WO2021068423A1 - 铝硅酸盐玻璃、强化玻璃及其制备方法和显示器件 - Google Patents

铝硅酸盐玻璃、强化玻璃及其制备方法和显示器件 Download PDF

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WO2021068423A1
WO2021068423A1 PCT/CN2019/130659 CN2019130659W WO2021068423A1 WO 2021068423 A1 WO2021068423 A1 WO 2021068423A1 CN 2019130659 W CN2019130659 W CN 2019130659W WO 2021068423 A1 WO2021068423 A1 WO 2021068423A1
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glass
mass percentage
aluminosilicate glass
aluminosilicate
mass
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PCT/CN2019/130659
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English (en)
French (fr)
Inventor
周翔磊
平文亮
肖子凡
王琰
刘红刚
陈志鸿
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清远南玻节能新材料有限公司
中国南玻集团股份有限公司
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Publication of WO2021068423A1 publication Critical patent/WO2021068423A1/zh

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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
    • 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
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the invention relates to the field of glass, in particular to aluminosilicate glass, strengthened glass, a preparation method thereof, and a display device.
  • Thin-plate glass is often used as a cover glass for protecting display devices or a cover glass for housings of portable terminal devices.
  • display devices such as these portable phones and PDAs have tended to be thinner and more functional, and require high mechanical strength. Therefore, it is generally necessary to chemically strengthen the thin glass substrate to obtain tempered glass.
  • This tempered glass can be chemically strengthened by performing ion exchange treatment in a molten salt containing potassium or sodium, so that the alkali metal ions on the glass surface can be exchanged with potassium ions or sodium ions in the ion exchange salt to form compression on the glass surface. Stress layer.
  • the traditional glass cover market is mainly based on (boron) aluminosilicate glass and lithium (boron) aluminosilicate glass, such as Corning’s Gorilla glass, NEG’s T2X-1, Asahi Glass’s Dragon Trace Glass, and domestic Xuhong’s Panda Glass and
  • the biggest advantage of CSG's KK3 glass is that it can be quickly chemically tempered, and a compressive stress layer is formed on the surface of the glass to increase the mechanical strength, impact resistance, friction resistance, and drop resistance of the glass. purpose.
  • the squeeze crack threshold of traditional glass is low, and it cannot provide a better protection when smart devices such as mobile phones accidentally fall to the ground.
  • An aluminosilicate glass by mass percentage, comprising: SiO 2 55% ⁇ 67%, Al 2 O 3 13% ⁇ 25%, B 2 O 3 0.5% ⁇ 4.0%, Li 2 O 1% ⁇ 8 %, Na 2 O 6% to 14%, ZrO 2 1% to 6%, K 2 O 0 to 4%, and MgO 0 to 4%.
  • a strengthened glass obtained by chemically strengthening the above-mentioned aluminosilicate glass obtained by chemically strengthening the above-mentioned aluminosilicate glass.
  • a method for preparing strengthened glass includes the following steps:
  • the above aluminosilicate glass is tempered for 2h-6h in a mixed melt of NaNO 3 and KNO 3 with a temperature of 390°C ⁇ 420°C and a mass ratio of 3:7 ⁇ 7:3, and then at a temperature of 380
  • the tempering treatment is carried out in the molten mixture of NaNO 3 and KNO 3 at a temperature of °C ⁇ 400°C and a mass ratio of 2:98 ⁇ 20:80 for 2h ⁇ 4h to obtain strengthened glass.
  • a display device includes the above-mentioned aluminosilicate glass or the above-mentioned strengthened glass or the strengthened glass prepared by the above-mentioned strengthened glass preparation method.
  • Fig. 1 is a process flow diagram of a method for preparing aluminosilicate glass according to an embodiment
  • FIG. 2 is a process flow diagram of a method for preparing strengthened glass according to an embodiment
  • Figure 3 is a schematic diagram of the calculation methods of a and b in the calculation formula of the crack threshold
  • Example 4 is a graph showing the relationship between the crack threshold value K of the strengthened glass of Example 1 to Example 21 and the value of A in the aluminosilicate glass.
  • the aluminosilicate glass of an embodiment includes, by mass percentage, SiO 2 55% to 67%, Al 2 O 3 13% to 25%, B 2 O 3 0.5% to 4.0%, Li 2 O 1% ⁇ 8%, Na 2 O 6% to 14%, ZrO 2 1% to 6%, K 2 O 0 to 4%, and MgO 0 to 4%.
  • the aluminosilicate glass also includes SrO with a mass percentage not exceeding 2%, ZnO with a mass percentage not exceeding 4%, P 2 O 5 with a mass percentage not exceeding 4%, and a mass percentage not exceeding 2 % Of at least one of TiO 2.
  • aluminosilicate glass further comprises not more than 3 percent by mass% of ZnO, less than 2% by mass percentage of P 2 O 5 mass percent and not more than 1% of at least one of TiO 2.
  • the aluminosilicate glass also includes P 2 O 5 with a mass percentage of not more than 1%.
  • the aluminosilicate glass further includes at least one of SnO 2 and CeO 2. Specifically, the mass percentage of SnO 2 does not exceed 2%. Further, the mass percentage of SnO 2 does not exceed 1%. The mass percentage of CeO 2 does not exceed 1%. Further, the mass percentage of CeO 2 does not exceed 0.5%.
  • the mass percentages of K 2 O and MgO can be zero independently of each other.
  • SrO, ZnO, P 2 O 5 , TiO 2 , SnO 2 and CeO 2 can all be omitted.
  • SiO 2 (silicon dioxide) is an important glass-forming oxide and an essential component for forming the glass skeleton. SiO 2 can improve the strength and chemical stability of the glass, and can make the glass obtain a higher strain point and a lower coefficient of thermal expansion. Therefore, in this embodiment, the mass percentage of SiO 2 is preferably 55% to 67%. The mass percentage of SiO 2 is more preferably 58% to 66%. The mass percentage of SiO 2 is most preferably 60% to 64%. If the mass percentage of SiO 2 is less than 55%, the glass main body network structure is poor, the mechanical properties are poor, and the weather resistance becomes poor.
  • the mass percentage of SiO 2 exceeds 67%, the melting temperature of the glass during the production process is too high, the energy consumption increases, and it is easy to cause frequent bubbles, stones and other defects. At the same time, the proportion of silica skeleton structure is high, and the network gap is small. It is not conducive to chemical enhancement of ion exchange and affects the efficiency of chemical enhancement.
  • Al 2 O 3 (aluminum oxide) can participate in the network to act as a network generator, and can reduce the crystallization tendency of glass, improve the chemical stability, thermal stability, mechanical strength, and hardness of the glass, and also improve the elastic mold of stretched glass. The amount of necessary ingredients. However, the addition of Al 2 O 3 will increase the viscosity of the glass. If there is too much Al 2 O 3 , it will be difficult to obtain glass with long material properties, making glass forming more difficult. In addition, the Al 3+ in the glass tends to form an aluminum-oxygen tetrahedral network [AlO 4 ], which is much larger than the silicon-oxygen tetrahedral [SiO 4 ] network, leaving larger gaps as channels for ion diffusion.
  • AlO 4 aluminum-oxygen tetrahedral network
  • the high content of Al 2 O 3 in the glass can promote the migration and replacement rate of alkali metal ions.
  • the higher the content of Al 2 O 3 the larger the gap of the framework network, which is more conducive to ion exchange.
  • the thermal expansion coefficient will not be due to excessive content. High and further decrease.
  • the high temperature viscosity of glass increases significantly, the melting temperature is too high during the production process, and the energy consumption increases, which is also not conducive to controlling defects such as bubbles and stones.
  • the mass percentage of Al 2 O 3 is preferably 13% to 25%.
  • the mass percentage of Al 2 O 3 is more preferably 16% to 22%.
  • the mass percentage of Al 2 O 3 is most preferably 18% to 20%.
  • B 2 O 3 (boron oxide) is one of the important components of boro-aluminosilicate glass. It is a bulk oxide, which can reduce the thermal expansion coefficient of aluminosilicate glass and improve the thermal stability of aluminosilicate glass. Chemical stability. The content of B 2 O 3 is too high, and boron volatilizes severely due to its viscosity-reducing effect at high temperature. At the same time , the content of B 2 O 3 is too high, which will narrow the forming temperature, which will make the boro-aluminosilicate glass draw tube forming a problem. It is difficult to control the wall thickness and pipe diameter accuracy.
  • the mass percentage of B 2 O 3 is preferably 0.5% to 4.0%.
  • the mass percentage of B 2 O 3 is more preferably 1% to 3%.
  • the mass percentage of B 2 O 3 is most preferably 1% to 2%.
  • Li 2 O (lithium oxide) is an ideal flux and the main component for ion exchange. Due to the polarization characteristics of Li + , it can effectively reduce the high temperature viscosity at high temperatures, and the radius of Li + is small, so it can be filled in the glass body In the air, free oxygen is balanced, and proper Li 2 O can significantly enhance the mechanical strength, surface hardness and chemical resistance of the glass body. Because the present invention uses the mixed molten salt of NaNO 3 and KNO 3 in the strengthening process, the Li + in the glass and the Na + in the molten salt are exchanged, which can increase the depth of the compressive stress layer in a short time, so that the glass has More excellent mechanical impact resistance.
  • the mass percentage of Li 2 O is preferably 1% to 8%.
  • the mass percentage of Li 2 O is more preferably 3% to 6%.
  • the mass percentage of Li 2 O is most preferably 4% to 5%.
  • Na 2 O sodium oxide
  • boro-aluminosilicate glass network which can provide free oxygen to break the Si-O bond, thereby reducing the viscosity and melting temperature of the aluminosilicate glass. If the content of Na 2 O is too high, it will increase the linear thermal expansion coefficient, reduce the chemical stability, and increase the volatility of Na 2 O, resulting in uneven composition of the aluminosilicate glass. The content of Na 2 O is too low, which is not conducive to the melting and molding of glass, and it is not conducive to the chemical exchange of Na ions and K ions to form a compressive stress layer on the glass surface to enhance the mechanical strength of the glass.
  • the Na 2 O component assumes the role of exchange with K ions in the molten liquid to form the compressive stress on the glass surface during tempering, which directly affects the strength performance of the glass.
  • the mass percentage of Na 2 O is preferably 6% to 14%.
  • the mass percentage of Na 2 O is more preferably 7% to 12%.
  • the mass percentage of Na 2 O is most preferably 8%-10%.
  • K 2 O (potassium oxide) and Na 2 O are both alkali metal oxides, and have similar functions in the glass structure. Substituting a small amount of K 2 O for Na 2 O can exert the "mixed alkali effect" and change a series of glass properties. Well, it is a component used to improve the melting properties and to increase the ion exchange rate in chemical strengthening to obtain the required surface compressive stress and stress layer depth. If the content of K 2 O is too high, the weather resistance will decrease.
  • the mass percentage of K 2 O is preferably set to 0-4%.
  • the mass percentage of K 2 O is more preferably 0.5% to 2.0%.
  • the mass percentage of K 2 O is preferably 0.5% to 1.0%.
  • MgO manganesium oxide
  • MgO is a kind of external body oxide. MgO helps to reduce the melting point of glass. It can reduce the viscosity of glass at high temperature, promote the melting and clarification of glass, improve uniformity, and increase hydrolysis resistance. MgO can also stabilize the glass, improve the durability of the glass, prevent the crystallization of the glass, inhibit the movement of alkali metal ions in the glass, and also has the function of improving the elastic modulus of the glass. MgO can enhance the stability of the glass network space at low temperatures and reduce the thermal expansion coefficient of the glass to a certain extent, but it has a hindering effect on ion exchange, so it is not an essential ingredient.
  • the mass percentage of MgO is preferably 0 to 4%.
  • the mass percentage of MgO is more preferably 0.5% to 2.0%.
  • the mass percentage of MgO is most preferably 0.5% to 1.0%.
