CN111777327A - Glass composition, glass article and method for producing same - Google Patents

Glass composition, glass article and method for producing same Download PDF

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Publication number
CN111777327A
CN111777327A CN202010697508.7A CN202010697508A CN111777327A CN 111777327 A CN111777327 A CN 111777327A CN 202010697508 A CN202010697508 A CN 202010697508A CN 111777327 A CN111777327 A CN 111777327A
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percent
glass
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毛露路
匡波
李赛
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides a glass composition, which comprises the following components in percentage by weight: SiO 22：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O: 5 to 40 percent. Through reasonable component design, the glass composition can realize low transmittance of ultraviolet light and visible light and near transmittanceHigh infrared transmittance.

Description

Glass composition, glass article and method for producing same
Technical Field
The invention relates to a glass composition, in particular to a glass composition with low ultraviolet and visible light transmittance and high near-infrared transmittance of 800-1000 nm.
Background
In recent years, with the development of the photoelectric industry, the detection application degree of the near-infrared band of 800-1000 nm is higher and higher, especially, the intelligent device urgently needs to use near-infrared laser to realize real-time perception of the surrounding environment, so that decisions are provided for the action and the movement of the intelligent device, and the realization is based on the requirement that an optical system greatly reduces the transmittance of ultraviolet and visible light bands which have interference on the near-infrared working band and requires higher transmittance in the near-infrared band of 800-1000 nm.
In the prior art, the ultraviolet and visible light cut-off is realized by coating a film on the surface of a transparent glass plate, and the problem is that the ultraviolet and visible light spectrum cut-off is realized by using a complex film layer and process, signal interference is formed when incident light deflects at a certain angle, and the use in related fields is not facilitated.
Disclosure of Invention
Based on the reasons, the invention aims to provide a glass composition with low ultraviolet and visible light transmittance and high near-infrared transmittance of 800-1000 nm.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) glass composition comprising, in percentages by weight: SiO 22：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％。
(2) The glass composition according to (1), which comprises the following components in percentage by weight: ZnO: 0 to 20 percent; and/or Al2O3: 0 to 10 percent; and/or ZrO2: 0 to 10 percent; and/or MgO + CaO + SrO + BaO: 0 to 30 percent; and/or Co2O3+ NiO: 0 to 3 percent; and/or P2O5: 0 to 5 percent; and/or F: 0 to 5 percent.
(3) Glass composition, the components of which are expressed in weight percentage by SiO2：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％；ZnO：0～20％；Al2O3：0～10％；ZrO2：0～10％；MgO+CaO+SrO+BaO：0～30％；Co2O3+NiO：0～3％；P2O5: 0 to 5 percent; f: 0 to 5 percent.
(4) The glass composition according to any one of (1) to (3), which comprises, in weight percent: SiO 22: 30-75%; and/or B2O3: 2-25%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 5-30%; and/or Li2O+Na2O+K2O: 7-35%; and/or ZnO: 0 to 15 percent; and/or Al2O3: 0-8%; and/or ZrO2: 0-6%; and/or MgO + CaO + SrO + BaO: 0 to 25 percent; and/or Co2O3+ NiO: 0.0001-3%; and/or P2O5: 0 to 3 percent; and/or F: 0 to 3 percent.
(5) The glass composition according to any one of (1) to (3), which comprises, in weight percent: SiO 22: 40-70%; and/or B2O3: 6-20%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 8-25%; and/or Li2O+Na2O+K2O: 8-30%; and/or ZnO: 0 to 9 percent; and/or Al2O3: 0 to 5 percent; and/or ZrO2: 0 to 4 percent; and/or MgO + CaO + SrO + BaO: 0.5-20%; and/or Co2O3+ NiO: 0.0001-2%; and/or P2O5: 0 to 1 percent; and/or F: 0 to 1 percent.
(6) The glass composition according to any one of (1) to (3), which comprises, in weight percent: SiO 22: 45-65%; and/or B2O3: 6-15%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 10-22%; and/or Li2O+Na2O+K2O: 10-25%; and/or ZnO: 0 to 5 percent; and/or Al2O3: 0.05-3%; and/or ZrO2: 0-2%; and/or MgO + CaO + SrO + BaO: 0.5-15%; and/or Co2O3+ NiO: 0.0002 to 1.5%, preferably Co2O3+NiO：0.0003～1％。
(7) The glass composition according to any one of (1) to (3), which comprises, in weight percent: b is2O3/SiO2Has a value of 0.02 to 0.75, preferably B2O3/SiO2Has a value of 0.05 to 0.6, more preferably B2O3/SiO2The value of (A) is 0.08 to 0.5, and B is more preferably2O3/SiO2The value of (b) is 0.1 to 0.35.
(8) The glass composition according to any one of (1) to (3), which comprises, in weight percent: fe2O3+V2O5+MnO2Is 8% or less, preferably Fe2O3+V2O5+MnO2Is 5% or less, more preferably Fe2O3+V2O5+MnO20.01 to 4%, and preferably Fe2O3+V2O5+MnO20.01 to 3%.
(9) The glass composition according to any one of (1) to (3), which comprises, in weight percent: (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 2.0 or less, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 1.5 or less, more preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.001 to 1.0, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.005 to 0.5.
(10) The glass composition according to any one of (1) to (3), which comprises, in weight percent: (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.1 to 8.0, preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (B) is 0.2 to 5.0, more preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.3 to 3.0, and (TiO) is more preferable2+WO3)/(Sb2O3+CeO2) The value of (b) is 0.5 to 2.0.
(11) The glass composition according to any one of (1) to (3), which comprises, in weight percent: NiO/Co2O3Has a value of (2) of 1.0 or less, preferably NiO/Co2O3Has a value of (2) of 0.8 or less, more preferably NiO/Co2O3The value of (A) is 0.5 or less, and NiO/Co is more preferable2O3The value of (A) is 0.3 or less.
(12) The glass composition according to any one of (1) to (3), which comprises, in weight percent: CeO (CeO)2/(B2O3+Al2O3) 0.1 to 10.0, preferably CeO2/(B2O3+Al2O3) 0.2 to 5.0, more preferably CeO2/(B2O3+Al2O3) 0.3 to 3.0, more preferably CeO2/(B2O3+Al2O3) 0.5 to 2.0.
(13) The glass composition as described in any one of (1) to (3), wherein the components are expressed by weight percentage：Li2O: 0 to 10%, preferably Li2O: 0 to 6%, more preferably Li2O: 0 to 5%, and more preferably Li2O: 0 to 3 percent; and/or Na2O: 0 to 20%, preferably Na2O: 1 to 18%, more preferably Na2O: 2 to 15%, and more preferably Na2O: 3-13%; and/or K2O: 0 to 20%, preferably K2O: 1 to 18%, more preferably K2O: 2 to 15%, and preferably K2O：2～12％。
(14) The glass composition according to any one of (1) to (3), which comprises, in weight percent: MgO: 0-10%, preferably MgO: 0 to 8%, more preferably MgO: 0 to 5%, and more preferably MgO: 0 to 3 percent; and/or CaO: 0-10%, preferably CaO: 0-8%, more preferably CaO: 0.1-5%, preferably CaO: 0.1-4%; and/or SrO: 0 to 15%, preferably SrO: 0 to 10%, more preferably SrO: 0 to 8%, and more preferably SrO: 0 to 5 percent; and/or BaO: 0-15%, preferably BaO: 0 to 10%, more preferably BaO: 0 to 8%, and more preferably BaO: 0.1 to 5 percent.
(15) The glass composition according to any one of (1) to (3), which comprises, in weight percent: TiO 22: 1 to 20%, preferably TiO2: 2 to 15%, more preferably TiO2: 3 to 12%, and preferably TiO2: 4-10%; and/or WO3: 0 to 5%, preferably WO3: 0 to 3%, more preferably WO3: 0-2%; and/or CeO2: 1 to 20%, preferably CeO2: 2 to 15%, more preferably CeO2: 3 to 13%, more preferably CeO2: 4-12%; and/or Sb2O3: 0 to 8%, preferably Sb2O3: 0 to 5%, more preferably Sb2O3: 0.01 to 4%, and preferably Sb2O3: 0.05-3%; and/or Co2O3: 0.0001-3%, preferably Co2O3: 0.0001-2%, more preferably Co2O3: 0.0001 to 1%; and/or NiO: 0-2%, preferably NiO: 0 to 1.5%, more preferably NiO: 0 to 1 percent.
(16) Root of herbaceous plantThe glass composition according to any one of (1) to (3), which does not contain CdO; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain WO3(ii) a And/or does not contain V2O5(ii) a And/or does not contain MnO2(ii) a And/or does not contain S; and/or does not contain C; and/or does not contain As2O3(ii) a And/or does not contain PbO.
