengthening the above-mentioned glass-ceramics.
  • the above-mentioned tempered glass is obtained by chemically strengthening the above-mentioned crystallized glass, and has both good transmittance and mechanical properties.
  • the surface stress value of strengthened glass exceeds 623MPa
  • the surface stress depth Dol-K exceeds 9.2 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 61MPa
  • the deep stress depth Dol-Na exceeds 132 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 746kgf/mm 2
  • the four-point bending strength exceeds 717MPa
  • the falling ball impact energy exceeds 0.39J
  • the ring pressure strength exceeds 1000N.
  • the surface stress value of the chemically strengthened glass-ceramic exceeds 623 MPa
  • the stress value at a depth of 30 ⁇ m exceeds 61 MPa
  • the surface stress depth Dol-K exceeds 9.2 ⁇ m
  • the deep stress depth Dol-Na exceeds 132 ⁇ m.
  • the surface Vickers hardness of the chemically strengthened glass-ceramic exceeds 746 kgf/mm 2 . Furthermore, the surface Vickers hardness of chemically strengthened glass-ceramics exceeds 762kgf/mm 2 .
  • the four-point bending strength of chemically strengthened glass-ceramics exceeds 717 MPa. Furthermore, the four-point bending strength of chemically strengthened glass-ceramics exceeds 781MPa, 796MPa, 803MPa or 828MPa.
  • the chemically strengthened glass-ceramics have a falling ball impact energy exceeding 0.39 J. Furthermore, the falling ball impact energy of chemically strengthened glass-ceramics exceeds 0.42J, 0.46J or 0.55J.
  • the ring crush strength of chemically strengthened glass-ceramics exceeds 1000 N. Furthermore, the ring compressive strength of chemically strengthened glass-ceramics exceeds 1012N, 1060N or 1233N.
  • Another embodiment of the present application also provides the above-mentioned preparation method of tempered glass.
  • the chemical strengthening process includes steps S210 to S220.
  • Step S210 First strengthening treatment: perform the first strengthening treatment on the crystallized glass in the first molten salt; in terms of mass percentage, the first molten salt includes 30% to 100% sodium nitrate and 0 to 70% potassium nitrate. . Preferably, in terms of mass percentage, the first molten salt includes 40% sodium nitrate and 60% potassium nitrate.
  • the temperature of the first strengthening treatment is 440°C to 500°C; the time of the first strengthening treatment is 4h to 12h.
  • Step S220 Second strengthening treatment: The first strengthened glass-ceramics are subjected to a second strengthening treatment in a second molten salt; in terms of mass percentage, the second molten salt includes 0 to 6% sodium nitrate and 94% ⁇ 100% potassium nitrate. Preferably, the second molten salt includes 100% potassium nitrate by mass percentage.
  • the temperature of the second strengthening treatment is 380°C to 400°C; the time of the second strengthening treatment is 2h to 6h.
  • Another embodiment of the present application also provides the application of the above-mentioned tempered glass in preparing protective glass, photoelectric glass, fire-proof glass or architectural glass.
  • Another embodiment of the present application also provides an electronic product, including a main body and a protective glass embedded in the main body, where the protective glass is the above-mentioned tempered glass.
  • Examples 1 to 41 and Comparative Examples 1 to 15 were cut into 50mm*50mm*0.7mm glass sheets by Shenyang Kejing's STX-1203 wire cutting machine, and cut into 50mm*50mm*0.7mm glass sheets by Shenzhen Haide's HD-640- Thinned and polished with a 5L double-sided grinding and polishing machine, and then edged by CNC.
  • the surface Vickers hardness was tested using the FALCON400 hardness tester from the Netherlands, and the Lambda950 UV-visible spectrophotometer from the American PerkinElmer company was used to test the transmittance in the wavelength range of 380nm to 780nm. Rate.
  • Example 1 to 41 and Comparative Examples 1 to 15 were heat treated in a Naber thermal crystallization furnace according to the crystallization process in Table 1, and the crystallized glass blocks were processed by Shenyang Kejing
  • the STX-1203 wire cutting machine is cut into 70mm*140mm*0.7mm glass sheets, which are thinned and polished by Shenzhen Haide's HD-640-5L double-sided grinding and polishing machine, and then CNC edged, using the FALCON400 hardness of the Netherlands' Inno
  • the surface Vickers hardness was tested with a meter, the Lambda950 UV-visible spectrophotometer of the American PerkinElmer Company was used to test the transmittance in the wavelength range of 380nm to 780nm, the SUGA optical HZ-V3 haze meter was used to test the sample haze, and the Bruker X-ray diffractometer Bruker D8 Test its crystal phase and grain size in advance.