  • SrO Stontium Oxide
  • SrO is similar to calcium oxide and magnesium oxide, both of which can reduce the high temperature viscosity of glass, which is good for melting, but because of its large ion radius, it will not hinder the exchange process of Li-Na-K ions in the glass structure. Therefore, a small amount of strontium oxide is used to replace part of calcium oxide and magnesium oxide.
  • the mass percentage of SrO is preferably 0 to 2%.
  • ZnO (zinc oxide) belongs to the ranks of divalent metal oxides, and also has the function of alkaline earth metal oxides.
  • adding some ZnO materials can effectively reduce the melting temperature of the glass and lower the glass transition temperature T g , it can also improve the alkali resistance of the glass matrix; in aluminosilicate glass, Zn is often in the two ligands [ZnO 6 ] and [ZnO 4 ], [ZnO 4 ] increases with the increase in alkali content Increase and increase the tendency of glass to crystallize.
  • partial zinc oxide is used to replace calcium oxide and magnesium oxide, which is beneficial to maintain the chemical stability of the glass while promoting the rapid progress of ion exchange.
  • the mass percentage of ZnO is preferably 0 to 4%.
  • the mass percentage of ZnO is more preferably 0 to 3%.
  • ZrO 2 is mainly in the form of cubic [ZrO 8 ] coordination in silicate glass. Due to the large ion radius, it is a network outside body in the glass structure, and its solubility in the glass is small, which will significantly increase the glass Viscosity, so its addition amount should not exceed 6%, which can improve the acid and alkali resistance and refractive index of the glass.
  • the mass percentage of ZrO 2 is preferably 1% to 6%.
  • the mass percentage of ZrO 2 is more preferably 2% to 5%.
  • the mass percentage of ZrO 2 is most preferably 3% to 4%.
  • the effect of TiO 2 is similar to that of ZrO 2 , and it is a transition element, has a certain coloring ability, is yellow, can improve the chemical stability of glass and increase the color temperature of glass. Therefore, the mass percentage of TiO 2 in this embodiment is 0-2%. The mass percentage of TiO 2 is further 0 to 1%.
  • SnO 2 and CeO 2 often exist in a glass body in a variety of valence states, which can increase the UV resistance of the glass and prevent the color change due to the valence of the colored ions. Moreover, when added alone or in combination, it can also increase the high temperature defoaming of the glass body.
  • Ability is a commonly used clarifying agent.
  • the mass percentage of SnO 2 is preferably 0 to 2%.
  • the mass percentage of SnO 2 is more preferably 0 to 1%.
  • the mass percentage of CeO 2 is preferably 0 to 1%.
  • the mass percentage of CeO 2 is more preferably 0 to 0.5%.
  • the aluminosilicate glass with the above ratio can increase the strength through chemical strengthening, and the chemically strengthened glass has a surface compressive stress> 900 MPa, a maximum stress depth> 145 ⁇ m, and an extrusion crack threshold greater than 7.5.
  • the above-mentioned aluminosilicate glass has high strength and can better protect the equipment when used as the protective glass of the equipment.
  • the total mass percentage of Li 2 O, Na 2 O, and K 2 O is greater than or equal to 9.8%.
  • Alkali metals as a typical glass network modification, can significantly reduce the melting temperature of glass; in addition, in the present invention, alkali metal ions are the key to whether the glass can be chemically strengthened to achieve ion exchange so as to obtain a sufficient compressive stress layer on the glass surface. The inventor found in a large number of experiments that when the total mass percentage of Li 2 O, Na 2 O, and K 2 O is greater than or equal to 9.8%, the obtained aluminosilicate glass has a larger surface stress value and better strength.
  • the main function of B 2 O 3 in glass is to exist as a network intermediate, and it mainly combines with oxygen to form boron-oxygen triangles and boron-oxygen tetrahedrons.
  • the boron-oxygen triangles generally exist in the gaps of the glass structure, and the boron-oxygen tetrahedrons.
  • the body participates in the construction process of the glass structure skeleton, and the two can be converted under certain conditions to improve the stability of the glass structure and increase the toughness of the glass, disperse the tip stress of the cracks in the glass, and increase the strength of the glass; and Li 2 O It exists in the glass body as a network outer body, which can be combined with the free oxygen in the glass body to exist in the gap of the glass structure, and because the radius of Li ions is very small, it has a very high field strength and can compact the glass structure.
  • ZrO 2 usually only exists in the gaps of the glass structure, but because its atomic radius is too large, it cannot be like Li 2 O and boron-oxygen triangles exist in very small structural gaps, but only in larger structural gaps.
  • Zr ions have a large ion radius, they also carry +4 positive charges, so they also have Very high field strength, the glass structure can also be compressed in the structural gap, so that the glass body has very good mechanical strength, hardness and corrosion resistance; combining the above-mentioned main action principles of B 2 O 3 , Li 2 O and ZrO 2,
  • the inventor has collected data and analyzed through a large number of experiments, and found that the A value is between 3.5% and 11%.
  • Aluminosilicate glass has very good crack resistance. The A value is around 9%.
  • the crack threshold of aluminosilicate glass is K The value appears to be an extreme value, and the glass has the best fracture toughness, which means that the glass has higher impact strength and higher mechanical processing performance. Therefore, in some embodiments, 3.5% ⁇ A ⁇ 11.0%.
  • a traditional technology discloses a thin lithium aluminum silicate glass. After tempering, the central tension of the glass is less than 50Mpa, the surface compressive stress of the glass is 600MPa ⁇ 1200Mpa, and the bending strength of the glass can reach 500MPa, so the stress layer of the glass The depth should be less than 50 ⁇ m. After the aluminosilicate glass in this embodiment is strengthened, the depth of the stress layer needs to be greater than 145 ⁇ m, which is much greater than the depth of the stress layer of the tempered glass in the above technology.
  • Another conventional technique content of B 2 O 3 and ZrO 2 are lower, and the content of the present embodiment B 2 O 3 and ZrO 2 are more than 0.1%, to participate in the vitreous skeleton structure is formed, there is It is beneficial to the later processing of the glass substrate and increases the fracture toughness of the glass. After tempering, it forms a surface stress value of more than 900MPa and a compressive stress value of more than 350MPa at a depth of 10 ⁇ m, which enhances the mechanical strength and drop resistance of the glass.
  • the traditional glass cover plate can be quickly chemically tempered, forming a compressive stress layer greater than 600 MPa on the glass surface, and the depth of the stress layer is generally higher than 35 ⁇ m.
  • the depth of the stress layer can be Reaching above 100 ⁇ m, in order to increase the mechanical strength, impact resistance, friction resistance and resistance of sand and gravel ground to the glass.
  • the strength of traditional glass is still low.
  • the above-mentioned aluminosilicate glass selects raw materials of a specific ratio so that the prepared glass has a thermal expansion coefficient of 80.8 ⁇ 10 -7 to 92.1 ⁇ 10 -7 at 20°C to 300°C.
  • the melting temperature T 2 is between 1536°C and 1613°C.
  • the glass transition point temperature T g is between 482°C and 558°C.
  • the strengthened glass obtained after chemical strengthening has a surface compressive stress CS0 of >900MPa, and a compressive stress of more than 300MPa CS10 at a depth of 10 ⁇ m from the glass surface.
  • the composite compressive stress produced by ion exchange drops to a stress depth of 0MPa (the detection limit of the instrument) Dol0> 145 ⁇ m, the depth of the stress layer with a composite compressive stress of 600MPa Dol600>5.5 ⁇ m.
  • the above-mentioned aluminosilicate glass has a strengthened extrusion crack threshold greater than 7.5, which can better protect smart devices such as mobile phones.
  • the aluminosilicate glass includes 58% to 66% of SiO 2 , 16% to 22% of Al 2 O 3 , and 1% to 3% of B 2 O 3 in terms of mass percentage. Li 2 O 3% to 6%, Na 2 O 7% to 12%, K 2 O 0.5% to 2%, MgO 0.5% to 2.0% and ZrO 2 2% to 5%.
  • the total mass percentage of Li 2 O, Na 2 O and K 2 O is greater than or equal to 10%
  • the aluminosilicate glass may also include at least one of ZnO, P 2 O 5 and TiO 2. Specifically, the mass percentage of ZnO does not exceed 3%. The mass percentage of P 2 O 5 does not exceed 2%. The mass percentage of TiO 2 does not exceed 1%. In this embodiment, the aluminosilicate glass may also include at least one of SnO 2 and CeO 2. Among them, the mass percentage of SnO 2 does not exceed 1%. The mass percentage of CeO 2 does not exceed 0.5%. It should be noted that in this embodiment, ZnO, P 2 O 5 , TiO 2 , SnO 2 and CeO 2 can all be omitted.
  • the glass prepared from the above-mentioned ratio of raw materials has a thermal expansion coefficient of 82.9 ⁇ 10 -7 to 89.8 ⁇ 10 -7 at 20°C to 300°C.
  • the melting temperature T 2 is between 1566°C and 1611°C.
  • the glass transition point temperature Tg is between 485°C and 546°C.
  • the strengthened glass obtained after chemical strengthening has a surface compressive stress CS0 of> 900 MPa, and a compressive stress of more than 300 MPa CS10 at a depth of 10 ⁇ m from the glass surface.
  • the composite compressive stress produced by ion exchange drops to a stress depth of 0 MPa (the detection limit of the instrument) Dol0> 155 ⁇ m, the depth of the stress layer with a composite compressive stress of 600MPa Dol600>6 ⁇ m.
  • the crack threshold of the glass obtained from the above-mentioned aluminosilicate glass is greater than 11.
  • the aluminosilicate glass may also include P 2 O 5 with a mass percentage of not more than 1%.
  • the glass prepared from the above-mentioned ratio of raw materials has a thermal expansion coefficient of 80.8 ⁇ 10 -7 to 85.6 ⁇ 10 -7 at 20°C to 300°C.
  • the melting temperature T 2 is between 1578°C and 1603°C.
  • the glass transition point temperature T g is between 500°C and 527°C.
  • the strengthened glass after chemical strengthening treatment has a surface compressive stress CS0 of >950MPa, and a compressive stress of more than 350MPa CS10 at a depth of 10 ⁇ m from the glass surface.
  • the composite compressive stress produced by ion exchange drops to a stress depth of 0MPa (the detection limit of the instrument) Dol0> 160 ⁇ m, the depth of the stress layer with a composite compressive stress of 600MPa Dol600>7 ⁇ m.
  • the crack threshold of the glass obtained from the above-mentioned aluminosilicate glass is greater than 24.
  • a method for preparing aluminosilicate glass in an embodiment is a method for preparing aluminosilicate glass in the above embodiment, and specifically includes the following steps:
  • Step S110 In terms of mass percentage, weigh the following raw materials: SiO 2 55% ⁇ 67%, Al 2 O 3 13% ⁇ 25%, B 2 O 3 0.5% ⁇ 4.0%, Li 2 O 1% ⁇ 8%, Na 2 O 6% to 14%, ZrO 2 1% to 6%, K 2 O 0 to 4%, and MgO 0 to 4%.
  • the total mass percentage of Li 2 O, Na 2 O and K 2 O is greater than or equal to 9.8%, and the mass percentage of B 2 O 3 , Li 2 O and ZrO 2 satisfies the following relationship: 3.5% ⁇ A ⁇ 11.0% .
  • Step S120 The above-mentioned raw materials are mixed and melted to obtain a glass paste.
  • the melting temperature in step S120 is 1650°C.
  • the melting time is 8h.
  • a platinum stirring blade is used for stirring at the same time.
  • Step S130 homogenize the glass slurry.
  • the temperature of the homogenization treatment in step S130 is 1500°C.
  • the homogenization treatment time is 1h.
  • Step S140 the glass slurry is shaped, and then annealed to obtain aluminosilicate glass.
  • the homogenized glass paste is poured on an iron mold preheated at 450° C. to solidify the glass paste.