(17) The glass composition according to any one of (1) to (3), wherein the glass composition has a transmittance of one or more of the following values at a thickness of 3 mm:
1) a maximum transmittance of 300 to 400nm of 5% or less, preferably a maximum transmittance of 300 to 400nm of 4% or less, more preferably a maximum transmittance of 300 to 400nm of 3% or less;
2) a maximum transmittance of 401 to 600nm of 15% or less, preferably a maximum transmittance of 401 to 600nm of 10% or less, more preferably a maximum transmittance of 401 to 600nm of 5% or less;
3) a maximum transmittance of 601 to 640nm of 10% or less, preferably a maximum transmittance of 601 to 640nm of 7% or less, more preferably a maximum transmittance of 601 to 640nm of 5% or less;
4) a minimum transmittance of 800. + -.24 nm of 80% or more, preferably a minimum transmittance of 800. + -.24 nm of 83% or more, more preferably a minimum transmittance of 800. + -.24 nm of 85% or more;
5) a minimum transmittance of 850. + -.24 nm of 80% or more, preferably a minimum transmittance of 850. + -.24 nm of 83% or more, more preferably a minimum transmittance of 850. + -.24 nm of 85% or more;
6) a minimum transmittance of 900. + -.24 nm of 80% or more, preferably a minimum transmittance of 900. + -.24 nm of 82% or more, more preferably a minimum transmittance of 900. + -.24 nm of 84% or more;
7) a minimum transmittance of 950. + -.24 nm of 78% or more, preferably a minimum transmittance of 950. + -.24 nm of 80% or more, more preferably a minimum transmittance of 950. + -.24 nm of 82% or more;
8) a minimum transmittance of 975 to 1000nm of 75% or more, preferably a minimum transmittance of 975 to 1000nm of 78% or more, more preferably a minimum transmittance of 975 to 1000nm of 80% or more.
(18) The glass composition according to any one of (1) to (3), wherein the glass composition has an acid resistance stability of 3 types or more, preferably 2 types or more, and more preferably 1 type; and/or a water resistance stability of 3 or more, preferably 2 or more, more preferably 1.
(19) The glass composition according to any one of (1) to (3), wherein the glass composition has a bubble degree of C class or more, preferably B class or more, more preferably A class or more, and still more preferably A class0More than grade; and/or the glass composition has a striae of grade D or more, preferably grade C or more; and/or the optical homogeneity of the glass composition is above the H4 rating.
(20) A glass article produced from the glass composition according to any one of (1) to (19).
(21) A glass preform produced from the glass composition as defined in any one of (1) to (19), or the glass product as defined in (20).
(22) A glass member made of the glass composition as defined in any one of (1) to (19), or made of the glass product as defined in (20), or made of the glass preform as defined in (21).
(23) An apparatus comprising the glass composition according to any one of (1) to (19), and/or comprising the glass article according to (20), and/or comprising the glass element according to (22).
(24) A method of making a glass article, the method comprising the steps of: forming a glass composition having components, expressed in weight percent, comprising: SiO 22：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％；
Forming a glass article from the glass composition by a strengthening process.
(25) The method for producing a glass article according to (24), wherein the glass composition further comprises, in terms of weight percent: ZnO:0 to 20 percent; and/or Al2O3: 0 to 10 percent; and/or ZrO2: 0 to 10 percent; and/or MgO + CaO + SrO + BaO: 0 to 30 percent; and/or Co2O3+ NiO: 0 to 3 percent; and/or P2O5: 0 to 5 percent; and/or F: 0 to 5 percent.
(26) The method for producing a glass article according to any one of (24) and (25), wherein the glass composition comprises the following components in percentage by weight:
SiO2: 30-75%, preferably SiO2: 40 to 70%, more preferably SiO2: 45-65%; and/or B2O3: 2 to 25%, preferably B2O3: 6 to 20%, more preferably B2O3: 6-15%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 5 to 30%, preferably TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 8 to 25%, more preferably TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 10-22%; and/or Li2O+Na2O+K2O: 7 to 35%, preferably Li2O+Na2O+K2O: 8 to 30%, more preferably Li2O+Na2O+K2O: 10-25%; and/or ZnO: 0-15%, preferably ZnO: 0 to 9%, more preferably ZnO: 0 to 5 percent; and/or Al2O3: 0 to 8%, preferably Al2O3: 0 to 5%, more preferably Al2O3: 0.05-3%; and/or ZrO2: 0 to 6%, preferably ZrO2: 0 to 4%, more preferably ZrO2: 0-2%; and/or MgO + CaO + SrO + BaO: 0-25%, preferably MgO + CaO + SrO + BaO: 0.5 to 20%, more preferably MgO + CaO + SrO + BaO:0.5-15%; and/or Co2O3+ NiO: 0.0001-3%, preferably Co2O3+ NiO: 0.0001-2%, more preferably Co2O3+ NiO: 0.0002 to 1.5%, more preferably Co2O3+ NiO: 0.0003 to 1 percent; and/or P2O5: 0 to 3%, preferably P2O5: 0 to 1 percent; and/or F: 0-3%, preferably F: 0 to 1 percent.
(27) The method for producing a glass article according to any one of (24) and (25), wherein the glass composition comprises the following components in percentage by weight: b is2O3/SiO2Has a value of 0.02 to 0.75, preferably B2O3/SiO2Has a value of 0.05 to 0.6, more preferably B2O3/SiO2The value of (A) is 0.08 to 0.5, and B is more preferably2O3/SiO2The value of (A) is 0.1 to 0.35; and/or Fe2O3+V2O5+MnO2Is 8% or less, preferably Fe2O3+V2O5+MnO2Is 5% or less, more preferably Fe2O3+V2O5+MnO20.01 to 4%, and preferably Fe2O3+V2O5+MnO20.01 to 3 percent; and/or (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 2.0 or less, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 1.5 or less, more preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.001 to 1.0, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.005 to 0.5; and/or (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.1 to 8.0, preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (B) is 0.2 to 5.0, more preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.3 to 3.0, and (TiO) is more preferable2+WO3)/(Sb2O3+CeO2) The value of (A) is 0.5 to 2.0; and/or NiO/Co2O3Has a value of (2) of 1.0 or less, preferably NiO/Co2O3Has a value of (2) of 0.8 or less, more preferably NiO/Co2O3The value of (A) is 0.5 or less, and NiO/Co is more preferable2O3The value of (A) is 0.3 or less; and/or CeO2/(B2O3+Al2O3) 0.1 to 10.0, preferably CeO2/(B2O3+Al2O3) 0.2 to 5.0, more preferably CeO2/(B2O3+Al2O3) 0.3 to 3.0, more preferably CeO2/(B2O3+Al2O3) 0.5 to 2.0.
(28) The method for producing a glass article according to any one of (24) and (25), wherein the glass composition comprises the following components in percentage by weight: li2O: 0 to 10%, preferably Li2O: 0 to 6%, more preferably Li2O: 0 to 5%, and more preferably Li2O: 0 to 3 percent; and/or Na2O: 0 to 20%, preferably Na2O: 1 to 18%, more preferably Na2O: 2 to 15%, and more preferably Na2O: 3-13%; and/or K2O: 0 to 20%, preferably K2O: 1 to 18%, more preferably K2O: 2 to 15%, and preferably K2O: 2-12%; and/or: MgO: 0-10%, preferably MgO: 0 to 8%, more preferably MgO: 0 to 5%, and more preferably MgO: 0 to 3 percent; and/or CaO: 0-10%, preferably CaO: 0-8%, more preferably CaO: 0.1-5%, preferably CaO: 0.1-4%; and/or SrO: 0 to 15%, preferably SrO: 0 to 10%, more preferably SrO: 0 to 8%, and more preferably SrO: 0 to 5 percent; and/or BaO: 0-15%, preferably BaO: 0 to 10%, more preferably BaO: 0 to 8%, and more preferably BaO: 0.1-5%; and/or: TiO 22: 1-20%, excellenceSelecting TiO2: 2 to 15%, more preferably TiO2: 3 to 12%, and preferably TiO2: 4-10%; and/or WO3: 0 to 5%, preferably WO3: 0 to 3%, more preferably WO3: 0-2%; and/or CeO2: 1 to 20%, preferably CeO2: 2 to 15%, more preferably CeO2: 3 to 13%, more preferably CeO2: 4-12%; and/or Sb2O3: 0 to 8%, preferably Sb2O3: 0 to 5%, more preferably Sb2O3: 0.01 to 4%, and preferably Sb2O3: 0.05-3%; and/or Co2O3: 0.0001-3%, preferably Co2O3: 0.0001-2%, more preferably Co2O3: 0.0001 to 1%; and/or NiO: 0-2%, preferably NiO: 0 to 1.5%, more preferably NiO: 0 to 1 percent.
(29) The method for producing a glass article according to any one of (24) or (25), wherein the glass composition does not contain CdO; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain WO3(ii) a And/or does not contain V2O5(ii) a And/or does not contain MnO2(ii) a And/or does not contain S; and/or does not contain C; and/or does not contain As2O3(ii) a And/or does not contain PbO.
(30) The method of manufacturing a glass article according to any of (24) or (25), wherein the strengthening process comprises one or more of a chemical strengthening process, an ion implantation process, and a thermal strengthening process.
