WO2022142526A1 - 微晶玻璃、微晶玻璃制品及其制造方法 - Google Patents

微晶玻璃、微晶玻璃制品及其制造方法 Download PDF

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Publication number
WO2022142526A1
WO2022142526A1 PCT/CN2021/120633 CN2021120633W WO2022142526A1 WO 2022142526 A1 WO2022142526 A1 WO 2022142526A1 CN 2021120633 W CN2021120633 W CN 2021120633W WO 2022142526 A1 WO2022142526 A1 WO 2022142526A1
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Prior art keywords
glass
ceramic
zro
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ceramic product
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PCT/CN2021/120633
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English (en)
French (fr)
Inventor
原保平
于天来
李赛
蒋焘
陈雪梅
粟勇
聂小兵
刘振禹
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成都光明光电股份有限公司
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Priority to EP21913271.9A priority Critical patent/EP4197979A4/en
Priority to JP2023528126A priority patent/JP2023548242A/ja
Priority to AU2021412144A priority patent/AU2021412144A1/en
Priority to US18/029,170 priority patent/US20230312404A1/en
Priority to CA3196558A priority patent/CA3196558A1/en
Priority to MX2023005911A priority patent/MX2023005911A/es
Priority to KR1020247009700A priority patent/KR20240042254A/ko
Priority to KR1020237014410A priority patent/KR20230078753A/ko
Publication of WO2022142526A1 publication Critical patent/WO2022142526A1/zh

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04Opacifiers, e.g. fluorides or phosphates; Pigments
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment 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
    • C03C21/002Treatment 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/0092Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/02Compositions for glass with special properties for coloured glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/18Compositions for glass with special properties for ion-sensitive glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2204/00Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a glass-ceramic, a glass-ceramic product and a manufacturing method thereof.
  • the present invention relates to a glass-ceramic and a glass-ceramic product which have excellent mechanical properties and optical properties and are suitable for electronic equipment or display equipment. and its manufacturing method.
  • Glass-ceramic is a material that precipitates crystals inside the glass by heat-treating the glass. It has better mechanical properties than conventional glass. When micro-crystals are formed in the glass, its bending resistance, wear resistance and drop resistance are relatively high. It has obvious advantages over conventional glass. On the other hand, glass-ceramic can also be chemically strengthened to further improve mechanical properties.
  • glass-ceramic or the glass products obtained after treatment are currently used in display devices or electronic devices with high requirements such as drop resistance, compression resistance, and scratch resistance, especially in portable electronic devices (such as mobile phones, watches, etc.). , PAD, etc.) for front and rear cover applications.
  • Optical properties refer to the properties exhibited by substances when they absorb, reflect and refract light, including transmission through ratio, haze, ⁇ B ⁇ value and refractive index.
  • the glass-ceramics currently on the market have problems such as poor chemical strengthening performance, high haze and large ⁇ B ⁇ value, which are difficult to apply to display devices or electronic devices with high requirements.
  • the technical problem to be solved by the present invention is to provide a glass-ceramic product with excellent mechanical properties and optical properties.
  • Glass-ceramic products whose components are expressed by weight percentage, including: SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5- 15%; P 2 O 5 : 2 to 10%; Y 2 O 3 : more than 0 but less than or equal to 8%.
  • the glass-ceramic product according to (1) whose components are expressed in weight percentage, and further contains: K 2 O: 0-5%; and/or MgO: 0-2%; and/or ZnO: and/or Na 2 O: 0-6%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or B 2 O 3 : 0-5%; and/or Ln 2 O 3 : 0-5%; and/or clarifying agent: 0-2%, wherein the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and the clarifying agent is one of Sb 2 O 3 , SnO 2 , SnO, CeO 2 , F, Cl and Br or more.
  • Glass-ceramic products whose components contain SiO 2 , Al 2 O 3 , Li 2 O, ZrO 2 and P 2 O 5 , the average light ⁇ B ⁇ of 400-800 nm for glass-ceramic products with a thickness of less than 1 mm The value is 0.6 or less.
  • a glass-ceramic product which contains a lithium monosilicate crystal phase, and the drop-ball test height of the glass-ceramic product is more than 1300 mm.
  • Glass-ceramic products the components of which are expressed by weight percentage, including SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5-15 %; P 2 O 5 : 2-10%; Y 2 O 3 : greater than 0 but less than or equal to 8%; K 2 O: 0-5%; MgO: 0-2%; ZnO: 0-2%; Na 2 O: 0-6%; SrO: 0-5%; BaO: 0-5%; CaO: 0-5%; TiO 2 : 0-5%; B 2 O 3 : 0-5%; Ln 2 O 3 : 0-5%; clarifying agent: 0-2% composition, wherein the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and the clarifying agent is Sb One or more of 2O3 , SnO2 , SnO , CeO2, F, Cl and Br.
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.16-0.9;
  • Na 2 O/Y 2 O 3 is below 6.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is greater than 0 but less than or equal to 0.15.
  • Y 2 O 3 /ZrO 2 is 0.1 to 1.0
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.18-0.6;
  • Na 2 O/Y 2 O 3 is 0.1 to 5.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is 0.01 to 0.12.
  • Y 2 O 3 /ZrO 2 is 0.2 to 0.6;
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.19-0.5;
  • Na 2 O/Y 2 O 3 is 0.3 to 2.0;
  • the present invention also provides a glass-ceramic with excellent mechanical properties and optical properties.
  • Glass-ceramic whose components are expressed by weight percentage, containing: SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5-15 %; P 2 O 5 : 2 to 10%; Y 2 O 3 : greater than 0 but less than or equal to 8%.
  • a glass-ceramic comprising SiO 2 , Al 2 O 3 , Li 2 O, ZrO 2 , P 2 O 5 and Y 2 O 3 in the composition, and the crystal phase of the glass-ceramic contains lithium monosilicate , lithium monosilicate has a higher weight percentage than other crystalline phases.
  • Glass-ceramic the composition of which contains SiO 2 , Al 2 O 3 , Li 2 O, ZrO 2 and P 2 O 5 , and the average light ⁇ B ⁇ value of 400-800 nm of glass-ceramic with a thickness of 1 mm or less 0.6 or less.
  • a glass-ceramic, containing a lithium silicate crystal phase, and the body of the glass-ceramic has a drop height of 1000 mm or more.
  • the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Y
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.16-0.9;
  • Na 2 O/Y 2 O 3 is below 6.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is greater than 0 but less than or equal to 0.15.
  • Y 2 O 3 /ZrO 2 is 0.1 to 1.0
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.18-0.6;
  • Na 2 O/Y 2 O 3 is 0.1 to 5.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is 0.01 to 0.12.
  • Y 2 O 3 /ZrO 2 is 0.2 to 0.6;
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.19-0.5;
  • Na 2 O/Y 2 O 3 is 0.3 to 2.0;
  • the present invention also provides a matrix glass.
  • Matrix glass the components of which are expressed by weight percentage, including: SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5-15% ; P 2 O 5 : 2 to 10%; Y 2 O 3 : greater than 0 but less than or equal to 8%.
  • Matrix glass the components of which are expressed by weight percentage, including: SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O : 10-25%; ZrO 2 : 5-15%; P 2 O 5 : 2-10%; Y 2 O 3 : greater than 0 but less than or equal to 8%; K 2 O: 0-5%; MgO: 0-2%; ZnO: 0-2%; Na 2 O : 0-6%; SrO: 0-5%; BaO: 0-5%; CaO: 0-5%; TiO 2 : 0-5%; B 2 O 3 : 0-5%; Ln 2 O 3 : 0 ⁇ 5%; clarifying agent: 0 ⁇ 2% composition, wherein the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and the clarifying agent is Sb 2 O 3.
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.16-0.9;
  • Na 2 O/Y 2 O 3 is below 6.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is greater than 0 but less than or equal to 0.15.
  • Y 2 O 3 /ZrO 2 is 0.1 to 1.0
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.18-0.6;
  • Na 2 O/Y 2 O 3 is 0.1 to 5.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is 0.01 to 0.12.
  • Y 2 O 3 /ZrO 2 is 0.2 to 0.6;
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.19-0.5;
  • Na 2 O/Y 2 O 3 is 0.3 to 2.0;
  • the present invention also provides a glass cover plate.
  • a glass cover plate comprising the glass-ceramic product according to any one of (1) to (40), and/or the glass-ceramic according to any one of (41) to (78), and/or (79) The matrix glass according to any one of to (99).
  • the present invention also provides a glass component.
  • a glass component comprising the glass-ceramic product according to any one of (1) to (40), and/or the glass-ceramic according to any one of (41) to (78), and/or (79) The matrix glass according to any one of to (99).
  • the present invention also provides a display device.
  • a display device comprising the glass-ceramic product according to any one of (1) to (40), and/or the glass-ceramic according to any one of (41) to (78), and/or (79) ⁇ (99)
  • the present invention also provides an electronic device.
  • the present invention also provides a manufacturing method of a glass-ceramic product.
  • the manufacture method of glass-ceramic product, described method may further comprise the steps:
  • a matrix glass is formed, and the components of the matrix glass are expressed by weight percentage, and contain: SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5- 15%; P 2 O 5 : 2-10%; Y 2 O 3 : greater than 0 but less than or equal to 8%;
  • a crystallized glass is formed on the base glass through a crystallization process, and a glass-ceramic product is formed on the glass-ceramic through a chemical strengthening process.
  • the manufacture method of glass-ceramic product, described method may further comprise the steps:
  • a matrix glass is formed, and the components of the matrix glass are expressed by weight percentage, including SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5-15 %; P 2 O 5 : 2-10%; Y 2 O 3 : greater than 0 but less than or equal to 8%; K 2 O: 0-5%; MgO: 0-2%; ZnO: 0-2%; Na 2 O: 0-6%; SrO: 0-5%; TiO 2 : 0-5%; BaO: 0-5%; CaO: 0-5%; B 2 O 3 : 0-5%; Ln 2 O 3 : 0-5%; clarifying agent: 0-2% composition, wherein the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and the clarifying agent is Sb One or more of 2 O 3 , SnO 2 , SnO, CeO 2 , F, Cl and Br;
  • a crystallized glass is formed on the base glass through a crystallization process, and a glass-ceramic product is formed on the glass-ceramic through a chemical strengthening process.
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.16-0.9;
  • Na 2 O/Y 2 O 3 is below 6.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is greater than 0 but less than or equal to 0.15.
  • Y 2 O 3 /ZrO 2 is 0.1 to 1.0
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.18-0.6;
  • Na 2 O/Y 2 O 3 is 0.1 to 5.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is 0.01 to 0.12.
  • Y 2 O 3 /ZrO 2 is 0.2 to 0.6;
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.19-0.5;
  • Na 2 O/Y 2 O 3 is 0.3 to 2.0;
  • the crystallization temperature is 600 to 750°C, preferably 650 to 700°C, and the holding time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.
  • the method for manufacturing a glass-ceramic product according to (124), wherein the crystallization process comprises the following steps: the first temperature is 470-630°C, the second temperature is 650-750°C; The holding time is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
  • (142) The method for producing a glass-ceramic product according to any one of (138) to (141), wherein the thickness of the glass-ceramic product is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, and more preferably 0.5 to 0.8 mm, more preferably 0.55mm or 0.6mm or 0.68mm or 0.72mm or 0.75mm.
  • the present invention also provides a method for manufacturing the glass-ceramic.
  • a matrix glass is formed, and the components of the matrix glass are expressed by weight percentage, and include: SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5- 15%; P 2 O 5 : 2-10%; Y 2 O 3 : greater than 0 but less than or equal to 8%;
  • a crystallized glass is formed on the base glass through a crystallization process.
  • the manufacture method of glass-ceramic, described method comprises the following steps:
  • a matrix glass is formed, and the components of the matrix glass are expressed by weight percentage, including SiO 2 : 45-70%; Al 2 O 3 : 8-18%; Li 2 O: 10-25%; ZrO 2 : 5-15 %; P 2 O 5 : 2-10%; Y 2 O 3 : greater than 0 but less than or equal to 8%; K 2 O: 0-5%; MgO: 0-2%; ZnO: 0-2%; Na 2 O: 0-6%; SrO: 0-5%; TiO 2 : 0-5%; BaO: 0-5%; CaO: 0-5%; B 2 O 3 : 0-5%; Ln 2 O 3 : 0-5%; clarifying agent: 0-2% composition, wherein the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and the clarifying agent is Sb One or more of 2 O 3 , SnO 2 , SnO, CeO 2 , F, Cl and Br;
  • a crystallized glass is formed on the base glass through a crystallization process.
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.16-0.9;
  • Na 2 O/Y 2 O 3 is below 6.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is greater than 0 but less than or equal to 0.15.
  • Y 2 O 3 /ZrO 2 is 0.1 to 1.0
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.18-0.6;
  • Na 2 O/Y 2 O 3 is 0.1 to 5.0;
  • Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is 0.01 to 0.12.
  • Y 2 O 3 /ZrO 2 is 0.2 to 0.6;
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.19-0.5;
  • Na 2 O/Y 2 O 3 is 0.3 to 2.0;
  • the coloring agent expressed as a percentage by weight, contains: NiO: 0.1 to 3%; and/or Ni 2 O 3 : 0.1 and/or CoO: 0.05-1.8%; and/or Co2O3: 0.05-1.8 %; and/or Fe2O3 : 0.2-5%; and/or MnO2 : 0.1-3 % and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 3 : 0.4-6 %; and/or CeO 2 : 0.5 to 3%.
  • the crystallization temperature is 600 to 750°C, preferably 650 to 700°C, and the holding time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.
  • the method for producing glass-ceramic according to (163), wherein the crystallization process comprises the following steps: the first temperature is 470-630°C, the second temperature is 650-750°C; The holding time is 0 to 24 hours, preferably 2 to 15 hours, and the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
  • the beneficial effects of the present invention are: through reasonable component design, the glass-ceramic and glass-ceramic products obtained by the present invention have excellent mechanical properties and optical properties, and are suitable for electronic equipment or display equipment.
  • the glass-ceramics and glass-ceramic articles of the present invention are materials having crystalline and vitreous phases, which are distinct from amorphous solids.
  • the crystalline phases of glass-ceramics and glass-ceramic articles can be identified by the angle of peaks appearing in the X-ray diffraction pattern of X-ray diffraction analysis and/or measured by TEMEDX.
  • the inventors of the present invention through repeated experiments and research, have determined the content and content ratio of specific components constituting glass-ceramics and glass-ceramic products to specific values and precipitated specific crystal phases, thereby reducing costs.
  • the glass-ceramic or glass-ceramic product of the present invention is obtained.
  • each component (component) of the matrix glass, glass-ceramics, and glass-ceramic products of the present invention will be described.
  • the content of each component is expressed as a percentage by weight (wt%) relative to the total amount of matrix glass, glass-ceramic, or glass-ceramic products converted into oxides.
  • the "composition in terms of oxides” refers to when the oxides, complex salts, hydroxides, etc. used as raw materials for the constituent components of the matrix glass, glass-ceramic or glass-ceramic products of the present invention are melted When decomposed and converted into an oxide, the total amount of the oxide is taken as 100%.
  • glass-ceramics when it is only called glass, it is the matrix glass before crystallization, and after the matrix glass is crystallized, it is called glass-ceramics, and glass-ceramic products refer to chemically strengthened glass-ceramics.
  • the crystal phase contains lithium monosilicate; and/or lithium phosphate.
  • the crystalline phase in the glass-ceramic or glass-ceramic product mainly contains a lithium monosilicate crystalline phase, the lithium monosilicate crystalline phase has a higher weight percentage than the other crystalline phases, monosilicic acid
  • the lithium crystalline phase accounts for 10-63.5% of the glass-ceramic or glass-ceramic product, and in some embodiments, the weight percentage ranges from 15-55%.
  • the crystal phase in the glass-ceramic or the glass-ceramic product contains a lithium phosphate crystal phase, and the crystal phase accounts for 3-15% by weight of the glass-ceramic or the glass-ceramic product. In some embodiments, the weight percentage ranges from 5 to 12%.
  • SiO 2 is an essential component of the glass of the present invention, and it is one of the main components that form crystals after heat treatment. If the content of SiO 2 is below 45%, it is difficult to form crystals in the glass. Therefore, the lower limit of the content of SiO 2 is 45%, Preferably it is 50%, more preferably 53%; if the content of SiO 2 is more than 70%, it is unfavorable for glass forming and affects the haze and ⁇ B ⁇ value of glass-ceramic and glass-ceramic products. Therefore, the upper limit of the SiO 2 content is 70%, preferably 65%, and more preferably 63%.
  • Al 2 O 3 can be used as a glass network structure, which is beneficial to the formation of glass, lowering the crystallization temperature of glass, which is beneficial to glass crystallization;
  • Al 2 O 3 is one of the components that form glass-ceramic crystals, which is beneficial to the chemical Strengthening and increasing the depth of the ion exchange layer of the glass-ceramic product, but if the content of the ion exchange layer is less than 8%, the above effect is not good, so the lower limit of the content of Al 2 O 3 is 8%.
  • the content of Al 2 O 3 exceeds 18%, the size of the chips after chemical strengthening of the glass-ceramic will be affected.
  • the upper limit of the content of Al 2 O 3 is 18%, preferably 15%, and more preferably 12%. In some embodiments, about 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% , 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18% Al 2 O 3 .
  • Li 2 O can promote the melting of glass and reduce the melting temperature. It is the main component of crystal formation, and it is also the component that is mainly replaced with sodium and potassium ions in chemical strengthening treatment, which can increase the surface stress of glass-ceramic products after chemical strengthening. Increase the ball drop height of glass-ceramic products, but if its content is less than 10%, the crystal phase of lithium monosilicate is not good, which affects the drop ball height and fragment size of glass-ceramic products. Therefore, the lower limit of Li 2 O content is 10%, preferably 13%, more preferably 14%. On the other hand, if Li 2 O is contained too much, the glass tends to separate during crystallization, which affects the transmittance of glass-ceramics and glass-ceramic products.
  • the upper limit of the Li 2 O content is 25%, preferably 22%, and more preferably 21%. In some embodiments, about 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5% , 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25 % Li2O .
  • Na 2 O is an optional component, which can reduce the melting temperature of the glass and is beneficial to the adjustment of the chemical strengthening process of the glass or glass-ceramic. Therefore, the lower limit of the Na 2 O content in the present invention is preferably 1%, more preferably 1.5% . On the other hand, if the glass contains too much Na 2 O, it will promote the phase separation of the glass, resulting in a decrease in the transmittance of the glass-ceramic and glass-ceramic products after crystallization. Therefore, the upper limit of the Na 2 O content is 6%, preferably 5%, and more preferably 4%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5% %, 6 % Na2O.
  • K 2 O is beneficial to glass forming and reduces the viscosity of glass, but if K 2 O is contained too much, chemical stability and hardness of glass are likely to decrease. Therefore, the upper limit of the K 2 O content is 5%, preferably 4%, and more preferably 2%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% of K may be included 2 O.
  • P 2 O 5 can form crystal nucleus in the process of glass crystallization, promote the formation of crystal, improve the crystallinity of glass-ceramic or glass-ceramic products, be beneficial to chemical strengthening, increase the hardness, ball height and resistance of glass-ceramic products
  • the lower limit of the P 2 O 5 content is 2%, preferably 3.5%, and more preferably 4%.
  • the upper limit of the P2O5 content is 10 %, preferably 9%, and more preferably 8%. In some embodiments, about 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5% , 9.0%, 9.5%, 10% P 2 O 5 .
  • ZrO 2 and P 2 O 5 can dissolve each other, reduce the phase separation of P 2 O 5 during glass forming, increase the crystallization temperature of the glass during crystallization, and ensure a lithium silicate crystal phase in glass-ceramic and glass-ceramic products.
