WO2019105250A1 - 微晶玻璃及其基板 - Google Patents

微晶玻璃及其基板 Download PDF

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Publication number
WO2019105250A1
WO2019105250A1 PCT/CN2018/116149 CN2018116149W WO2019105250A1 WO 2019105250 A1 WO2019105250 A1 WO 2019105250A1 CN 2018116149 W CN2018116149 W CN 2018116149W WO 2019105250 A1 WO2019105250 A1 WO 2019105250A1
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Prior art keywords
glass
content
less
tio
zro
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PCT/CN2018/116149
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English (en)
French (fr)
Inventor
于天来
原保平
聂小兵
Original Assignee
成都光明光电股份有限公司
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Priority claimed from CN201711248375.XA external-priority patent/CN107902909B/zh
Priority claimed from CN201711247883.6A external-priority patent/CN109867447B/zh
Application filed by 成都光明光电股份有限公司 filed Critical 成都光明光电股份有限公司
Priority to US16/768,633 priority Critical patent/US11680009B2/en
Priority to KR1020207017851A priority patent/KR102554280B1/ko
Priority to JP2020547268A priority patent/JP7079851B2/ja
Publication of WO2019105250A1 publication Critical patent/WO2019105250A1/zh
Priority to US18/308,772 priority patent/US20230286856A1/en