(31) The method for manufacturing a glass article according to any one of (24) or (25), the strengthening process comprising: immersing the glass composition in a salt bath of molten Na salt at a temperature of 430-470 ℃ for 6-20 hours, preferably at a temperature of 435-460 ℃ for 8-13 hours; and/or immersing the glass composition in a salt bath for melting K salt at the temperature of 400-450 ℃ for 1-8 hours, wherein the preferable time range is 2-4 hours; and/or immersing the glass composition in a salt bath in which K salt and Na salt are mixed, at a temperature of 350-450 ℃ for 0.5-8 hours, preferably for 1-4 hours.
(32) The method for manufacturing a glass article according to any one of (24) or (25), the strengthening process comprising: the glass composition is placed in an etching solution formed by NaOH and/or KOH solution.
(33) The method for producing a glass product according to item (32), wherein the concentration of the etching solution is 3 to 40%, preferably 5 to 30%, and more preferably 5 to 20%; and/or the corrosion temperature is 50-150 ℃, preferably 60-120 ℃, more preferably 70-110 ℃, and/or the corrosion time is 1-60 minutes, preferably 1-40 minutes, more preferably 2-30 minutes.
(34) A glass article having the composition, expressed in weight percent, comprising: SiO 22：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％。
(35) The glass article of (34), further comprising, in weight percent: ZnO: 0 to 20 percent; and/or Al2O3: 0 to 10 percent; and/or ZrO2: 0 to 10 percent; and/or MgO + CaO + SrO + BaO: 0 to 30 percent; and/or Co2O3+ NiO: 0 to 3 percent; and/or P2O5: 0 to 5 percent; and/or F: 0 to 5 percent.
(36) The glass article according to any one of (34) or (35), having a composition, expressed in weight percent, wherein: SiO 22: 30-75%, preferably SiO2: 40 to 70%, more preferably SiO2: 45-65%; and/or B2O3: 2 to 25%, preferably B2O3: 6 to 20%, more preferably B2O3: 6-15%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 5 to 30%, preferably TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 8 to 25%, more preferably TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 10-22%; and/or Li2O+Na2O+K2O: 7 to 35%, preferably Li2O+Na2O+K2O: 8 to 30%, more preferably Li2O+Na2O+K2O: 10-25%; and/or ZnO: 0-15%, preferably ZnO: 0 to 9%, more preferably ZnO: 0 to 5 percent; and/or Al2O3: 0 to 8%, preferably Al2O3: 0 to 5%, more preferably Al2O3: 0.05-3%; and/or ZrO2: 0 to 6%, preferably ZrO2: 0 to 4%, more preferably ZrO2: 0-2%; and/or MgO + CaO + SrO + BaO: 0-25%, preferably MgO + CaO + SrO + BaO: 0.5 to 20%, more preferably MgO + CaO + SrO + BaO: 0.5-15%; and/or Co2O3+ NiO: 0.0001-3%, preferably Co2O3+ NiO: 0.0001-2%, more preferably Co2O3+ NiO: 0.0002 to 1.5%, more preferably Co2O3+ NiO: 0.0003 to 1 percent; and/or P2O5: 0 to 3%, preferably P2O5: 0 to 1 percent; and/or F: 0-3%, preferably F: 0 to 1 percent.
(37) The glass article according to any one of (34) or (35), having a composition, expressed in weight percent, wherein: b is2O3/SiO2Has a value of 0.02 to 0.75, preferably B2O3/SiO2Has a value of 0.05 to 0.6, more preferably B2O3/SiO2The value of (A) is 0.08 to 0.5, and B is more preferably2O3/SiO2The value of (A) is 0.1 to 0.35; and/or Fe2O3+V2O5+MnO2Is 8% or less, preferably Fe2O3+V2O5+MnO2Is 5% or less, more preferably Fe2O3+V2O5+MnO20.01 to 4%, and preferably Fe2O3+V2O5+MnO20.01 to 3 percent; and/or (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 2.0 or less, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 1.5 or less, more preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.001 to 1.0, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.005 to 0.5; and/or (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.1 to 8.0, preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (B) is 0.2 to 5.0, more preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.3 to 3.0, and (TiO) is more preferable2+WO3)/(Sb2O3+CeO2) The value of (A) is 0.5 to 2.0; and/or NiO/Co2O3Has a value of (2) of 1.0 or less, preferably NiO/Co2O3Has a value of (2) of 0.8 or less, more preferably NiO/Co2O3The value of (A) is 0.5 or less, and NiO/Co is more preferable2O3The value of (A) is 0.3 or less; and/or CeO2/(B2O3+Al2O3) 0.1 to 10.0, preferably CeO2/(B2O3+Al2O3) 0.2 to 5.0, more preferably CeO2/(B2O3+Al2O3) 0.3 to 3.0, more preferably CeO2/(B2O3+Al2O3) 0.5 to 2.0.
(38) The glass article according to any one of (34) or (35), wherein the components are expressed in weight percent, wherein：Li2O: 0 to 10%, preferably Li2O: 0 to 6%, more preferably Li2O: 0 to 5%, and more preferably Li2O: 0 to 3 percent; and/or Na2O: 0 to 20%, preferably Na2O: 1 to 18%, more preferably Na2O: 2 to 15%, and more preferably Na2O: 3-13%; and/or K2O: 0 to 20%, preferably K2O: 1 to 18%, more preferably K2O: 2 to 15%, and preferably K2O: 2-12%; and/or: MgO: 0-10%, preferably MgO: 0 to 8%, more preferably MgO: 0 to 5%, and more preferably MgO: 0 to 3 percent; and/or CaO: 0-10%, preferably CaO: 0-8%, more preferably CaO: 0.1-5%, preferably CaO: 0.1-4%; and/or SrO: 0 to 15%, preferably SrO: 0 to 10%, more preferably SrO: 0 to 8%, and more preferably SrO: 0 to 5 percent; and/or BaO: 0-15%, preferably BaO: 0 to 10%, more preferably BaO: 0 to 8%, and more preferably BaO: 0.1-5%; and/or: TiO 22: 1 to 20%, preferably TiO2: 2 to 15%, more preferably TiO2: 3 to 12%, and preferably TiO2: 4-10%; and/or WO3: 0 to 5%, preferably WO3: 0 to 3%, more preferably WO3: 0-2%; and/or CeO2: 1 to 20%, preferably CeO2: 2 to 15%, more preferably CeO2: 3 to 13%, more preferably CeO2: 4-12%; and/or Sb2O3: 0 to 8%, preferably Sb2O3: 0 to 5%, more preferably Sb2O3: 0.01 to 4%, and preferably Sb2O3: 0.05-3%; and/or Co2O3: 0.0001-3%, preferably Co2O3: 0.0001-2%, more preferably Co2O3: 0.0001 to 1%; and/or NiO: 0-2%, preferably NiO: 0 to 1.5%, more preferably NiO: 0 to 1 percent.
(39) The glass article of any of (34) or (35), which does not contain CdO; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain WO3(ii) a And/or does not contain V2O5(ii) a And/or does not contain MnO2(ii) a And/or does not contain S; and/or does not contain C; and/or does not contain As2O3(ii) a And/or does not contain PbO.
(40) The glass article of any of (34) or (35), wherein the glass article has a transmittance of one or more of the following at a thickness of 3 mm:
1) a maximum transmittance of 300 to 400nm of 5% or less, preferably a maximum transmittance of 300 to 400nm of 4% or less, more preferably a maximum transmittance of 300 to 400nm of 3% or less;
2) a maximum transmittance of 401 to 600nm of 15% or less, preferably a maximum transmittance of 401 to 600nm of 10% or less, more preferably a maximum transmittance of 401 to 600nm of 5% or less;
3) a maximum transmittance of 601 to 640nm of 10% or less, preferably a maximum transmittance of 601 to 640nm of 7% or less, more preferably a maximum transmittance of 601 to 640nm of 5% or less;
4) a minimum transmittance of 800. + -.24 nm of 80% or more, preferably a minimum transmittance of 800. + -.24 nm of 83% or more, more preferably a minimum transmittance of 800. + -.24 nm of 85% or more;
5) a minimum transmittance of 850. + -.24 nm of 80% or more, preferably a minimum transmittance of 850. + -.24 nm of 83% or more, more preferably a minimum transmittance of 850. + -.24 nm of 85% or more;
6) a minimum transmittance of 900. + -.24 nm of 80% or more, preferably a minimum transmittance of 900. + -.24 nm of 82% or more, more preferably a minimum transmittance of 900. + -.24 nm of 84% or more;
7) a minimum transmittance of 950. + -.24 nm of 78% or more, preferably a minimum transmittance of 950. + -.24 nm of 80% or more, more preferably a minimum transmittance of 950. + -.24 nm of 82% or more;
8) a minimum transmittance of 975 to 1000nm of 75% or more, preferably a minimum transmittance of 975 to 1000nm of 78% or more, more preferably a minimum transmittance of 975 to 1000nm of 80% or more.
(41) The glass article according to any one of (34) or (35), which has stability against acid action of 3 types or more, preferably 2 types or more, more preferably 1 type; and/or a water resistance stability of 3 or more, preferably 2 or more, more preferably 1.