  • the degree of integrity of the glass-ceramics and glass-ceramics reduces the haze and ⁇ B ⁇ values of the glass-ceramics and improves the drop resistance of the glass-ceramics. Therefore, the lower limit of the ZrO 2 content is 5%, preferably 6%, more preferably 7%.
  • the upper limit of the ZrO 2 content is 15%, preferably 12%.
  • Y 2 O 3 can promote the melting of ZrO 2 , reduce the difficulty of smelting glass, reduce the phase separation in the glass, and reduce the haze and ⁇ B ⁇ value of glass-ceramic and glass-ceramic products.
  • the lower limit of the content of Y 2 O 3 is greater than 0%, preferably 1%, more preferably 2%.
  • the upper limit of the content of Y 2 O 3 is 8%, preferably 7% , more preferably 6%.
  • the relative content of Y 2 O 3 and ZrO 2 has an important influence on the haze and ⁇ B ⁇ value of glass-ceramic and glass-ceramic products, especially making Y
  • 2 O 3 /ZrO 2 is greater than 0, the haze and ⁇ B ⁇ value of glass-ceramic and glass-ceramic products can be reduced, and the photographic and photographic effects of end products can be improved. Therefore, Y 2 O 3 /ZrO 2 is preferably greater than 0, more preferably Y 2 O 3 /ZrO 2 is 0.1 to 1.0, and still more preferably Y 2 O 3 /ZrO 2 is 0.2 to 0.6.
  • the value of Y2O3 /ZrO2 may be greater than 0 , 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0.
  • making (Li 2 O + ZrO 2 +P 2 O 5 )/Y 2 O 3 in the range of 2.5 to 50.0 can make the matrix glass refine the crystal grains during the crystallization process, so that the Glass-ceramic and glass-ceramic products obtain finer grains and reduce haze of glass-ceramic and glass-ceramic products. Therefore, (Li 2 O+ZrO 2 +P 2 O 5 )/Y 2 O 3 is preferably 2.5 to 50.0, and more preferably (Li 2 O+ZrO 2 +P 2 O 5 )/Y 2 O 3 is 3.0 to 40.0 , more preferably (Li 2 O+ZrO 2 +P 2 O 5 )/Y 2 O 3 is 4.0 to 21.0.
  • the value of (Li 2 O+ZrO 2 +P 2 O 5 )/Y 2 O 3 may be 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 22.0, 23.0, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0.
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is in the range of 0.16-0.9, which can make the glass-ceramic products withstand the impact of falling balls of 1300mm and above, more preferably Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is 0.18 to 0.6.
  • Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) when Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) is in the range of 0.19-0.5, it is easier to form a lithium monosilicate crystal phase, and the microcrystalline Glass products are easy to obtain excellent fracture toughness, and the fracture toughness can be above 1MPa ⁇ m 1/2 , preferably above 1.1MPa ⁇ m 1/2 , more preferably above 1.2MPa ⁇ m 1/2 ; at the same time, further optimize the falling ball test Since it has high bearing capacity, it is more preferable that Al 2 O 3 /(Li 2 O+ZrO 2 +P 2 O 5 ) be 0.19 to 0.5.
  • Al 2 O 3 /(Li 2 O + ZrO 2 +P 2 O 5 ) may be 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90.
  • the inventors have found that the relative content of Na 2 O and Y 2 O 3 has an important influence on the surface stress and the depth of the ion exchange layer of glass-ceramic products, especially when Na 2 O/Y 2 O 3 is below 6.0. , can improve the surface stress and the depth of the ion exchange layer of the glass-ceramic product, more preferably Na 2 O/Y 2 O 3 is 0.1-5.0. In some embodiments, it is further preferred that Na 2 O/Y 2 O 3 is 0.3-2.0, which can also improve the fragment size of the glass-ceramic product.
  • the surface stress of the glass-ceramic product is more than 600MPa, preferably It is 650 MPa or more, more preferably 700 MPa or more; the depth of the ion exchange layer of the glass-ceramic product is 20 ⁇ m or more, preferably 30 ⁇ m or more, and more preferably 40 ⁇ m or more.
  • the value of Na2O/ Y2O3 can be 0 , greater than 0 , 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.3, 2.5, 2.7, 3.0, 3.3, 3.5, 3.7, 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.7, 6.0.
  • the crystallization performance of the glass can be optimized, and the glass-ceramic and
  • the crystallized glass product has an appropriate amount of crystallinity, so that the crystallized glass and the crystallized glass product have excellent performance; preferably Y 2 O 3 /(Al 2 O 3 +SiO 2 ) is 0.01 ⁇ 0.12, more preferably 0.03 ⁇ 0.09, the drop test height of glass-ceramics and glass-ceramic products increases.
  • the drop-ball test height of glass-ceramic products is preferably 1300mm or more, more preferably 1400mm or more, and even more preferably 1500mm or more.
  • the value of Y 2 O 3 /(Al 2 O 3 +SiO 2 ) may be greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12 , 0.13, 0.14, 0.15.
  • B 2 O 3 can improve the network structure of glass, optimize the chemical strengthening properties of glass and glass-ceramic, and improve the drop height of glass-ceramic products.
  • the content of B 2 O 3 exceeds 5%, it is not conducive to glass forming, and it is easy to form during forming.
  • the upper limit of the B 2 O 3 content is 5%, preferably 3%, more preferably 2%, and further preferably not containing B 2 O 3 .
  • about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% of B may be included 2 O 3 .
  • ZnO can reduce the difficulty of smelting glass, but when the content is high, it will promote the crystallization of glass at low temperature, reduce the crystallinity and transmittance of glass-ceramic and glass-ceramic products, and increase the haze of glass-ceramic and glass-ceramic products. Therefore, the upper limit of its content is 2%, preferably 1%, and more preferably no ZnO is contained. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0% ZnO may be included.
  • MgO can reduce the difficulty of glass smelting and is beneficial to increase the falling ball height of glass-ceramic and glass-ceramic products, but it is easy to promote the low-temperature crystallization of glass and reduce the crystallinity and transmittance of glass-ceramic and glass-ceramic products, so its content
  • the upper limit is 2%, preferably 1%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0% MgO may be included.
  • SrO is an optional component that improves the low temperature melting properties of the glass and inhibits crystallization during glass forming.
  • the content of SrO is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably not containing SrO. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% SrO may be included .
  • BaO is an optional component that helps to improve the glass-forming properties of glass, and when the content is too large, it is unfavorable for glass forming. Therefore, the BaO content of the present invention is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably not containing BaO. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% BaO may be included .
  • the CaO content is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably not containing CaO. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% CaO may be included .
  • TiO 2 is an optional component that helps to reduce the melting temperature of the matrix glass and improve the chemical stability.
  • the content of TiO 2 below 5% can make the crystallization process of the matrix glass easy to control, preferably 3 % or less, more preferably 1% or less.
  • Ln 2 O 3 (Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 ) is to improve the hardness and chemical stability of glass-ceramics, and inhibit the formation and devitrification of glass.
  • Optional component if the content is too large, it will affect the chemical strengthening performance of glass and reduce the strength of glass-ceramic products. Therefore, in the present invention, the content of Ln 2 O 3 is in the range of 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%, and further preferably not containing Ln 2 O 3 . In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% of Ln may be included 2 O 3 .
  • the glass, glass-ceramic or glass-ceramic article may further include 0-2% fining agent to improve the defoaming ability of the glass, glass-ceramic or glass-ceramic article.
  • Such clarifying agents include, but are not limited to, one or more of Sb 2 O 3 , SnO 2 , SnO, CeO 2 , F, Cl and Br, preferably Sb 2 O 3 as the clarifying agent.
  • the upper limit of the content thereof is preferably 1%, more preferably 0.5%.
  • one or more of the above clarifying agents is present at about 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% , 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.
  • the present invention preferably does not contain PbO and As 2 O 3 .
  • a colorant by containing a colorant, a matrix glass, a glass-ceramic or a glass-ceramic product with a color can be prepared, and the matrix glass, the glass-ceramic or the glass-ceramic product can exhibit different colors, and the coloring
  • the agent contains: NiO: 0-4%; and/or Ni 2 O 3 : 0-4%; and/or CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 : 0-4%; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O: 0 to 4%; and/or Pr 2 O 5 : 0 to 8%; and/or CeO 2 : 0 to 4%.
  • Its colorant weight percentage content and its function are described in detail as follows:
  • the brown or green matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses NiO, Ni 2 O 3 or Pr 2 O 5 as colorant.
  • NiO and Ni 2 O 3 are colorants used to prepare brown or green matrix glass, glass-ceramic or glass-ceramic products.
  • the two components can be used alone or in combination, and their respective contents are generally below 4%, preferably Below 3%, if the content exceeds 4%, the colorant cannot be well dissolved in the matrix glass, glass-ceramic or glass-ceramic products, and the lower limit of its respective content is above 0.1%, if it is less than 0.1%, the matrix glass, micro-ceramic The color of crystal glass or glass-ceramic products is not obvious.
  • the general content is less than 8%, preferably less than 6%, the lower limit of the content is more than 0.4%, such as less than 0.4% %, the color of the matrix glass, glass-ceramic or glass-ceramic products is not obvious.
  • the blue matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses CoO or Co 2 O 3 as colorant, and the two colorant components can be used alone or in combination, and their respective contents are generally 2 % or less, preferably 1.8% or less, if the content exceeds 2%, the colorant cannot be well dissolved in the matrix glass, glass-ceramic or glass-ceramic products, and the lower limit of the respective content is above 0.05%, such as less than 0.05% %, the color of the matrix glass, glass-ceramic or glass-ceramic products is not obvious.
  • the yellow matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses Cu 2 O or CeO 2 as colorant, the two colorant components are used alone or in combination, and the lower limit of their respective contents is above 0.5%, If it is less than 0.5%, the color of the matrix glass, glass-ceramic or glass-ceramic products is not obvious, and Cu 2 O alone is less than 4%, preferably less than 3%. If the content exceeds 4%, the matrix glass is easy to crystallize.
  • the total amount is generally less than 4%, and the lower limit of the total amount is more than 0.5%. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8% , 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5 %, 3.6%, 3.7%, 3.8%, 3.9%, 4.0 % CeO2 and Cu2O .
  • Fe 2 O 3 is used alone as a colorant; or a colorant of Fe 2 O 3 and CoO is used in combination; or Fe 2 O 3 and Co 2 O 3 are mixed as colorants; or Fe 2 O 3 , CoO and NiO are mixed as colorants; or Fe 2 O 3 , Co 2 O 3 and NiO are used as mixed colorants of colorants.
  • the colorant for preparing black and smoke gray matrix glass, glass-ceramic or glass-ceramic products is mainly colored with Fe2O3 , the content is 7 % or less, preferably 5% or less, and the lower limit of its content is more than 0.2%, in some implementations In a way, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6% , 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3 %, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0 % Fe2O3 .
  • CoO and Co 2 O 3 have visible light absorption, which can deepen the coloring degree of the matrix glass, glass-ceramic or glass-ceramic products.
  • the content of each is less than 0.6%, and the lower limit is more than 0.2%. .
  • about 0.2%, 0.3%, 0.4%, 0.5 %, 0.6% CoO and/or Co2O3 may be included.
  • NiO absorbs visible light and can deepen the coloring degree of matrix glass, glass-ceramic or glass-ceramic products.
  • the content of NiO is less than 1% when used in combination, and the lower limit of the total amount is more than 0.2%.
  • about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% NiO may be included.
  • the purple matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses MnO 2 as a colorant, and its content is generally less than 4%, preferably less than 3%, and the lower limit of its content is more than 0.1%, such as less than 0.1% %, the color of the matrix glass, glass-ceramic or glass-ceramic products is not obvious.
  • the pink matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses Er 2 O 3 as a colorant, and its content is generally below 8%, preferably below 6%. Due to the low coloring efficiency of rare earth element Er 2 O 3 , when the content exceeds 8%, the color of the matrix glass, glass-ceramic or glass-ceramic products cannot be further deepened, but the cost is increased.
  • the lower limit of its content is more than 0.4%. If it is less than 0.4%, the color of the matrix glass, glass-ceramic or glass-ceramic products is not obvious.
  • the purple-red matrix glass, glass-ceramic or glass-ceramic product prepared by the present invention uses Nd 2 O 3 as a colorant, and its content is generally below 8%, preferably below 6%. Due to the low coloring efficiency of rare earth element Nd 2 O 3 , the content of Nd 2 O 3 exceeds 8%, and the color of the matrix glass, glass-ceramic or glass-ceramic products cannot be further deepened, but the cost is increased. The lower limit of its content is more than 0.4%. If it is less than 0.4%, the color of the matrix glass, glass-ceramic or glass-ceramic products is not obvious.
  • the red matrix glass, glass-ceramic or glass-ceramic product prepared by the invention uses Er 2 O 3 , Nd 2 O 3 and MnO 2 mixed colorants, Er ions in the glass have absorption at 400-500nm, and Mn ions are mainly at 500nm There is absorption at 580nm, and Nd ions mainly have strong absorption at 580nm.
  • the mixture of three substances can prepare red matrix glass, glass-ceramic or glass-ceramic products.
  • Er 2 O 3 and Nd 2 O 3 are rare earth coloring, The coloring ability is relatively weak, the usage amount of Er 2 O 3 is within 6%, the usage amount of Nd 2 O 3 is within 4%, the coloring of MnO 2 is strong, the usage amount is within the range of 2%, and the lower limit of the total amount of mixed colorants used is 0.9% or more.
  • Does not contain and "0%” as described herein means that the compound, molecule or element is not intentionally added as a raw material to the matrix glass, glass-ceramic or glass-ceramic product of the present invention;
  • the raw materials and/or equipment of crystallized glass or glass-ceramic products may have certain impurities or components that are not intentionally added, and may be contained in small or trace amounts in the final matrix glass, glass-ceramic or glass-ceramic products. This situation is also within the protection scope of the patent of the present invention.
  • the crystalline phase of the glass-ceramic and the glass-ceramic product contains lithium monosilicate crystals, which provides high strength for the glass-ceramic and the glass-ceramic product of the present invention.
  • the glass-ceramic of the invention has excellent chemical strengthening performance, and can also obtain additional mechanical strength through chemical strengthening. Through reasonable component design, the glass-ceramic and the glass-ceramic product of the present invention can obtain a suitable grain size, so that the glass-ceramic and the glass-ceramic product of the present invention have high strength.
  • the glass-ceramic and the glass-ceramic product of the present invention have good crystallinity, so that the glass-ceramic and the glass-ceramic product of the present invention have excellent mechanical properties.
  • the degree of crystallinity referred to in this article refers to the degree of completeness of crystallization.
  • the crystals with complete crystallization have relatively regular arrangement of particles, the diffraction lines are strong, sharp and symmetrical, and the half-height width of the diffraction peak is close to the width measured by the instrument; in the crystal with poor crystallinity There are defects such as dislocations, which make the peak shape of the diffraction lines wide and diffuse.
  • the crystallinity of the glass-ceramic article or glass-ceramic is 50% or higher, preferably 60% or higher, and more preferably 70% or higher.
  • the size and type of crystal grains in the glass-ceramic or glass-ceramic products of the present invention will affect the haze and transmittance of the glass-ceramic or glass-ceramic products, the smaller the crystal grains, the higher the transmittance; the smaller the haze, the higher the transmittance. The higher the pass rate.
  • the haze of a glass-ceramic article or glass-ceramic with a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, and more preferably 0.1% or less.
  • the crystallites or glass-ceramics have a grain size of 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less.
  • the crystalline phase content and refractive index of the glass-ceramic or glass-ceramic product of the present invention affect the ⁇ B ⁇ value of the glass-ceramic or glass-ceramic product, and the glass-ceramic or glass-ceramic product is observed in the visible light range It appears bluish or yellowish, which affects the optical properties of the product. It is marked with ⁇ B ⁇ value in LAB (chromaticity value of material color).
  • the glass-ceramic or glass-ceramic products exhibit a low ⁇ B ⁇ value in the visible light range, and in some embodiments, the average light ⁇ B ⁇ value of the glass-ceramic products or glass-ceramics with a thickness of 1 mm or less at 400-800 nm is below 0.6, It is preferably 0.55 or less, and more preferably 0.5 or less.
  • the glass-ceramics or glass-ceramic articles of the present invention exhibit high transparency in the visible light range (ie, the glass-ceramics or glass-ceramic articles are transparent).
  • the glass-ceramic or glass-ceramic products exhibit high transmittance in the visible light range.
  • the average light transmittance of glass-ceramic products or glass-ceramics with a thickness of 1 mm or less at 400 to 800 nm is preferably 89% or more.
  • the light transmittance of glass-ceramic products with a thickness of 1 mm or less or glass-ceramics at 550 nm is preferably 91% or more.
  • antimicrobial ingredients can be added to the matrix glass, glass-ceramic or glass-ceramic article.
  • the glass-ceramic or glass-ceramic articles described herein can be used in applications such as kitchen or dining countertops where exposure to harmful bacteria is likely.
  • Antimicrobial components that may be added to the matrix glass, glass-ceramic or glass-ceramic article include, but are not limited to, Ag, AgO, Cu, CuO , Cu2O, and the like. In some embodiments, the above-mentioned antimicrobial components alone or in combination are present in an amount of 2% or less, preferably 1% or less.
  • the matrix glass, glass-ceramic and glass-ceramic articles of the present invention can be produced and manufactured by the following methods:
  • Generating matrix glass Mix the raw materials uniformly according to the proportion of components, put the uniform mixture into a crucible made of platinum or quartz, according to the melting difficulty of the glass composition, in an electric furnace or a gas furnace at a temperature of 1250 ⁇ 1650 °C within the range of 5 to 24 hours. After melting, stirring to make it uniform, it is lowered to the appropriate temperature and poured into the mold, and slowly cooled.
  • the matrix glass of the present invention can be formed by a well-known method.
  • the matrix glass of the present invention is crystallized by a crystallization process after forming or after forming, and crystals are uniformly precipitated inside the glass.
  • This crystallization treatment may be carried out in one stage or in two stages, and it is preferable to carry out the crystallization treatment in two stages.
  • the nucleation process is performed at the first temperature, and then the crystal growth process is performed at a second temperature higher than the nucleation process temperature.
  • the crystallization process performed at the 1st temperature is called a 1st crystallization process
  • the crystallization process performed at a 2nd temperature is called a 2nd crystallization process.
  • the preferred crystallization process is:
  • the nucleation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization treatment temperature, and after reaching the crystallization treatment temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered.
  • the crystallization temperature is preferably 600 to 750°C, and in order to precipitate a desired crystal phase, it is more preferably 650 to 700°C, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 0 to 8 hours. 1 to 6 hours.
  • the first temperature is preferably 470 to 630°C
  • the second temperature is preferably 650 to 750°C.
  • the holding time at the first temperature is preferably 0 to 24 hours, and more preferably 2 to 15 hours.
  • the holding time at the second temperature is preferably 0 to 10 hours, and more preferably 0.5 to 6 hours.
  • the above-mentioned holding time of 0 hours means that the temperature decreases or the temperature rises again less than 1 minute after reaching the temperature.
  • the matrix glass or glass-ceramic described herein can be fabricated into shaped bodies, including but not limited to sheets, by various processes including, but not limited to, slot drawing, Float, rolling and other sheet forming processes known in the art.
  • the matrix glass or glass-ceramic may be formed by float or roll pressing methods known in the art.
  • the matrix glass or glass-ceramic of the present invention can be used to produce a glass formed body of a sheet by methods such as grinding or polishing, but the method of producing the glass formed body is not limited to these methods.
  • the matrix glass or glass-ceramic shaped body of the present invention can be prepared into various shapes by methods such as hot bending or pressing at a certain temperature, and is not limited to these methods.
  • the matrix glass, glass-ceramic, and glass-ceramic articles described herein can have any thickness that is reasonably useful.