  • the temperature of the annealing treatment is 580°C to 600°C.
  • the glass in the above-mentioned preparation method of aluminosilicate glass, the glass can be obtained in the traditional flat glass manufacturing process, and the manufacturing method is not limited to the float forming process, the overflow down-draw method, the pull-up method, the flat drawing method, and the calendering method. Law and so on.
  • the preparation method of the aluminosilicate glass is simple in process and easy to industrialized production.
  • the strengthened glass of one embodiment is obtained by chemically strengthening the aluminosilicate glass of the above-mentioned embodiment.
  • the squeeze crack threshold of the strengthened glass is greater than 7.5, which can effectively prevent or reduce the situation that the screen or other cover glass breaks due to accidental dropping of mobile phones and other smart devices on the ground.
  • a method for preparing strengthened glass according to an embodiment is a method for preparing strengthened glass according to the above embodiment, and specifically includes the following steps:
  • Step S210 Provide the above-mentioned aluminosilicate glass.
  • Step S220 firstly, the aluminosilicate glass is tempered in a molten mixture of NaNO 3 and KNO 3 at a temperature of 390°C to 420°C and a mass ratio of 3:7 to 7:3 for 2h to 6h.
  • the mass ratio of NaNO 3 and KNO 3 in step S220 is 9:11 to 11:9.
  • Step S230 Then aluminosilicate glass at a temperature of 380 °C ⁇ 400 °C, mass ratio of 2: tempering treatment for 2h ⁇ 4h 80 of NaNO molten mixture of KNO 3 and 3: 98 to 20.
  • the mass ratio of NaNO 3 and KNO 3 in step S230 is 5:95-15:85.
  • the effect of strengthening aluminosilicate glass in a two-step mixed salt method is to selectively exchange ion species through a two-step chemical tempering method.
  • the first step is mainly the Li ion in the glass and the tempering salt. Exchange of Na and K ions, Na-Li exchange will produce a compressive stress layer with a smaller compressive stress value and high stress depth, which is accompanied by part of the Li-K and Na-K exchange, forming a larger stress to compensate for the high depth direction
  • the problem of low upper stress value; the second step is to use tempering salt with low temperature and high K ion content for tempering.
  • the stress layer with depth and high pressure stress finally forms a composite stress layer. Its main feature is that it has a high stress layer exceeding 900 MPa on the glass surface, and the depth of the stress layer exceeds 145 ⁇ m or even higher in the depth direction.
  • the mass ratio of sodium nitrate and potassium nitrate in step S220 is set to 3:7-7:3 mainly to realize the chemical exchange of Na ions and Li ions in the glass to form a sufficiently deep stress layer, but due to Na and Li
  • the ionic radius is not much different, and there is enough space in the glass structure to meet the conversion of Na-Li ions, so the depth of the stress layer formed is deep, but the stress value is low; by adding K with a large ionic radius to the tempered salt, the stress Realize the exchange of Li-K and Na-K in the direction and increase the partial compressive stress value. Therefore, the mass ratio of sodium nitrate and potassium nitrate in the first step is between 3:7 and 7:3.
  • step S230 setting the mass ratio of sodium nitrate and potassium nitrate to 2:98-20:80 is mainly to realize the replacement of Na ions in the glass and K ions in the tempering salt, so as to achieve a high compressive stress value on the glass surface.
  • the temperature of the mixed molten liquid in step S220 is generally higher than the temperature of the mixed molten liquid in step S230 by 10°C to 20°C. Because for the two elements of the tempering process: temperature and time, the longer the same tempering salt treatment time, the higher the temperature, the deeper the depth of the stress layer formed, but the stress value will be significantly reduced.
  • the first step is to form a sufficiently deep stress layer (greater than 100 ⁇ m), and the second is that the higher the stress value, the better. Therefore, the higher temperature is selected in the first step, usually The temperature is between 390°C and 420°C, and the time is between 2 hours and 6 hours.
  • the second step is to form a certain depth of high-stress stress layer (more than 700MPa), so in the second step, a lower temperature and a short time are required, usually between 380°C and 400°C, and the time is 2 hours to 4 hours.
  • a lower temperature and a short time are required, usually between 380°C and 400°C, and the time is 2 hours to 4 hours.
  • the main reason for not choosing long time is that the tempering cycle is too long, the efficiency and output are low, and the cost is high and it is not suitable for mass production.
  • the squeeze crack threshold of the strengthened glass strengthened by the above-mentioned aluminosilicate glass is greater than 7.5, which can effectively prevent or reduce the breakage of the screen or other cover glass of smart devices such as mobile phones accidentally dropped to the ground.
  • the display device of one embodiment includes the aluminosilicate glass of the above embodiment or the strengthened glass of the above embodiment or the strengthened glass prepared by the method of preparing the strengthened glass of the above embodiment.
  • the preparation process of the aluminosilicate glass of Example 1 to Example 21 is specifically as follows:
  • Example 1 ⁇ Example 21 were designed according to the ingredients (mass percentage) in Table 1 ⁇ Table 3, after fully mixing, melted with platinum crucible at 1650 °C for 8 hours, while stirring with platinum stirring paddle, waiting to be extracted After stirring the paddle, cool down to 1500°C, keep for 1h to homogenize, and cast on the iron mold to form a glass block of about 80mm ⁇ 160mm. The mold is preheated to 450°C before casting. After the glass block is hardened, it is immediately transferred to the annealing furnace. Anneal at 590°C, heat preservation for 2 hours, then cool down to 140°C for 6 hours, and then cool naturally to obtain glass products, which are taken out for later use.
  • the strengthening process of the aluminosilicate glass of Example 1 to Example 12 is specifically as follows:
  • the strengthening process of the aluminosilicate glass of Example 13 to Example 14 is specifically as follows:
  • the aluminosilicate glass obtained in the above Examples 13 to 14 was processed into 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheets, which were subjected to a temperature of 390°C and a mass ratio of 3:7 NaNO 3 and KNO 3 After the tempering treatment in the mixed melt for 6 hours, it is transferred to a tempering treatment in a mixed melt of NaNO 3 and KNO 3 at a temperature of 380° C. and a mass ratio of 2:98 for 4 hours to obtain a strengthened glass.
  • the strengthening process of the aluminosilicate glass of Example 15 to Example 21 is specifically as follows:
  • the aluminosilicate glass obtained in Example 15 to Example 21 was processed into a 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheet, which was processed by NaNO 3 and KNO 3 with a temperature of 420°C and a mass ratio of 7:3. After 2 hours of tempering treatment in the mixed melt, it was transferred to a tempering treatment in a mixed melt of NaNO 3 and KNO 3 at a temperature of 400° C. and a mass ratio of 20:80 for 2 hours to obtain a strengthened glass.
  • the preparation process of the aluminosilicate glass of Comparative Example 1 to Comparative Example 19 is similar to the preparation process of the aluminosilicate glass of Example 1 to Example 21, except that the aluminosilicate glass of Comparative Example 1 to Comparative Example 19
  • the raw material ratio of the glass is shown in Table 4 to Table 6.
  • the strengthening process of the aluminosilicate glass of Comparative Example 1 to Comparative Example 14 is the same as the strengthening process of the aluminosilicate glass of Example 1 to Example 12, and will not be repeated here.
  • the aluminosilicate glass prepared in Comparative Example 15 was processed into a 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheet, and passed through a mixed melt of NaNO 3 and KNO 3 at a temperature of 400 °C and a mass ratio of 3:2 The tempered glass was processed for 4 hours to obtain strengthened glass.
  • the aluminosilicate glass of Comparative Example 16 was processed into a 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheet, which was tempered in a molten mixture of NaNO 3 and KNO 3 at a temperature of 385°C and a mass ratio of 1:9 After 2 hours, strengthened glass was obtained.
  • the aluminosilicate glass of Comparative Example 17 was processed into a 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheet, which was tempered in a molten mixture of NaNO 3 and KNO 3 with a temperature of 385°C and a mass ratio of 3:2 After 4 hours, it was transferred to a tempering process in a mixed melt of NaNO 3 and KNO 3 at a temperature of 400° C. and a mass ratio of 1:9 for 2 hours to obtain strengthened glass.
  • the aluminosilicate glass of Comparative Example 18 was processed into a 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheet, which was tempered in a molten mixture of NaNO 3 and KNO 3 at a temperature of 400 °C and a mass ratio of 1:9 After 4 hours, it was transferred to a tempering process for 2 hours in a mixed molten liquid of NaNO 3 and KNO 3 with a temperature of 385° C. and a mass ratio of 3:2 to obtain strengthened glass.
  • the aluminosilicate glass of Comparative Example 19 was processed into a 50mm ⁇ 50mm ⁇ 0.7mm double-sided polished glass sheet, which was tempered in a melt of NaNO 3 at a temperature of 400°C for 4 hours, and then transferred to a temperature of 385°C The KNO 3 melt is tempered for 2 hours to obtain strengthened glass.
  • the aluminosilicate glass prepared in the above-mentioned Example 1 to Example 21 and Comparative Example 1 to Comparative Example 14 were all processed into glass samples of ⁇ 5mm ⁇ 50mm, and used NETZSCH-DIL 402 PC at 4°C/
  • the thermal expansion curve is measured at a heating rate of min.
  • the strain point T g and the expansion softening point T s of the glass and the thermal expansion coefficient CTE in the range of 20°C to 300°C are measured through the built-in software, and recorded in Table 1 to Table 5. in.
  • Example 1 to Example 21 and Comparative Example 1 to Comparative Example 19 was tested by the stress tester FSM6000UV and SLP1000 of Japan Orihara to test the surface stress value CS0, the compressive stress value CS10 and the stress value of the strengthened glass at a depth of 10 ⁇ m, respectively.
  • the maximum stress layer depth Dol0 and the stress layer depth Dol600 at 600MPa are recorded in Table 1 to Table 6.
  • the squeeze crack threshold values obtained by testing the glass samples of each example and comparative example are recorded in Table 1 to Table
  • the aluminosilicate glass of Example 1 to Example 7 in Table 1, in terms of mass percentage, includes: SiO 2 55% ⁇ 67%, Al 2 O 3 13% ⁇ 25%, B 2 O 3 0.5% ⁇ 4.0 %, Li 2 O 1% ⁇ 8%, Na 2 O 6% ⁇ 14%, ZrO2 1% ⁇ 6%, K 2 O 0 ⁇ 4%, MgO 0 ⁇ 4%, SrO 0 ⁇ 2%, ZnO 0 ⁇ 4%, P 2 O 5 0 to 4%, TiO 2 0 to 2%, SnO 2 0 to 2% and CeO 2 0 to 1%.
  • the total mass percentage of Li 2 O, Na 2 O, and K 2 O is greater than or equal to 9.8%, and the mass percentage of B 2 O 3 , Li 2 O, and ZrO 2 satisfies: 3.5% ⁇ A ⁇ 11.0%.
  • the glass with the above composition characteristics has 82.4 ⁇ 10 -7 -92.1 ⁇ 10 -at 20°C to 300°C Coefficient of thermal expansion of 7.
  • the melting temperature T 2 is between 1536°C and 1613°C.
  • the glass transition point temperature T g is between 482°C and 558°C.
  • the strengthened glass obtained has a surface compressive stress CS0 of >900MPa, and a compressive stress of more than 300MPa CS10 at a depth of 10 ⁇ m from the glass surface.
  • the composite compressive stress produced by ion exchange drops to 0MPa (instrument The detection limit) stress depth Dol0>145 ⁇ m, and the composite compressive stress is 600MPa stress layer depth Dol600>5.5 ⁇ m.
  • the squeeze crack threshold of strengthened glass is greater than 7.5.
  • CS0 surface stress value
  • CS10 compressive stress value at a depth of 10 ⁇ m
  • Dol0 maximum stress layer depth
  • Dol600 stress layer depth at 600MPa.