(42) The glass product according to any one of (34) and (35), wherein the glass product has a bubble degree of C class or more, preferably B class or more, more preferably A class or more, and still more preferably A class0More than grade; and/or the degree of streaking is at least class D, preferably at least class C; and/or optical uniformity above the H4 rating.
The invention has the beneficial effects that: through reasonable component design, the glass composition can realize low transmittance of ultraviolet and visible light and high transmittance of near infrared.
Drawings
FIG. 1 is a graph of the spectral transmittance of the glass composition of example 1 of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, although the description of the overlapping portions may be appropriately omitted, the gist of the present invention is not limited thereto, and the glass composition of the present invention may be simply referred to as glass in the following description. The glass composition of the present invention is referred to as a glass article after being subjected to a strengthening process.
[ glass composition ]
The ranges of the respective components (ingredients) of the glass composition of the present invention are explained below. In the present specification, the contents and total contents of the respective components are all expressed by weight percent (wt%), unless otherwise specified.
Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
SiO2Is one of the main components of the glass of the invention,if the content of the glass is less than 20%, the glass is easy to crystallize to form scattering particles, so that the near-infrared transmittance of 800-1000 nm is reduced, and meanwhile, crystallization also brings great difficulty to production; on the other hand, the chemical stability of the glass is lowered and the durability requirement of the glass cannot be satisfied. Thus, SiO2The lower limit of the content of (b) is 20%, preferably 30%, more preferably 40%, and still more preferably 45%. On the other hand, if SiO2The content of (b) exceeds 80%, the high-temperature viscosity of the glass rapidly rises, the production difficulty becomes large, the bubble degree, the streak degree, the optical uniformity and the like are deteriorated, and the design requirements are difficult to achieve. Thus, SiO2The upper limit of the content of (b) is 80%, preferably 75%, more preferably 70%, and still more preferably 65%.
B2O3The glass of the invention can improve the melting performance of the glass, improve the bubble degree, the stripe degree and the optical uniformity of the glass, and improve the chemical stability of the glass, if B is B2O3The content of (A) is less than 1%, and the above-mentioned effects are not significant. Thus, B2O3The content of (B) is 1% or more, preferably B2O3The content of (B) is 2% or more, and B is more preferably2O3The content of (A) is 6% or more. If B is2O3The content of (2) is more than 30%, which can cause the rapid reduction of the transmittance of 800-1000 nm and the rapid reduction of the water resistance and acid resistance of the glass. Thus, B2O3The content of (b) is 30% or less, preferably 25% or less, more preferably 20% or less, and further preferably 15% or less.
In some embodiments of the invention, by controlling B2O3/SiO2The value of (A) is within the range of 0.02-0.75, so that the glass can obtain excellent chemical stability, and the glass is beneficial to strengthening, and a glass product with excellent mechanical properties is obtained. Preferably B2O3/SiO2Has a value of 0.05 to 0.6, more preferably B2O3/SiO2The value of (A) is 0.08 to 0.5, and B is more preferably2O3/SiO2The value of (b) is 0.1 to 0.35.
Al2O3Beneficial to reduce the thickness of 300-600 nm in glassA transmittance. If Al is present2O3The content of (A) is more than 10%, the 800-1000 nm transmittance of the glass is rapidly reduced, the design requirement cannot be met, the melting difficulty of the glass is rapidly increased, and a high-quality product cannot be easily obtained. Thus, Al2O3The content of (b) is limited to 10% or less, preferably 8% or less, and more preferably 5% or less. In some embodiments, if Al2O3Less than 0.05%, the effect of reducing the transmittance in the visible light band is not significant, and the chemical stability of the glass tends to be lowered, so that Al is more preferable2O3The content of (A) is 0.05-3%.
ZnO in the glass is beneficial to reducing the transmittance of 300-600 nm, the chemical stability and the internal quality level of the glass are improved, and the high-temperature viscosity of the glass is reduced. If the content of ZnO exceeds 20%, the glass tends to crystallize. Therefore, the ZnO content is 20% or less, preferably 15% or less, more preferably 9% or less, and still more preferably 5% or less. In some embodiments, it is even more preferred that no ZnO be present.
ZrO2The chemical stability and the anti-crystallization performance of the glass can be improved in the glass, and if the content of the glass exceeds 10%, the glass is easy to generate stones, so that the inherent quality is reduced. Thus, ZrO2The content of (b) is limited to 10% or less, preferably 6% or less, more preferably 4% or less, and still more preferably 2% or less. In some embodiments, it is even more preferred that ZrO not be present2。
MgO, CaO, SrO and BaO belong to alkaline earth metal oxides, and can adjust the stability of glass and improve the devitrification resistance of the glass in the glass. If the total amount of MgO + CaO + SrO + BaO exceeds 30%, the glass becomes unstable and the refractive index increases, resulting in a decrease in the near-infrared transmittance. Therefore, MgO + CaO + SrO + BaO is 30% or less, preferably MgO + CaO + SrO + BaO is 25% or less, more preferably MgO + CaO + SrO + BaO is 0.5 to 20%, and still more preferably MgO + CaO + SrO + BaO is 0.5 to 15%.
Through a great deal of experimental research by the inventor, the influence of alkaline earth metal oxides such as MgO, CaO, SrO, BaO and the like on the capability of reducing 300-600 nm and the transmittance of 800-1000 nm in glass is different.
MgO can improve the thermal shock resistance of glass in the glass, but can inhibit the transmittance from being improved by 800-1000 nm. If the content of MgO exceeds 10%, the transmittance of the glass in the range of 300 to 600nm does not meet the design requirement. Therefore, the content of MgO is limited to 10% or less, preferably 8% or less, more preferably 5% or less, and still more preferably 3% or less.
CaO in the glass can reduce the high-temperature viscosity of the glass and adjust the stability of the glass. If the content of the glass exceeds 10%, the glass has the risk of crystallization, and the improvement of the transmittance of 800-1000 nm can be inhibited. Therefore, the content of CaO is limited to 10% or less, preferably 8% or less, more preferably 0.1 to 5%, and still more preferably 0.1 to 4%.
BaO and SrO have stronger free oxygen supply capability than MgO and CaO, so that the glass can contribute to the improvement of the 800-1000 nm transmittance of the glass in some embodiments. However, when the contents of BaO and SrO exceed 15%, the transmittance of the glass at 300 to 600nm is rather increased. Therefore, the content of BaO is limited to 15% or less, preferably 10% or less, more preferably 8% or less, and still more preferably 0.1 to 5%. The SrO content is limited to 15% or less, preferably 10% or less, more preferably 8% or less, and still more preferably 5% or less.
Li2O、Na2O、K2O belongs to alkali metal oxide, and can reduce the high-temperature viscosity of the glass in the glass, so that the high-quality glass can be obtained more easily. More importantly, the alkali metal oxide can obviously influence the transmittances of the glass of 300-600 nm and 800-1000 nm. Total amount of the above three alkali metals Li2O+Na2O+K2If the O content is lower than 5%, the high-temperature viscosity of the glass is higher, so that the glass is subjected to large negative effects on melting, clarification and forming, and high-quality glass is not easy to obtain; on the other hand, the glass system has insufficient free oxygen, and the transmittance of 800 to 1000nm is rapidly reduced. Thus, Li2O+Na2O+K2O is 5% or more, and Li is preferable2O+Na2O+K2O is 7% or more, and Li is more preferable2O+Na2O+K2O is 8 percentAs above, Li is more preferable2O+Na2O+K2O is more than 10 percent. If Li2O+Na2O+K2The content of O exceeds 40 percent, the chemical stability of the glass is reduced, and the devitrification resistance of the glass is rapidly deteriorated; meanwhile, the transmittance of the glass is increased rapidly from 300 nm to 600nm, and the design requirement cannot be met. Thus, Li2O+Na2O+K2O is 40% or less, and Li is preferable2O+Na2O+K2O is 35% or less, and Li is more preferable2O+Na2O+K2O is 30% or less, and Li is more preferable2O+Na2O+K2O is 25% or less.
Three alkali metal oxides Li2O、Na2O、K2In O, Li2The O has the strongest capacity of reducing the high-temperature viscosity, can also improve the chemical stability of the glass in the glass, and if the content of the O exceeds 10 percent, the time for cooling the glass from a liquid state to a solid state is greatly prolonged, and particularly when the glass is molded into a specification of more than 40mm, the optical uniformity of the glass can be seriously reduced. On the other hand, since the field intensity of Li ions is large, when the content is large, the formation of a colored complex is disturbed, and the transmittance of 300 to 600nm is increased, so that the design requirement cannot be met. Thus, Li2The content of O is 10% or less, preferably 6% or less, more preferably 5% or less, and further preferably 3% or less.
Na2O in the glass can reduce the high-temperature viscosity of the glass, enhance the stability of the glass and improve the transmittance of the glass to 800-1000 nm compared with Li2O is stronger. If however Na2The content of O is more than 20%, the chemical stability of the glass is rapidly deteriorated, and the transmittance of the glass is obviously increased by 300-600 nm. Thus, Na2The content of O is 20% or less, preferably 1 to 18%, more preferably 2 to 15%, and further preferably 3 to 13%.