  • the glass-ceramic of the present invention can not only improve the mechanical properties by precipitation crystallization, but also obtain higher strength by forming a compressive stress layer, so as to be made into a glass-ceramic product.
  • the matrix glass or glass-ceramic may be processed into sheets, and/or shaped (eg, punched, thermally bent, etc.), polished and/or polished after shaping, and then chemically strengthened by a chemical strengthening process .
  • the chemical strengthening in the present invention is the ion exchange method.
  • Both the matrix glass and the glass-ceramic of the present invention can be ion-exchanged by a method known in the art.
  • ion exchange smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" with larger metal ions of the same valence near the matrix or glass-ceramic.
  • Replacing smaller ions with larger ions builds up compressive stress in the matrix glass or glass-ceramic, forming a compressive stress layer.
  • the metal ion is a monovalent alkali metal ion (eg, Na + , K + , Rb + , Cs + , etc.), and the ion exchange is performed by immersing the matrix glass or glass-ceramic in at least one metal ion containing the larger metal ion.
  • the larger metal ions are used to displace the smaller metal ions in the matrix glass.
  • other monovalent metal ions such as Ag + , Tl + , Cu + etc. can also be used to exchange monovalent ions.
  • the one or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to, immersion in a single salt bath, or immersion in multiple salt baths of the same or different compositions , there are washing and/or annealing steps between immersion.
  • the matrix glass or glass-ceramic may be ion-exchanged by immersion in a salt bath of molten Na salt (eg, NaNO 3 ) at a temperature of about 430°C to 470°C for about 6 to 20 hours, preferably the temperature The range is 435°C to 460°C, and the preferred time range is 8 to 13 hours.
  • Na ions replace part of the Li ions in the matrix glass or glass-ceramic, thereby forming a surface compression layer and exhibiting high mechanical properties.
  • the matrix glass or glass-ceramic may be ion-exchanged by immersion in a salt bath of molten K salt (eg, KNO3 ) at a temperature of about 400°C to 450°C for 1 to 8 hours, a preferred time range 2 to 4 hours.
  • molten K salt eg, KNO3
  • ion implantation methods in which ions are implanted into the surface layer of the matrix glass or glass-ceramic
  • thermal strengthening methods in which the matrix glass or glass-ceramic is heated and then rapidly cooled.
  • the performance indicators of the glass-ceramic and/or the glass-ceramic product and/or the matrix glass of the present invention are tested by the following methods:
  • the haze tester EEL57D is used to prepare samples with a size of less than 1mm, and the test is carried out according to GB2410-80.
  • the SEM scanning electron microscope was used for the measurement.
  • the glass-ceramic was surface-treated in HF acid, and then the surface of the glass-ceramic was sprayed with gold, and the surface was scanned under the SEM scanning electron microscope to determine the size of its crystal grains.
  • the light transmittances mentioned herein are all external transmittances, sometimes referred to as transmittances.
  • the sample was processed to be 1 mm or less, and the opposite surfaces were polished in parallel, and the average light transmittance of 400 to 800 nm was measured with a Hitachi U-41000 spectrophotometer.
  • the sample was processed to be 1 mm or less, and the opposite surfaces were polished in parallel, and the light transmittance at 550 nm was measured with a Hitachi U-41000 spectrophotometer.
  • the XRD diffraction peaks were compared with the database pattern, and the crystallinity was calculated by calculating the proportion of the diffraction intensity of the crystalline phase in the overall pattern intensity, and was internally calibrated by using pure quartz crystals.
  • the ion-exchange layer depth was measured using a glass surface stress meter SLP-2000.
  • the refractive index of the sample was 1.54 and the optical elastic constant was 25.3 [(nm/cm)/Mpa].
  • the 150 ⁇ 57 ⁇ 0.55mm glass-ceramic product sample is placed on the glass bearing fixture, and the 132g steel ball is dropped from the specified height.
  • the maximum drop test height that the sample can withstand without breaking Specifically, the test was carried out starting from the drop ball test height of 800 mm, and the height was changed sequentially through 850 mm, 900 mm, 950 mm, 1000 mm and above without breaking.
  • the glass-ceramic article was used as the test object.
  • the test data recorded as 1000 mm in the examples shows that even if the steel ball is dropped from a height of 1000 mm, the glass-ceramic product does not break and is impacted.
  • the height of the drop test is sometimes referred to as the drop height.
  • the 150 ⁇ 57 ⁇ 0.55mm glass-ceramic sample is placed on the glass carrier fixture, and the 32g steel ball is dropped from the specified height.
  • the maximum drop test height that the sample can withstand without breaking is the body drop height.
  • the test was carried out from the drop ball test height of 500 mm, and the height was sequentially changed through 550 mm, 600 mm, 650 mm, 700 mm and above without breaking.
  • glass-ceramic was used as the test object.
  • the test data recorded as 1000 mm in the examples shows that even if a steel ball is dropped from a height of 1000 mm, the glass-ceramic does not break and has received an impact.
  • the size of the sample is 2mm ⁇ 4mm ⁇ 20mm.
  • a Vickers hardness indenter is used to add a force of 49N to the sample.
  • the breaking strength was measured by the method of three-point bending.
  • the microcomputer-controlled electronic universal testing machine CMT6502 was used, and the thickness of the sample was less than 1mm, and the test was carried out according to ASTM C 158-2002.
  • the sample thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still more preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • the Vickers hardness may be simply referred to as hardness.
  • B-value detection was performed using Minolta CM-700d. Use the matching calibration long cylinder and short cylinder to carry out the zero calibration and white calibration of the instrument respectively. After calibration, use the long cylinder to conduct the air test to determine the stability and calibration reliability of the instrument (B ⁇ 0.05). After the calibration of the instrument is qualified, place the product at zero. Test on a long tube.
  • the ⁇ B ⁇ value is the absolute value of the B value.
  • the thermal expansion coefficient ( ⁇ 20°C-120°C ) is tested according to the GB/T7962.16-2010 test method.
  • Refractive index (nd) is tested according to GB/T7962.1-2010 method.
  • the glass-ceramic product of the present invention has the following properties:
  • the surface stress of the glass-ceramic product is 600 MPa or more, preferably 650 MPa or more, and more preferably 700 MPa or more.
  • the four-point bending strength of the glass-ceramic product is 600 MPa or more, preferably 650 MPa or more, and more preferably 700 MPa or more.
  • the depth of the ion exchange layer of the glass-ceramic product is 20 ⁇ m or more, preferably 30 ⁇ m or more, and more preferably 40 ⁇ m or more.
  • the drop test height of the glass-ceramic product is 1300 mm or more, preferably 1400 mm or more, and more preferably 1500 mm or more.
  • the fracture toughness of the glass-ceramic product is 1 MPa ⁇ m 1/2 or more, preferably 1.1 MPa ⁇ m 1/2 or more, and more preferably 1.2 MPa ⁇ m 1/2 or more.
  • the Vickers hardness (H v ) of the glass-ceramic product is 700 kgf/mm 2 or more, preferably 720 kgf/mm 2 or more, and more preferably 730 kgf/mm 2 or more.
  • the crystallinity of the glass-ceramic product is 50% or more, preferably 60% or more, and more preferably 70% or more.
  • the crystallite size of the glass-ceramic product is 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less.
  • the haze of a glass-ceramic article with a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, and more preferably 0.1% or less.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • a glass-ceramic product with a thickness of 1 mm or less has an average transmittance of 89% or more at a wavelength of 400-800 nm.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • a glass-ceramic product with a thickness of 1 mm or less has a transmittance of 91% or more at a wavelength of 550 nm.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • the average light ⁇ B ⁇ value at 400-800 nm is 0.6 or less, preferably 0.55 or less, and more preferably 0.5 or less.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • the glass-ceramic of the present invention has the following properties:
  • the crystallinity of the glass-ceramic is 50% or more, preferably 60% or more, and more preferably 70% or more.
  • the crystallite size of the glass-ceramic is 50 nm or less, preferably 40 nm or less, preferably 30 nm or less.
  • the haze of the glass-ceramic with a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, and more preferably 0.1% or less.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • the glass-ceramic with a thickness of 1 mm or less has an average transmittance of 89% or more at a wavelength of 400-800 nm.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • a glass-ceramic with a thickness of 1 mm or less has a transmittance of 91% or more at a wavelength of 550 nm.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • the drop height of the glass-ceramic body is 1000mm or more, preferably 1100mm or more, more preferably 1200mm or more.
  • the average light ⁇ B ⁇ value at 400 to 800 nm is 0.6 or less, preferably 0.55 or less, and more preferably 0.5 or less.
  • the thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, still more preferably 0.55 mm or 0.6 mm or 0.68 mm or 0.72 mm or 0.75 mm.
  • the Vickers hardness (H v ) of the glass-ceramic is 650 kgf/mm 2 or more, preferably 680 kgf/mm 2 or more, and more preferably 700 kgf/mm 2 or more.
  • the thermal expansion coefficient ( ⁇ 20°C-120°C ) of the glass-ceramic is 75-95 ⁇ 10 -7 /K.
  • the glass-ceramic has a refractive index (n d ) of 1.5700 to 1.5800.
  • the matrix glass of the present invention has the following properties:
  • the thermal expansion coefficient ( ⁇ 20°C-120°C ) of the matrix glass is 50 ⁇ 10 -7 /K to 70 ⁇ 10 -7 /K.
  • the refractive index (n d ) of the matrix glass is 1.5600-1.5700.
  • the glass-ceramic, the glass-ceramic product and the matrix glass of the present invention can be widely made into glass cover plates or glass components because of the above-mentioned excellent properties; meanwhile, the glass-ceramic, the glass-ceramic product and the matrix glass of the present invention are applied to In electronic equipment or display equipment, such as mobile phones, watches, computers, touch screens, etc., for the manufacture of protective glass for mobile phones, smart phones, tablet computers, notebook computers, PDAs, TV sets, personal computers, MTA machines or industrial displays , or for the manufacture of touch screens, protective windows, car windows, train windows, aerospace mechanical windows, touch screen protective glass, or for the manufacture of hard disk substrates or solar cell substrates, or for the manufacture of white goods, such as for manufacturing Refrigerator parts or kitchenware.
  • electronic equipment or display equipment such as mobile phones, watches, computers, touch screens, etc.
  • protective glass for mobile phones, smart phones, tablet computers, notebook computers, PDAs, TV sets, personal computers, MTA machines or industrial displays
  • touch screens protective windows, car
  • the glass-ceramics having the compositions shown in Tables 5 to 8 were obtained by using the above-described method for producing glass-ceramics.
  • the properties of each glass-ceramic was measured by the test method of the present invention, and the measurement results are shown in Tables 5 to 8.
  • the glass-ceramic products having the compositions shown in Tables 9 to 12 were obtained by using the above-mentioned manufacturing method of the glass-ceramic products.
  • the properties of each glass-ceramic product were measured by the test method of the present invention, and the measurement results are shown in Tables 9 to 12.

Abstract

本发明提供一种微晶玻璃制品,所述微晶玻璃制品的组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于等于8%。通过合理的组分设计,本发明获得的微晶玻璃和微晶玻璃制品具有优异的机械性能和光学性能,适用于电子设备或显示设备。

Description

微晶玻璃、微晶玻璃制品及其制造方法 技术领域
本发明涉及一种微晶玻璃、微晶玻璃制品及其制造方法,本发明特别是涉及一种具有优异的机械性能和光学性能,适用于电子设备或显示设备的微晶玻璃、微晶玻璃制品及其制造方法。
背景技术
微晶玻璃是一种通过对玻璃进行热处理而在玻璃内部析出结晶的材料,具有比常规的玻璃更优异的机械性能,在玻璃中形成微晶,其抗弯、耐磨以及抗摔等性能相对于常规的玻璃都有明显的优势。另一方面,微晶玻璃还可以通过化学强化,进一步提高机械性能。
基于以上优点,目前有将微晶玻璃或其处理后得到的玻璃制品应用于抗摔、抗压、耐划等要求较高的显示设备或电子设备中,尤其在便携式电子设备(如手机、手表、PAD等)的前后盖应用中。
随着科技的发展,电子设备或显示设备对用于其中的玻璃材料的光学性能提出了更高的要求,光学性能是指物质对光线的吸收、反射和折射时所表现的性能,包括透过率、雾度、∣B∣值以及折射率等。但是目前市面上的微晶玻璃存在化学强化性能差、雾度高和∣B∣值大等问题,难以应用于要求较高的显示设备或电子设备中。
因此开发一款具有优异的机械性能和光学性能且适用于显示设备或电子设备的微晶玻璃及微晶玻璃制品,成了科技人员所追求的目标。
发明内容
本发明所要解决的技术问题是提供一种具有优异的机械性能和光学性能的微晶玻璃制品。
本发明解决技术问题所采用的技术方案是:
(1)微晶玻璃制品,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于 0但小于或等于8%。
(2)根据(1)所述的微晶玻璃制品,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或TiO 2:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(3)微晶玻璃制品,其组分中含有SiO 2、Al 2O 3、Li 2O、ZrO 2、P 2O 5和Y 2O 3,所述微晶玻璃制品的晶相含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数。