  • Table 2 lists the preferred formulations of aluminosilicate glass.
  • aluminosilicate glass of Example 8 to Example 14 in terms of mass percentage, it includes: SiO 2 58% to 66%, Al 2 O 3 16% to 22%, B 2 O 3 1% to 3%, Li 2 O 3% ⁇ 6%, Na 2 O 7% ⁇ 12%, K 2 O 0.5% ⁇ 2%, MgO 0.5% ⁇ 2%, ZrO 2 2% ⁇ 5%, ZnO 0 ⁇ 3%, P 2 O 5 0 ⁇ 2%, TiO 2 0 ⁇ 1%, SnO 2 0 ⁇ 1% and CeO 2 0 ⁇ 0.5%.
  • the total mass percentage of Li 2 O, Na 2 O, and K 2 O is greater than or equal to 10%
  • the mass percentage of B 2 O 3 , Li 2 O, and ZrO 2 satisfies: 5.5% ⁇ A ⁇ 11.0%.
  • the aluminosilicate glass with the above composition characteristics has a thermal expansion coefficient of 82.9 ⁇ 10 -7 to 89.8 ⁇ 10 -7 at 20°C to 300°C.
  • the melting temperature T 2 is between 1566°C and 1611°C.
  • the glass transition point temperature Tg is between 485°C and 546°C.
  • the strengthened glass obtained has a surface compressive stress CS0 of >900MPa, and a compressive stress of more than 300MPa CS10 at a depth of 10 ⁇ m from the glass surface.
  • the composite compressive stress produced by ion exchange drops to 0MPa (instrument The detection limit) stress depth Dol0>155 ⁇ m, and the composite compressive stress is 600MPa stress layer depth Dol600>6 ⁇ m.
  • the squeeze crack threshold of strengthened glass is greater than 11.
  • Table 3 lists further preferred formulations of aluminosilicate glass.
  • aluminosilicate glass of Example 15 to Example 21 in terms of mass percentage, it includes: SiO 2 60% to 64%, Al 2 O 3 18% ⁇ 20%, B 2 O 3 1% ⁇ 2%, Li 2 O 4% ⁇ 5%, Na 2 O 8% ⁇ 10%, K 2 O 0.5% ⁇ 1%, MgO 0.5% ⁇ 1.0%, ZrO 2 3% to 4% and P 2 O 5 0 to 1%, wherein the total mass percentage of Li 2 O, Na 2 O and K 2 O is greater than or equal to 12.8%, and B 2 O 3 , Li 2 O and The mass percentage of ZrO 2 satisfies: 8% ⁇ A ⁇ 9%.
  • the aluminosilicate glass with the above ratio has a thermal expansion coefficient of 80.8 ⁇ 10 -7 to 85.6 ⁇ 10 -7 at 20°C to 300°C.
  • the melting temperature T 2 is between 1578°C and 1603°C.
  • the glass transition point temperature Tg is between 500°C and 527°C.
  • the strengthened glass obtained has a surface compressive stress CS0 of >950MPa, and a compressive stress CS10 of more than 350MPa at a depth of 10 ⁇ m from the glass surface.
  • the composite compressive stress produced by ion exchange drops to 0MPa (instrument The detection limit) stress depth Dol0>160 ⁇ m, and the composite compressive stress of 600MPa stress layer depth Dol600>7 ⁇ m.
  • the squeeze crack threshold of strengthened glass is greater than 24.
  • composition and experimental data of the aluminosilicate glass of Comparative Example 1 to Comparative Example 7 are shown in Table 4 below. It can be seen from Table 4 that there is no B 2 O 3 in the aluminosilicate glass of Comparative Example 1, and the A value is 8%, but because no boron oxide is involved in the glass network structure, when the glass is subjected to external impact When there is no buffer structure, stress concentration is easy to form, so that the crack threshold of the aluminosilicate glass of Comparative Example 1 is significantly lower than that of the aluminosilicate glass of Example 1.
  • the percentage of B 2 O 3 in the aluminosilicate glass of Comparative Example 2 is 5%, and the content is high, which significantly reduces the ion exchange capacity of the glass. Therefore, the CS0 value, Dol600, and crack threshold are significantly reduced, and the strength of the glass is reduced.
  • composition and experimental data of the aluminosilicate glass of Comparative Example 8 to Comparative Example 14 are shown in Table 5 below. It can be seen from Table 5 that when the content of ZrO 2 in the aluminosilicate glass of Comparative Example 8 is low, a sufficiently stable glass structure space cannot be formed. When impacted by an external force, stress concentration is likely to occur, which makes the glass easy to break. , Significantly reduce the crack threshold of the glass; and when the content of ZrO 2 in the aluminosilicate glass of Comparative Example 9 increases, the viscosity of the glass will increase significantly, resulting in the glass design formula being unable to be mass-produced and easy to crystallize.
  • Comparative Example 10 and Comparative Example 11 when the A value is less than 3.5% or the A value is greater than 11%, it is used as the main component to form the voids of the aluminosilicate glass body, boron oxygen triangle body, high field strength lithium oxide and Zirconia, the A value is greater than 11%, the structural gap occupies a larger space in the entire glass body, which reduces the strength of the glass structure. If the A value is less than 3.5%, it acts as a structural gap filler ion and cannot form enough structural gaps and cannot achieve Li- The rapid exchange and migration of the three Na-K ions are for the purpose of increasing the strength of the glass. Therefore, the crack threshold of the aluminosilicate glass is less than the crack threshold when the A value is between 3.5% and 11%.
  • composition and experimental data of the aluminosilicate glass of Comparative Example 15 to Comparative Example 19 are shown in Table 6 below. It can be seen from Table 6 that in the strengthening process of Comparative Example 15, only the first step of strengthening was carried out, so that Na-K ion exchange and Li-K ion exchange could not be carried out.
  • the surface stress value of the glass was only 386MPa, the maximum stress layer The depth is only 135 ⁇ m, the extrusion crack threshold is only 4.84, which is 17.83 lower than the crack threshold of Example 8, and the maximum stress depth is reduced by 37 ⁇ m.