K2The O has the capability of improving the 800-1000 nm transmittance of the glass better than that of Li2O and Na2O, but the deterioration of the chemical stability of the glass is also the strongest. If K2The content of O is more than 20%, the chemical stability of the glass is rapidly reduced, and the transmittance of the glass is rapidly increased at 300-600 nm. Thus, K2The content of O is 20% or less, preferably 1 to 18%, more preferably 2 to 15%, and further preferably 2 to 12%.
TiO2、WO3、Sb2O3、AgO、SnO2、CeO2、Fe2O3、V2O5、MnO2、Te2O5、SeO2The valence state of metal ions of the components in the glass can change along with the change of the glass structure, and the components and other components in the glass form coloring substances, so that the absorption of 300-600 nm is formed, and if the total content of TiO is equal to that of the coloring substances, the coloring substances are mixed with the other components in the glass to form a mixture2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2Less than 4%, the above effects are not significant, and TiO is preferred2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2Is 5% or more, more preferably 8% or more, and still more preferably 10% or more. If it contains TiO in total2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2If the amount exceeds 35%, the glass is deteriorated in stability and the glass rapidly decreases in transmittance at 800 to 1000nm, so that TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2Is 35% or less, preferably 30% or less, more preferably 25% or less, and further preferably 22% or less.
TiO2The transmittance of the glass is reduced by 300-600 nm, the chemical stability and the thermal shock resistance of the glass can be obviously enhanced, if the content of the glass is lower than 1%, the effect is not obvious, and TiO is preferably used2The content of (A) is 2% or more, more preferably 3% or more, and still more preferablyIs more than 4 percent. If TiO, however2The content is more than 20%, the transmittance of 800-1000 nm is not easy to increase, and the devitrification resistance of the glass is rapidly reduced. Thus, TiO2The content of (b) is 20% or less, preferably 15% or less, more preferably 12% or less, and further preferably 10% or less.
In the glass of the invention, WO3When the content of (3) is more than 5%, the transmittance of the glass at 800 to 1000nm is rapidly lowered, and therefore the content is limited to 5% or less, preferably 3% or less, more preferably 2% or less. In some embodiments, it is further preferred that WO is absent3。
In the glass of the present invention, Sb2O3If the content of (b) exceeds 8%, the glass becomes extremely liable to corrode platinum vessels, and even cannot be produced by using platinum vessels, and it is difficult to obtain a product of high intrinsic quality. Thus, Sb2O3The content of (B) is limited to 8% or less, preferably 5% or less, more preferably 0.01 to 4%, and still more preferably 0.05 to 3%.
In the glass of the invention, CeO2Can promote the valence state transition of coloring ions, thereby obtaining glass with low transmittance of 300-600 nm and high transmittance of 800-1000 nm, such as CeO2Less than 1%, the above effects are not significant, and CeO is preferred2The content of (A) is 2% or more, more preferably CeO2The content of (A) is 3% or more, and CeO is more preferable2The content of (A) is 4% or more. If CeO2In excess of 20%, the glass becomes unstable and even severe devitrification occurs, and thus, CeO2The content of (A) is 20% or less, preferably CeO2The content of (A) is 15% or less, more preferably CeO2The content of (A) is 13% or less, and CeO is more preferable2The content of (B) is 12% or less.
The inventor finds that Fe through a large amount of experimental researches2O3、V2O5、MnO2Etc. can promote TiO2、WO3、Sb2O3、CeO2The structural change in the glass forms complex coloring centers, further reduces the transmittance of 300-600 nm when Fe2O3、V2O5、MnO2The total content of (A) is more than 8%, and the 800-1000 nm transmittance of the glass is rapidly reduced, so that the design requirement cannot be met. So that the total content of Fe2O3+V2O5+MnO2Is 8% or less, preferably 5% or less, more preferably 0.01 to 4%, and further preferably 0.01 to 3%. In some embodiments, it is preferred not to contain V2O5And/or does not contain MnO2。
In some embodiments of the invention, (Fe) is2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) When the glass grain size exceeds 2.0, the devitrification resistance of the glass is rapidly reduced, even the glass is vitrified in serious cases, and meanwhile, the 900-1000 nm transmittance of the glass is rapidly reduced. Therefore, (Fe) is preferred in the present invention2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) The value of (b) is 2.0 or less, more preferably 1.5 or less. On the other hand, if (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) A value of less than 0.001, promoting TiO2、WO3、Sb2O3、CeO2And the effect of structural change in the glass is not obvious, so that the transmittance of 300-600 nm cannot meet the design requirement. Therefore, (Fe) is further preferable2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.001 to 1.0, more preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.005 to 0.5.
The inventors have found, through extensive experimental studies, that in some embodiments of the invention, TiO2、Sb2O3、WO3、CeO2When the glass contains different contents, a complex redox effect occurs, so that the glass has a transmittance of 300-600 nm and an E-The transmittance at 1000nm has a large influence. Specifically, if (TiO)2+WO3)/(Sb2O3+CeO2) When the value of (A) is less than 0.1, the transmittance of the glass is rapidly increased from 300 to 600 nm; if (TiO)2+WO3)/(Sb2O3+CeO2) The value of (A) is higher than 8.0, and the transmittance of 300 to 600nm can be reduced to a desired range, but the transmittance of 800 to 1000nm of the glass is rapidly reduced. Therefore, in order to obtain a low transmittance of 300 to 600nm and a high transmittance of 800 to 1000nm, (TiO)2+WO3)/(Sb2O3+CeO2) The value of (b) is preferably 0.1 to 8.0, more preferably 0.2 to 5.0, further preferably 0.3 to 3.0, and further preferably 0.5 to 2.0.
P2O5The crystal nucleating agent can be formed in the glass, and can form a complex with Ag ions, Fe ions, V ions, Co ions, Ce ions, Mn ions, etc. in the glass, thereby further reducing the transmittance of 300-600 nm, but if P is present2O5When the content of (B) exceeds 5%, the glass is liable to crystallize, resulting in a rapid decrease in the transmittance of 800 to 1000 nm. Thus, P2O5The content of (b) is 5% or less, preferably 3% or less, more preferably 1% or less.
F can reduce the high-temperature viscosity of the glass in the glass, meanwhile, the transmittance of 800-1000 nm is improved to a small extent, if the content of F exceeds 5%, the volatilization of the glass is increased, the spectral transmittance and the internal quality of the glass are unstable, and meanwhile, the production environment is greatly damaged. Therefore, the content of F is limited to 5% or less, preferably 3% or less, and more preferably 1% or less.
In some embodiments of the invention, Co2O3And NiO has very obvious absorption effect in a visible spectrum region, and can be matched with other components to reduce the light transmittance of 400-640 nm, particularly 600-640 nm. If the total content of Co2O3The content of NiO is higher than 3%, the transmittance of the glass is rapidly reduced from 900 nm to 1000nm, and the design requirement cannot be met, so that Co2O3The + NiO content is 3% or less. In some embodiments, if their combined contentCo2O3The + NiO is less than 0.0001%, and the transmittance of 300-400 nm and the transmittance of 600-640 nm are difficult to meet the design requirements. Thus, Co in the present invention2O3The + NiO is preferably 0.0001 to 3%, more preferably 0.0001 to 2%, further preferably 0.0002 to 1.5%, and further preferably 0.0003 to 1%. Wherein, Co2O3The content of (B) is preferably 0.0001 to 3%, more preferably Co2O3The content of (B) is 0.0001-2%, and Co is more preferable2O3The content of (A) is 0.0001-1%; the content of NiO is preferably 0 to 2%, more preferably 0 to 1.5%, and still more preferably 0 to 1%.
In some embodiments of the invention, when NiO/Co2O3When the value of (A) is 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, and further preferably 0.3 or less, the transmittance of 300 to 640nm is advantageously reduced, and the transmittance of 300 to 640nm is more easily brought to a desired range.
In some embodiments of the invention, CeO2、B2O3And Al2O3The content ratio of (A) has a great influence on the structure of the glass, and also has a great influence on the absorption of valence-variable metal ions (such as Ti ions, W ions, Sb ions, V ions and the like) in the glass to 300-600 nm. When CeO is present2/(B2O3+Al2O3) When the value of (A) is less than 0.1, the valence-variable ions are easy to change to a high valence state, so that the transmittance of 300-600 nm cannot meet the design requirement; if CeO2/(B2O3+Al2O3) If the value of (A) exceeds 10.0, the glass becomes liable to devitrify, even resulting in ceramming of the glass. Thus, CeO is preferred2/(B2O3+Al2O3) 0.1 to 10.0, more preferably CeO2/(B2O3+Al2O3) 0.2 to 5.0, more preferably CeO2/(B2O3+Al2O3) 0.3 to 3.0, more preferably CeO2/(B2O3+Al2O3) 0.5 to 2.0.
< component which should not be contained >
CdO、As2O3PbO causes serious environmental pollution, and therefore, in order to achieve environmental friendliness, the glass of the present invention preferably contains no CdO, and/or no As2O3And/or does not contain PbO.