(4)微晶玻璃制品,其组分中含有SiO 2、Al 2O 3、Li 2O、ZrO 2和P 2O 5,1mm以下厚度的微晶玻璃制品400~800nm的平均光∣B∣值为0.6以下。
(5)微晶玻璃制品,含有一硅酸锂晶相,所述微晶玻璃制品的落球试验高度为1300mm以上。
(6)根据(3)~(5)任一所述的微晶玻璃制品,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
(7)根据(3)~(6)任一所述的微晶玻璃制品,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或TiO 2:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(8)微晶玻璃制品,其组分按重量百分比表示,由SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;K 2O:0~5%;MgO:0~2%;ZnO:0~2%;Na 2O:0~6%;SrO:0~5%;BaO:0~5%;CaO:0~5%;TiO 2:0~5%;B 2O 3:0~5%;Ln 2O 3: 0~5%;澄清剂:0~2%组成,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(9)根据(1)~(8)任一所述的微晶玻璃制品,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为大于0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
4)Na 2O/Y 2O 3为6.0以下;
5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
(10)根据(1)~(9)任一所述的微晶玻璃制品,其组分按重量百分比表示,其中:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或BaO:0~3%;和/或CaO:0~3%;和/或TiO 2:0~3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(11)根据(1)~(10)任一所述的微晶玻璃制品,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.1~1.0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
4)Na 2O/Y 2O 3为0.1~5.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
(12)根据(1)~(11)任一所述的微晶玻璃制品,其组分按重量百分比表示,其中:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或 Y 2O 3:2~6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(13)根据(1)~(12)任一所述的微晶玻璃制品,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.2~0.6;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
4)Na 2O/Y 2O 3为0.3~2.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
(14)根据(1)~(13)任一所述的微晶玻璃制品,其组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
(15)根据(1)~(14)任一所述的微晶玻璃制品,所述微晶玻璃制品的晶相含有一硅酸锂;和/或磷酸锂。
(16)根据(1)~(15)任一所述的微晶玻璃制品,所述微晶玻璃制品的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃制品的10~63.5%,优选为15~55%。
(17)根据(1)~(16)任一所述的微晶玻璃制品,所述微晶玻璃制品中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃制品的重量百分比为3~15%,优选为5~12%。
(18)根据(1)~(17)任一所述的微晶玻璃制品,所述微晶玻璃制品的表面应力为600MPa以上,优选为650MPa以上,更优选为700MPa以上。
(19)根据(1)~(18)任一所述的微晶玻璃制品,所述微晶玻璃制 品的四点弯曲强度为600MPa以上,优选为650MPa以上,更优选为700MPa以上。
(20)根据(1)~(19)任一所述的微晶玻璃制品,所述微晶玻璃制品的离子交换层深度为20μm以上,优选为30μm以上,更优选40μm以上。
(21)根据(1)~(20)任一所述的微晶玻璃制品,所述微晶玻璃制品的落球试验高度为1300mm以上,优选为1400mm以上,更优选为1500mm以上。
(22)根据(1)~(21)任一所述的微晶玻璃制品,所述微晶玻璃制品的和/或断裂韧性为1MPa·m 1/2以上,优选为1.1MPa·m 1/2以上,更优选为1.2MPa·m 1/2以上。
(23)根据(1)~(22)任一所述的微晶玻璃制品,所述微晶玻璃制品的维氏硬度为700kgf/mm 2以上,优选为720kgf/mm 2以上,更优选为730kgf/mm 2以上。
(24)根据(1)~(23)任一所述的微晶玻璃制品,所述微晶玻璃制品的结晶度为50%以上,优选为60%以上,更优选为70%以上;
(25)根据(1)~(24)任一所述的微晶玻璃制品,所述微晶玻璃制品的晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
(26)根据(1)~(15)任一所述的微晶玻璃制品,1mm以下厚度的微晶玻璃制品的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。
(27)根据(1)~(26)任一所述的微晶玻璃制品,1mm以下厚度的微晶玻璃制品的400~800nm波长的平均透过率89%以上。
(28)根据(1)~(27)任一所述的微晶玻璃制品,1mm以下厚度的微晶玻璃制品的550nm波长的透过率为91%以上。
(29)根据(1)~(28)任一所述的微晶玻璃制品,1mm以下厚度的微晶玻璃制品的400~800nm的平均光∣B∣值为0.6以下,优选为0.55以 下,更优选为0.5以下。
(30)根据(26)~(29)任一所述的微晶玻璃制品,所述微晶玻璃制品的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
(31)根据(1)~(7)任一所述的微晶玻璃制品,所述微晶玻璃制品含有着色剂。
(32)根据(31)所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
(33)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:NiO:0.1~4%;和/或Ni 2O 3:0.1~4%;和/或CoO:0.05~2%;和/或Co 2O 3:0.05~2%;和/或Fe 2O 3:0.2~7%;和/或MnO 2:0.1~4%;和/或Er 2O 3:0.4~8%;和/或Nd 2O 3:0.4~8%;和/或Cu 2O:0.5~4%;和/或Pr 2O 3:0.4~8%;和/或CeO 2:0.5~4%。
(34)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%;和/或CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%;和/或Fe 2O 3:0.2~5%;和/或MnO 2:0.1~3%;和/或Er 2O 3:0.4~6%;和/或Nd 2O 3:0.4~6%;和/或Cu 2O:0.5~3%;和/或Pr 2O 3:0.4~6%;和/或CeO 2:0.5~3%。
(35)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%。
(36)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%。
(37)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:Cu 2O:0.5~3%;和/或CeO 2:0.5~3%。
(38)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:Fe 2O 3:0.2~5%、CoO:0.05~0.3%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%;或者Fe 2O 3:0.2~5%、CoO:0.05~0.3%、NiO:0.1~1%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%、NiO:0.1~1%。
(39)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:Pr 2O 3:0.4~6%;或者Fe 2O 3:0.2~5%;或者MnO 2:0.1~3%;或者Er 2O 3:0.4~6%;或者Nd 2O 3:0.4~6%。
(40)根据(31)或(32)任一所述的微晶玻璃制品,所述着色剂按重量百分比表示,含有:Er 2O 3:0.4~6%、Nd 2O 3:0.4~4%、MnO 2:0.1~2%。
本发明还供一种具有优异的机械性能和光学性能的微晶玻璃。
本发明解决技术问题所采用的技术方案是:
(41)微晶玻璃,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
(42)根据(41)所述的微晶玻璃,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或TiO 2:0~5%;和/或CaO:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(43)微晶玻璃,其组分中含有SiO 2、Al 2O 3、Li 2O、ZrO 2、P 2O 5和Y 2O 3,所述微晶玻璃的晶相含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数。
(44)微晶玻璃,其组分中含有SiO 2、Al 2O 3、Li 2O、ZrO 2和P 2O 5,1mm以下厚度的微晶玻璃400~800nm的平均光∣B∣值为0.6以下。
(45)微晶玻璃,含有一硅酸锂晶相,所述微晶玻璃的本体落球高度为1000mm以上。
(46)根据(43)~(45)任一所述的微晶玻璃,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
(47)根据(43)~(46)任一所述的微晶玻璃,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或TiO 2:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(48)微晶玻璃,其组分按重量百分比表示,由SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;K 2O:0~5%;MgO:0~2%;ZnO:0~2%;Na 2O:0~6%;SrO:0~5%;BaO:0~5%;CaO:0~5%;TiO 2:0~5%;B 2O 3:0~5%;Ln 2O 3:0~5%;澄清剂:0~2%组成,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(49)根据(41)~(48)任一所述的微晶玻璃,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为大于0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
4)Na 2O/Y 2O 3为6.0以下;
5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
(50)根据(41)~(49)任一所述的微晶玻璃,其组分按重量百分比表示,其中:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或TiO 2:0~3%;和/或BaO:0~3%;和/或CaO:0~ 3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(51)根据(41)~(50)任一所述的微晶玻璃,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.1~1.0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
4)Na 2O/Y 2O 3为0.1~5.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
(52)根据(41)~(51)任一所述的微晶玻璃,其组分按重量百分比表示,其中:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或Y 2O 3:2~6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(53)根据(41)~(52)任一所述的微晶玻璃,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.2~0.6;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
4)Na 2O/Y 2O 3为0.3~2.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
(54)根据(41)~(53)任一所述的微晶玻璃,其组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3; 和/或不含有F;和/或不含有Ta 2O 5
(55)根据(41)~(54)任一所述的微晶玻璃,所述微晶玻璃的晶相含有一硅酸锂;和/或磷酸锂。
(56)根据(41)~(55)任一所述的微晶玻璃,所述微晶玻璃的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃的10~63.5%,优选为15~55%。
(57)根据(41)~(56)任一所述的微晶玻璃,所述微晶玻璃中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃的重量百分比为3~15%,优选为5~12%。
(58)根据(41)~(57)任一所述的微晶玻璃,所述微晶玻璃的结晶度为50%以上,优选为60%以上,更优选为70%以上。
(59)根据(41)~(58)任一所述的微晶玻璃,所述微晶玻璃的晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
(60)根据(41)~(59)任一所述的微晶玻璃,所述微晶玻璃的热膨胀系数为75~95×10 -7/K。
(61)根据(41)~(60)任一所述的微晶玻璃,所述微晶玻璃的折射率为1.5700~1.5800。
(62)根据(41)~(61)任一所述的微晶玻璃,所述微晶玻璃的本体落球高度为1000mm以上,优选为1100mm以上,更优选为1200mm以上。
(63)根据(41)~(62)任一所述的微晶玻璃,所述微晶玻璃的维氏硬度为650kgf/mm 2以上,优选为680kgf/mm 2以上,更优选为700kgf/mm 2以上。
(64)根据(41)~(63)任一所述的微晶玻璃,1mm以下厚度的微晶玻璃的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。
(65)根据(41)~(64)任一所述的微晶玻璃,1mm以下厚度的微晶玻璃400~800nm波长的平均透过率89%以上。
(66)根据(41)~(65)任一所述的微晶玻璃,1mm以下厚度的微 晶玻璃550nm波长的透过率为91%以上。
(67)根据(41)~(66)任一所述的微晶玻璃,1mm以下厚度的微晶玻璃400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
(68)根据(64)~(67)任一所述的微晶玻璃,所述微晶玻璃的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
(69)根据(41)~(47)任一所述的微晶玻璃,所述微晶玻璃含有着色剂。
(70)根据(69)所述的微晶玻璃,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
(71)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:NiO:0.1~4%;和/或Ni 2O 3:0.1~4%;和/或CoO:0.05~2%;和/或Co 2O 3:0.05~2%;和/或Fe 2O 3:0.2~7%;和/或MnO 2:0.1~4%;和/或Er 2O 3:0.4~8%;和/或Nd 2O 3:0.4~8%;和/或Cu 2O:0.5~4%;和/或Pr 2O 3:0.4~8%;和/或CeO 2:0.5~4%。
(72)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%;和/或CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%;和/或Fe 2O 3:0.2~5%;和/或MnO 2:0.1~3%;和/或Er 2O 3:0.4~6%;和/或Nd 2O 3:0.4~6%;和/或Cu 2O:0.5~3%;和/或Pr 2O 3:0.4~6%;和/或CeO 2:0.5~3%。
(73)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%。
(74)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量 百分比表示,含有:CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%。
(75)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:Cu 2O:0.5~3%;和/或CeO 2:0.5~3%。
(76)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:Fe 2O 3:0.2~5%、CoO:0.05~0.3%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%;或者Fe 2O 3:0.2~5%、CoO:0.05~0.3%、NiO:0.1~1%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%、NiO:0.1~1%。
(77)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:Pr 2O 3:0.4~6%;或者Fe 2O 3:0.2~5%;或者MnO 2:0.1~3%;或者Er 2O 3:0.4~6%;或者Nd 2O 3:0.4~6%。
(78)根据(69)或(70)任一所述的微晶玻璃,所述着色剂按重量百分比表示,含有:Er 2O 3:0.4~6%、Nd 2O 3:0.4~4%、MnO 2:0.1~2%。
本发明还提供一种基质玻璃。
本发明解决技术问题所采用的技术方案是:
(79)基质玻璃,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
(80)根据(79)所述的基质玻璃,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或TiO 2:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(81)基质玻璃,其组分按重量百分比表示,由SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;K 2O:0~5%;MgO:0~2%;ZnO:0~2%;Na 2O:0~6%;SrO:0~5%;BaO:0~5%;CaO:0~5%;TiO 2:0~5%;B 2O 3:0~5%;Ln 2O 3:0~ 5%;澄清剂:0~2%组成,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(82)根据(79)~(81)任一所述的基质玻璃,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为大于0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
4)Na 2O/Y 2O 3为6.0以下;
5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
(83)根据(79)~(82)任一所述的基质玻璃,其组分按重量百分比表示,其中:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或TiO 2:0~3%;和/或BaO:0~3%;和/或CaO:0~3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(84)根据(79)~(83)任一所述的基质玻璃,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.1~1.0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
4)Na 2O/Y 2O 3为0.1~5.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
(85)根据(79)~(84)任一所述的基质玻璃,其组分按重量百分比表示,其中:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或Y 2O 3:2~ 6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(86)根据(79)~(85)任一所述的基质玻璃,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.2~0.6;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
4)Na 2O/Y 2O 3为0.3~2.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
(87)根据(79)~(86)任一所述的基质玻璃,其组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
(88)根据(79)~(87)任一所述的基质玻璃,所述基质玻璃的热膨胀系数为50×10 -7/K~70×10 -7/K。
(89)根据(79)~(88)任一所述的基质玻璃,所述基质玻璃的折射率为1.5600~1.5700。
(90)根据(79)或(80)任一所述的基质玻璃,所述基质玻璃含有着色剂。
(91)根据(90)所述的基质玻璃,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
(92)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量 百分比表示,含有:NiO:0.1~4%;和/或Ni 2O 3:0.1~4%;和/或CoO:0.05~2%;和/或Co 2O 3:0.05~2%;和/或Fe 2O 3:0.2~7%;和/或MnO 2:0.1~4%;和/或Er 2O 3:0.4~8%;和/或Nd 2O 3:0.4~8%;和/或Cu 2O:0.5~4%;和/或Pr 2O 3:0.4~8%;和/或CeO 2:0.5~4%。
(93)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%;和/或CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%;和/或Fe 2O 3:0.2~5%;和/或MnO 2:0.1~3%;和/或Er 2O 3:0.4~6%;和/或Nd 2O 3:0.4~6%;和/或Cu 2O:0.5~3%;和/或Pr 2O 3:0.4~6%;和/或CeO 2:0.5~3%。
(94)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%。
(95)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%。
(96)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:Cu 2O:0.5~3%;和/或CeO 2:0.5~3%。
(97)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:Fe 2O 3:0.2~5%、CoO:0.05~0.3%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%;或者Fe 2O 3:0.2~5%、CoO:0.05~0.3%、NiO:0.1~1%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%、NiO:0.1~1%。
(98)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:Pr 2O 3:0.4~6%;或者Fe 2O 3:0.2~5%;或者MnO 2:0.1~3%;或者Er 2O 3:0.4~6%;或者Nd 2O 3:0.4~6%。
(99)根据(90)或(91)任一所述的基质玻璃,所述着色剂按重量百分比表示,含有:Er 2O 3:0.4~6%、Nd 2O 3:0.4~4%、MnO 2:0.1~2%。
本发明还提供一种玻璃盖板。
(100)玻璃盖板,含有(1)~(40)任一所述的微晶玻璃制品,和/或(41)~(78)任一所述的微晶玻璃,和/或(79)~(99)任一所述的 基质玻璃。
本发明还提供一种玻璃元器件。
(101)玻璃元器件,含有(1)~(40)任一所述的微晶玻璃制品,和/或(41)~(78)任一所述的微晶玻璃,和/或(79)~(99)任一所述的基质玻璃。
本发明还提供一种显示设备。
(102)显示设备,其含有(1)~(40)任一所述的微晶玻璃制品,和/或(41)~(78)任一所述的微晶玻璃,和/或(79)~(99)任一所述的基质玻璃,和/或(100)所述的玻璃盖板,和/或(101)所述的玻璃元器件。
本发明还提供一种电子设备。
(103)电子设备,其含有(1)~(40)任一所述的微晶玻璃制品,和/或(41)~(78)任一所述的微晶玻璃,和/或(79)~(99)任一所述的基质玻璃,和/或(100)所述的玻璃盖板,和/或(101)所述的玻璃元器件。
本发明还提供一种微晶玻璃制品的制造方法。
(104)微晶玻璃制品的制造方法,所述方法包括以下步骤:
形成基质玻璃,所述基质玻璃的组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;
对所述基质玻璃通过晶化工艺形成微晶玻璃,再对所述微晶玻璃通过化学强化工艺形成微晶玻璃制品。
(105)根据(104)所述的微晶玻璃制品的制造方法,所述基质玻璃的组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或TiO 2:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一 种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(106)微晶玻璃制品的制造方法,所述方法包括以下步骤:
形成基质玻璃,所述基质玻璃的组分按重量百分比表示,由SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;K 2O:0~5%;MgO:0~2%;ZnO:0~2%;Na 2O:0~6%;SrO:0~5%;TiO 2:0~5%;BaO:0~5%;CaO:0~5%;B 2O 3:0~5%;Ln 2O 3:0~5%;澄清剂:0~2%组成,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种;
对所述基质玻璃通过晶化工艺形成微晶玻璃,再对所述微晶玻璃通过化学强化工艺形成微晶玻璃制品。
(107)根据(104)~(106)任一所述的微晶玻璃制品的制造方法,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为大于0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
4)Na 2O/Y 2O 3为6.0以下;
5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
(108)根据(104)~(107)任一所述的微晶玻璃制品的制造方法,所述基质玻璃的组分按重量百分比表示,其中:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或TiO 2:0~3%;和/或BaO:0~3%;和/或CaO:0~3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(109)根据(104)~(108)任一所述的微晶玻璃制品的制造方法,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.1~1.0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
4)Na 2O/Y 2O 3为0.1~5.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