  • Comparative Example 16 only carried out the second step of strengthening, so that Li-Na ion exchange could not be carried out, and only Li-K and Na-K exchange were carried out.
  • the glass surface has a high compressive stress value, but the maximum stress depth is only 10.2 It is about ⁇ m, much lower than the maximum stress depth of 178 ⁇ m in Example 9, and its CS10 is only 36 MPa, resulting in a crack threshold of only 4.32.
  • the first strengthening temperature is lower than the second strengthening temperature. Because the first strengthening is mainly to form a stress layer with sufficient depth, when the strengthening temperature is lower, a deeper stress layer depth can still be formed;
  • the second step of strengthening is mainly to increase the stress value of the stress layer. When the strengthening temperature is higher, stress relaxation occurs, and the resulting surface compressive stress is only 754 MPa, which is much lower than the 936 MPa in the embodiment.
  • the ratio of sodium nitrate and potassium nitrate in the first step of strengthening and the second step of strengthening is not within the ratio of this case, so that the maximum stress layer depth is less than 100 ⁇ m, and the surface stress value is only 584MPa.
  • the toughening effect is much lower than the embodiment, so that the crack threshold is only 4.86.
  • the melt in the first step only contains sodium nitrate
  • the melt in the second step only contains potassium nitrate, so Li-K and Na-K cannot be exchanged in the first step of strengthening. Li-Na ion exchange cannot be carried out in the step strengthening, so that the strength of the glass is reduced, and the crack threshold is lower.
  • Comparative example 15 Comparative example 16 Comparative example 17 Comparative example 18 Comparative example 19 SiO 2 59 61 58 62 60 Al 2 O 3 17.5 16 19 18.5 twenty two B 2 O 3 1 1 3 1.5 1 Li 2 O 4 3 6 4.5 4 Na 2 O 7 12 9 7.5 8 K 2 O 2 1 0.8 1 0.5 MgO 1 2 0.7 0.5 1 SrO - - - - - ZnO 3 - - 1 - ZrO 2 3 2 3.5 3 3 3 P 2 O 5 0.5 2 - - - TiO 2 1 - - - 0.5 SnO 2 1 - - - - CeO 2 - - - 0.5 - A 7.5 5.5 11 8.25 7.5 Li 2 O+Na 2 O+K 2 O 13 16 15.8 13 12.5 CS0(MPa) 386 985 754 584 1088 CS10(MPa) 294 36 285 269 342 Dol0( ⁇ m) 135 10.2 172 94

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Abstract

一种铝硅酸盐玻璃，按质量百分比计，包括：SiO 2 55％～67％、Al 2O 3 13％～25％、B 2O 3 0.5％～4.0％、Li 2O 1％～8％、Na 2O 6％～14％、ZrO 2 1％～6％、K 2O 0～4％和MgO 0～4％。

Description

铝硅酸盐玻璃、强化玻璃及其制备方法和显示器件 技术领域
本发明涉及玻璃领域，特别是涉及一种铝硅酸盐玻璃、强化玻璃及其制备方法和显示器件。
背景技术
薄板玻璃常被用作对显示器件进行保护的玻璃盖片或便携式终端装置的壳体用的玻璃盖片。近年来，这些便携式电话和PDA等显示器件存在向更加薄型、高功能化发展的趋势，并要求很高的机械强度。因此，一般需要对薄板玻璃基板进行化学强化，得到钢化玻璃。这种钢化玻璃能够通过在含有钾或钠的熔融盐中进行离子交换处理来进行化学强化，以使玻璃表面的碱金属离子与离子交换盐中的钾离子或钠离子交换，在玻璃表面形成压缩应力层。
传统的玻璃盖板市场主要以(硼)铝硅玻璃和锂(硼)铝硅玻璃为主，例如康宁的Gorilla玻璃、NEG的T2X-1、旭硝子的龙迹玻璃和国内旭虹的熊猫玻璃及南玻的KK3玻璃等，其最大的优势在于能进行快速地化学钢化，在玻璃表面形成压应力层，以便增加玻璃的机械强度、抗冲击性能、耐摩擦性能以及抗砂石地面落摔性能等目的。但传统的玻璃的挤压裂纹阈值较低，在手机等智能设备不小心跌落在地面时不能起到较好的保护作用。
发明内容
基于此，有必要提供一种挤压裂纹阈值较高的铝硅酸盐玻璃。
此外，还提供一种强化玻璃、强化玻璃的制备方法和显示器件。
一种铝硅酸盐玻璃，按质量百分比计，包括：SiO 2 55％～67％、Al 2O 3 13％～25％、B 2O 3 0.5％～4.0％、Li 2O 1％～8％、Na 2O 6％～14％、ZrO 2 1％～6％、K 2O 0～4％和MgO 0～4％。
一种强化玻璃，由上述铝硅酸盐玻璃经化学强化后得到。
一种强化玻璃的制备方法，包括如下步骤：
提供上述铝硅酸盐玻璃；及
先将上述铝硅酸盐玻璃在温度为390℃～420℃、质量比为3:7～7:3的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～6h，然后在温度为380℃～400℃、质量比为2:98～20:80的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～4h，得到强化玻璃。
一种显示器件，包括上述铝硅酸盐玻璃或上述强化玻璃或由上述强化玻璃的制备方法制备得到的强化玻璃。
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
图1为一实施方式的铝硅酸盐玻璃的制备方法的工艺流程图；
图2为一实施方式的强化玻璃的制备方法的工艺流程图；
图3为裂纹阈值的计算公式中a、b的计算方式的示意图；
图4为实施例1～实施例21的强化玻璃的裂纹阈值K与铝硅酸盐玻璃中A的取值的关系曲线图。
具体实施方式
为了便于理解本发明，下面将结合具体实施方式对本发明进行更全面的描述。具体实施方式中给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体地实施例的目的，不是旨在于限制本发明。
一实施方式的铝硅酸盐玻璃，按质量百分比计，包括：SiO 2 55％～67％、Al 2O 3 13％～25％、B 2O 3 0.5％～4.0％、Li 2O 1％～8％、Na 2O 6％～14％、ZrO 2 1％～6％、K 2O 0～4％和MgO 0～4％。
在其中一个实施例中，铝硅酸盐玻璃中还包括质量百分比不超过2％的SrO、质量百分比不超过4％的ZnO、质量百分比不超过4％的P 2O 5及质量百分比不超过2％的TiO 2中的至少一种。
进一步地，铝硅酸盐玻璃还包括质量百分比不超过3％的ZnO、质量百分比不超过2％的P 2O 5及质量百分比不超过1％的TiO 2中的至少一种。
更进一步地，铝硅酸盐玻璃还包括质量百分比不超过1％的P 2O 5。
在另一个实施例中，铝硅酸盐玻璃中还包括SnO 2及CeO 2中的至少一种。具体地，SnO 2的质量百分比不超过2％。进一步地，SnO 2的质量百分比不超过1％。CeO 2的质量百分比不超过1％。进一步地，CeO 2的质量百分比不超过0.5％。
需要说明的是，在该实施例中，K 2O和MgO的质量百分比可以相互独立地为零。且在该实施例中，SrO、ZnO、P 2O 5、TiO 2、SnO 2及CeO 2均可以省略。
SiO 2(二氧化硅)是重要的玻璃形成氧化物，是形成玻璃骨架所必需的成分。SiO 2能提高玻璃的强度、化学稳定性等，可以使玻璃获得更高的应变点和较低的热膨胀系数。因此，在本实施方式中，SiO 2的质量百分比优选为55％～67％。SiO 2的质量百分比更优选为58％～66％。SiO 2的质量百分比最优选为60％～64％。若SiO 2的质量百分比不足55％，玻璃主体网络结构较差，机械性能不佳，且耐候性变差。若SiO 2的质量百分比超过67％，玻璃在生产过程中熔制温度过高，能耗增加，且容易造成频繁的气泡、结石等缺陷，同时硅氧骨架结构比例偏高，网络间隙较小，不利于化学强化离子交换，影响化学增强的效率。
Al 2O 3(三氧化二铝)能参与网络起网络生成体作用，以及能降低玻璃的结晶倾向，提高玻璃的化学稳定性、热稳定性、机械强度、硬度，也是提高拉伸玻璃弹性模量的必要成分。但是Al 2O 3的加入会增加玻璃粘度，如果Al 2O 3过多，就难以得到料性长的玻璃，使玻璃成型较为困难。此外，玻璃中的Al 3+倾向于形成铝氧四面体网络[AlO 4]，这比硅氧四面体[SiO 4]网络要大得多，留下较大的空隙作为离子扩散的通道，因此玻璃中高的Al 2O 3含量能促进碱金属离子的迁移和置换速率，Al 2O 3含量越高，骨架网络的间隙越大，越有利于离子交换，然而热膨胀系数却不会因为其含量过高而进一步降低，相反，玻璃高温黏度明显增大，生产过程中熔制温度过高，能耗增加，同样不利于控制气泡、结石等缺陷。然而，Al 2O 3含量偏低时，网络空间的空隙变小，不利于离子迁移，严重影响化学增强的效率。因此，在本实施方式中，Al 2O 3的质量百分比优选为13％～25％。Al 2O 3的质量百分比进一步优选为16％～22％。Al 2O 3的质量百分比最优选为18％～20％。
B 2O 3(氧化硼)是硼铝硅酸盐玻璃的重要组分之一，属于形成体氧化物， 能降低铝硅酸盐玻璃的热膨胀系数，提高铝硅酸盐玻璃的热稳定性、化学稳定性。B 2O 3的含量太高，在高温下由于其降低粘度的作用导致硼挥发严重，同时B 2O 3的含量过高会缩窄成型温度，给硼铝硅酸盐玻璃拉管成型中对壁厚、管径精度控制带来困难。另外当B 2O 3引入量过高时，由于硼氧三角体[BO 3]增多，硼铝硅酸盐玻璃的膨胀系数等反而增大，发生反常现象，B 2O 3含量过高时，玻璃的离子交换能力显著降低。因此，在本实施方式中，B 2O 3的质量百分比优选为含量为0.5％～4.0％。B 2O 3的质量百分比更优选为1％～3％。B 2O 3的质量百分比最优选1％～2％。
Li 2O(氧化锂)是理想的助熔剂，是进行离子交换的主要成分，由于Li +的极化特性，在高温下能有效减低高温黏度，且Li +的半径较小，可以填充在玻璃体空气中，平衡游离氧，适当的Li 2O可以显著增强玻璃体的机械强度、表面硬度和抗化学侵蚀性等。由于本发明在强化工艺的中使用NaNO 3与KNO 3的混合熔盐，通过玻璃中Li +与熔盐中Na +进行离子交换，可以在较短的时间内提升压应力层深度，使玻璃具有更加优异的抗力学冲击性能。在本实施方式中，若Li 2O的质量百分比低于1％，则玻璃基本难以获得更高的应力层深度。若Li 2O的质量百分比高于8％，增加了玻璃制造成本，玻璃膨胀系数显著增大，且玻璃析晶倾向过高，玻璃生成结石缺陷的概率明显增加。因此，在本实施方式中，Li 2O的质量百分比优选为1％～8％。Li 2O的质量百分比更优选为3％～6％。Li 2O的质量百分比最优选为4％～5％。