S (sulfur) and C (carbon) can corrode platinum utensils and other metal products, and if the glass component contains S and/or C, only non-platinum utensils such as quartz, corundum mullite and the like can be used for production. The glass is produced by adopting a non-platinum vessel, has higher production difficulty, and is difficult to obtain products with bubble degree and stripe degree meeting the imaging quality. In addition, S and/or C are very volatile in the production process of glass, the volatility is unstable, and the problem of unstable spectral performance is brought. It is therefore preferred in some embodiments of the invention that S is absent and/or C is absent.
"0%" or "free" as used herein means that the compound, molecule or element is not intentionally added as a raw material to the glass of the present invention, but that the compound, molecule or element is not intentionally added as a raw material and/or equipment for producing the glass, and that the compound, molecule or element is not intentionally added, and is contained in a small amount or a trace amount in the final glass.
Next, the properties of the glass composition of the present invention will be described.
< spectral transmittance Performance >
A3 mm glass sample is tested for a transmittance curve of 300-1000 nm of glass by using a spectrometer according to a GB/T7962.12-2010 method.
In some embodiments of the invention, the glass compositions of the invention have one or more of the following:
1) a maximum transmittance of 300 to 400nm of 5% or less, preferably a maximum transmittance of 300 to 400nm of 4% or less, more preferably a maximum transmittance of 300 to 400nm of 3% or less;
2) a maximum transmittance of 401 to 600nm of 15% or less, preferably a maximum transmittance of 401 to 600nm of 10% or less, more preferably a maximum transmittance of 401 to 600nm of 5% or less;
3) a maximum transmittance of 601 to 640nm of 10% or less, preferably a maximum transmittance of 601 to 640nm of 7% or less, more preferably a maximum transmittance of 601 to 640nm of 5% or less;
4) a minimum transmittance of 800. + -.24 nm of 80% or more, preferably a minimum transmittance of 800. + -.24 nm of 83% or more, more preferably a minimum transmittance of 800. + -.24 nm of 85% or more;
5) a minimum transmittance of 850. + -.24 nm of 80% or more, preferably a minimum transmittance of 850. + -.24 nm of 83% or more, more preferably a minimum transmittance of 850. + -.24 nm of 85% or more;
6) a minimum transmittance of 900. + -.24 nm of 80% or more, preferably a minimum transmittance of 900. + -.24 nm of 82% or more, more preferably a minimum transmittance of 900. + -.24 nm of 84% or more;
7) a minimum transmittance of 950. + -.24 nm of 78% or more, preferably a minimum transmittance of 950. + -.24 nm of 80% or more, more preferably a minimum transmittance of 950. + -.24 nm of 82% or more;
8) a minimum transmittance of 975 to 1000nm of 75% or more, preferably a minimum transmittance of 975 to 1000nm of 78% or more, more preferably a minimum transmittance of 975 to 1000nm of 80% or more.
< stability against acid Effect >
Stability of the acid resistance of the glass (D)A) (powder method) the test was carried out according to the method prescribed in GB/T17129. Acid resistance stability is sometimes referred to herein simply as acid resistance or acid resistance stability.
In some embodiments of the invention, the glass composition is stable against acid action (D)A) Is 3 or more, preferably 2 or more, and more preferably 1.
< stability against Water action >
Stability of the glass to Water action (D)W) (powder method) the test was carried out according to the method prescribed in GB/T17129. Stability to hydrolytic action is sometimes referred to herein simply as water resistance or hydrolytic stability.
In some embodiments of the invention, the glass composition has stability to water action (D)W) Is 3 or more, preferably 2 or more, and more preferably 1.
< degree of bubbling >
The bubble degree of the glass of the invention is tested according to the method specified in GB/T7962.8-2010.
In some embodiments of the present invention, the glass composition has a bubble degree of C class or more, preferably B class or more, more preferably a class or more, and still more preferably a class0More than grade.
< degree of striae >
The degree of striae of the glass of the present invention was measured according to the method specified in MLL-G-174B. The method is that a fringe instrument composed of a point light source and a lens is used for comparing and checking with a standard sample from the direction of most easily seeing the fringes, the 4 grades are respectively A, B, C, D grades, A grade is the fringe without being seen by naked eyes under the specified detection condition, B grade is the fringe with fineness and dispersion under the specified detection condition, C grade is the slight parallel fringe under the specified detection condition, and D grade is the rough fringe under the specified detection condition.
In some embodiments of the present invention, the glass composition has a striae of grade D or greater, preferably grade C or greater.
< optical uniformity >
The optical homogeneity of the glasses according to the invention was tested according to the method specified in GB/T7962.2-2010.
In some embodiments of the present invention, the glass composition has an optical uniformity above the H4 rating.
[ production method ]
The method for producing the glass composition of the present invention comprises the steps of:
1) mixing the raw materials according to the component proportion of the glass composition, and putting the uniformly mixed raw materials into a 1300-1500 ℃ smelting furnace for smelting to form molten glass;
2) stirring and homogenizing the molten glass;
3) and pouring or leaking molten glass into the mold for molding.
Further, as the raw material of the glass composition, a complex salt (e.g., carbonate, sulfate, nitrate, etc.), and/or hydroxide, and/or oxide, and/or fluoride, and/or simple substance, etc. may be used.
[ glass product ]
The glass compositions of the present invention can be formed into glass articles by a strengthening process.
In some embodiments, the glass compositions described herein can be fabricated into shaped bodies including, but not limited to, sheets by various processes including, but not limited to, slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the glass composition may be formed by a float process or a roll process as is well known in the art.
The glass composition of the present invention can be used for producing a sheet-shaped glass molded product by a method such as grinding or polishing, but the method for producing a glass molded product is not limited to these methods.
The glass composition molded product of the present invention can be produced into various shapes at a certain temperature by a method such as hot bending or press molding, and is not limited to these methods.
The glass composition or glass article of the present invention can have any thickness that is reasonably useful.
In some embodiments, the strengthening process comprises a chemical strengthening process.
In some embodiments, the glass composition can be chemically strengthened by a chemical strengthening process, or the glass composition can be processed into a shaped body (e.g., a sheet) and then chemically strengthened by a chemical strengthening process.
In some embodiments, the chemical strengthening of the present invention comprises ion exchange. During the ion exchange process, the smaller metal ions in the glass composition are replaced or "exchanged" with larger metal ions having the same valence state that are closer to the glass composition. Replacing the smaller ions with larger ions creates a compressive stress in the glass composition, forming a compressive stress layer.
In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na)+、K+、Rb+、Cs+Etc.), ion exchange is performed by immersing the glass composition in a salt bath of at least one molten salt containing larger metal ions that are larger than the metal ionsFor replacing the smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag+、Tl+、Cu+Etc. may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the glass composition may include, but are not limited to: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.
In some embodiments, the glass composition may be formed by melting a Na salt (e.g., NaNO) by immersion at a temperature of about 430 ℃ to 470 ℃3) The salt bath is subjected to ion exchange for about 6 to 20 hours, preferably at a temperature of between 435 and 460 ℃ for 8 to 13 hours. In this embodiment, Na ions replace a part of Li ions in the glass composition, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the glass composition may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 400 ℃ to 450 ℃3) The salt bath is subjected to ion exchange for 1 to 8 hours, and the preferable time range is 2 to 4 hours. In this embodiment, the K ions replace a part of Li ions and/or Na ions in the glass composition, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the glass composition may be mixed by melting the K salt and Na salt (e.g., KNO) by immersion at a temperature of about 350 ℃ to 450 ℃3And NaNO3) The salt bath is subjected to ion exchange for 0.5 to 8 hours, and the preferable time range is 1 to 4 hours.
In some embodiments, the chemical strengthening process of the present invention further comprises a chemical etching process. The glass composition is placed in corrosive liquid formed by NaOH and/or KOH solution with certain temperature and certain concentration for chemical corrosion, and the mechanical property of the glass composition is enhanced by passivating the microcracks remained in the glass processing. Preferably, the concentration of the corrosive liquid is 3-40%, more preferably 5-30%, and further preferably 5-20%; the corrosion temperature is preferably 50-150 ℃, more preferably 60-120 ℃, and further preferably 70-110 ℃, and the chemical corrosion time is preferably 1-60 minutes, more preferably 1-40 minutes, and further preferably 2-30 minutes.
In some embodiments, the strengthening process includes an ion implantation process that implants ions into a surface layer of the glass.
In some embodiments, the strengthening process includes a thermal strengthening process in which the glass is heated and then rapidly cooled.
The glass product obtained by the invention has the same or similar formula composition of the glass composition; the glass product obtained by the invention has various excellent properties of the glass composition, including but not limited to spectral transmittance, stability of acid action resistance, stability of water action resistance, bubble degree, fringe degree, optical uniformity and the like.
[ glass preform and glass Member ]
The glass preform can be produced from the glass composition or the glass product obtained by the press molding such as the grinding or the reheat press molding or the precision press molding. That is, a glass preform can be produced by subjecting a glass composition or a glass product to mechanical processing such as grinding and polishing, or a glass preform can be produced by producing a preform for press molding from a glass composition or a glass product, subjecting the preform to reheat press molding, and then performing polishing, or a glass preform can be produced by subjecting a preform obtained by performing polishing to precision press molding.