(110)根据(104)~(109)任一所述的微晶玻璃制品的制造方法,所述基质玻璃的组分按重量百分比表示,其中:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或Y 2O 3:2~6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(111)根据(104)~(110)任一所述的微晶玻璃制品的制造方法,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.2~0.6;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
4)Na 2O/Y 2O 3为0.3~2.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
(112)根据(104)~(111)任一所述的微晶玻璃制品的制造方法,所述基质玻璃的组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2; 和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
(113)根据(104)或(105)任一所述的微晶玻璃制品的制造方法,所述基质玻璃含有着色剂。
(114)根据(113)所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
(115)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:NiO:0.1~4%;和/或Ni 2O 3:0.1~4%;和/或CoO:0.05~2%;和/或Co 2O 3:0.05~2%;和/或Fe 2O 3:0.2~7%;和/或MnO 2:0.1~4%;和/或Er 2O 3:0.4~8%;和/或Nd 2O 3:0.4~8%;和/或Cu 2O:0.5~4%;和/或Pr 2O 3:0.4~8%;和/或CeO 2:0.5~4%。
(116)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%;和/或CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%;和/或Fe 2O 3:0.2~5%;和/或MnO 2:0.1~3%;和/或Er 2O 3:0.4~6%;和/或Nd 2O 3:0.4~6%;和/或Cu 2O:0.5~3%;和/或Pr 2O 3:0.4~6%;和/或CeO 2:0.5~3%。
(117)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%。
(118)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%。
(119)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:Cu 2O:0.5~3%;和/或CeO 2:0.5~3%。
(120)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:Fe 2O 3:0.2~5%、CoO:0.05~0.3%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%;或者Fe 2O 3:0.2~5%、CoO:0.05~0.3%、NiO:0.1~1%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%、NiO:0.1~1%。
(121)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:Pr 2O 3:0.4~6%;或者Fe 2O 3:0.2~5%;或者MnO 2:0.1~3%;或者Er 2O 3:0.4~6%;或者Nd 2O 3:0.4~6%。
(122)根据(113)或(114)任一所述的微晶玻璃制品的制造方法,所述着色剂按重量百分比表示,含有:Er 2O 3:0.4~6%、Nd 2O 3:0.4~4%、MnO 2:0.1~2%。
(123)根据(104)~(122)任一所述的微晶玻璃制品的制造方法,所述晶化工艺包括以下步骤:升温至规定的晶化处理温度,在达到晶化处理温度之后,将其温度保持一定的时间,然后再进行降温。该晶化处理温度为600~750℃,优选为650~700℃,在晶化处理温度下的保持时间为0~8小时,优选为1~6小时。
(124)根据(104)~(122)任一所述的微晶玻璃制品的制造方法,所述晶化工艺包括以下步骤:在第1温度下进行成核工艺的处理,然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。
(125)根据(124)所述的微晶玻璃制品的制造方法,所述晶化工艺包括以下步骤:第1温度为470~630℃,第2温度为650~750℃;在第1温度下的保持时间为0~24小时,优选为2~15小时;在第2温度下的保持时间为0~10小时,优选为0.5~6小时。
(126)根据(104)~(125)任一所述的微晶玻璃制品的制造方法,所述化学强化工艺包括:微晶玻璃浸没于430℃~470℃的温度的熔融Na盐的盐浴中6~20小时,优选温度范围为435℃~460℃,优选时间范围为8~13小时;和/或微晶玻璃浸没于400℃~450℃的温度下熔融K盐的盐浴 中1~8小时,优选时间范围为2~4小时。
(127)根据(104)~(126)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的晶相含有一硅酸锂;和/或磷酸锂。
(128)根据(104)~(127)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃制品的10~63.5%,优选为15~55%。
(129)根据(104)~(128)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃制品的重量百分比为3~15%,优选为5~12%。
(130)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的表面应力为600MPa以上,优选为650MPa以上,更优选为700MPa以上。
(131)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的四点弯曲强度为600MPa以上,优选为650MPa以上,更优选为700MPa以上。
(132)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的离子交换层深度为20μm以上,优选为30μm以上,更优选40μm以上。
(133)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的落球试验高度为1300mm以上,优选为1400mm以上,更优选为1500mm以上。
(134)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的断裂韧性为1MPa·m 1/2以上,优选为1.1MPa·m 1/2以上,更优选为1.2MPa·m 1/2以上
(135)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的维氏硬度为700kgf/mm 2以上,优选为720kgf/mm 2以上,更优选为730kgf/mm 2以上。
(136)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的结晶度为50%以上,优选为60%以上,更优选为70%以上。
(137)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
(138)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,1mm以下厚度的微晶玻璃制品的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。
(139)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,1mm以下厚度的微晶玻璃制品400~800nm波长的平均透过率89%以上。
(140)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,1mm以下厚度的微晶玻璃制品550nm波长的透过率为91%以上。
(141)根据(104)~(112)任一所述的微晶玻璃制品的制造方法,1mm以下厚度的微晶玻璃制品400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
(142)根据(138)~(141)任一所述的微晶玻璃制品的制造方法,所述微晶玻璃制品的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
本发明还提供一种微晶玻璃的制造方法。
(143)微晶玻璃的制造方法,所述方法包括以下步骤:
形成基质玻璃,所述基质玻璃的组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;
对所述基质玻璃通过晶化工艺形成微晶玻璃。
(144)根据(143)所述的微晶玻璃的制造方法,所述基质玻璃的组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO: 0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或TiO 2:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(145)微晶玻璃的制造方法,所述方法包括以下步骤:
形成基质玻璃,所述基质玻璃的组分按重量百分比表示,由SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;K 2O:0~5%;MgO:0~2%;ZnO:0~2%;Na 2O:0~6%;SrO:0~5%;TiO 2:0~5%;BaO:0~5%;CaO:0~5%;B 2O 3:0~5%;Ln 2O 3:0~5%;澄清剂:0~2%组成,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种;
对所述基质玻璃通过晶化工艺形成微晶玻璃。
(146)根据(143)~(145)任一所述的微晶玻璃的制造方法,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为大于0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
4)Na 2O/Y 2O 3为6.0以下;
5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
(147)根据(143)~(146)任一所述的微晶玻璃的制造方法,所述基质玻璃的组分按重量百分比表示,其中:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或TiO 2:0~3%;和/或BaO:0~3%;和/或CaO:0~3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/ 或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(148)根据(143)~(147)任一所述的微晶玻璃的制造方法,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.1~1.0;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
4)Na 2O/Y 2O 3为0.1~5.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
(149)根据(143)~(148)任一所述的微晶玻璃的制造方法,所述基质玻璃的组分按重量百分比表示,其中:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或Y 2O 3:2~6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
(150)根据(143)~(149)任一所述的微晶玻璃的制造方法,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
1)Y 2O 3/ZrO 2为0.2~0.6;
2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
4)Na 2O/Y 2O 3为0.3~2.0;
5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
(151)根据(143)~(150)任一所述的微晶玻璃的制造方法,所述 基质玻璃的组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
(152)根据(143)或(144)任一所述的微晶玻璃的制造方法,所述基质玻璃含有着色剂。
(153)根据(152)所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
(154)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:NiO:0.1~4%;和/或Ni 2O 3:0.1~4%;和/或CoO:0.05~2%;和/或Co 2O 3:0.05~2%;和/或Fe 2O 3:0.2~7%;和/或MnO 2:0.1~4%;和/或Er 2O 3:0.4~8%;和/或Nd 2O 3:0.4~8%;和/或Cu 2O:0.5~4%;和/或Pr 2O 3:0.4~8%;和/或CeO 2:0.5~4%。
(155)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%;和/或CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%;和/或Fe 2O 3:0.2~5%;和/或MnO 2:0.1~3%;和/或Er 2O 3:0.4~6%;和/或Nd 2O 3:0.4~6%;和/或Cu 2O:0.5~3%;和/或Pr 2O 3:0.4~6%;和/或CeO 2:0.5~3%。
(156)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:NiO:0.1~3%;和/或Ni 2O 3:0.1~3%。
(157)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:CoO:0.05~1.8%;和/或Co 2O 3:0.05~1.8%。
(158)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:Cu 2O:0.5~3%;和/或CeO 2:0.5~3%。
(159)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:Fe 2O 3:0.2~5%、CoO:0.05~0.3%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%;或者Fe 2O 3:0.2~5%、CoO:0.05~0.3%、NiO:0.1~1%;或者Fe 2O 3:0.2~5%、Co 2O 3:0.05~0.3%、NiO:0.1~1%。
(160)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:Pr 2O 3:0.4~6%;或者Fe 2O 3:0.2~5%;或者MnO 2:0.1~3%;或者Er 2O 3:0.4~6%;或者Nd 2O 3:0.4~6%。
(161)根据(152)或(153)任一所述的微晶玻璃的制造方法,所述着色剂按重量百分比表示,含有:Er 2O 3:0.4~6%、Nd 2O 3:0.4~4%、MnO 2:0.1~2%。
(162)根据(143)~(161)任一所述的微晶玻璃的制造方法,所述晶化工艺包括以下步骤:升温至规定的晶化处理温度,在达到晶化处理温度之后,将其温度保持一定的时间,然后再进行降温。该晶化处理温度为600~750℃,优选为650~700℃,在晶化处理温度下的保持时间为0~8小时,优选为1~6小时。
(163)根据(143)~(161)任一所述的微晶玻璃的制造方法,所述晶化工艺包括以下步骤:在第1温度下进行成核工艺的处理,然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。
(164)根据(163)所述的微晶玻璃的制造方法,所述晶化工艺包括以下步骤:第1温度为470~630℃,第2温度为650~750℃;在第1温度下的保持时间为0~24小时,优选为2~15小时;在第2温度下的保持时间为0~10小时,优选为0.5~6小时。
(165)根据(143)~(164)任一所述的微晶玻璃的制造方法,所述微晶玻璃的晶相含有一硅酸锂;和/或磷酸锂。
(166)根据(143)~(165)任一所述的微晶玻璃的制造方法,所述微晶玻璃的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量 百分数,一硅酸锂占微晶玻璃的10~63.5%,优选为15~55%。
(167)根据(143)~(166)任一所述的微晶玻璃的制造方法,所述微晶玻璃中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃的重量百分比为3~15%,优选为5~12%。
(168)根据(143)~(151)任一所述的微晶玻璃的制造方法,所述微晶玻璃的结晶度为50%以上,优选为60%以上,更优选为70%以上。
(169)根据(143)~(151)任一所述的微晶玻璃的制造方法,所述微晶玻璃的晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下;和/或热膨胀系数为75~95×10 -7/K。
(170)根据(143)~(151)任一所述的微晶玻璃的制造方法,所述微晶玻璃的折射率为1.5700~1.5800。
(171)根据(143)~(151)任一所述的微晶玻璃的制造方法,所述微晶玻璃的本体落球高度为1000mm以上,优选为1100mm以上,更优选为1200mm以上。
(172)根据(143)~(151)任一所述的微晶玻璃的制造方法,所述微晶玻璃的维氏硬度为650kgf/mm 2以上,优选为680kgf/mm 2以上,更优选为700kgf/mm 2以上。
(173)根据(143)~(151)任一所述的微晶玻璃的制造方法,1mm以下厚度的微晶玻璃的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。
(174)根据(143)~(151)任一所述的微晶玻璃的制造方法,1mm以下厚度的微晶玻璃400~800nm波长的平均透过率89%以上。
(175)根据(143)~(151)任一所述的微晶玻璃的制造方法,1mm以下厚度的微晶玻璃550nm波长的透过率为91%以上
(176)根据(143)~(151)任一所述的微晶玻璃的制造方法,1mm以下厚度的微晶玻璃400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
(177)根据(173)~(176)任一所述的微晶玻璃的制造方法,所述微晶玻璃的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
本发明的有益效果是:通过合理的组分设计,本发明获得的微晶玻璃和微晶玻璃制品具有优异的机械性能和光学性能,适用于电子设备或显示设备。
具体实施方式
本发明的微晶玻璃和微晶玻璃制品是具有晶相和玻璃相的材料,其有别于非晶质固体。微晶玻璃和微晶玻璃制品的晶相可以通过X射线衍射分析的X射线衍射图案中出现的峰值角度进行辨别和/或通过TEMEDX测得。
本发明的发明人经过反复试验和研究,对于构成微晶玻璃和微晶玻璃制品的特定成分,通过将其含量以及含量比例规定为特定值并使其析出特定的晶相,以较低的成本得到了本发明的微晶玻璃或微晶玻璃制品。
下面,对本发明基质玻璃、微晶玻璃及微晶玻璃制品的各组分(成分)的范围进行说明。在本说明书中,如果没有特殊说明,各组分的含量全部采用相对于换算成氧化物的组成的基质玻璃、或微晶玻璃、或微晶玻璃制品物质总量的重量百分比(wt%)表示。在这里,所述“换算成氧化物的组成”是指,作为本发明的基质玻璃、微晶玻璃或微晶玻璃制品组成成分的原料而使用的氧化物、复合盐及氢氧化物等熔融时分解并转变为氧化物的情况下,将该氧化物的物质总量作为100%。此外,在本说明书中仅称为玻璃时为结晶化前的基质玻璃,基质玻璃结晶化后称为微晶玻璃,微晶玻璃制品是指经化学强化后的微晶玻璃。
除非在具体情况下另外指出,本文所列出的数值范围包括上限和下限值,“以上”和“以下”包括端点值,以及在该范围内的所有整数和分数,而不限于所限定范围时所列的具体值。本文所使用的术语“约”指配方、参数和其他数量以及特征不是、且无需是精确的,如有需要,可以近似和/或更大或更低,这反映公差、换算因子和测量误差等。本文所称“和/或” 是包含性的,例如“A;和/或B”,是指只有A,或者只有B,或者同时有A和B。
在本发明微晶玻璃和微晶玻璃制品中,晶相含有一硅酸锂;和/或磷酸锂。
在本发明的一些实施方式中,微晶玻璃或微晶玻璃制品中的晶相主要含有一硅酸锂晶相,一硅酸锂晶相具有比其他晶相更高的重量百分数,一硅酸锂晶相占微晶玻璃或微晶玻璃制品的10~63.5%,在一些实施方式中,重量百分比范围为15~55%。
在本发明的一些实施方式中,微晶玻璃或微晶玻璃制品中的晶相含有磷酸锂晶相,该晶相占微晶玻璃或微晶玻璃制品的重量百分比范围为3~15%,在一些实施方式中,重量百分比范围为5~12%。
SiO 2是本发明玻璃的必要成分,其是热处理后形成晶体的主要成分之一,如果SiO 2的含量在45%以下,玻璃中较难形成晶体,因此,SiO 2含量的下限为45%,优选为50%,进一步优选为53%;如果SiO 2含量在70%以上,不利玻璃成型,影响微晶玻璃和微晶玻璃制品的雾度和∣B∣值。因此,SiO 2含量的上限为70%,优选为65%,进一步优选为63%。在一些实施方式中,可包含约45%、46%、47%、48%、49%、50%、51%、52%、53%、54%、55%、56%、57%、58%、59%、60%、61%、62%、63%、64%、65%、66%、67%、68%、69%、70%的SiO 2
Al 2O 3可作为玻璃网络结构,有利于玻璃的成型,降低玻璃晶化温度,有利于玻璃晶化;Al 2O 3是形成微晶玻璃晶体的成分之一,有利于微晶玻璃的化学强化,增加微晶玻璃制品的离子交换层深度,但如果其含量不足8%,则上述效果不佳,因此,Al 2O 3含量的下限为8%。另一方面,如果Al 2O 3的含量超过18%,影响微晶玻璃化学强化后的碎片大小,因此Al 2O 3含量的上限为18%,优选为15%,进一步优选为12%。在一些实施方式中,可包含约8%、8.5%、9%、9.5%、10%、10.5%、11%、11.5%、12%、12.5%、13%、13.5%、14%、14.5%、15%、15.5%、16%、16.5%、17%、17.5%、18%的Al 2O 3
Li 2O可促进玻璃熔化,降低熔炼温度,是晶体形成主要成分,同时也是化学强化处理中主要与钠、钾离子进行置换的组分,可增大化学强化后微晶玻璃制品的表面应力,提升微晶玻璃制品的落球高度,但如果其含量不足10%,则形成一硅酸锂的晶相不佳,影响微晶玻璃制品的落球高度和碎片大小,因此,Li 2O含量的下限为10%,优选为13%,进一步优选为14%。另一方面,如果过多地含有Li 2O,在晶化时,玻璃容易分相,影响微晶玻璃和微晶玻璃制品的透过率。因此,Li 2O含量的上限为25%,优选为22%,进一步优选为21%。在一些实施方式中,可包含约10%、10.5%、11%、11.5%、12%、12.5%、13%、13.5%、14%、14.5%、15%、15.5%、16%、16.5%、17%、17.5%、18%、18.5%、19%、19.5%、20%、20.5%、21%、21.5%、22%、22.5%、23%、23.5%、24%、24.5%、25%的Li 2O。
Na 2O为任选组分,可以降低玻璃的熔炼温度,有利于玻璃或微晶玻璃化学强化工艺的调整,因此,本发明中Na 2O含量的下限优选为1%,更优选为1.5%。另一方面,若玻璃中过多含有Na 2O,会促使玻璃产生分相,导致晶化后微晶玻璃和微晶玻璃制品的透过率下降。因此,Na 2O含量的上限为6%,优选为5%,进一步优选为4%。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%的Na 2O。
K 2O有利于玻璃成型,降低玻璃的粘度,但如果过多地含有K 2O,则容易导致玻璃化学稳定性以及硬度的下降。因此,K 2O含量的上限为5%,优选为4%,进一步优选为2%。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%的K 2O。
P 2O 5能够在玻璃晶化过程中形成晶核,促进晶体的形成,提高微晶玻璃或微晶玻璃制品的结晶度,有利于化学强化,增加微晶玻璃制品的硬度、落球高度和抗弯强度,P 2O 5含量的下限为2%,优选为3.5%,进一步优选为4%。但如果过多地含有P 2O 5,则很容易导致玻璃的分相和降低玻璃的化学稳定性。因此,P 2O 5含量的上限为10%,优选为9%,进一步优选为8%。在一些实 施方式中,可包含约2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%、5.5%、6.0%、6.5%、7.0%、7.5%、8.0%、8.5%、9.0%、9.5%、10%的P 2O 5
ZrO 2与P 2O 5可相互溶解,降低P 2O 5在玻璃成型时分相,晶化时可升高玻璃的晶化温度,保证微晶玻璃和微晶玻璃制品中一硅酸锂晶相的完整程度,降低微晶玻璃和微晶玻璃制品的雾度和∣B∣值,提高微晶玻璃制品的耐摔性,因此,ZrO 2含量的下限为5%,优选为6%,进一步优选为7%。另一方面,如果过多地含有ZrO 2,则玻璃熔化困难,因此ZrO 2含量的上限为15%,优选为12%。在一些实施方式中,可包含约5.0%、5.5%、6.0%、6.5%、7.0%、7.5%、8.0%、8.5%、9.0%、9.5%、10.0%、10.5%、11.0%、11.5%、12%、12.5%、13.0%、13.5%、14.0%、14.5%、15.0%的ZrO 2
Y 2O 3可促进ZrO 2的熔化,降低玻璃的熔炼难度,减少玻璃中分相,降低微晶玻璃和微晶玻璃制品的雾度和∣B∣值,Y 2O 3含量的下限为大于0%,优选为1%,进一步优选为2%。另一方面,若Y 2O 3含量过多,玻璃晶化时形成晶体困难,微晶玻璃和微晶玻璃制品的结晶度下降,因此Y 2O 3含量的上限为8%,优选为7%,进一步优选为6%。在一些实施方式中,可包含约大于0%、0.1%、0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%、5.5%、6.0%、6.5%、7.0%、7.5%、8.0%的Y 2O 3
经发明人大量实验研究发现,在一些实施方式中,Y 2O 3和ZrO 2的相对含量,对微晶玻璃和微晶玻璃制品的雾度和∣B∣值有重要影响,尤其是使Y 2O 3/ZrO 2大于0,可降低微晶玻璃和微晶玻璃制品的雾度和∣B∣值,改善终端产品摄影和照相效果。因此,优选Y 2O 3/ZrO 2为大于0,更优选Y 2O 3/ZrO 2为0.1~1.0,进一步优选Y 2O 3/ZrO 2为0.2~0.6。在一些实施方式中,Y 2O 3/ZrO 2的值可为大于0、0.05、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0。
在本发明的一些实施方式中,使(Li 2O+ZrO 2+P 2O 5)/Y 2O 3在2.5~50.0范围内,可使基质玻璃在晶化过程中细化晶粒,使微晶玻璃和微晶玻璃制品获得更为细小的晶粒,降低微晶玻璃和微晶玻璃制品的雾度。因此,优选 (Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0,更优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0,进一步优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0。在一些实施方式中,(Li 2O+ZrO 2+P 2O 5)/Y 2O 3的值可为2.5、3.0、4.0、5.0、6.0、7.0、8.0、9.0、10.0、11.0、12.0、13.0、14.0、15.0、16.0、17.0、18.0、19.0、20.0、21.0、22.0、23.0、24.0、25.0、26.0、27.0、28.0、29.0、30.0、31.0、32.0、33.0、34.0、35.0、36.0、37.0、38.0、39.0、40.0、41.0、42.0、43.0、44.0、45.0、46.0、47.0、48.0、49.0、50.0。
在大量实验研究过程中,本发明人发现,通过控制Al 2O 3与P 2O 5、Li 2O和ZrO 2的合计含量Li 2O+ZrO 2+P 2O 5之间的比值Al 2O 3/(Li 2O+ZrO 2+P 2O 5)在0.16~0.9范围内,可使微晶玻璃制品经受1300mm及以上的落球冲击,更优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6。进一步的,在一些实施方式中,进一步优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)在0.19~0.5范围内时,较易形成一硅酸锂晶相,且微晶玻璃制品较易获得优异的断裂韧性,断裂韧性可为1MPa·m 1/2以上,优选为1.1MPa·m 1/2以上,更优选为1.2MPa·m 1/2以上;同时进一步优化落球试验高度的承受能力,因此进一步优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5。在一些实施方式中,Al 2O 3/(Li 2O+ZrO 2+P 2O 5)可为0.16、0.17、0.18、0.19、0.2、0.21、0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.55、0.60、0.65、0.70、0.75、0.80、0.85、0.90。