  • the glass components of Examples 1 to 6 include, in terms of mass percentage: SiO 2 60.5% to 80%, Al 2 O 3 3% to 18.5%, Li 2 O 5% to 15%, and P 2 O 5 1% ⁇ 2%, ZrO 2 2.5% ⁇ 4%, Na 2 O 2% ⁇ 9% and B 2 O 3 0 ⁇ 1%, and Na 2 O / (P 2 O 5 +ZrO 2 + TiO 2 ) is 0.44 ⁇ 1.50.
  • the crystal phases of lithium feldspar and lithium disilicate are uniformly precipitated, and may also contain a small amount of lithium metasilicate.
  • the grain size is 28nm to 68nm.
  • the average transmittance before crystallization treatment is greater than 87.2 %, haze is less than 0.89%.
  • the surface stress value CS of the glass exceeds 623MPa
  • the surface stress depth Dol-K exceeds 9.2 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 61MPa
  • the deep stress depth Dol-Na exceeds 132 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 746kgf/mm 2
  • the four-point bending strength exceeds 803MPa
  • the falling ball impact energy exceeds 0.39J
  • the ring pressure strength exceeds 1012N.
  • the glass components of Examples 7 to 12 in terms of mass percentage, include: SiO 2 70.5%, Al 2 O 3 7%, Li 2 O 7%, P 2 O 5 1% to 7%, ZrO 2 2% to 8%, Na 2 O 4% ⁇ 4.5%, K 2 O 0 ⁇ 0.5%, MgO 0 ⁇ 1.5% and B 2 O 3 0 ⁇ 1.5%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.44 ⁇ 0.75.
  • the crystal phases of lithium feldspar and lithium disilicate are uniformly precipitated. Secondly, it may also contain a small amount of lithium metasilicate or lithium phosphate.
  • the grain size is 34nm ⁇ 79nm.
  • the average permeability before crystallization treatment is The rate is greater than 83.8%, and the haze is less than 2.65%.
  • the surface stress value CS of the glass exceeds 658MPa
  • the surface stress depth Dol-K exceeds 13.5 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 95MPa
  • the deep stress depth Dol-Na exceeds 142 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 753kgf/mm 2
  • the four-point bending strength exceeds 717MPa
  • the falling ball impact energy exceeds 0.39J
  • the ring pressure strength exceeds 1048N.
  • the crystalline phases in the crystallized glass prepared in Example 9 include lithium disilicate (Li 2 Si 2 O 5 ), lithium feldspar (LiAlSi 4 O 10 ) and lithium phosphate (Li 3 PO 4 ).
  • the intensity of the characteristic peaks of lithium disilicate (Li 2 Si 2 O 5 ) and lithium feldspar (LiAlSi 4 O 10 ) is relatively large, while the intensity of the characteristic peaks of lithium phosphate (Li 3 PO 4 ) is small.
  • the main crystal phases in crystallized glass are lithium disilicate (Li 2 Si 2 O 5 ) and lithium feldspar (LiAlSi 4 O 10 ), and contain a small amount of lithium phosphate (Li 3 PO 4 ).
  • the glass components of Examples 13 to 18, in terms of mass percentage, include: SiO 2 66.5%, Al 2 O 3 7.5%, Li 2 O 10.5%, P 2 O 5 2%, ZrO 2 4%, Na 2 O 5.5%, MgO 0-3%, CaO 0-3%, ZnO 0-3% and B 2 O 3 0-1%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.92.
  • the crystal phases of lithium feldspar and lithium disilicate are uniformly precipitated, and may also contain a small amount of lithium metasilicate.
  • the grain size is 44nm to 65nm.
  • the average transmittance before crystallization treatment is greater than 84.6 %, the haze is less than 2.17%.
  • the surface stress value CS of the glass exceeds 734MPa
  • the surface stress depth Dol-K exceeds 12.1 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 117MPa
  • the deep stress depth Dol-Na exceeds 139 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 763kgf/mm 2
  • the four-point bending strength exceeds 785MPa
  • the falling ball impact energy exceeds 0.42J
  • the ring pressure strength exceeds 1040N.
  • the glass components of Examples 19 to 24, in terms of mass percentage, include: SiO 2 66.5% to 73.5%, Al 2 O 3 6.5% to 7%, Li 2 O 9.5% to 10.5%, and P 2 O 5 2% , ZrO 2 4%, Na 2 O 3.5% ⁇ 8%, K 2 O 0 ⁇ 2%, TiO 2 0 ⁇ 2% and SrO 0 ⁇ 2%, and Na 2 O/(P 2 O 5 +ZrO 2 + TiO 2 ) is 0.50 to 1.33.