It should be noted that the means for producing the glass preform is not limited to the above means.
The glass member of the present invention is made of the above-described glass composition or glass article or glass preform of the present invention. The glass preform of the present invention has excellent characteristics possessed by the glass composition or the glass article; the glass element of the present invention has excellent characteristics of a glass composition or a glass product, and can provide glass elements such as various filters, lenses, prisms, and the like, which are valuable.
[ apparatus ]
The glass composition of the present invention, and the glass product or glass element formed therefrom, can be used for manufacturing devices such as optical filters, photographic devices, image pickup devices, display devices, monitoring devices, electronic devices, and intelligent devices.
Examples
To further clearly illustrate and explain the technical solution of the present invention, the following non-limiting examples 1 to 15 are provided.
Examples 1 to 15 glass compositions having compositions shown in tables 1 to 2 were obtained by the above-described methods for producing glass compositions. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2.
TABLE 1
Figure BDA0002591844960000231
Figure BDA0002591844960000241
Figure BDA0002591844960000251
TABLE 2
Figure BDA0002591844960000252
Figure BDA0002591844960000261

Claims (33)

1. Glass composition, characterized in that it comprises, expressed in weight percent: SiO 22：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％。
2. The glass combination of claim 1The compound is characterized by also comprising the following components in percentage by weight: ZnO: 0 to 20 percent; and/or Al2O3: 0 to 10 percent; and/or ZrO2: 0 to 10 percent; and/or MgO + CaO + SrO + BaO: 0 to 30 percent; and/or Co2O3+ NiO: 0 to 3 percent; and/or P2O5: 0 to 5 percent; and/or F: 0 to 5 percent.
3. Glass composition, characterized in that its constituents, expressed in weight percentage, are represented by SiO2：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％；ZnO：0～20％；Al2O3：0～10％；ZrO2：0～10％；MgO+CaO+SrO+BaO：0～30％；Co2O3+NiO：0～3％；P2O5: 0 to 5 percent; f: 0 to 5 percent.
4. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 22: 30-75%; and/or B2O3: 2-25%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 5-30%; and/or Li2O+Na2O+K2O: 7-35%; and/or ZnO: 0 to 15 percent; and/or Al2O3: 0-8%; and/or ZrO2: 0-6%; and/or MgO + CaO + SrO + BaO: 0 to 25 percent; and/or Co2O3+ NiO: 0.0001-3%; and/or P2O5: 0 to 3 percent; and/or F: 0 to 3 percent.
5. According to claimThe glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 22: 40-70%; and/or B2O3: 6-20%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 8-25%; and/or Li2O+Na2O+K2O: 8-30%; and/or ZnO: 0 to 9 percent; and/or Al2O3: 0 to 5 percent; and/or ZrO2: 0 to 4 percent; and/or MgO + CaO + SrO + BaO: 0.5-20%; and/or Co2O3+ NiO: 0.0001-2%; and/or P2O5: 0 to 1 percent; and/or F: 0 to 1 percent.
6. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 22: 45-65%; and/or B2O3: 6-15%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 10-22%; and/or Li2O+Na2O+K2O: 10-25%; and/or ZnO: 0 to 5 percent; and/or Al2O3: 0.05-3%; and/or ZrO2: 0-2%; and/or MgO + CaO + SrO + BaO: 0.5-15%; and/or Co2O3+ NiO: 0.0002 to 1.5%, preferably Co2O3+NiO：0.0003～1％。
7. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: b is2O3/SiO2Has a value of 0.02 to 0.75, preferably B2O3/SiO2Has a value of 0.05 to 0.6, more preferably B2O3/SiO2Has a value of0.08 to 0.5, and preferably B2O3/SiO2The value of (b) is 0.1 to 0.35.
8. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: fe2O3+V2O5+MnO2Is 8% or less, preferably Fe2O3+V2O5+MnO2Is 5% or less, more preferably Fe2O3+V2O5+MnO20.01 to 4%, and preferably Fe2O3+V2O5+MnO20.01 to 3%.
9. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 2.0 or less, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 1.5 or less, more preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.001 to 1.0, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.005 to 0.5.
10. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.1 to 8.0, preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (B) is 0.2 to 5.0, more preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.3 to 3.0, and (TiO) is more preferable2+WO3)/(Sb2O3+CeO2) The value of (b) is 0.5 to 2.0.
11. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: NiO/Co2O3Has a value of (2) of 1.0 or less, preferably NiO/Co2O3Has a value of (2) of 0.8 or less, more preferably NiO/Co2O3The value of (A) is 0.5 or less, and NiO/Co is more preferable2O3The value of (A) is 0.3 or less.
12. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: CeO (CeO)2/(B2O3+Al2O3) 0.1 to 10.0, preferably CeO2/(B2O3+Al2O3) 0.2 to 5.0, more preferably CeO2/(B2O3+Al2O3) 0.3 to 3.0, more preferably CeO2/(B2O3+Al2O3) 0.5 to 2.0.
13. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: li2O: 0 to 10%, preferably Li2O: 0 to 6%, more preferably Li2O: 0 to 5%, and more preferably Li2O: 0 to 3 percent; and/or Na2O: 0 to 20%, preferably Na2O: 1 to 18%, more preferably Na2O: 2 to 15%, and more preferably Na2O: 3-13%; and/or K2O: 0 to 20%, preferably K2O: 1 to 18%, more preferably K2O: 2 to 15%, and preferably K2O：2～12％。
14. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: MgO: 0-10%, preferably MgO: 0 to 8%, more preferably MgO: 0 to 5%, and more preferably MgO: 0 to 3 percent; and/or CaO: 0-10%, preferably CaO: 0-8%, more preferably CaO: 0.1-5%, preferably CaO: 0.1-4%; and/or SrO: 0 to 15%, preferably SrO: 0 to 10%, more preferably SrO: 0 to 8%, and more preferably SrO: 0 to 5 percent; and/or BaO: 0-15%, preferably BaO: 0 to 10%, more preferably BaO: 0 to 8%, and more preferably BaO: 0.1 to 5 percent.
15. The glass composition according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: TiO 22: 1 to 20%, preferably TiO2: 2 to 15%, more preferably TiO2: 3 to 12%, and preferably TiO2: 4-10%; and/or WO3: 0 to 5%, preferably WO3: 0 to 3%, more preferably WO3: 0-2%; and/or CeO2: 1 to 20%, preferably CeO2: 2 to 15%, more preferably CeO2: 3 to 13%, more preferably CeO2: 4-12%; and/or Sb2O3: 0 to 8%, preferably Sb2O3: 0 to 5%, more preferably Sb2O3: 0.01 to 4%, and preferably Sb2O3: 0.05-3%; and/or Co2O3: 0.0001-3%, preferably Co2O3: 0.0001-2%, more preferably Co2O3: 0.0001 to 1%; and/or NiO: 0-2%, preferably NiO: 0 to 1.5%, more preferably NiO: 0 to 1 percent.
16. The glass composition of any of claims 1-3, wherein the glass composition is free of CdO; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain WO3(ii) a And/or does not contain V2O5(ii) a And/or does not contain MnO2(ii) a And/or does not contain S; and/or does not contain C; and/or does not contain As2O3(ii) a And/orDoes not contain PbO.
17. The glass composition of any of claims 1-3, wherein the glass composition has a transmittance of one or more of the following at a thickness of 3 mm:
1) a maximum transmittance of 300 to 400nm of 5% or less, preferably a maximum transmittance of 300 to 400nm of 4% or less, more preferably a maximum transmittance of 300 to 400nm of 3% or less;
2) a maximum transmittance of 401 to 600nm of 15% or less, preferably a maximum transmittance of 401 to 600nm of 10% or less, more preferably a maximum transmittance of 401 to 600nm of 5% or less;
3) a maximum transmittance of 601 to 640nm of 10% or less, preferably a maximum transmittance of 601 to 640nm of 7% or less, more preferably a maximum transmittance of 601 to 640nm of 5% or less;
4) a minimum transmittance of 800. + -.24 nm of 80% or more, preferably a minimum transmittance of 800. + -.24 nm of 83% or more, more preferably a minimum transmittance of 800. + -.24 nm of 85% or more;
5) a minimum transmittance of 850. + -.24 nm of 80% or more, preferably a minimum transmittance of 850. + -.24 nm of 83% or more, more preferably a minimum transmittance of 850. + -.24 nm of 85% or more;
6) a minimum transmittance of 900. + -.24 nm of 80% or more, preferably a minimum transmittance of 900. + -.24 nm of 82% or more, more preferably a minimum transmittance of 900. + -.24 nm of 84% or more;
7) a minimum transmittance of 950. + -.24 nm of 78% or more, preferably a minimum transmittance of 950. + -.24 nm of 80% or more, more preferably a minimum transmittance of 950. + -.24 nm of 82% or more;
8) a minimum transmittance of 975 to 1000nm of 75% or more, preferably a minimum transmittance of 975 to 1000nm of 78% or more, more preferably a minimum transmittance of 975 to 1000nm of 80% or more.