Na 2O(氧化钠)是硼铝硅酸盐玻璃网络外体氧化物，能提供游离氧使Si-O键断开，从而降低铝硅酸盐玻璃的粘度和熔制温度。Na 2O的含量过高，会增大线热膨胀系数，降低化学稳定性，且Na 2O挥发量增大，导致铝硅酸盐玻璃成分不均一。Na 2O的含量过低，不利于玻璃的熔制和成型，且不利于Na 离子与K离子的化学交换从而在玻璃表面形成压应力层，起到增强玻璃机械强度的目的，在本发明中Na 2O成分在钢化时承担与熔融液中的K离子交换来形成玻璃表面的压应力的作用，直接影响玻璃的强度性能。在本实施方式中，Na 2O的质量百分比优选为6％～14％。Na 2O的质量百分比更优选为7％～12％。Na 2O的质量百分比最优选为8％～10％。
K 2O(氧化钾)和Na 2O同属于碱金属氧化物，在玻璃结构中的作用类似，以少量K 2O取代Na 2O能发挥“混合碱效应”，使玻璃的一系列性能变好，是用于提高熔融性质和用于在化学强化中提高离子交换率以获得所需表面压缩应力和应力层深的组分。若K 2O的含量过高，则耐候性会降低。本发明中通过对玻璃中碱金属含量的分析，设置K 2O的质量百分比优选为0～4％。K 2O的质量百分比进一步优选为0.5％～2.0％。K 2O的质量百分比优选为0.5％～1.0％。
MgO(氧化镁)是一种网络外体氧化物，MgO有助于降低玻璃熔点，高温时能降低玻璃的黏度，促进玻璃的熔化和澄清，改善均匀性，增加抗水解性。MgO也能使玻璃趋于稳定，提高玻璃的耐久性，防止玻璃产生结晶，抑制玻璃中碱金属离子的移动，也同样具有提高玻璃弹性模量的功能。MgO在低温下可以增强玻璃网络空间的稳定性，一定程度上可以降低玻璃的热膨胀系数，但其对离子交换存在阻碍的作用，因此不是必需的成分。若MgO的质量百分比高于4％，Mg 2+严重阻碍玻璃的离子交换能力，导致压应力层深度明显减小。因此，在本实施方式中，MgO的质量百分比优选为0～4％。MgO的质量百分比更优选为0.5％～2.0％。MgO的质量百分比最优选为0.5％～1.0％。
SrO(氧化锶)和氧化钙及氧化镁类似，均能降低玻璃高温粘度，有利于熔化，但是因为其离子半径较大，所以在玻璃结构体中不会阻碍Li-Na-K离 子的交换过程，因此采用少量氧化锶取代部分的氧化钙和氧化镁。在本实施方式中，SrO的质量百分比优选为0～2％。
ZnO(氧化锌)属于二价金属氧化物行列，同样具有碱土金属氧化物的作用，在硅酸盐玻璃体系中，加入部分的ZnO物料，可有效降低玻璃的熔化温度，降低玻璃的转变温度T g，同时还可以提高玻璃基体的耐碱性；在铝硅酸盐玻璃体中，Zn常处于[ZnO 6]和[ZnO 4]两种配位体中，[ZnO 4]随碱含量的增高而增大，增加玻璃的析晶倾向，本发明中采用部分氧化锌取代氧化钙和氧化镁，有利于维持玻璃化学稳定性的同时还能促进离子交换的快速进行。在本实施方式中，ZnO的质量百分比优选为0～4％。ZnO的质量百分比更优选为0～3％。
ZrO 2在硅酸盐玻璃中主要是以立方体[ZrO 8]配位形式存在，由于离子半径较大，在玻璃结构中属网络外体，且其在玻璃中溶度较小，会显著增加玻璃黏度，因此其添加量不宜超过6％，可提高玻璃的耐酸碱性能和折射率。在本实施方式中，ZrO 2的质量百分比优选为1％～6％。ZrO 2的质量百分比更优选为2％～5％。ZrO 2的质量百分比最优选为3％～4％。
TiO 2的作用于ZrO 2类似，而且其属于过渡元素，具有一定着色能力，显黄色，可提高玻璃的化学稳定性和提高玻璃色温。因此在本实施方式中TiO 2的质量百分比为0～2％。TiO 2的质量百分比进一步为0～1％。
SnO 2和CeO 2在玻璃体中经常会以多种价态存在，可以增加玻璃的抗紫外性能，防止因着色离子变价而发生颜色变化，而且其单独或混合添加，还可增加玻璃体高温的排泡能力，是常用的澄清剂。在本实施方式中，SnO 2的质量百分比优选为0～2％。SnO 2的质量百分比进一步优选为0～1％。CeO 2的质量百分比优选为0～1％。CeO 2的质量百分比进一步优选为0～0.5％。
上述配比的铝硅酸盐玻璃能够通过化学强化提高强度，且化学强化后的强化玻璃具有＞900MPa表面压应力，最大应力深度＞145μm，且挤压裂纹阈值大于7.5。上述铝硅酸盐玻璃具有较高的强度，作为设备的保护玻璃时能够较好地保护设备。
进一步地，在一些实施例中，Li 2O、Na 2O与K 2O的总质量百分比大于或等于9.8％。碱金属作为典型的玻璃网络修饰体，其可以显著降低玻璃的熔化温度；此外在本发明中碱金属离子是玻璃能否经化学强化实现离子交换从而在玻璃表面获得足够的压应力层的关键，发明人在大量实验过程中发现，当Li 2O、Na 2O和K 2O的总质量百分比大于或等于9.8％时，得到的铝硅酸盐玻璃的表面应力值更大，强度更好。
在一些实施例中，B 2O 3、Li 2O和ZrO 2的质量百分比满足如下关系：3.5％≤A≤11.0％，A＝0.5×B 2O 3质量百分比+Li 2O质量百分比+ZrO 2质量百分比。
B 2O 3在玻璃中的主要作用是作为网络中间体存在，主要和氧结合生成硼氧三角体及硼氧四面体，硼氧三角体普遍存在于玻璃结构体的间隙中，而硼氧四面体则参与到玻璃结构骨架的构建过程中，两者在一定条件下可以相互转换，提高玻璃体结构的稳定性并增加玻璃的韧性，分散玻璃中裂纹的尖端应力，提高玻璃强度；而Li 2O在玻璃体中作为网络外体的形式存在，可以和玻璃体中的游离氧结合而存在于玻璃结构的间隙中，且由于Li离子的半径非常小，因此具有非常高的场强，能紧缩玻璃结构，使得玻璃具有更高的抵抗外物冲击和侵蚀的性能，同时也能分散玻璃体裂纹的尖端应力；ZrO 2通常也只存在于玻璃结构的间隙中，但由于其原子半径太大，因此不能像Li 2O及硼氧三角体那样存在于很小的结构间隙中，只存在于较大体积的结构间隙中，Zr离子虽然离子半径很大，但是由于其携带了+4正电荷，因此其也具有很高 的场强，在结构间隙中同样可以紧缩玻璃结构，使玻璃体具有非常好的机械强度、硬度和抗侵蚀等性能；综合上述B 2O 3、Li 2O及ZrO 2的主要作用原理，发明人通过大量实验收集数据分析，发现A值在3.5％～11％之间，铝硅酸盐玻璃具有非常好的抗裂纹能力，A值在9％附近，铝硅酸盐玻璃的裂纹阈值K值出现极值，玻璃具有最优的断裂韧性，也就是意味着玻璃具有更高的抗冲击强度和更高的机械加工性能。因此，在一些实施例中，3.5％≤A≤11.0％。
传统的一种技术中公开了一种薄锂铝硅玻璃，钢化后玻璃的中心张力小于50Mpa，玻璃的表面压应力为600MPa～1200Mpa，玻璃的抗弯强度可达500MPa，因此其玻璃的应力层深度应小于50μm。而本实施方式中的铝硅酸盐玻璃经强化后，应力层深度需大于145μm以上，远大于上述技术中钢化玻璃的应力层深度。
另有一种传统技术中的B 2O 3和ZrO 2的含量均较低，而本实施方式中的B 2O 3和ZrO 2的含量都超过0.1％，参与到形成玻璃体结构的骨架中，有利于玻璃基板在后期的加工，增加玻璃的断裂韧性，钢化后形成超过900MPa的表面应力值和10μm深度仍有超过350MPa的压应力值，增强玻璃的机械强度和抗跌落性能。
因此，传统玻璃盖板能进行快速的化学钢化，在玻璃表面形成大于600MPa的压应力层，应力层深度普遍高于35μm以上，锂铝硅酸盐玻璃通过特殊的钢化工艺，其应力层深度可以到达100μm以上，以便增加玻璃的机械强度、抗冲击性能、耐摩擦性能以及抗砂石地面落摔性能等目的。但传统的玻璃的强度仍较低。
而上述铝硅酸盐玻璃至少具有以下优点：
(1)上述铝硅酸盐玻璃通过选择特定配比的原料，使得制备得到的玻璃 在20℃～300℃具有80.8×10 -7～92.1×10 -7的热膨胀系数。熔化温度T 2在1536℃～1613℃。玻璃转变点温度T g在482℃～558℃。经过化学强化后得到的强化玻璃具有＞900MPa表面压应力CS0，距离玻璃表面10μm深度仍有超过300MPa的压应力CS10，离子交换产生的复合压应力降至0MPa(仪器检测极限)的应力深度Dol0＞145μm，复合压应力为600MPa的应力层深度Dol600＞5.5μm。
(2)上述铝硅酸盐玻璃经强化后的挤压裂纹阈值大于7.5，能较好地保护手机等智能设备。
在其中一些实施例中，优选地，按质量百分比计，铝硅酸盐玻璃包括：SiO 2 58％～66％，Al 2O 3 16％～22％，B 2O 3 1％～3％，Li 2O 3％～6％，Na 2O 7％～12％，K 2O 0.5％～2％，MgO 0.5％～2.0％和ZrO 2 2％～5％。其中，Li 2O、Na 2O与K 2O的总质量百分比大于或等于10％，且B 2O 3、Li 2O和ZrO 2的质量百分比满足如下关系：5.5％≤A≤11.0％，A＝0.5×B 2O 3质量百分比+Li 2O质量百分比+ZrO 2质量百分比。
在该实施例中，铝硅酸盐玻璃还可以包括ZnO、P 2O 5及TiO 2中的至少一种。具体地，ZnO的质量百分比不超过3％。P 2O 5的质量百分比不超过2％。TiO 2的质量百分比不超过1％。在该实施例中，铝硅酸盐玻璃还可以包括SnO 2及CeO 2中的至少一种。其中，SnO 2的质量百分比不超过1％。CeO 2的质量百分比不超过0.5％。需要说明的是，在该实施例中，ZnO、P 2O 5、TiO 2、SnO 2及CeO 2均可以省略。
由上述配比的原料制备得到的玻璃在20℃～300℃具有82.9×10 -7～89.8×10 -7的热膨胀系数。熔化温度T 2在1566℃～1611℃。玻璃转变点温度Tg在485℃～546℃。经过化学强化后得到的强化玻璃具有＞900MPa 表面压应力CS0，距离玻璃表面10μm深度仍有超过300MPa的压应力CS10，离子交换产生的复合压应力降至0MPa(仪器检测极限)的应力深度Dol0＞155μm，复合压应力为600MPa的应力层深度Dol600＞6μm。且上述铝硅酸盐玻璃得到的玻璃的裂纹阈值大于11。
在另一些实施例中，进一步优选地，按质量百分比计，铝硅酸盐玻璃包括：SiO 2 60％～64％、Al 2O 3 18％～20％、B 2O 3 1％～2％、Li 2O 4％～5％、Na 2O 8％～10％、K 2O 0.5％～1％、MgO 0.5％～1.0％和ZrO 2 3％～4％。其中，Li 2O、Na 2O与K 2O的总质量百分比大于或等于12.8％，且B 2O 3、Li 2O和ZrO 2的质量百分比满足如下关系：8％≤A≤9％，A＝0.5×B 2O 3质量百分比+Li 2O质量百分比+ZrO 2质量百分比。
在该实施例中，铝硅酸盐玻璃还可以包括质量百分比不超过1％的P 2O 5。
由上述配比的原料制备得到的玻璃在20℃～300℃具有80.8×10 -7～85.6×10 -7的热膨胀系数。熔化温度T 2在1578℃～1603℃。玻璃转变点温度T g在500℃～527℃。经化学强化处理后的强化玻璃具有＞950MPa表面压应力CS0，距离玻璃表面10μm深度仍有超过350MPa的压应力CS10，离子交换产生的复合压应力降至0MPa(仪器检测极限)的应力深度Dol0＞160μm，复合压应力为600MPa的应力层深度Dol600＞7μm。且上述铝硅酸盐玻璃得到的玻璃的裂纹阈值大于24。
请参阅图1，一实施方式的铝硅酸盐玻璃的制备方法，为上述实施方式的铝硅酸盐玻璃的一种制备方法，具体包括如下步骤：
步骤S110：按质量百分比计，称取如下原料：SiO 2 55％～67％、Al 2O 3 13％～25％、B 2O 3 0.5％～4.0％、Li 2O 1％～8％、Na 2O 6％～14％、ZrO 2 1％～6％、K 2O 0～4％和MgO 0～4％。
进一步地，Li 2O、Na 2O与K 2O的总质量百分比大于或等于9.8％，且B 2O 3、Li 2O和ZrO 2的质量百分比满足如下关系：3.5％≤A≤11.0％。
步骤S120：将上述原料混合，并进行熔制，得到玻璃浆料。
在其中一个实施例中，步骤S120中熔制的温度为1650℃。熔制的时间为8h。在熔制的过程中同时用铂金搅拌桨进行搅拌。
步骤S130：将玻璃浆料进行均化处理。
具体地，步骤S130中均化处理的温度为1500℃。均化处理的时间为1h。
步骤S140：将玻璃浆料成型，再经退火处理，得到铝硅酸盐玻璃。
具体地，将玻璃浆料成型的步骤中，采用浇注成型的方式。在其中一个实施例中，将经过均化处理的玻璃浆料浇注在经过450℃预热后的铁质模具上，使玻璃浆料固化成型。在其中一个实施例中，退火处理的温度为580℃～600℃。
需要说明的是，上述铝硅酸盐玻璃的制备方法中可以在传统平板玻璃制造工艺过程获得玻璃，且制造方法不限于浮法成形工艺、溢流下拉法、引上法、平拉法、压延法等。
上述铝硅酸盐玻璃的制备方法工艺简单，易于工业化生产。
一实施方式的强化玻璃，由上述实施方式的铝硅酸盐玻璃经化学强化后得到。该强化玻璃的挤压裂纹阈值大于7.5，可以有效避免或减少手机等智能设备因不小心跌落地面而屏幕或其他盖板玻璃破裂的情况。
请参阅图2，一实施方式的强化玻璃的制备方法，为上述实施方式的强化玻璃的一种制备方法，具体包括如下步骤：
步骤S210：提供上述铝硅酸盐玻璃。