经发明人大量实验研究发现,Na 2O和Y 2O 3的相对含量,对微晶玻璃制品的表面应力和离子交换层深度有重要影响,尤其是Na 2O/Y 2O 3为6.0以下,可提高微晶玻璃制品的表面应力和离子交换层深度,更优选Na 2O/Y 2O 3为0.1~5.0。在一些实施方式中,进一步优选Na 2O/Y 2O 3为0.3~2.0,还可改善微晶玻璃制品的碎片大小,在一些实施方式中,微晶玻璃制品的表面应力为600MPa以上,优选为650MPa以上,更优选为700MPa以上;微晶玻璃制品的离子交换层深度为20μm以上,优选为30μm以上,更优选40μm以上。在一 些实施方式中,Na 2O/Y 2O 3的值可为0、大于0、0.1、0.2、0.3、0.4、、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.3、2.5、2.7、3.0、3.3、3.5、3.7、4.0、4.3、4.5、4.7、5.0、5.3、5.5、5.7、6.0。
在本发明的一些实施方式中,当控制Y 2O 3与Al 2O 3和SiO 2的合计含量
(Al 2O 3+SiO 2)的含量比例Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15时,可优化玻璃的晶化性能,使微晶玻璃和微晶玻璃制品具有合适量的结晶度,从而使微晶玻璃及微晶玻璃制品具有优异的性能;优选Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12,更优选为0.03~0.09,微晶玻璃和微晶玻璃制品的落球试验高度变大,在一些实施方式中,微晶玻璃制品的落球试验高度优选为1300mm以上,更优选为1400mm以上,进一步优选为1500mm以上。在一些实施方式中,Y 2O 3/(Al 2O 3+SiO 2)的值可为大于0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.11、0.12、0.13、0.14、0.15。
B 2O 3可以改善玻璃的网络结构,优化玻璃和微晶玻璃的化学强化性能,提升微晶玻璃制品的落球高度,B 2O 3含量超过5%时,不利于玻璃成型,在成型时容易析晶,因此B 2O 3含量上限为5%,优选为3%,更优选为2%,进一步优选不含有B 2O 3。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%的B 2O 3
ZnO可降低玻璃的熔炼难度,但含量高时会促进玻璃低温晶化,降低微晶玻璃和微晶玻璃制品的结晶度和透过率,升高微晶玻璃和微晶玻璃制品的雾度,因此其含量上限为2%,优选为1%,更优选不含有ZnO。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%的ZnO。
MgO可降低玻璃熔炼难度,有利于增加微晶玻璃和微晶玻璃制品的落球高度,但是容易促进玻璃低温晶化,降低微晶玻璃和微晶玻璃制品的结晶度和透过率,因此其含量上限为2%,优选为1%。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%的MgO。
SrO是提高玻璃的低温熔化性和抑制玻璃成型时析晶的任选组分。含量 过多时,影响玻璃成型,成型时易析晶。因此本发明中SrO含量的范围为0~5%,优选为0~3%,更优选0~1%,进一步优选不含有SrO。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%的SrO。
BaO是有助于提高玻璃的成玻性能的任选组分,含量过多时,不利玻璃成型。因此本发明BaO含量的范围为0~5%,优选为0~3%,更优选0~1%,进一步优选不含有BaO。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%的BaO。
CaO可以增加玻璃的硬度,含量过多时,玻璃成型时容易发乳。因此本发明中CaO含量的范围为0~5%,优选为0~3%,更优选0~1%,进一步优选不含有CaO。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%的CaO。
TiO 2是一种有助于降低基质玻璃的熔化温度、提高化学稳定性的可选成分,本发明中含有5%以下的TiO 2,可以使基质玻璃晶化过程变得容易控制,优选为3%以下,更优选为1%以下。在一些实施方式中,进一步优选不含有TiO 2。在一些实施方式中,可包含约0%、大于0%、0.1%、0.3%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%的TiO 2
Ln 2O 3(Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种)是提高微晶玻璃的硬度和化学稳定性,抑制玻璃成型析晶的任选组分,含量过多时会影响玻璃的化学强化性能,降低微晶玻璃制品的强度。因此本发明中Ln 2O 3含量的范围为0~5%,优选为0~4%,更优选0~3%,进一步优选不含有Ln 2O 3。在一些实施方式中,可包含约0%、大于0%、0.1%、0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%的Ln 2O 3
在一些实施方式中,玻璃、微晶玻璃或微晶玻璃制品还可包括0~2%的澄清剂,以提高玻璃、微晶玻璃或微晶玻璃制品的除泡能力。这种澄清剂包括但不限于Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种,优选Sb 2O 3作为澄清剂。上述澄清剂单独或组合存在时,其含量的上限优选为1%,更 优选为0.5%。在一些实施方式中,上述澄清剂中的一种或多种的含量约为0%、、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%。
为使本发明玻璃、微晶玻璃或微晶玻璃制品获得期望的机械性能、光学性能、生产性能和化学强化性能等优异性能,在本发明的一些实施方式中优选不含有F;和/或不含有Ta 2O 5
PbO和As 2O 3是有毒物质,即使少量的加入也不符合环保的要求,因此本发明在一些实施方式中优选不含有PbO和As 2O 3
本发明的一些实施方式中,通过含有着色剂,可以制备出具有颜色的基质玻璃、微晶玻璃或微晶玻璃制品,可使基质玻璃、微晶玻璃或微晶玻璃制品呈现不同的颜色,着色剂含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 5:0~8%;和/或CeO 2:0~4%。其着色剂重量百分比含量及其作用详述如下:
本发明制备的褐色或绿色基质玻璃、微晶玻璃或微晶玻璃制品,使用NiO、Ni 2O 3或Pr 2O 5为着色剂。NiO和Ni 2O 3为着色剂,用于制备褐色或绿色基质玻璃、微晶玻璃或微晶玻璃制品,两种组分可以单独使用或者混合使用,其分别含量一般为4%以下,优选为3%以下,如果含量超过4%,着色剂不能很好溶于基质玻璃、微晶玻璃或微晶玻璃制品中,其分别的含量下限在0.1%以上,如低于0.1%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中,可包含约0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%的NiO或Ni 2O 3。如混合使用时,NiO和Ni 2O 3合计量一般为4%以下,合计量下限在0.1%以上。在一些实施方式中,可包含约0.1%、0.2%、0.3%、 0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%的NiO和Ni 2O 3。使用Pr 2O 5作为绿色基质玻璃、微晶玻璃或微晶玻璃制品着色剂,单独使用,一般含量为8%以下,优选含量为6%以下,其含量下限在0.4%以上,如低于0.4%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中,可包含约0.4%、0.6%、0.8%、1.0%、1.2%、1.4%、1.6%、1.8%、2.0%、2.2%、2.4%、2.6%、2.8%、3.0%、3.2%、3.4%、3.6%、3.8%、4.0%、4.2%、4.4%、4.6%、4.8%、5.0%、5.2%、5.4%、5.6%、5.8%、6.0%、6.2%、6.4%、6.6%、6.8%、7.0%、7.2%、7.4%、7.6%、7.8%、8.0%的Pr 2O 5
本发明制备的蓝色基质玻璃、微晶玻璃或微晶玻璃制品,使用CoO或Co 2O 3为着色剂,两种着色剂组分可以单独使用或者混合使用,其分别的含量都一般为2%以下,优选为1.8%以下,如果含量超过了2%,着色剂不能很好溶于基质玻璃、微晶玻璃或微晶玻璃制品中,其分别的含量下限在0.05%以上,如低于0.05%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中,可包含约0.05%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%的CoO或Co 2O 3。如混合使用时,CoO和Co 2O 3合计量不超过2%,合计量下限在0.05%以上。在一些实施方式中,可包含约0.05%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%的CoO和Co 2O 3
本发明制备的黄色基质玻璃、微晶玻璃或微晶玻璃制品,使用Cu 2O或CeO 2为着色剂,两种着色剂组分单独使用或者混合使用,其分别的含量下限在0.5%以上,如低于0.5%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显,单独使用Cu 2O为4%以下,优选为3%以下,如果含量超过4%,容易 使基质玻璃析晶。在一些实施方式中,可包含约0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%的Cu 2O。单独使用CeO 2含量一般为4%以下,优选为3%以下,如含量超过4%,基质玻璃、微晶玻璃或微晶玻璃制品光泽不好。在一些实施方式中,可包含约0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%的CeO 2。同时,少量的CeO 2加入玻璃中具有除泡的效果,CeO 2在玻璃中还可以作为澄清剂使用。如果两种着色剂混合使用时,其合计量一般为4%以下,合计量下限在0.5%以上。在一些实施方式中,可包含约0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%的CeO 2和Cu 2O。
本发明制备的黑色或烟灰色基质玻璃、微晶玻璃或微晶玻璃制品,单独使用Fe 2O 3为着色剂;或者使用Fe 2O 3和CoO两种混合使用的着色剂;或者使用Fe 2O 3和Co 2O 3两种混合使用的着色剂;或者使用Fe 2O 3、CoO和NiO三种混合使用的着色剂;或者使用Fe 2O 3、Co 2O 3和NiO三种混合使用的着色剂。制备黑色和烟灰色基质玻璃、微晶玻璃或微晶玻璃制品的着色剂主要使用Fe 2O 3着色,含量为7%以下,优选为5%以下,其含量下限在0.2%以上,在一些实施方式中,可包含约0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%、4.5%、5.0%、5.5%、6.0%、6.5%、7.0%的Fe 2O 3。CoO和Co 2O 3在可见光有吸收,可 以加深基质玻璃、微晶玻璃或微晶玻璃制品的着色程度,一般与Fe 2O 3混合使用时各自的含量为0.6%以下,下限在0.2%以上。在一些实施方式中,可包含约0.2%、0.3%、0.4%、0.5%、0.6%的CoO和/或Co 2O 3。NiO在可见光有吸收,可以加深基质玻璃、微晶玻璃或微晶玻璃制品的着色程度,一般混合使用时其含量为1%以下,合计量下限在0.2%以上。在一些实施方式中,可包含约0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%的NiO。
本发明制备的紫色基质玻璃、微晶玻璃或微晶玻璃制品,使用MnO 2为着色剂,使用含量一般为4%以下,优选在3%以下,其含量下限在0.1%以上,如低于0.1%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中,可包含约0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3.0%、3.1%、3.2%、3.3%、3.4%、3.5%、3.6%、3.7%、3.8%、3.9%、4.0%的MnO 2
本发明制备的粉色基质玻璃、微晶玻璃或微晶玻璃制品,使用Er 2O 3为着色剂,使用含量一般为8%以下,优选在6%以下。由于稀土元素Er 2O 3着色效率低,当使用含量超过8%,也不能使基质玻璃、微晶玻璃或微晶玻璃制品的颜色进一步的加深,反而增加成本,其含量下限在0.4%以上,如低于0.4%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中,可包含约0.4%、0.6%、0.8%、1.0%、1.2%、1.4%、1.6%、1.8%、2.0%、2.2%、2.4%、2.6%、2.8%、3.0%、3.2%、3.4%、3.6%、3.8%、4.0%、4.2%、4.4%、4.6%、4.8%、5.0%、5.2%、5.4%、5.6%、5.8%、6.0%、6.2%、6.4%、6.6%、6.8%、7.0%、7.2%、7.4%、7.6%、7.8%、8.0%的Er 2O 3
本发明制备的紫红色基质玻璃、微晶玻璃或微晶玻璃制品,使用Nd 2O 3为着色剂,使用含量一般为8%以下,优选在6%以下。由于稀土元素Nd 2O 3着色效率低,使用含量超过了8%,也不能使基质玻璃、微晶玻璃或微晶玻璃制品的颜色进一步的加深,反而增加成本,其含量下限在0.4%以上,如低 于0.4%,基质玻璃、微晶玻璃或微晶玻璃制品颜色不明显。在一些实施方式中,可包含约0.4%、0.6%、0.8%、1.0%、1.2%、1.4%、1.6%、1.8%、2.0%、2.2%、2.4%、2.6%、2.8%、3.0%、3.2%、3.4%、3.6%、3.8%、4.0%、4.2%、4.4%、4.6%、4.8%、5.0%、5.2%、5.4%、5.6%、5.8%、6.0%、6.2%、6.4%、6.6%、6.8%、7.0%、7.2%、7.4%、7.6%、7.8%、8.0%的Nd 2O 3
本发明制备的红色基质玻璃、微晶玻璃或微晶玻璃制品,使用Er 2O 3、Nd 2O 3和MnO 2混合着色剂,玻璃中Er离子在400-500nm有吸收,Mn离子主要在500nm处有吸收,Nd离子主要在580nm处有强的吸收,三种物质的混合,可以制备红色基质玻璃、微晶玻璃或微晶玻璃制品,由于Er 2O 3和Nd 2O 3为稀土着色,着色能力比较弱,Er 2O 3使用量在6%以内,Nd 2O 3使用量在4%以内,MnO 2着色强,使用量在2%范围内,其使用混合着色剂合计量的下限在0.9%以上。
本文所记载的“不含有”“0%”是指没有故意将该化合物、分子或元素等作为原料添加到本发明基质玻璃、微晶玻璃或微晶玻璃制品中;但作为生产基质玻璃、微晶玻璃或微晶玻璃制品的原材料和/或设备,会存在某些不是故意添加的杂质或组分,会在最终的基质玻璃、微晶玻璃或微晶玻璃制品中少量或痕量含有,此种情形也在本发明专利的保护范围内。
本发明的一些实施方式中,微晶玻璃和微晶玻璃制品中晶相含有一硅酸锂晶体,为本发明微晶玻璃和微晶玻璃制品提供高的强度,微晶玻璃和微晶玻璃制品断裂韧性变高;微晶玻璃和微晶玻璃制品的落球试验高度和四点弯曲强度变大。本发明微晶玻璃化学强化性能优异,还可通过化学强化以获得额外的机械强度。通过合理的组分设计,可使本发明微晶玻璃和微晶玻璃制品获得合适的晶粒大小,使本发明微晶玻璃和微晶玻璃制品具有高的强度。本发明中微晶玻璃和微晶玻璃制品具有良好的结晶度,使本发明微晶玻璃和微晶玻璃制品具有优异的机械性能。本文所称的结晶度是指结晶的完整程度,结晶完整的晶体内部质点的排列比较规则,衍射线强、尖锐且对称,衍射峰的半高宽接近仪器测量的宽度;结晶度差的晶体中有 位错等缺陷,使衍射线峰形宽而弥散。结晶度越差,衍射能力越弱,衍射峰越宽,直到消失在背景之中。在一些实施方式中,微晶玻璃制品或微晶玻璃的结晶度为50%以上,优选为60%以上,更优选为70%以上。
本发明微晶玻璃或微晶玻璃制品中晶粒尺寸和种类会影响微晶玻璃或微晶玻璃制品的雾度和透过率,晶粒越小透过率越高;雾度越小,透过率越高。在一些实施方式中,1mm以下厚度的微晶玻璃制品或微晶玻璃的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。在一些实施方式中,微晶玻璃制品或微晶玻璃的晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
在一些实施方式中,本发明微晶玻璃或微晶玻璃制品中晶相含量和折射率影响微晶玻璃或微晶玻璃制品的∣B∣值,在可见光范围观察微晶玻璃或微晶玻璃制品出现偏蓝或者偏黄,影响产品的光学性能,在LAB(物质颜色的色度值)中用∣B∣值进行标示。微晶玻璃或微晶玻璃制品在可见光范围中呈现低∣B∣值,在一些实施方式中1mm以下厚度的微晶玻璃制品或微晶玻璃400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
在一些实施方式中,本发明微晶玻璃或微晶玻璃制品在可见光范围中呈现高的透明度(即微晶玻璃或微晶玻璃制品是透明的)。微晶玻璃或微晶玻璃制品在可见光范围中呈现高的透过率,在一些实施方式中1mm以下厚度的微晶玻璃制品或微晶玻璃400~800nm的平均光透过率优选为89%以上。在一些优选的实施方式中,1mm以下厚度的微晶玻璃制品或微晶玻璃550nm的光透过率优选为91%以上。
在一些实施方式中,可将抗微生物成分添加到基质玻璃、微晶玻璃或微晶玻璃制品中。本文所述的微晶玻璃或微晶玻璃制品可用于例如厨房或餐饮工作台面的应用,其中很可能暴露于有害细菌。可添加到基质玻璃、微晶玻璃或微晶玻璃制品的抗微生物组分包括但不限Ag,AgO,Cu,CuO,Cu 2O等。在一些实施方式中,上述抗微生物组分的单独或组合含量为2%以下,优 选为1%以下。
本发明的基质玻璃、微晶玻璃和微晶玻璃制品可以通过如下方法进行生产和制造:
生成基质玻璃:按照组分比例将原料混合均匀,将均匀的混合物放入铂制或石英制的坩埚中,根据玻璃组成的熔化难易度,在电炉或燃气炉中在1250~1650℃的温度范围内进行5~24小时。熔化,搅拌使其均匀后,降至适当的温度并浇铸到模具中,缓慢冷却而成。
本发明的基质玻璃可以通过众所周知的方法进行成型。
本发明的基质玻璃,在成型后或成型加工后通过晶化工艺进行晶化处理,在玻璃内部均匀地析出结晶。该晶化处理可以通过1个阶段进行,也可以通过2个阶段进行,优选采用2个阶段进行晶化处理。在第1温度下进行成核工艺的处理,然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。将在第1温度下进行的晶化处理称为第1晶化处理,将在第2温度下进行的晶化处理称为第2晶化处理。
为了使微晶玻璃得到所期望的物理性质,优选的晶化工艺为:
上述通过1个阶段进行晶化处理,可以连续地进行核形成工艺与结晶生长工艺。即,升温至规定的晶化处理温度,在达到晶化处理温度之后,将其温度保持一定的时间,然后再进行降温。该晶化处理温度优选为在600~750℃,为了能够析出所期望的晶相,更优选为650~700℃,在晶化处理温度下的保持时间,优选为0~8小时,更优选为1~6小时。
上述通过2个阶段进行晶化处理时,第1温度优选为470~630℃,第2温度优选为650~750℃。在第1温度下的保持时间,优选为0~24小时,更优选为2~15小时。在第2温度下的保持时间,优选为0~10小时,更优选为0.5~6小时。
上述保持时间0小时,是指在达到其温度后不到1分钟又开始降温或升温。
在一些实施方式中,可通过各种工艺将本文所述的基质玻璃或微晶玻 璃制造成成形体,所述成形体包括但不限于片材,所述工艺包括但不限于狭缝拉制、浮法、辊压和本领域公知的其他形成片材的工艺。或者,可通过本领域所公知的浮法或辊压法来形成基质玻璃或微晶玻璃。
本发明的基质玻璃或微晶玻璃,可以采用研磨或抛光加工等方法制造片材的玻璃成形体,但制造玻璃成形体的方法,并不限定于这些方法。
本发明的基质玻璃或微晶玻璃成形体,可以在一定温度下采用热弯或压型等方法制备形成各种形状,并不限定于这些方法。
本发明所述的基质玻璃、微晶玻璃和微晶玻璃制品可具有合理有用的任何厚度。
本发明的微晶玻璃除了通过析出结晶提高机械特性之外,还可以通过形成压缩应力层获得更高的强度,从而制成微晶玻璃制品。
在一些实施方式中,可将基质玻璃或微晶玻璃加工成片材,和/或造型(如打孔、热弯等),定形后抛光和/或扫光,再通过化学强化工艺进行化学强化。
本发明所述的化学强化,即是离子交换法。本发明的基质玻璃、微晶玻璃都是可通过本技术领域所公知的方法进行离子交换。在离子交换过程中,基质玻璃或微晶玻璃中的较小的金属离子被靠近基质玻璃或微晶玻璃的具有相同价态的较大金属离子置换或“交换”。用较大的离子置换较小的离子,在基质玻璃或微晶玻璃中构建压缩应力,形成压缩应力层。
在一些实施方式中,金属离子是单价碱金属离子(例如Na +、K +、Rb +、Cs +等),离子交换通过将基质玻璃或微晶玻璃浸没在包含较大的金属离子的至少一种熔融盐的盐浴中来进行,该较大的金属离子用于置换基质玻璃中的较小的金属离子。或者,其他单价金属离子例如Ag +、Tl +、Cu +等也可用于交换单价离子。用来化学强化基质玻璃或微晶玻璃的一种或更多种离子交换过程可包括但不限于:将其浸没在单一盐浴中,或者将其浸没在具有相同或不同组成的多个盐浴中,在浸没之间有洗涤和/或退火步骤。
在一些实施方式中,基质玻璃或微晶玻璃可通过在浸没于约430℃~ 470℃的温度的熔融Na盐(如NaNO 3)的盐浴中约6~20小时来进行离子交换,优选温度范围为435℃~460℃,优选时间范围为8~13小时。在这种实施方式中,Na离子置换基质玻璃或微晶玻璃中的部分Li离子,从而形成表面压缩层且呈现高机械性能。在一些实施方式中,基质玻璃或微晶玻璃可通过在浸没于约400℃~450℃的温度下熔融K盐(如KNO 3)的盐浴中1~8小时来进行离子交换,优选时间范围为2~4小时。
在一些实施方式中,还有向基质玻璃或微晶玻璃的表层注入离子的离子注入法,以及对基质玻璃或微晶玻璃进行加热,然后快速冷却的热强化法。
本发明微晶玻璃和/或微晶玻璃制品和/或基质玻璃各项性能指标采用以下方法测试:
[雾度]
采用雾度测试仪EEL57D,以1mm以下的样品制备,以GB2410-80为标准进行测试。
[晶粒尺寸]
利用SEM扫描电镜进行测定,微晶玻璃通过在HF酸中进行表面处理,再对微晶玻璃表面进行喷金,在SEM扫描电镜下进行表面扫描,确定其晶粒的大小。
[光透过率]
本文所述的光透过率均为外部透过率,有时候简称透过率。
将样品加工成1mm以下并进行相对面平行抛光,利用日立U-41000形分光光度计测定400~800nm的平均光透过率。
将样品加工成1mm以下并进行相对面平行抛光,利用日立U-41000形分光光度计测定550nm的光透过率。
[结晶度]
将XRD衍射峰与数据库图谱进行对比,结晶度是通过计算结晶相衍射强度在整体图谱强度中所占比例所得,并且通过使用纯石英晶体进行内部标 定。
[表面应力]和[离子交换层深度]
利用玻璃表面应力仪FSM-6000LEUV进行表面应力测定。
利用玻璃表面应力仪SLP-2000进行离子交换层深度测定。
作为测定条件以样品的折射率为1.54、光学弹性常数为25.3[(nm/cm)/Mpa]进行计算。
[落球试验高度]
将150×57×0.55mm的微晶玻璃制品样品放置在玻璃承载夹具上,使132g的钢球从规定高度落下,样品不发生断裂而能够承受的冲击的最大落球试验高度。具体地说,试验从落球试验高度800mm开始实施,在不发生断裂的情况下,通过850mm、900mm、950mm、1000mm及以上依次改变高度。对于具有“落球试验高度”的实施例,以微晶玻璃制品为试验对象。在实施例中记录为1000mm的试验数据,表示即使从1000mm的高度使钢球落下微晶玻璃制品也不发生断裂而承受了冲击。本发明中落球试验高度有时候简称落球高度。
[本体落球高度]
将150×57×0.55mm的微晶玻璃样品放置在玻璃承载夹具上,使32g的钢球从规定高度落下,样品不发生断裂而能够承受的冲击的最大落球试验高度即为本体落球高度。具体地说,试验从落球试验高度500mm开始实施,在不发生断裂的情况下,通过550mm、600mm、650mm、700mm及以上依次改变高度。对于具有“本体落球高度”的实施例,以微晶玻璃为试验对象。在实施例中记录为1000mm的试验数据,表示即使从1000mm的高度使钢球落下微晶玻璃也不发生断裂而承受了冲击。
[断裂韧性]
使用直接测量压痕扩展裂纹尺寸的方法,试样规格为2mm×4mm×20mm,经过倒角、磨平和抛光,试样制备完成后,用维氏硬度压头在试样上加49N的力并维持30s的时间,打出压痕后,用三点弯曲的方法测定其断裂强度。
[四点弯曲强度]
采用微机控制电子万能试验机CMT6502,样品规格为1mm以下厚度,以ASTM C 158-2002为标准进行测试。
样品厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
[维氏硬度]
用相对面夹角为136°的金刚石四角锥压头在试验面上压入金字塔形状的凹陷时的负荷(N)除以通过凹陷的长度计算出的表面积(mm 2)的值表示。使试验负荷为100(N)、保持时间为15(秒)进行。本发明中有时候将维氏硬度简称为硬度。
[∣B∣值]
使用美能达CM-700d进行B值检测。用配套校正长筒和短筒分别进行仪器零位校准和白板校准,校准后用长筒再进行对空测试,判定仪器稳定校准可靠性(B≤0.05),仪器校正合格后将产品放置在零位长筒上进行测试。
∣B∣值是B值的绝对值。
[热膨胀系数]
热膨胀系数(α 20℃-120℃)按照GB/T7962.16-2010测试方法进行测试。
[折射率]
折射率(nd)按照GB/T7962.1-2010方法测试。
本发明微晶玻璃制品具有以下性能:
1)在一些实施方式中,微晶玻璃制品的表面应力为600MPa以上,优选为650MPa以上,更优选为700MPa以上。
2)在一些实施方式中,微晶玻璃制品的四点弯曲强度为600MPa以上,优选为650MPa以上,更优选为700MPa以上。
3)在一些实施方式中,微晶玻璃制品的离子交换层深度为20μm以上,优选为30μm以上,更优选40μm以上。
4)在一些实施方式中,微晶玻璃制品的落球试验高度为1300mm以上,优选为1400mm以上,更优选为1500mm以上。
5)在一些实施方式中,微晶玻璃制品的断裂韧性为1MPa·m 1/2以上,优选为1.1MPa·m 1/2以上,更优选为1.2MPa·m 1/2以上。
6)在一些实施方式中,微晶玻璃制品的维氏硬度(H v)为700kgf/mm 2以上,优选为720kgf/mm 2以上,更优选为730kgf/mm 2以上。
7)在一些实施方式中,微晶玻璃制品的结晶度为50%以上,优选为60%以上,更优选为70%以上。
8)在一些实施方式中,微晶玻璃制品的晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
9)在一些实施方式中,1mm以下厚度的微晶玻璃制品的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
10)在一些实施方式中,1mm以下厚度的微晶玻璃制品,400~800nm波长的平均透过率89%以上。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
11)在一些实施方式中,1mm以下厚度的微晶玻璃制品,550nm波长的透过率为91%以上。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
12)在一些实施方式中,1mm以下厚度的微晶玻璃制品,400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
本发明微晶玻璃具有以下性能:
1)在一些实施方式中,微晶玻璃的结晶度为50%以上,优选为60%以上,更优选为70%以上。
2)在一些实施方式中,微晶玻璃的晶粒尺寸为50nm以下,优选为40nm以下,优选为30nm以下。
3)在一些实施方式中,1mm以下厚度的微晶玻璃的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
4)在一些实施方式中,1mm以下厚度的微晶玻璃,400~800nm波长的平均透过率89%以上。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
5)在一些实施方式中,1mm以下厚度的微晶玻璃,550nm波长的透过率为91%以上。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
6)在一些实施方式中,微晶玻璃本体落球高度为1000mm以上,优选为1100mm以上,更优选为1200mm以上。
7)在一些实施方式中,1mm以下厚度的微晶玻璃,400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。该厚度优选为0.2~1mm,更优选为0.3~0.9mm,进一步优选为0.5~0.8mm,更进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
8)在一些实施方式中,微晶玻璃的维氏硬度(H v)为650kgf/mm 2以上,优选为680kgf/mm 2以上,更优选为700kgf/mm 2以上。
9)在一些实施方式中,微晶玻璃的热膨胀系数(α 20℃-120℃)为75~95×10 -7/K。
10)在一些实施方式中,微晶玻璃的折射率(n d)为1.5700~1.5800。
本发明基质玻璃具有以下性能:
1)在一些实施方式中,基质玻璃的热膨胀系数(α 20℃-120℃)为50×10 -7/K~70×10 -7/K。
2)在一些实施方式中,基质玻璃的折射率(n d)为1.5600~1.5700。
本发明的微晶玻璃、微晶玻璃制品和基质玻璃由于具有上述优异的性能,可广泛制作成玻璃盖板或玻璃元器件;同时,本发明微晶玻璃、微晶玻璃制品和基质玻璃应用于电子设备或显示设备中,如手机、手表、电脑、触摸显示屏等,用于制造移动电话、智能电话、平板电脑、笔记本电脑、PDA、电视机、个人电脑、MTA机器或工业显示器的防护玻璃,或用于制造触摸屏、防护窗、汽车车窗、火车车窗、航空机械窗、触摸屏防护玻璃,或用于制造硬盘基材或太阳能电池基材,或用于制造白色家电,如用于制造冰箱部件或厨具。
实施例
为了进一步清楚地阐释和说明本发明的技术方案,提供以下的非限制性实施例。本发明实施例经过诸多努力以确保数值(例如数量、温度等)的精确性,但是必须考虑到存在一些误差和偏差。组成自身基于氧化物以重量%给出,且已标准化成100%。
<基质玻璃实施例>
本实施例采用上述基质玻璃的制造方法得到具有表1~表4所示的组成的基质玻璃。另外,通过本发明所述的测试方法测定各基质玻璃的特性,并将测定结果表示在表1~表4中。
表1.