  • the crystal phases of lithium feldspar and lithium disilicate are uniformly precipitated, and may also contain a small amount of lithium metasilicate.
  • the grain size is 26nm to 69nm.
  • the average transmittance before crystallization treatment is greater than 88.5 %, haze is less than 0.59%.
  • the surface stress value CS of the glass exceeds 693MPa
  • the surface stress depth Dol-K exceeds 9.8 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 83.6MPa
  • the deep stress depth Dol-Na exceeds 133.2 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 762kgf/mm 2
  • the four-point bending strength exceeds 796MPa
  • the falling ball impact energy exceeds 0.46J
  • the ring pressure strength exceeds 1042N.
  • the glass components of Examples 25 to 30, in terms of mass percentage, include: SiO 2 70.5%, Al 2 O 3 7.5% to 8.5%, Li 2 O 7% to 11%, P 2 O 5 2%, ZrO 2 3% ⁇ 4%, Na 2 O 3% ⁇ 8%, MgO 0 ⁇ 1% and B 2 O 3 0 ⁇ 1%, and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) is 0.50 ⁇ 1.33.
  • lithium feldspar and lithium disilicate crystal phases are uniformly precipitated, with the grain size ranging from 35nm to 67nm.
  • the average transmittance before crystallization treatment is greater than 89.1%, and the haze is less than 0.38%.
  • the surface stress value CS of the glass exceeds 693.1MPa
  • the surface stress depth Dol-K exceeds 10.4 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 78.5MPa
  • the deep stress depth Dol-Na exceeds 138.9 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 759kgf/mm 2
  • the four-point bending strength exceeds 803MPa
  • the falling ball impact energy exceeds 0.46J
  • the ring pressure strength exceeds 1045N.
  • the glass components of Examples 31 to 36 include: SiO 2 72.5%, Al 2 O 3 7.5%, Li 2 O 9% to 11%, P 2 O 5 1% to 2.5%, ZrO 2 3% ⁇ 5%, Na 2 O 2% ⁇ 5.5%, K2O 0 ⁇ 1%, MgO 0 ⁇ 0.5% and B 2 O 3 0 ⁇ 1%, and Na 2 O/(P 2 O 5 +ZrO 2 + TiO 2 ) is 0.44 to 1.25.
  • lithium feldspar and lithium disilicate crystal phases are uniformly precipitated, with the grain size ranging from 29nm to 62nm.
  • the average transmittance before crystallization treatment is greater than 89.9%, and the haze is less than 0.31%.
  • the surface stress value CS of the glass exceeds 704.5MPa
  • the surface stress depth Dol-K exceeds 12.9 ⁇ m
  • the stress value CS30 at a depth of 30 ⁇ m exceeds 109.3MPa
  • the deep stress depth Dol-Na exceeds 143.2 ⁇ m.
  • the surface Vickers hardness of crystallized glass exceeds 759kgf/mm 2
  • the four-point bending strength exceeds 828MPa
  • the falling ball impact energy exceeds 0.52J
  • the ring pressure strength exceeds 1233N.
  • the glass components of Examples 37 to 41 include: SiO 2 66.5%, Al 2 O 3 7% to 7.5%, Li 2 O 10% to 10.5%, P 2 O 5 2%, ZrO 2 4%, Na 2 O 5.5% ⁇ 8%, MgO 0 ⁇ 4%, CaO 0 ⁇ 4%, ZnO 0 ⁇ 4%, SrO 0 ⁇ 2.5% and B 2 O 3 0 ⁇ 1%, and Na 2 O/ (P 2 O 5 +ZrO 2 +TiO 2 ) is 0.92 to 1.33. After uniform crystallization heat treatment, the crystal phases of lithium feldspar and lithium disilicate are uniformly precipitated, with the grain size ranging from 68nm to 122nm.
  • the average transmittance before crystallization treatment is 80.6% to 86.9%, and the haze is 1.63% to 1.63%. 6.17%.
  • the surface stress value CS of the glass is 595MPa ⁇ 692MPa, and the surface stress depth Dol-K is 5.8 ⁇ m ⁇ 10.3 ⁇ m.
  • the surface Vickers hardness of crystallized glass is 709kgf/mm 2 ⁇ 753kgf/mm 2 , the four-point bending strength is 639MPa ⁇ 785MPa, the falling ball impact energy is 0.32J ⁇ 0.36J, and the ring pressure strength is 726N ⁇ 885N.