步骤S220：先将铝硅酸盐玻璃在温度为390℃～420℃、质量比为3:7～7:3 的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～6h。
进一步地，步骤S220中的NaNO 3和KNO 3的质量比为9:11～11:9。
步骤S230：然后将铝硅酸盐玻璃在温度为380℃～400℃、质量比为2:98～20:80的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～4h。
进一步地，步骤S230中NaNO 3和KNO 3的质量比为5:95～15:85。
将铝硅酸盐玻璃采用两步混盐方式进行强化的作用是：通过两步化学钢化的方法，有选择性地进行离子种类的交换，第一步主要为玻璃中的Li离子和钢化盐中的Na离子、K离子交换，Na-Li交换会产生较小压应力值、高应力深度的压应力层，其中伴随着部分Li-K和Na-K交换，形成较大应力去弥补高深度方向上应力值偏低的问题；第二步，采用低温高K离子含量的钢化盐去进行钢化，玻璃中的Na离子和钢化盐中的K离子进行快速交换，在玻璃表面形成致密的较低应力深度、高压应力值的应力层，最终形成复合应力层，其主要特征是在玻璃表面具有超过900MPa的高应力层，深度方向上具有超过145μm甚至更高的应力层深度。
其中，将步骤S220中硝酸钠和硝酸钾的质量比设置为3:7～7:3主要是实现Na离子与玻璃中的Li离子进行化学交换，形成足够深度的应力层，但由于Na和Li离子半径相差不大，且玻璃结构中有足够的空间满足Na-Li离子的转换，因此形成的应力层深度深，但是应力值低；通过在钢化盐中添加大离子半径的K，从而在应力方向上实现Li-K和Na-K交换，增加部分压应力值，因此第一步的硝酸钠和硝酸钾的质量比在3:7～7:3之间。
步骤S230中将硝酸钠和硝酸钾的质量比设置为2:98～20:80主要是实现玻璃中的Na离子和钢化盐中的K离子进行置换，从而在玻璃表面实现高压缩应力值的应力层，与第一步的钢化形成复合压应力层，从而增加玻璃的强度 和韧性。
两步化学钢化过程中，步骤S220中的混合熔融液的温度通常比步骤S230中的混合熔融液的温度高10℃～20℃。因为对于钢化工艺中两要素：温度和时间来说，相同的钢化盐处理的时间越长，温度越高，形成的应力层深度越深，然而应力值会显著降低。根据本发明中两步钢化方法的目的不同，第一步是为了形成足够深度的应力层(大于100μm)，其次是应力值是越高越好，因此第一步中选择较高的温度，通常为390℃～420℃，时间在2小时～6小时之间。第二步是为了形成一定深度的高应力的应力层(大于700MPa)，因此在第二步中需要较低温度，较短时间，通常为380℃～400℃之间，时间为2小时～4小时，不选择长时间的原因主要在于钢化周期过长，效率和产量低，成本高不适宜量产。
铝硅酸盐玻璃经过上述方法强化后的强化玻璃的挤压裂纹阈值大于7.5，可以有效避免或减少手机等智能设备因不小心跌落地面而屏幕或其他盖板玻璃破裂的情况。
一实施方式的显示器件，包括上述实施方式的铝硅酸盐玻璃或上述实施方式的强化玻璃或由上述实施方式的强化玻璃的制备方法制备得到的强化玻璃。
以下为具体实施例部分：
实施例1～实施例21的铝硅酸盐玻璃的制备过程具体如下：
将实施例1～实施例21分别按照表1～表3中设计组分配料(质量百分比)，经充分混合均匀后，用铂金坩埚在1650℃熔制8h，同时用铂金搅拌桨搅拌，待抽出搅拌桨后，降温至1500℃，保温1h均化，浇铸到铁质模具上形成80mm×160mm左右大小的玻璃块，模具浇铸前预热到450℃，玻璃块硬化后 立即转移至退火炉中在590℃下进行退火，保温2h，然后6小时降温140℃，随后自然冷却，得到玻璃制品，取出后备用。
实施例1～实施例12的铝硅酸盐玻璃的强化过程具体如下：
将上述实施例1～实施例12得到的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为400℃、质量比为3:2的NaNO 3和KNO 3的混合熔融液中钢化处理4小时后，再转移至温度为385℃、质量比为1:9的NaNO 3和KNO 3的混合熔融液中钢化处理2小时，得到强化玻璃。
实施例13～实施例14的铝硅酸盐玻璃的强化过程具体如下：
将上述实施例13～实施例14得到的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为390℃、质量比为3:7的NaNO 3和KNO 3的混合熔融液中钢化处理6小时后，再转移至温度为380℃、质量比为2:98的NaNO 3和KNO 3的混合熔融液中钢化处理4小时，得到强化玻璃。
实施例15～实施例21的铝硅酸盐玻璃的强化过程具体如下：
将上述实施例15～实施例21得到的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为420℃、质量比为7:3的NaNO 3和KNO 3的混合熔融液中钢化处理2小时后，再转移至温度为400℃、质量比为20:80的NaNO 3和KNO 3的混合熔融液中钢化处理2小时，得到强化玻璃。
对比例1～对比例19的铝硅酸盐玻璃的制备过程与实施例1～实施例21的铝硅酸盐玻璃的制备过程相似，区别在于，对比例1～对比例19的铝硅酸盐玻璃的原料配比如表4～表6所示。
对比例1～对比例14的铝硅酸盐玻璃的强化过程与实施例1～实施例12的铝硅酸盐玻璃的强化过程相同，在此不再赘述。
对比例15的铝硅酸盐玻璃的强化过程具体如下：
将对比例15制备得到的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为400℃、质量比为3:2的NaNO 3和KNO 3的混合熔融液中钢化处理4小时，得到强化玻璃。
对比例16的铝硅酸盐玻璃的强化过程具体如下：
将对比例16的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为385℃、质量比为1:9的NaNO 3和KNO 3的混合熔融液中钢化处理2小时，得到强化玻璃。
对比例17的铝硅酸盐玻璃的强化过程具体如下：
将对比例17的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为385℃、质量比为3:2的NaNO 3和KNO 3的混合熔融液中钢化处理4小时后，再转移至温度为400℃、质量比为1:9的NaNO 3和KNO 3的混合熔融液中钢化处理2小时，得到强化玻璃。
对比例18的铝硅酸盐玻璃的强化过程具体如下：
将对比例18的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为400℃、质量比为1:9的NaNO 3和KNO 3的混合熔融液中钢化处理4小时后，再转移至温度为385℃、质量比为3:2的NaNO 3和KNO 3的混合熔融液中钢化处理2小时，得到强化玻璃。
对比例19
将对比例19的铝硅酸盐玻璃加工成50mm×50mm×0.7mm双面抛光的玻璃片，经过温度为400℃的NaNO 3的熔融液中钢化处理4小时后，再转移至 温度为385℃的KNO 3的熔融液中钢化处理2小时，得到强化玻璃。
以下为测试部分：
将上述实施例1～实施例21和对比例1～对比例14制备得到的铝硅酸盐玻璃均加工成φ5mm×50mm的玻璃试样，用耐驰热膨胀仪NETZSCH-DIL 402 PC在4℃/min的升温速度下测得热膨胀曲线，通过自带软件，测得玻璃的应变点T g和膨胀软化点T s以及20℃～300℃范围内的热膨胀系数CTE，并记录于表1～表5中。
将实施例1～实施例21和对比例1～对比例14制备得到的铝硅酸盐玻璃选取250g通过ORTON的RSV-1600型号玻璃高温黏度计测试高温黏度，将黏度为102dPa.S的温度定义为玻璃熔化温度T 2，黏度为103dPa.S、104dPa.S和105dPa.S的温度分别定义为T 3、T 4、T 5，并将测得的数值记录于表1～表5中。
将实施例1～实施例21和对比例1～对比例19得到的强化玻璃通过日本折原的应力测试仪FSM6000UV和SLP1000分别测试强化玻璃的表面应力值CS0，10μm深度的压应力值CS10，应力值的最大应力层深度Dol0和600MPa时的应力层深度Dol600，并对应记录于表1～表6中。
将实施例1～实施例21和对比例1～对比例19得到的强化玻璃加工成50mm×50mm×0.7mm玻璃样品。然后用上海标誉的HV-50MDX维氏硬度计测量表面维氏硬度，选择试验力分别为0.2kgf、0.5kgf、1kgf、2kgf、3kgf、5kgf、10kgf、20kgf及30kgf，保压20s，然后在徕卡DM2500显微镜下测量压痕对角线和裂纹尺寸，通过以下公式：挤压裂纹阈值K＝F×a/b，其中，F为出现裂纹的最小施加力(单位N)，a值为压痕的对角线长度，b为裂纹在压痕对角线方向的长度，a、b的计算方式具体如图3所示，计算出产生挤压裂纹的阈值K。将各实施例和对比例的玻璃样品测试得到的挤压裂纹阈值对 应记录在表1～表5中。
表1中实施例1～实施例7的铝硅酸盐玻璃，按质量百分比计，包括：SiO 2 55％～67％、Al 2O 3 13％～25％、B 2O 3 0.5％～4.0％、Li 2O 1％～8％、Na 2O 6％～14％、ZrO2 1％～6％、K 2O 0～4％、MgO 0～4％、SrO 0～2％、ZnO 0～4％、P 2O 5 0～4％，TiO 2 0～2％、SnO 2 0～2％和CeO 2 0～1％。其中Li 2O、Na 2O与K 2O的总质量百分比大于或等于9.8％，且B 2O 3、Li 2O和ZrO 2的质量百分比满足：3.5％≤A≤11.0％。
针对上述实施例1～实施例7制备得到的铝硅酸盐玻璃，从表1中可以看出，具有上述组分特征的玻璃在20℃～300℃具有82.4×10 -7～92.1×10 -7的热膨胀系数。熔化温度T 2在1536℃～1613℃。玻璃转变点温度T g在482℃～558℃。
另外，实施例1～实施例7的铝硅酸盐玻璃经过400℃的NaNO 3：KNO 3＝3:2混合熔融液中钢化4小时后，再转移至385℃的NaNO 3：KNO 3＝1:9的混合熔融液中钢化2小时后，得到的强化玻璃具有＞900MPa表面压应力CS0，距离玻璃表面10μm深度仍有超过300MPa的压应力CS10，离子交换产生的复合压应力降至0MPa(仪器检测极限)的应力深度Dol0＞145μm，复合压应力为600MPa的应力层深度Dol600＞5.5μm。强化玻璃的挤压裂纹阈值大于7.5。
表1实施例1～实施例7的铝硅酸盐玻璃的组成和实验数据
Figure PCTCN2019130659-appb-000001
Figure PCTCN2019130659-appb-000002
备注：CS0：表面应力值；CS10：10μm深度的压应力值；Dol0：最大应力层深度；Dol600：600MPa时的应力层深度。
表2中列出了铝硅酸盐玻璃的优选配方。实施例8～实施例14的铝硅酸盐玻璃中，按质量百分比计，包括：SiO 2 58％～66％、Al 2O 3 16％～22％、B 2O 3 1％～3％、Li 2O 3％～6％、Na 2O 7％～12％、K 2O 0.5％～2％、MgO 0.5％～2％、ZrO 2 2％～5％、ZnO 0～3％、P 2O 5 0～2％、TiO 2 0～1％、SnO 2 0～1％和CeO 2 0～0.5％。其中，Li 2O、Na 2O与K 2O的总质量百分比大于或等于10％，且B 2O 3、Li 2O和ZrO 2的质量百分比满足：5.5％≤A≤11.0％。
从表2中可以看出，具有上述组分特征的铝硅酸盐玻璃在20℃～300℃具有82.9×10 -7～89.8×10 -7的热膨胀系数。熔化温度T 2在1566℃～1611℃。玻璃转变点温度Tg在485℃～546℃。
另外，实施例8～实施例14的铝硅酸盐玻璃经过400℃的NaNO 3：KNO 3＝3:2混合熔融液中钢化4小时后，再转移至385℃的NaNO 3：KNO 3＝1:9的混合熔融液中钢化2小时后，得到的强化玻璃具有＞900MPa表面压应力CS0，距离玻璃表面10μm深度仍有超过300MPa的压应力CS10，离子交换产生的复合压应力降至0MPa(仪器检测极限)的应力深度Dol0＞155μm，复合压应力为600MPa的应力层深度Dol600＞6μm。强化玻璃的挤压裂纹阈值大于11。
表2实施例8～实施例14的铝硅酸盐玻璃的组成和实验数据
Figure PCTCN2019130659-appb-000003
Figure PCTCN2019130659-appb-000004
表3中列出了铝硅酸盐玻璃的进一步优选配方，实施例15～实施例21的铝硅酸盐玻璃中，按质量百分比计，包括：SiO 2 60％～64％、Al 2O 3 18％～20％、B 2O 3 1％～2％、Li 2O 4％～5％、Na 2O 8％～10％、K 2O 0.5％～1％、MgO 0.5％～1.0％、ZrO 2 3％～4％和P 2O 5 0～1％，其中，Li 2O、Na 2O与K 2O的总质量百分比大于或等于12.8％，且B 2O 3、Li 2O和ZrO 2的质量百分比满足：8％≤A≤9％。
从表3中可以看出，具有上述配比的铝硅酸盐玻璃在20℃～300℃具有80.8×10 -7～85.6×10 -7的热膨胀系数。熔化温度T 2在1578℃～1603℃。玻璃转变点温度Tg在500℃～527℃。