18. The glass composition of any one of claims 1 to 3, wherein the glass composition has an acid resistance stability of 3 or more types, preferably 2 or more types, and more preferably 1 type; and/or a water resistance stability of 3 or more, preferably 2 or more, more preferably 1.
19. The glass composition according to any one of claims 1 to 3, wherein the glass composition has a bubble degree of C or more, preferably B or more, more preferably A or more, and further preferably A0More than grade; and/or the glass composition has a striae of grade D or more, preferably grade C or more; and/or the optical homogeneity of the glass composition is above the H4 rating.
20. A glass article characterized by being produced from the glass composition according to any one of claims 1 to 19.
21. A glass preform made from the glass composition of any one of claims 1 to 19 or the glass article of claim 20.
22. A glass component made from the glass composition of any of claims 1 to 19, or made from the glass article of claim 20, or made from the glass preform of claim 21.
23. An apparatus comprising the glass composition of any of claims 1 to 19, and/or comprising the glass article of claim 20, and/or comprising the glass element of claim 22.
24. A method of making a glass article, comprising the steps of:
forming a glass composition having components, expressed in weight percent, comprising: SiO 22：20～80％；B2O3：1～30％；TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2：4～35％；Li2O+Na2O+K2O：5～40％；
Forming a glass article from the glass composition by a strengthening process.
25. A method for making a glass article according to claim 24, wherein the glass composition comprises, in weight percent: ZnO: 0 to 20 percent; and/or Al2O3: 0 to 10 percent; and/or ZrO2: 0 to 10 percent; and/or MgO + CaO + SrO + BaO: 0 to 30 percent; and/or Co2O3+ NiO: 0 to 3 percent; and/or P2O5: 0 to 5 percent; and/or F: 0 to 5 percent.
26. A method for making a glass article according to claim 24 or 25, wherein the components of the glass composition are expressed in weight percent, wherein:
SiO2: 30-75%, preferably SiO2: 40 to 70%, more preferably SiO2: 45-65%; and/or B2O3: 2 to 25%, preferably B2O3: 6 to 20%, more preferably B2O3: 6-15%; and/or TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 5 to 30%, preferably TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 8 to 25%, more preferably TiO2+WO3+Sb2O3+AgO+SnO2+CeO2+Fe2O3+V2O5+MnO2+Te2O5+SeO2: 10-22%; and/or Li2O+Na2O+K2O: 7 to 35%, preferably Li2O+Na2O+K2O: 8 to 30%, more preferably Li2O+Na2O+K2O: 10-25%; and/or ZnO: 0-15%, preferably ZnO: 0 to 9%, more preferably ZnO: 0 to 5 percent; and/or Al2O3: 0 to 8%, preferably Al2O3: 0 to 5%, more preferably Al2O3: 0.05-3%; and/or ZrO2: 0 to 6%, preferably ZrO2: 0 to 4%, more preferably ZrO2: 0-2%; and/or MgO + CaO + SrO + BaO: 0-25%, preferably MgO + CaO + SrO + BaO: 0.5 to 20%, more preferably MgO + CaO + SrO + BaO: 0.5-15%; and/or Co2O3+ NiO: 0.0001-3%, preferably Co2O3+ NiO: 0.0001-2%, more preferably Co2O3+ NiO: 0.0002 to 1.5%, more preferably Co2O3+ NiO: 0.0003 to 1 percent; and/or P2O5: 0 to 3%, preferably P2O5: 0 to 1 percent; and/or F: 0-3%, preferably F: 0 to 1 percent.
27. A method for making a glass article according to claim 24 or 25, wherein the components of the glass composition are expressed in weight percent, wherein: b is2O3/SiO2Has a value of 0.02 to 0.75, preferably B2O3/SiO2Has a value of 0.05 to 0.6, more preferably B2O3/SiO2The value of (A) is 0.08 to 0.5, and B is more preferably2O3/SiO2The value of (A) is 0.1 to 0.35; and/or Fe2O3+V2O5+MnO2Is 8% or less, preferably Fe2O3+V2O5+MnO2Is 5% or less, more preferably Fe2O3+V2O5+MnO20.01 to 4%, and preferably Fe2O3+V2O5+MnO20.01 to 3 percent; and/or (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 2.0 or less, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) Is 1.5 or less, more preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.001 to 1.0, preferably (Fe)2O3+V2O5+MnO2)/(TiO2+WO3+Sb2O3+CeO2) 0.005 to 0.5; and/or (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.1 to 8.0, preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (B) is 0.2 to 5.0, more preferably (TiO)2+WO3)/(Sb2O3+CeO2) The value of (D) is 0.3 to 3.0, and (TiO) is more preferable2+WO3)/(Sb2O3+CeO2) The value of (A) is 0.5 to 2.0; and/or NiO/Co2O3Has a value of (2) of 1.0 or less, preferably NiO/Co2O3Has a value of (2) of 0.8 or less, more preferably NiO/Co2O3The value of (A) is 0.5 or less, and NiO/Co is more preferable2O3The value of (A) is 0.3 or less; and/or CeO2/(B2O3+Al2O3) 0.1 to 10.0, preferably CeO2/(B2O3+Al2O3) 0.2 to 5.0, more preferably CeO2/(B2O3+Al2O3) 0.3 to 3.0, more preferably CeO2/(B2O3+Al2O3) 0.5 to 2.0.
28. A method for making a glass article according to claim 24 or 25, wherein the components of the glass composition are expressed in weight percent, wherein: li2O: 0 to 10%, preferably Li2O: 0 to 6%, more preferably Li2O: 0 to 5%, and more preferably Li2O: 0 to 3 percent; and/or Na2O: 0 to 20%, preferably Na2O: 1 to 18%, more preferably Na2O: 2 to 15%, and more preferably 2 to 15%Na2O: 3-13%; and/or K2O: 0 to 20%, preferably K2O: 1 to 18%, more preferably K2O: 2 to 15%, and preferably K2O: 2-12%; and/or: MgO: 0-10%, preferably MgO: 0 to 8%, more preferably MgO: 0 to 5%, and more preferably MgO: 0 to 3 percent; and/or CaO: 0-10%, preferably CaO: 0-8%, more preferably CaO: 0.1-5%, preferably CaO: 0.1-4%; and/or SrO: 0 to 15%, preferably SrO: 0 to 10%, more preferably SrO: 0 to 8%, and more preferably SrO: 0 to 5 percent; and/or BaO: 0-15%, preferably BaO: 0 to 10%, more preferably BaO: 0 to 8%, and more preferably BaO: 0.1-5%; and/or: TiO 22: 1 to 20%, preferably TiO2: 2 to 15%, more preferably TiO2: 3 to 12%, and preferably TiO2: 4-10%; and/or WO3: 0 to 5%, preferably WO3: 0 to 3%, more preferably WO3: 0-2%; and/or CeO2: 1 to 20%, preferably CeO2: 2 to 15%, more preferably CeO2: 3 to 13%, more preferably CeO2: 4-12%; and/or Sb2O3: 0 to 8%, preferably Sb2O3: 0 to 5%, more preferably Sb2O3: 0.01 to 4%, and preferably Sb2O3: 0.05-3%; and/or Co2O3: 0.0001-3%, preferably Co2O3: 0.0001-2%, more preferably Co2O3: 0.0001 to 1%; and/or NiO: 0-2%, preferably NiO: 0 to 1.5%, more preferably NiO: 0 to 1 percent.
29. The method of manufacturing a glass article according to claim 24 or 25, wherein the glass composition is free of CdO; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain WO3(ii) a And/or does not contain V2O5(ii) a And/or does not contain MnO2(ii) a And/or does not contain S; and/or does not contain C; and/or does not contain As2O3(ii) a And/or does not contain PbO.
30. The method of claim 24 or 25, wherein the strengthening process comprises one or more of a chemical strengthening process, an ion implantation process, and a thermal strengthening process.
31. The method of manufacturing a glass article according to claim 24 or 25, wherein the strengthening process comprises: immersing the glass composition in a salt bath of molten Na salt at a temperature of 430-470 ℃ for 6-20 hours, preferably at a temperature of 435-460 ℃ for 8-13 hours; and/or immersing the glass composition in a salt bath for melting K salt at the temperature of 400-450 ℃ for 1-8 hours, wherein the preferable time range is 2-4 hours; and/or immersing the glass composition in a salt bath in which K salt and Na salt are mixed, at a temperature of 350-450 ℃, for 0.5-8 hours, preferably for 1-4 hours.
32. The method of manufacturing a glass article according to claim 24 or 25, wherein the strengthening process comprises: the glass composition is placed in an etching solution formed by NaOH and/or KOH solution.
33. The method for producing a glass product according to claim 32, wherein the concentration of the etching solution is 3 to 40%, preferably 5 to 30%, and more preferably 5 to 20%; and/or the corrosion temperature is 50-150 ℃, preferably 60-120 ℃, more preferably 70-110 ℃, and/or the corrosion time is 1-60 minutes, preferably 1-40 minutes, more preferably 2-30 minutes.
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