  • the surface stress CS and surface stress depth Dol-K formed by exchanging Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ) in Tables 1 to 7 with Na ions in the glass and K ions in the strengthening salt
  • the product of is considered to be the embodiment of Na-K exchange ability.
  • Carry out mapping analysis on both. Refer to Figure 4, which is a graph showing the relationship between ion exchange capacity CS*Dol-K and Na 2 O/(P 2 O 5 +ZrO 2 +TiO 2 ).
  • Comparative Examples 1 to 15 the component ratio of the glass-ceramics was adjusted, and the obtained glass-ceramics were inferior to the examples in varying degrees in performance stresses such as strengthening stress, Vickers hardness, four-point bending strength, ring crush strength, and impact resistance. It is difficult for the prepared glass-ceramics to take into account high Vickers hardness, four-point bending strength, ring crush strength and appropriate strengthening stress.

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Abstract

La présente demande concerne un vitrocéramique, un verre trempé et son procédé de préparation et son utilisation. La vitrocéramique comprend, en pourcentages en masse : 60,5-80 % de SiO2, 3-18,5 % of Al2O3, 5-15 % de Li2O, 1-7 % de P2O5, 2-8 % de ZrO2, 2-9 % de Na2O, 0-2% de K2O et 0-2 % de TiO2. En outre, le rapport de la masse de Na2O à la somme de la masse de P2O5, ZrO2 et TiO2 est de 0,44-1,55. La phase cristalline de la vitrocéramique comprend du disilicate de lithium et de la pétalite.
PCT/CN2022/088998 2022-04-25 2022-04-25 Vitrocéramique, verre trempé, leur procédé de préparation et leur utilisation WO2023206002A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002097037A (ja) * 2000-02-01 2002-04-02 Ohara Inc ガラスセラミックス
CN107001120A (zh) * 2014-10-08 2017-08-01 康宁股份有限公司 具有透锂长石和硅酸锂结构的高强玻璃‑陶瓷
CN107840578A (zh) * 2017-12-01 2018-03-27 成都光明光电股份有限公司 微晶玻璃及其基板
CN107902909A (zh) * 2017-12-01 2018-04-13 成都光明光电股份有限公司 微晶玻璃及其基板
CN107963815A (zh) * 2017-12-01 2018-04-27 成都光明光电股份有限公司 微晶玻璃及其基板
CN109867447A (zh) * 2017-12-01 2019-06-11 成都光明光电股份有限公司 微晶玻璃及其基板
CN111087174A (zh) * 2019-12-19 2020-05-01 深圳市东丽华科技有限公司 一种具有高弹性模量的玻璃陶瓷、强化玻璃陶瓷及其制备方法
CN111757858A (zh) * 2018-02-27 2020-10-09 Ａｇｃ株式会社 三维形状的晶化玻璃、三维形状的化学强化玻璃以及它们的制造方法
CN112585101A (zh) * 2018-08-20 2021-03-30 康宁股份有限公司 具有改进的应力分布的玻璃陶瓷制品
CN113754289A (zh) * 2021-09-18 2021-12-07 重庆鑫景特种玻璃有限公司 一种低翘曲的强化微晶玻璃、及其制备方法和用途

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002097037A (ja) * 2000-02-01 2002-04-02 Ohara Inc ガラスセラミックス
CN107001120A (zh) * 2014-10-08 2017-08-01 康宁股份有限公司 具有透锂长石和硅酸锂结构的高强玻璃‑陶瓷
CN107840578A (zh) * 2017-12-01 2018-03-27 成都光明光电股份有限公司 微晶玻璃及其基板
CN107902909A (zh) * 2017-12-01 2018-04-13 成都光明光电股份有限公司 微晶玻璃及其基板
CN107963815A (zh) * 2017-12-01 2018-04-27 成都光明光电股份有限公司 微晶玻璃及其基板
CN109867447A (zh) * 2017-12-01 2019-06-11 成都光明光电股份有限公司 微晶玻璃及其基板
CN111757858A (zh) * 2018-02-27 2020-10-09 Ａｇｃ株式会社 三维形状的晶化玻璃、三维形状的化学强化玻璃以及它们的制造方法
CN112585101A (zh) * 2018-08-20 2021-03-30 康宁股份有限公司 具有改进的应力分布的玻璃陶瓷制品
CN111087174A (zh) * 2019-12-19 2020-05-01 深圳市东丽华科技有限公司 一种具有高弹性模量的玻璃陶瓷、强化玻璃陶瓷及其制备方法
CN113754289A (zh) * 2021-09-18 2021-12-07 重庆鑫景特种玻璃有限公司 一种低翘曲的强化微晶玻璃、及其制备方法和用途

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