另外，实施例15～实施例21的铝硅酸盐玻璃经过400℃的NaNO 3：KNO 3＝3:2混合熔融液中钢化4小时后，再转移至385℃的NaNO 3：KNO 3＝1:9的混合熔融液中钢化2小时后，得到的强化玻璃具有＞950MPa表面压应力CS0，距离玻璃表面10μm深度仍有超过350MPa的压应力CS10，离子交换产生的复合压应力降至0MPa(仪器检测极限)的应力深度Dol0＞160μm，复合压应力为600MPa的应力层深度Dol600＞7μm。强化玻璃的挤压裂纹阈值大于24。
表3实施例15～实施例21的铝硅酸盐玻璃的组成和实验数据
Figure PCTCN2019130659-appb-000005
Figure PCTCN2019130659-appb-000006
对上述实施例1～实施例21的强化玻璃的挤压裂纹阈值K与铝硅酸盐玻璃中的A＝0.5×B 2O 3+Li 2O+ZrO 2的关系进行研究，得到如图4所示的关系曲线图。
从图4中可以看出，当铝硅酸盐玻璃中，A值处于3.5％～11.0％时，强化玻璃具有较强的抗裂纹强度。当铝硅酸盐玻璃中，A值处于5.5％～11.0％，强化玻璃具有更好的裂纹阈值。当铝硅酸盐玻璃中，A值处于8％～9％时，铝硅酸盐玻璃具有最佳的挤压裂纹阈值K，具有最高的抗裂纹能力和最高的机械强度。
对比例1～对比例7的铝硅酸盐玻璃的组成和实验数据如下表4所示。从表4中可以看出，对比例1的铝硅酸盐玻璃中没有B 2O 3，且A值为8％，但由于没有硼氧化物参与到玻璃网络结构中，当玻璃受到外部冲击力时，没有缓冲结构，容易形成应力集中，使得对比例1的铝硅酸盐玻璃的裂纹阈值较实施例1的铝硅酸盐玻璃的裂纹阈值显著降低。对比例2的铝硅酸盐玻璃中B 2O 3的百分比为5％，含量较高，使得玻璃的离子交换能力显著降低，因此，CS0值以及Dol600、裂纹阈值明显降低，玻璃的强度降低。
从对比例3～对比例5与实施例3～实施例5的对比中可以看出，Al 2O 3含量增加，导致高温粘度明显增大。Al 2O 3含量较低时，裂纹阈值明显降低，玻璃的强度降低。SiO 2的含量较高时，增加了熔化温度，形成结构稳定的硅氧四面体结构，不利于化学强化离子交换，使得CS0值以及Dol600、裂纹阈值明显降低，玻璃的强度降低。
从对比例6～对比例7与实施例6～实施例7的对比中可以看出，Li 2O含量增加时，玻璃膨胀系数显著增大，玻璃体稳定的空间骨架结构被破坏，因此玻璃强度明显降低。Li 2O含量较低时，不利于Li-Na离子交换，无法形成足够深的压应力层，因此Dol0仅为92μm，强度较低，难以作为保护玻璃使用。
表4对比例1～对比例7的玻璃组分和相关性能数据
Figure PCTCN2019130659-appb-000007
Figure PCTCN2019130659-appb-000008
对比例8～对比例14的铝硅酸盐玻璃的组成和实验数据如下表5所示。从表5中可以看出，对比例8的铝硅酸盐玻璃中ZrO 2的含量较低时，无法形成足够稳定的玻璃结构空间，当受到外力冲击时，容易产生应力集中，使玻璃易破裂，显著降低玻璃的裂纹阈值；而对比例9的铝硅酸盐玻璃中ZrO 2的含量增加时，会显著增加玻璃粘度，导致玻璃设计配方无法进行实际量产，且容易析晶。
从对比例10和对比例11中可以看出，当A值小于3.5％或A值大于11％，其作为形成铝硅玻璃体结构空隙的主要成分组成，硼氧三角体、大场强氧化锂和氧化锆，A值大于11％，则结构间隙占据整个玻璃体的空间较大，降低玻璃结构强度，A值小于3.5％，则其作为结构间隙填充离子，无法形成足够 的结构间隙，不能实现Li-Na-K三种离子的快速交换和迁移，提高玻璃强度的目的，因此其铝硅酸盐玻璃的裂纹阈值均小于A值在3.5％～11％时的裂纹阈值。
从对比例12和对比例13中可以看出，氧化钠含量过高或过低，均不利于玻璃强度的增加；其中氧化钠含量过高，直接导致玻璃的网络骨架被破坏，玻璃体强度降低，而氧化钠含量过低时，作为化学钢化离子交换的主要离子，无法发挥通过离子交换提高玻璃强度的作用。
从对比例14中可以看出，氧化钾含量较高时，作为网络外体的氧化钾，显著破坏玻璃骨架结构，导致玻璃的裂纹阈值降低明显，无法起到保护玻璃的作用。
表5对比例8～对比例14的铝硅酸盐玻璃的组成和实验数据
Figure PCTCN2019130659-appb-000009
Figure PCTCN2019130659-appb-000010
对比例15～对比例19的铝硅酸盐玻璃的组成和实验数据如下表6所示。从表6中可以看出，对比例15的强化过程中仅进行了第一步强化，从而无法进行Na-K离子交换和Li-K离子交换，玻璃的表面应力值仅为386MPa，最大应力层深度仅为135μm，挤压裂纹阈值仅为4.84，较实施例8的裂纹阈值降低了17.83，最大应力深度降低了37μm。
对比例16的强化过程仅进行了第二步强化，从而无法进行Li-Na离子交换，仅进行Li-K和Na-K交换，玻璃表面具有较高的压应力值，但是最大应力深度仅10.2μm左右，远低于实施例9的最大应力深度178μm，且其CS10仅为36MPa，导致其裂纹阈值仅为4.32。
对比例17的强化过程中第一步强化温度较第二步强化温度低，由于第一步强化主要是形成足够深度的应力层，强化温度较低时，仍能形成较深的应力层深度；而第二步强化主要是提高应力层的应力值，强化温度较高时，发生了应力松弛现象，其形成的表面压应力仅为754MPa，远低于实施例中的936MPa。
对比例18的强化过程中第一步强化和第二步强化的硝酸钠和硝酸钾的配比不在本案的配比范围内，使得最大应力层深度低于100μm，表面应力值仅为584MPa，化学钢化效果远低于实施例，从而使得裂纹阈值仅为4.86。
对比例19的强化过程中第一步的熔融液中仅含有硝酸钠，第二步的熔融液中仅含有硝酸钾，从而第一步强化中无法进行Li-K和Na-K交换，第二步强化中无法进行Li-Na离子交换，使得玻璃的强度降低，裂纹阈值较低。
表6对比例15～对比例19的铝硅酸盐玻璃的组成和实验数据
成分 对比例15 对比例16 对比例17 对比例18 对比例19
SiO 2 59 61 58 62 60
Al 2O 3 17.5 16 19 18.5 22
B 2O 3 1 1 3 1.5 1
Li 2O 4 3 6 4.5 4
Na 2O 7 12 9 7.5 8
K 2O 2 1 0.8 1 0.5
MgO 1 2 0.7 0.5 1
SrO - - - - -
ZnO 3 - - 1 -
ZrO 2 3 2 3.5 3 3
P 2O 5 0.5 2 - - -
TiO 2 1 - - - 0.5
SnO 2 1 - - - -
CeO 2 - - - 0.5 -
A 7.5 5.5 11 8.25 7.5
Li 2O+Na 2O+K 2O 13 16 15.8 13 12.5
CS0(MPa) 386 985 754 584 1088
CS10(MPa) 294 36 285 269 342
Dol0(μm) 135 10.2 172 94 165
Dol600(μm) 0 4.2 4.4 0 3.8
裂纹阈值K 4.84 4.32 8.42 4.68 15.63
从上述实验结果中可以看出，实施例1～实施例21制备的铝硅酸盐玻璃在经过化学强化后的挤压裂纹阈值均大于7.5，优于对比例中的铝硅酸盐玻璃经化学强化后的挤压裂纹阈值。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细， 但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (20)

  1. 一种铝硅酸盐玻璃，按质量百分比计，包括：SiO 2 55％～67％、Al 2O 3 13％～25％、B 2O 3 0.5％～4.0％、Li 2O 1％～8％、Na 2O 6％～14％、ZrO 2 1％～6％、K 2O 0～4％和MgO 0～4％。
  2. 根据权利要求1所述的铝硅酸盐玻璃，其特征在于，所述Li 2O、所述Na 2O与所述K 2O的总质量百分比≥9.8％。
  3. 根据权利要求2所述的铝硅酸盐玻璃，其特征在于，所述Li 2O、所述Na 2O与所述K 2O的总质量百分比≥10％。
  4. 根据权利要求3所述的铝硅酸盐玻璃，其特征在于，所述Li 2O、所述Na 2O与所述K 2O的总质量百分比≥12.8％。
  5. 根据权利要求1所述的铝硅酸盐玻璃，其特征在于，所述B 2O 3、所述Li 2O和所述ZrO 2的质量百分比满足如下关系：3.5％≤A≤11.0％，A＝0.5×B 2O 3质量百分比+Li 2O质量百分比+ZrO 2质量百分比。
  6. 根据权利要求5所述的铝硅酸盐玻璃，其特征在于，5.5％≤A≤11.0％。
  7. 根据权利要求6所述的铝硅酸盐玻璃，其特征在于，8％≤A≤9％。
  8. 根据权利要求1所述的铝硅酸盐玻璃，其特征在于，所述B 2O 3的质量百分比为1％～3％，所述ZrO 2的质量百分比为2％～5％。
  9. 根据权利要求1所述的铝硅酸盐玻璃，其特征在于，所述Li 2O的质量百分比为3％～6％，所述Na 2O的质量百分比为7％～12％，所述K 2O的质量百分比为0.5％～2.0％。
  10. 根据权利要求1所述的铝硅酸盐玻璃，其特征在于，按质量百分比计，包括：SiO 2 58％～66％、Al 2O 3 16％～22％、B 2O 3 1％～3％、Li 2O 3％～6％、Na 2O 7％～12％、K 2O 0.5％～2.0％、MgO 0.5％～2.0％和ZrO 2 2％～5％，其中，所 述Li 2O、所述Na 2O与所述K 2O的总质量百分比≥10％，且5.5％≤A≤11.0％，A＝0.5×B 2O 3质量百分比+Li 2O质量百分比+ZrO 2质量百分比。
  11. 根据权利要求10所述的铝硅酸盐玻璃，其特征在于，按质量百分比计，包括：SiO 2 60％～64％、Al 2O 3 18％～20％、B 2O 3 1％～2％、Li 2O 4％～5％、Na 2O 8％～10％、K 2O 0.5％～1.0％、MgO 0.5％～1.0％和ZrO 2 3％～4％，其中，所述Li 2O、所述Na 2O与所述K 2O的总质量百分比≥12.8％，且8％≤A≤9％。
  12. 根据权利要求1～11任一项所述的铝硅酸盐玻璃，其特征在于，所述铝硅酸盐玻璃还包括质量百分比不超过2％的SrO、质量百分比不超过4％的ZnO、质量百分比不超过4％的P 2O 5、质量百分比不超过2％的TiO 2、质量百分比不超过2％的SnO 2及质量百分比不超过1％的CeO 2中的至少一种。
  13. 根据权利要求1～11任一项所述的铝硅酸盐玻璃，其特征在于，所述铝硅酸盐玻璃还包括质量百分比不超过3％的ZnO、质量百分比不超过2％的P 2O 5、质量百分比不超过1％的TiO 2、质量百分比不超过1％的SnO 2及质量百分比不超过0.5％的CeO 2中的至少一种。
  14. 根据权利要求1～11任一项所述的铝硅酸盐玻璃，其特征在于，所述铝硅酸盐玻璃还包括质量百分比不超过1％的P 2O 5。
  15. 一种强化玻璃，由权利要求1～14任一项所述的铝硅酸盐玻璃经化学强化后得到。
  16. 一种强化玻璃的制备方法，包括如下步骤：
    提供权利要求1～14任一项所述的铝硅酸盐玻璃；及
    先将所述铝硅酸盐玻璃在温度为390℃～420℃、质量比为3:7～7:3的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～6h，然后在温度为380℃～400℃、质量比为2:98～20:80的NaNO 3和KNO 3的混合熔融液中进行钢化处 理2h～4h，得到强化玻璃。
  17. 根据权利要求16所述的强化玻璃的制备方法，其特征在于，所述先将所述铝硅酸盐玻璃在温度为390℃～420℃、质量比为3:7～7:3的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～6h的步骤中，NaNO 3和KNO 3的质量比为9:11～11:9。
  18. 根据权利要求16所述的强化玻璃的制备方法，其特征在于，所述在温度为380℃～400℃、质量比为2:98～20:80的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～4h的步骤中，NaNO 3和KNO 3的质量比为5:95～15:85。
  19. 根据权利要求16所述的强化玻璃的制备方法，其特征在于，所述先将所述铝硅酸盐玻璃在温度为390℃～420℃、质量比为3:7～7:3的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～6h的步骤中的温度比所述在温度为380℃～400℃、质量比为2:98～20:80的NaNO 3和KNO 3的混合熔融液中进行钢化处理2h～4h的步骤中的温度高10℃～20℃。
  20. 一种显示器件，包括权利要求1～14任一项所述的铝硅酸盐玻璃或权利要求15所述的强化玻璃或由权利要求16～19任一项所述的强化玻璃的制备方法制备得到的强化玻璃。
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