组分(wt%) 1# 2# 3# 4# 5# 6# 7# 8# 9#
SiO 2 53 54 55 56 57 58 59 60 61
Al 2O 3 11.5 11 10 11 11 8 8 8 9
Li 2O 13 13.5 15 14.5 15 16 18 13 13
Na 2O 1 1 2 1 2 1 1 1 3
P 2O 5 4 4 4 4 5 6 4 5 4
ZrO 2 10 11 8.5 8 7 8 7 10 7
Y 2O 3 6 5 4 3 3 3 3 3 3
K 2O 1 0 0 0 0 0 0 0 0
B 2O 3 0 0 0 2 0 0 0 0 0
ZnO 0 0 0 0 0 0 0 0 0
MgO 0 0 1 0 0 0 0 0 0
SrO 0 0 0 0 0 0 0 0 0
BaO 0 0 0 0 0 0 0 0 0
TiO 2 0 0 0 0 0 0 0 0 0
CaO 0 0 0 0 0 0 0 0 0
La 2O 3 0 0 0 0 0 0 0 0 0
Gd 2O 3 0 0 0 0 0 0 0 0 0
Yb 2O 3 0 0 0 0 0 0 0 0 0
Sb 2O 3 0.5 0.5 0.5 0.5 0 0 0 0 0
合计 100 100 100 100 100 100 100 100 100
Y 2O 3/ZrO 2 0.6 0.5 0.5 0.4 0.4 0.4 0.4 0.3 0.4
(Li 2O+ZrO 2+P 2O 5)/Y 2O 3 4.5 5.7 6.9 8.8 9.0 10.0 9.7 9.3 8.0
Al 2O 3/(Li 2O+ZrO 2+P 2O 5) 0.43 0.39 0.36 0.42 0.41 0.27 0.28 0.29 0.38
Na 2O/Y 2O 3 0.2 0.2 0.5 0.3 0.7 0.3 0.3 0.3 1.0
Y 2O 3/(Al 2O 3+SiO 2) 0.09 0.08 0.06 0.04 0.04 0.05 0.04 0.04 0.04
α 20℃-120℃(×10 -7/K) 62 65 65 63 63 68 68 65 68
n d 1.5629 1.5615 1.5601 1.5659 1.5633 1.5619 1.5689 1.5642 1.5677
表2.
组分(wt%) 10# 11# 12# 13# 14# 15# 16# 17# 18#
SiO 2 62 63 53 53 50 51 52 64 65
Al 2O 3 8 8 12 9 15 8 14 8 8
Li 2O 14.5 13 20 15 13 22 15 13 13
Na 2O 1 1 1 1 0 1 4 0 0
P 2O 5 4 5 4 7 9 4 4 4 4
ZrO 2 7 7 7 12 6 12 8 7 8
Y 2O 3 3 3 3 3 7 2 3 1 1
K 2O 0 0 0 0 0 0 0 0 0
B 2O 3 0 0 0 0 0 0 0 3 0
ZnO 0 0 0 0 0 0 0 0 1
MgO 0 0 0 0 0 0 0 0 0
SrO 0 0 0 0 0 0 0 0 0
BaO 0 0 0 0 0 0 0 0 0
TiO 2 0 0 0 0 0 0 0 0 0
CaO 0 0 0 0 0 0 0 0 0
La 2O 3 0 0 0 0 0 0 0 0 0
Gd 2O 3 0 0 0 0 0 0 0 0 0
Yb 2O 3 0 0 0 0 0 0 0 0 0
Sb 2O 3 0.5 0 0 0 0 0 0 0 0
合计 100 100 100 100 100 100 100 100 100
Y 2O 3/ZrO 2 0.4 0.4 0.4 0.3 1.2 0.2 0.4 0.1 0.1
(Li 2O+ZrO 2+P 2O 5)/Y 2O 3 8.5 8.3 10.3 11.3 4.0 19.0 9.0 24.0 25.0
Al 2O 3/(Li 2O+ZrO 2+P 2O 5) 0.31 0.32 0.39 0.26 0.54 0.21 0.52 0.33 0.32
Na 2O/Y 2O 3 0.3 0.3 0.3 0.3 0.0 0.5 1.3 0.0 0.0
Y 2O 3/(Al 2O 3+SiO 2) 0.04 0.04 0.05 0.05 0.11 0.03 0.05 0.01 0.01
α 20℃-120℃(×10 -7/K) 69 69 68 65 60 58 59 62 70
n d 1.5601 1.5622 1.5610 1.5612 1.5611 1.5610 1.5608 1.5602 1.5626
表3.
组分(wt%) 19# 20# 21# 22# 23# 24# 25# 26# 27#
SiO 2 54 55 55 45 46 47 48 49 66
Al 2O 3 8 8 8 10 17 16 10 10 8
Li 2O 15 15 15 25 18 18 24 23 10
Na 2O 0 4 2 0 0 0 0 0 0
P 2O 5 4 4 4 4 4 4 4 4 4
ZrO 2 9 9 9 8 9 9 9 9 9
Y 2O 3 4 3 3 8 3 3 3 3 3
K 2O 4 0 2 0 0 0 0 0 0
B 2O 3 0 0 0 0 0 0 0 0 0
ZnO 0 0 0 0 0 0 2 0 0
MgO 0 0 0 0 0 0 0 2 0
SrO 2 0 0 0 3 0 0 0 0
BaO 0 2 0 0 0 3 0 0 0
TiO 2 0 0 2 0 0 0 0 0 0
CaO 0 0 0 0 0 0 0 0 0
La 2O 3 0 0 0 0 0 0 0 0 0
Gd 2O 3 0 0 0 0 0 0 0 0 0
Yb 2O 3 0 0 0 0 0 0 0 0 0
Sb 2O 3 0 0 0 0 0 0 0 0 0
合计 100 100 100 100 100 100 100 100 100
Y 2O 3/ZrO 2 0.4 0.3 0.3 1.0 0.3 0.3 0.3 0.3 0.3
(Li 2O+ZrO 2+P 2O 5)/Y 2O 3 7.0 9.3 9.3 4.6 10.3 10.3 12.3 12.0 7.7
Al 2O 3/(Li 2O+ZrO 2+P 2O 5) 0.29 0.29 0.29 0.27 0.55 0.52 0.27 0.28 0.35
Na 2O/Y 2O 3 0.0 1.3 0.7 0.0 0.0 0.0 0.0 0.0 0.0
Y 2O 3/(Al 2O 3+SiO 2) 0.06 0.05 0.05 0.15 0.05 0.05 0.05 0.05 0.04
α 20℃-120℃(×10 -7/K) 62 70 70 53 52 52 65 64 63
n d 1.5650 1.5625 1.5608 1.5632 1.5667 1.5611 1.5632 1.5688 1.5655
表4.
组分(wt%) 28# 29# 30# 31# 32# 33# 34#
SiO 2 67 68 69 70 49 50 55
Al 2O 3 8 8 8 8 10 10 8
Li 2O 10 10 10 10 12 15 15
Na 2O 1 0 0 0 2 6 2
P 2O 5 2 2 2 2 4 4 4
ZrO 2 9 9 8 7 15 9 9
Y 2O 3 3 3 3 3 8 1 2
K 2O 0 0 0 0 0 0 5
B 2O 3 0 0 0 0 0 5 0
ZnO 0 0 0 0 0 0 0
MgO 0 0 0 0 0 0 0
SrO 0 0 0 0 0 0 0
BaO 0 0 0 0 0 0 0
TiO 2 0 0 0 0 0 0 0
CaO 0 0 0 0 0 0 0
La 2O 3 0 0 0 0 0 0 0
Gd 2O 3 0 0 0 0 0 0 0
Yb 2O 3 0 0 0 0 0 0 0
Sb 2O 3 0 0 0 0 0 0 0
合计 100 100 100 100 100 100 100
Y 2O 3/ZrO 2 0.3 0.3 0.4 0.4 0.5 0.1 0.2
(Li 2O+ZrO 2+P 2O 5)/Y 2O 3 7.0 7.0 6.7 6.3 3.9 28.0 14.0
Al 2O 3/(Li 2O+ZrO 2+P 2O 5) 0.38 0.38 0.40 0.42 0.32 0.36 0.29
Na 2O/Y 2O 3 0.3 0.0 0.0 0.0 0.3 6.0 1.0
Y 2O 3/(Al 2O 3+SiO 2) 0.04 0.04 0.04 0.04 0.14 0.02 0.03
α 20℃-120℃(×10 -7/K) 68 69 70 65 65 65 65
n d 1.5666 1.5689 1.5634 1.5641 1.5625 1.5618 1.5625
<微晶玻璃实施例>
本实施例采用上述微晶玻璃的制造方法得到具有表5~表8所示的组成的微晶玻璃。另外,通过本发明所述的测试方法测定各微晶玻璃的特性,并将测定结果表示在表5~表8中。
表5.
Figure PCTCN2021120633-appb-000001
Figure PCTCN2021120633-appb-000002
表6.
Figure PCTCN2021120633-appb-000003
Figure PCTCN2021120633-appb-000004
表7.
Figure PCTCN2021120633-appb-000005
Figure PCTCN2021120633-appb-000006
表8.
Figure PCTCN2021120633-appb-000007
Figure PCTCN2021120633-appb-000008
<微晶玻璃制品实施例>
本实施例采用上述微晶玻璃制品的制造方法得到具有表9~表12所示的组成的微晶玻璃制品。另外,通过本发明所述的测试方法测定各微晶玻璃制品的特性,并将测定结果表示在表9~表12中。
表9.
Figure PCTCN2021120633-appb-000009
Figure PCTCN2021120633-appb-000010
表10.
Figure PCTCN2021120633-appb-000011
Figure PCTCN2021120633-appb-000012
表11.
Figure PCTCN2021120633-appb-000013
Figure PCTCN2021120633-appb-000014
表12.
Figure PCTCN2021120633-appb-000015
Figure PCTCN2021120633-appb-000016

Claims (77)

  1. 微晶玻璃制品,其特征在于,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
  2. 如权利要求1所述的微晶玻璃制品,其特征在于,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或TiO 2:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  3. 如权利要求1或2所述的微晶玻璃制品,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为大于0;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
    4)Na 2O/Y 2O 3为6.0以下;
    5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
  4. 如权利要求1或2所述的微晶玻璃制品,其特征在于,其组分按重量百分比表示,含有:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或BaO:0~3%;和/或CaO:0~3%;和/或TiO 2:0~3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  5. 如权利要求1或2所述的微晶玻璃制品,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为0.1~1.0;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
    4)Na 2O/Y 2O 3为0.1~5.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
  6. 如权利要求1或2所述的微晶玻璃制品,其特征在于,其组分按重量百分比表示,含有:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或Y 2O 3:2~6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  7. 如权利要求1或2所述的微晶玻璃制品,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为0.2~0.6;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
    4)Na 2O/Y 2O 3为0.3~2.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
  8. 如权利要求1或2所述的微晶玻璃制品,其特征在于,其组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
  9. 如权利要求1或2所述的微晶玻璃制品,其特征在于,所述微晶玻璃制品的晶相含有一硅酸锂;和/或磷酸锂。
  10. 如权利要求1或2所述的微晶玻璃制品,其特征在于,所述微晶玻 璃制品的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃制品的10~63.5%,优选为15~55%。
  11. 如权利要求1或2所述的微晶玻璃制品,其特征在于,所述微晶玻璃制品中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃制品的重量百分比为3~15%,优选为5~12%。
  12. 如权利要求1或2所述的微晶玻璃制品,其特征在于,所述微晶玻璃制品的表面应力为600MPa以上,优选为650MPa以上,更优选为700MPa以上;和/或四点弯曲强度为600MPa以上,优选为650MPa以上,更优选为700MPa以上;和/或离子交换层深度为20μm以上,优选为30μm以上,更优选40μm以上;和/或落球试验高度为1300mm以上,优选为1400mm以上,更优选为1500mm以上;和/或断裂韧性为1MPa·m 1/2以上,优选为1.1MPa·m 1/2以上,更优选为1.2MPa·m 1/2以上;和/或维氏硬度为700kgf/mm 2以上,优选为720kgf/mm 2以上,更优选为730kgf/mm 2以上。
  13. 如权利要求1或2所述的微晶玻璃制品,其特征在于,所述微晶玻璃制品的结晶度为50%以上,优选为60%以上,更优选为70%以上;和/或晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
  14. 如权利要求1或2所述的微晶玻璃制品,其特征在于,1mm以下厚度的微晶玻璃制品的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下;和/或400~800nm波长的平均透过率89%以上;和/或550nm波长的透过率为91%以上;和/或400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
  15. 如权利要求14所述的微晶玻璃制品,其特征在于,所述微晶玻璃制品的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
  16. 如权利要求1或2所述的微晶玻璃制品,其特征在于,所述微晶玻璃制品含有着色剂。
  17. 如权利要求16所述的微晶玻璃制品,其特征在于,所述着色剂按 重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
  18. 微晶玻璃,其特征在于,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
  19. 如权利要求18所述的微晶玻璃,其特征在于,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或TiO 2:0~5%;和/或CaO:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  20. 如权利要求18或19所述的微晶玻璃,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为大于0;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9;
    4)Na 2O/Y 2O 3为6.0以下;
    5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15。
  21. 如权利要求18或19所述的微晶玻璃,其特征在于,其组分按重量百分比表示,含有:SiO 2:50~65%;和/或Al 2O 3:8~15%;和/或Li 2O:13~22%;和/或ZrO 2:6~12%;和/或P 2O 5:3.5~9%;和/或K 2O:0~4%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%;和/或Y 2O 3:1~7%;和/或SrO:0~3%;和/或TiO 2:0~3%;和/或BaO:0~3%;和/或CaO:0~3%;和/或B 2O 3:0~3%;和/或Ln 2O 3:0~4%;和/或澄清剂:0~1%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、 SnO、CeO 2、F、Cl和Br中的一种或多种。
  22. 如权利要求18或19所述的微晶玻璃,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为0.1~1.0;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6;
    4)Na 2O/Y 2O 3为0.1~5.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12。
  23. 如权利要求18或19所述的微晶玻璃,其特征在于,其组分按重量百分比表示,含有:SiO 2:53~63%;和/或Al 2O 3:8~12%;和/或Li 2O:14~21%;和/或ZrO 2:7~12%;和/或P 2O 5:4~8%;和/或K 2O:0~2%;和/或Y 2O 3:2~6%;和/或B 2O 3:0~2%;和/或Na 2O:1.5~4%;和/或SrO:0~1%;和/或TiO 2:0~1%;和/或BaO:0~1%;和/或CaO:0~1%;和/或Ln 2O 3:0~3%;和/或澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  24. 如权利要求18或19所述的微晶玻璃,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为0.2~0.6;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
    4)Na 2O/Y 2O 3为0.3~2.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
  25. 如权利要求18或19所述的微晶玻璃,其特征在于,其组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
  26. 如权利要求18或19所述的微晶玻璃,其特征在于,所述微晶玻璃的晶相含有一硅酸锂;和/或磷酸锂。
  27. 如权利要求18或19所述的微晶玻璃,其特征在于,所述微晶玻璃的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃的10~63.5%,优选为15~55%。
  28. 如权利要求18或19所述的微晶玻璃,其特征在于,所述微晶玻璃中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃的重量百分比为3~15%,优选为5~12%。
  29. 如权利要求18或19所述的微晶玻璃,其特征在于,所述微晶玻璃的结晶度为50%以上,优选为60%以上,更优选为70%以上;和/或晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下;和/或热膨胀系数为75~95×10 -7/K;和/或折射率为1.5700~1.5800。
  30. 如权利要求18或19所述的微晶玻璃,其特征在于,所述微晶玻璃的本体落球高度为1000mm以上,优选为1100mm以上,更优选为1200mm以上;和/或维氏硬度为650kgf/mm 2以上,优选为680kgf/mm 2以上,更优选为700kgf/mm 2以上。
  31. 如权利要求18或19所述的微晶玻璃,其特征在于,1mm以下厚度的微晶玻璃的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下;和/或400~800nm波长的平均透过率89%以上;和/或550nm波长的透过率为91%以上;和/或400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
  32. 如权利要求31所述的微晶玻璃,其特征在于,所述微晶玻璃的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
  33. 如权利要求18或19所述的微晶玻璃,其特征在于,所述微晶玻璃含有着色剂。
  34. 如权利要求33所述的微晶玻璃,其特征在于,所述着色剂按重量 百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
  35. 基质玻璃,其特征在于,其组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%。
  36. 如权利要求35所述的基质玻璃,其特征在于,其组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或TiO 2:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  37. 如权利要求35或36所述的基质玻璃,其特征在于,其组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为大于0,优选Y 2O 3/ZrO 2为0.1~1.0,更优选Y 2O 3/ZrO 2为0.2~0.6;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0,优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0,更优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9,优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6,更优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
    4)Na 2O/Y 2O 3为6.0以下,优选Na 2O/Y 2O 3为0.1~5.0,更优选Na 2O/Y 2O 3为0.3~2.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15,优选Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12,更优选Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
  38. 如权利要求35或36所述的基质玻璃,其特征在于,其组分按重量百分比表示,含有:SiO 2:50~65%,优选SiO 2:53~63%;和/或Al 2O 3: 8~15%,优选Al 2O 3:8~12%;和/或Li 2O:13~22%,优选Li 2O:14~21%;和/或ZrO 2:6~12%,优选ZrO 2:7~12%;和/或P 2O 5:3.5~9%,优选P 2O 5:4~8%;和/或K 2O:0~4%,优选K 2O:0~2%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%,优选Na 2O:1.5~4%;和/或Y 2O 3:1~7%,优选Y 2O 3:2~6%;和/或SrO:0~3%,优选SrO:0~1%;和/或BaO:0~3%,优选BaO:0~1%;和/或TiO 2:0~3%,优选TiO 2:0~1%;和/或CaO:0~3%,优选CaO:0~1%;和/或B 2O 3:0~3%,优选B 2O 3:0~2%;和/或Ln 2O 3:0~4%,优选Ln 2O 3:0~3%;和/或澄清剂:0~1%,优选澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  39. 如权利要求35或36所述的基质玻璃,其特征在于,其组分中不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
  40. 如权利要求35或36所述的基质玻璃,其特征在于,所述基质玻璃的热膨胀系数为50×10 -7/K~70×10 -7/K;和/或折射率为1.5600~1.5700。
  41. 如权利要求35或36所述的基质玻璃,其特征在于,所述基质玻璃含有着色剂。
  42. 如权利要求41所述的基质玻璃,其特征在于,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
  43. 玻璃盖板,其特征在于,含有权利要求1~17任一权利要求所述的微晶玻璃制品,和/或权利要求18~34任一权利要求所述的微晶玻璃,和/或权利要求35~42任一权利要求所述的基质玻璃。
  44. 玻璃元器件,其特征在于,含有权利要求1~17任一权利要求所述的微晶玻璃制品,和/或权利要求18~34任一权利要求所述的微晶玻璃,和/或权利要求35~42任一权利要求所述的基质玻璃。
  45. 显示设备,其特征在于,含有权利要求1~17任一权利要求所述的微晶玻璃制品,和/或权利要求18~34任一权利要求所述的微晶玻璃,和/或权利要求35~42任一权利要求所述的基质玻璃,和/或权利要求43所述的玻璃盖板,和/或权利要求44所述的玻璃元器件。
  46. 电子设备,其特征在于,含有权利要求1~17任一权利要求所述的微晶玻璃制品,和/或权利要求18~34任一权利要求所述的微晶玻璃,和/或权利要求35~42任一权利要求所述的基质玻璃,和/或权利要求43所述的玻璃盖板,和/或权利要求44所述的玻璃元器件。
  47. 微晶玻璃制品的制造方法,其特征在于,所述方法包括以下步骤:
    形成基质玻璃,所述基质玻璃的组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;
    对所述基质玻璃通过晶化工艺形成微晶玻璃,再对所述微晶玻璃通过化学强化工艺形成微晶玻璃制品。
  48. 如权利要求47所述的微晶玻璃制品的制造方法,其特征在于,所述基质玻璃的组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或TiO 2:0~5%;和/或BaO:0~5%;和/或CaO:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  49. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为大于0,优选Y 2O 3/ZrO 2为0.1~1.0,更优选Y 2O 3/ZrO 2为0.2~0.6;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0,优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0,更优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9,优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6,更优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
    4)Na 2O/Y 2O 3为6.0以下,优选Na 2O/Y 2O 3为0.1~5.0,更优选Na 2O/Y 2O 3为0.3~2.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15,优选Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12,更优选Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
  50. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述基质玻璃的组分按重量百分比表示,含有:SiO 2:50~65%,优选SiO 2:53~63%;和/或Al 2O 3:8~15%,优选Al 2O 3:8~12%;和/或Li 2O:13~22%,优选Li 2O:14~21%;和/或ZrO 2:6~12%,优选ZrO 2:7~12%;和/或P 2O 5:3.5~9%,优选P 2O 5:4~8%;和/或K 2O:0~4%,优选K 2O:0~2%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%,优选Na 2O:1.5~4%;和/或Y 2O 3:1~7%,优选Y 2O 3:2~6%;和/或SrO:0~3%,优选SrO:0~1%;和/或BaO:0~3%,优选BaO:0~1%;和/或TiO 2:0~3%,优选TiO 2:0~1%;和/或CaO:0~3%,优选CaO:0~1%;和/或B 2O 3:0~3%,优选B 2O 3:0~2%;和/或Ln 2O 3:0~4%,优选Ln 2O 3:0~3%;和/或澄清剂:0~1%,优选澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  51. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述基质玻璃不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
  52. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述基质玻璃含有着色剂,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
  53. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述晶化工艺包括以下步骤:升温至规定的晶化处理温度,在达到晶化处理温度之后,将其温度保持一定的时间,然后再进行降温,该晶化处理温度为600~750℃,优选为650~700℃,在晶化处理温度下的保持时间为0~8小时,优选为1~6小时。
  54. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述晶化工艺包括以下步骤:在第1温度下进行成核工艺的处理,然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。
  55. 如权利要求54所述的微晶玻璃制品的制造方法,其特征在于,所述晶化工艺包括以下步骤:第1温度为470~630℃,第2温度为650~750℃;在第1温度下的保持时间为0~24小时,优选为2~15小时;在第2温度下的保持时间为0~10小时,优选为0.5~6小时。
  56. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述化学强化工艺包括:微晶玻璃浸没于430℃~470℃的温度的熔融Na盐的盐浴中6~20小时,优选温度范围为435℃~460℃,优选时间范围为8~13小时;和/或微晶玻璃浸没于400℃~450℃的温度下熔融K盐的盐浴中1~8小时,优选时间范围为2~4小时。
  57. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述微晶玻璃制品的晶相含有一硅酸锂;和/或磷酸锂。
  58. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述微晶玻璃制品的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃制品的10~63.5%,优选为15~55%。
  59. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述微晶玻璃制品中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃制品的重量百分比为3~15%,优选为5~12%。
  60. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,所述微晶玻璃制品的表面应力为600MPa以上,优选为650MPa以上,更优选为700MPa以上;和/或四点弯曲强度为600MPa以上,优选为650MPa以上,更优选为700MPa以上;和/或离子交换层深度为20μm以上,优选为30μm以上,更优选40μm以上;和/或落球试验高度为1300mm以上,优选为1400mm以上,更优选为1500mm以上;和/或断裂韧性为1MPa·m 1/2以上,优选为1.1MPa·m 1/2以上,更优选为1.2MPa·m 1/2以上;和/或维氏硬度为700kgf/mm 2以上,优选为720kgf/mm 2以上,更优选为730kgf/mm 2以上;和/或结晶度为50%以上,优选为60%以上,更优选为70%以上;和/或晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下。
  61. 如权利要求47或48所述的微晶玻璃制品的制造方法,其特征在于,1mm以下厚度的微晶玻璃制品的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下;和/或400~800nm波长的平均透过率89%以上;和/或550nm波长的透过率为91%以上;和/或400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
  62. 如权利要求61所述的微晶玻璃制品的制造方法,其特征在于,所述微晶玻璃制品的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
  63. 微晶玻璃的制造方法,其特征在于,所述方法包括以下步骤:
    形成基质玻璃,所述基质玻璃的组分按重量百分比表示,含有:SiO 2:45~70%;Al 2O 3:8~18%;Li 2O:10~25%;ZrO 2:5~15%;P 2O 5:2~10%;Y 2O 3:大于0但小于或等于8%;
    对所述基质玻璃通过晶化工艺形成微晶玻璃。
  64. 如权利要求63所述的微晶玻璃的制造方法,其特征在于,所述基 质玻璃的组分按重量百分比表示,还含有:K 2O:0~5%;和/或MgO:0~2%;和/或ZnO:0~2%;和/或Na 2O:0~6%;和/或SrO:0~5%;和/或BaO:0~5%;和/或TiO 2:0~5%;和/或CaO:0~5%;和/或B 2O 3:0~5%;和/或Ln 2O 3:0~5%;和/或澄清剂:0~2%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  65. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述基质玻璃的组分按重量百分比表示,各组分含量满足以下5种情形中的一种以上:
    1)Y 2O 3/ZrO 2为大于0,优选Y 2O 3/ZrO 2为0.1~1.0,更优选Y 2O 3/ZrO 2为0.2~0.6;
    2)(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为2.5~50.0,优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为3.0~40.0,更优选(Li 2O+ZrO 2+P 2O 5)/Y 2O 3为4.0~21.0;
    3)Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.16~0.9,优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.18~0.6,更优选Al 2O 3/(Li 2O+ZrO 2+P 2O 5)为0.19~0.5;
    4)Na 2O/Y 2O 3为6.0以下,优选Na 2O/Y 2O 3为0.1~5.0,更优选Na 2O/Y 2O 3为0.3~2.0;
    5)Y 2O 3/(Al 2O 3+SiO 2)为大于0但小于或等于0.15,优选Y 2O 3/(Al 2O 3+SiO 2)为0.01~0.12,更优选Y 2O 3/(Al 2O 3+SiO 2)为0.03~0.09。
  66. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述基质玻璃的组分按重量百分比表示,含有:SiO 2:50~65%,优选SiO 2:53~63%;和/或Al 2O 3:8~15%,优选Al 2O 3:8~12%;和/或Li 2O:13~22%,优选Li 2O:14~21%;和/或ZrO 2:6~12%,优选ZrO 2:7~12%;和/或P 2O 5:3.5~9%,优选P 2O 5:4~8%;和/或K 2O:0~4%,优选K 2O:0~2%;和/或MgO:0~1%;和/或ZnO:0~1%;和/或Na 2O:1~5%,优选Na 2O:1.5~4%;和/或Y 2O 3:1~7%,优选Y 2O 3:2~6%;和/或SrO:0~3%,优选SrO:0~1%;和/或BaO:0~3%,优选BaO:0~1%;和/或CaO:0~3%,优选CaO:0~1%;和/或TiO 2:0~3%,优选TiO 2:0~1%;和/或B 2O 3:0~3%,优选 B 2O 3:0~2%;和/或Ln 2O 3:0~4%,优选Ln 2O 3:0~3%;和/或澄清剂:0~1%,优选澄清剂:0~0.5%,其中所述Ln 2O 3为La 2O 3、Gd 2O 3、Yb 2O 3中的一种或多种,澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2、F、Cl和Br中的一种或多种。
  67. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述基质玻璃不含有SrO;和/或不含有BaO;和/或不含有CaO;和/或不含有ZnO;和/或不含有PbO;和/或不含有As 2O 3;和/或不含有TiO 2;和/或不含有B 2O 3;和/或不含有Ln 2O 3;和/或不含有F;和/或不含有Ta 2O 5
  68. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述基质玻璃含有着色剂,所述着色剂按重量百分比表示,含有:NiO:0~4%;和/或Ni 2O 3:0~4%;和/或CoO:0~2%;和/或Co 2O 3:0~2%;和/或Fe 2O 3:0~7%;和/或MnO 2:0~4%;和/或Er 2O 3:0~8%;和/或Nd 2O 3:0~8%;和/或Cu 2O:0~4%;和/或Pr 2O 3:0~8%;和/或CeO 2:0~4%。
  69. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述晶化工艺包括以下步骤:升温至规定的晶化处理温度,在达到晶化处理温度之后,将其温度保持一定的时间,然后再进行降温,该晶化处理温度为600~750℃,优选为650~700℃,在晶化处理温度下的保持时间为0~8小时,优选为1~6小时。
  70. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述晶化工艺包括以下步骤:在第1温度下进行成核工艺的处理,然后在比成核工艺温度高的第2温度下进行晶体生长工艺的处理。
  71. 如权利要求70所述的微晶玻璃的制造方法,其特征在于,所述晶化工艺包括以下步骤:第1温度为470~630℃,第2温度为650~750℃;在第1温度下的保持时间为0~24小时,优选为2~15小时;在第2温度下的保持时间为0~10小时,优选为0.5~6小时。
  72. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述微晶玻璃的晶相含有一硅酸锂;和/或磷酸锂。
  73. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所 述微晶玻璃的晶相主要含有一硅酸锂,一硅酸锂具有比其他晶相更高的重量百分数,一硅酸锂占微晶玻璃的10~63.5%,优选为15~55%。
  74. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述微晶玻璃中含有磷酸锂晶相,磷酸锂晶相占微晶玻璃的重量百分比为3~15%,优选为5~12%。
  75. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,所述微晶玻璃的结晶度为50%以上,优选为60%以上,更优选为70%以上;和/或晶粒尺寸为50nm以下,优选为40nm以下,更优选为30nm以下;和/或热膨胀系数为75~95×10 -7/K;和/或折射率为1.5700~1.5800;和/或本体落球高度为1000mm以上,优选为1100mm以上,更优选为1200mm以上;和/或维氏硬度为650kgf/mm 2以上,优选为680kgf/mm 2以上,更优选为700kgf/mm 2以上。
  76. 如权利要求63或64所述的微晶玻璃的制造方法,其特征在于,1mm以下厚度的微晶玻璃的雾度为0.15%以下,优选为0.12%以下,更优选为0.1%以下;和/或400~800nm波长的平均透过率89%以上;和/或550nm波长的透过率为91%以上;和/或400~800nm的平均光∣B∣值为0.6以下,优选为0.55以下,更优选为0.5以下。
  77. 如权利要求76所述的微晶玻璃的制造方法,其特征在于,所述微晶玻璃的厚度为0.2~1mm,优选为0.3~0.9mm,更优选为0.5~0.8mm,进一步优选为0.55mm或0.6mm或0.68mm或0.72mm或0.75mm。
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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111099825B (zh) * 2018-10-26 2021-02-02 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN113754287A (zh) * 2020-12-31 2021-12-07 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN112939469B (zh) * 2021-03-23 2022-03-08 成都光明光电股份有限公司 微晶玻璃和微晶玻璃制品
CN115959831A (zh) * 2021-07-08 2023-04-14 荣耀终端有限公司 素微晶玻璃、化学强化微晶玻璃及其制备方法与应用
CN117326802A (zh) * 2022-07-01 2024-01-02 常熟佳合显示科技有限公司 一种陶瓷材料及其制备方法和应用
CN115893849A (zh) * 2022-10-26 2023-04-04 彩虹集团(邵阳)特种玻璃有限公司 一种微晶玻璃、微晶玻璃前驱体及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080268295A1 (en) * 2007-04-27 2008-10-30 Ohara Inc. Glass-ceramics
CN109320091A (zh) * 2018-10-26 2019-02-12 成都创客之家科技有限公司 电子设备盖板用微晶玻璃制品和微晶玻璃
CN110482866A (zh) * 2019-08-21 2019-11-22 成都光明光电股份有限公司 微晶玻璃制品、微晶玻璃及其制造方法
CN111099828A (zh) * 2018-10-26 2020-05-05 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN111807706A (zh) * 2020-06-29 2020-10-23 成都光明光电股份有限公司 微晶玻璃和微晶玻璃制品
US20200346969A1 (en) * 2018-02-27 2020-11-05 AGC Inc. Crystallized glass of three-dimensional shape, chemically strengthened glass of three-dimensional shape, and method for producing crystallized glass of three-dimensional shape and chemically strengthened glass of three-dimensional shape
CN112592065A (zh) * 2020-12-31 2021-04-02 李群 微晶玻璃、微晶玻璃制品及其制造方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002203311A (ja) * 2000-11-09 2002-07-19 Minolta Co Ltd 情報記録媒体用の結晶化ガラス基板
US6677046B2 (en) * 2001-03-27 2004-01-13 Hoya Corporation Glass ceramic
CN1944305A (zh) * 2005-10-07 2007-04-11 株式会社小原 无机组合物
JP4467597B2 (ja) * 2007-04-06 2010-05-26 株式会社オハラ 無機組成物物品
US20090258778A1 (en) * 2008-04-11 2009-10-15 James R., Glidewell Dental Ceramics, Inc. Lithium silicate glass ceramic for fabrication of dental appliances
CN105601115A (zh) * 2014-11-19 2016-05-25 成都光明光电股份有限公司 以尖晶石为主的微晶玻璃及其制备方法
CN111348835A (zh) * 2014-11-19 2020-06-30 成都光明光电股份有限公司 高硬度透明微晶玻璃及其制备方法
CN105731791B (zh) * 2016-03-07 2021-01-15 东旭光电科技股份有限公司 一种玻璃用组合物和高透过率玻璃及其制备方法和应用
DE102016119934A1 (de) * 2016-10-19 2018-05-03 Degudent Gmbh Verfahren zur Herstellung eines Rohlings, Rohling sowie eine dentale Restauration
CN111099829B (zh) * 2018-10-26 2021-03-09 成都光明光电股份有限公司 透明微晶玻璃、微晶玻璃制品及其制备方法
CN111099825B (zh) * 2018-10-26 2021-02-02 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN111936439B (zh) * 2018-10-26 2022-07-29 成都光明光电股份有限公司 电子设备盖板用微晶玻璃制品和微晶玻璃
JP7347449B2 (ja) * 2019-02-08 2023-09-20 Agc株式会社 結晶化ガラス、化学強化ガラスおよび半導体支持基板
CN110510879A (zh) * 2019-08-21 2019-11-29 成都光明光电股份有限公司 微晶玻璃制品、微晶玻璃及其制造方法
CN110436788A (zh) * 2019-08-21 2019-11-12 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN114907014B (zh) * 2020-06-29 2023-09-29 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN111943514B (zh) * 2020-06-29 2022-04-05 成都光明光电股份有限公司 玻璃陶瓷和玻璃陶瓷制品

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080268295A1 (en) * 2007-04-27 2008-10-30 Ohara Inc. Glass-ceramics
US20200346969A1 (en) * 2018-02-27 2020-11-05 AGC Inc. Crystallized glass of three-dimensional shape, chemically strengthened glass of three-dimensional shape, and method for producing crystallized glass of three-dimensional shape and chemically strengthened glass of three-dimensional shape
CN109320091A (zh) * 2018-10-26 2019-02-12 成都创客之家科技有限公司 电子设备盖板用微晶玻璃制品和微晶玻璃
CN111099828A (zh) * 2018-10-26 2020-05-05 成都光明光电股份有限公司 微晶玻璃、微晶玻璃制品及其制造方法
CN110482866A (zh) * 2019-08-21 2019-11-22 成都光明光电股份有限公司 微晶玻璃制品、微晶玻璃及其制造方法
CN111807706A (zh) * 2020-06-29 2020-10-23 成都光明光电股份有限公司 微晶玻璃和微晶玻璃制品
CN112592065A (zh) * 2020-12-31 2021-04-02 李群 微晶玻璃、微晶玻璃制品及其制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4197979A4 *

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