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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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a glass-ceramic and a substrate based on the glass-ceramic.
  • the present invention particularly relates to a protective member suitable for a portable electronic device or an optical device, which has high thermal conductivity and high strength. Glass ceramics and substrates.
  • a back cover is required to protect the internal electronics.
  • these protective materials for the back cover especially for electronic devices with wireless signals, high thermal conductivity, different personality colors and high strength are required, which can be used in harsh environments, and Good processing performance.
  • metal is used for the back cover protection material, but the metal back cover will seriously affect the signal acceptance. Only the segment type can be designed. With the development of the 5G signal, the metal back cover can no longer be used.
  • Glass-ceramic also known as glass-ceramic, is a material that precipitates crystals inside a glass by heat-treating the glass.
  • the crystallized glass can have a physical property value that cannot be obtained in the glass by the crystal dispersed inside.
  • the mechanical strength such as Young's modulus and fracture toughness, the etching property of an acidic or alkaline chemical solution, the thermal properties such as a thermal expansion coefficient, the increase and disappearance of the glass transition temperature, and the like.
  • Glass-ceramics have higher mechanical properties, and the thermal conductivity of the glass can be improved by forming crystallites in the glass.
  • the conventional glass-ceramics are not suitable for the above-mentioned protective materials because of poor thermal conductivity and strength. Further, since the conventional glass-ceramics have a high viscosity of the green glass or a high devitrification property, the productivity is low, and it is difficult to use the protective material.
  • Japanese Laid-Open Patent Publication No. 2014-114200 discloses a glass-ceramic substrate for an information recording medium which cannot obtain a sufficient compressive stress value after chemical tempering, and cannot form a deep stress layer.
  • the technical problem to be solved by the present invention is to provide a glass ceramic and a substrate thereof having high thermal conductivity and strength.
  • the glass ceramics the composition of which comprises: SiO 2 60-80%; Al 2 O 3 4-20%; Li 2 O 0-15%; Na 2 O is greater than 0 but less than or equal to 12%; K 2 O 0 to 5%; ZrO 2 is greater than 0 but less than or equal to 5%; P 2 O 5 0 to 5%; TiO 2 is 0 to 10%, and the crystal phase contains R 2 SiO 3 , R 2 Si 2 O 5 , R 2 TiO 3 , R 4 Ti 5 O 12 , R 3 PO 3 , RAlSi 2 O 6 , RAlSiO 4 O 10 , R 2 Al 2 Si 2 O 8 , R 4 One or more selected from the group consisting of Al 4 Si 5 O 18 , quartz, and quartz solid solution, wherein R is one or more selected from the group consisting of Li, Na, and K.
  • B 2 O 3 0 to 5% and/or MgO 0 to 2%; and/or ZnO 0 to 2%; and/or CaO 0 to 5%; and/or BaO 0 to 5%.
  • Glass-ceramic the composition of which is composed by weight %: SiO 2 60-80%; Al 2 O 3 4-20%; Li 2 O 0-15%; Na 2 O is greater than 0 but less than or equal to 12%; ZrO 2 Greater than 0 but less than or equal to 5%; P 2 O 5 0 to 5%; TiO 2 0 to 10%; B 2 O 3 0 to 5%; K 2 O 0 to 5%; MgO 0 to 2%; ⁇ 2%; CaO 0 to 5%; BaO 0 to 5%; FeO 0 to 3%; SnO 2 0 to 2%; SrO 0 to 5%; La 2 O 3 0 to 10%; Y 2 O 3 0 to 10%; Nb 2 O 5 0 to 10%; Ta 2 O 5 0 to 10%; WO 30 to 5%; clarifier 0 to 5%, and the crystal phase contains from R 2 SiO 3 , R 2 Si 2 O 5 , R 2 TiO 3 , R 4 Ti 5 O 12
  • SiO 2 is 65 to 78%; and/or Al 2 O 3 is 5 to 18%; and/or Li 2 O is 0 to 12%; and/or Na 2 O is 0.5 to 10%; and/or ZrO 2 0.4 ⁇ 3%; and/or P 2 O 5 0.4 to 3%; and/or B 2 O 3 0 to 4%; and/or K 2 O 0.5 to 4%; and/or MgO greater than 0 but less than or equal to 2 %; and / or ZnO is greater than 0 but less than or equal to 2%; and / or CaO 0 ⁇ 4%; and / or BaO 0 ⁇ 4%; and / or FeO 0 ⁇ 1%; and / or SnO 2 0.01 ⁇ 1 And/or SrO 0 to 3%; and/or La 2 O 3 0 to 9%; and/or Y 2 O 3 0 to 9%; and/or Nb 2 O 5 to 8%; and/or Ta 2 O 5 0 to 0
  • SiO 2 /Li 2 O is 4 to 10; and/or ZrO 2 /Li 2 O is 0 to 0.5; and/or Al 2 O 3 /(Na 2 O+Li 2 O) is 0.5 to 2; And/or Li 2 O/Na 2 O is 0.8 to 8.
  • SiO 2 is 68 to 75%; and/or Al 2 O 3 6 to 15%; and/or Li 2 O 6 to 10%; and/or Na 2 O 2 to 8%; and/or ZrO 2 0.8 ⁇ 2%; and/or P 2 O 5 0.8 to 2%; and/or TiO 2 1-4%; and/or B 2 O 3 0 to less than 2%; and/or K 2 O 0.8 to 3%; And/or CaO 0 to 3%; and/or BaO0 to 3%; and/or SnO 2 0.05 to 0.4%; and/or SrO 0 to 1%; and/or La 2 O 3 greater than 0 but less than or equal to 8 And/or Y 2 O 3 is greater than 0 but less than or equal to 8%; and/or Nb 2 O 5 0 to 5%; and/or Ta 2 O 5 0 to 5%; and/or WO 3 0 to 1 %; and / or clarifying agent 0 ⁇ 2%.
  • SiO 2 /Li 2 O is 4.5 to 9.5; and/or ZrO 2 /Li 2 O is greater than 0 but less than 0.35; and/or Al 2 O 3 /(Na 2 O+Li 2 O) is 0.7 to 1.8; and/or Li 2 O/Na 2 O is 1.5 to 7.5.
  • TiO 2 is 0.5 to 5%, preferably TiO 2 is 1.5 to 4%; and/or ZrO 2 + P 2 O 5 + TiO 2 is 0.5 to 10%, preferably ZrO 2 + P 2 O 5 + TiO 2 It is 1 to 8%, and more preferably ZrO 2 + P 2 O 5 + TiO 2 is 2 to 6%.
  • TiO 2 is 2 to 9.5%, preferably TiO 2 is 5 to 8.5%; and/or ZrO 2 + P 2 O 5 + TiO 2 is 1 to 16%, preferably ZrO 2 + P 2 O 5 + TiO 2 It is 2 to 12%.
  • NiO and/or Ni 2 O 3 in a total amount of not more than 6%, preferably not more than 4%, more preferably not more than 3%, and the lower limit of the total amount is 0.1% or more; or contains Pr 2 O 5 .
  • the lower limit of content is 0.4% or more; or containing CoO and/or Co 2 O 3 in a total amount of not more than 2%, preferably not more than 1.8%, in total
  • the lower limit of the amount is 0.05% or more; or contains Cu 2 O and/or CeO 2 , the total amount is not more than 4%, preferably not more than 3%, the lower limit of the total amount is 0.5% or more; or the content of Fe 2 O 3 is not more than 8 %, preferably not more than 5%, more preferably not more than 3%; or containing Fe 2 O 3 and CoO, CoO not exceeding 0.3%; or containing Fe 2 O 3 and Co 2 O 3 , Co 2 O 3 not exceeding 0.3% Or containing Fe 2 O 3 , CoO and NiO; or containing Fe 2 O 3 , Co 2 O 3 and NiO; or containing Fe 2 O 3 , CoO and Co 2 O 3 , wherein CoO and Co 2
  • the content is not more than 4%, preferably not more than 3%, more preferably not more than 2%, the lower limit is 0.2% or more; or containing V 2 O 5 , the content is not more than 4%
  • the content is not more than 3%, more preferably not more than 2%, and the lower limit of the content is 0.2% or more.
  • the Li 2 Si 2 O 5 crystal phase accounts for 20 to 40% by weight of the glass ceramics, preferably 20 to 35%, more preferably 20 to 30%, still more preferably 20 to 25%.
  • the crystal phase of the quartz and the quartz solid solution accounts for 15 to 30% by weight, preferably 20 to 30%, more preferably 25 to 30% by weight of the glass ceramic.
  • the Li 2 Si 2 O 5 crystal phase and the quartz and the quartz solid solution are the main crystal phases, and the total content thereof is less than 50% by weight, preferably 48% by weight or less of the glass ceramics in the glass ceramics. More preferably, it is 46% or less.
  • LiAlSi 4 O 10 crystal phase accounts for no more than 15% by weight of the glass ceramics.
  • the upper limit of the glass liquidus temperature is 1450 ° C, preferably 1400 ° C, more preferably 1380 ° C, and most preferably 1320 ° C.
  • the thermal conductivity of the glass at room temperature is 2 W/m ⁇ k or more.
  • the glass-ceramic substrate is made by chemical tempering using the above-mentioned glass ceramics.
  • the Vickers hardness (Hv) is 600 kgf/mm 2 or more, preferably 650 kgf/mm 2 or more, and more preferably 700 kgf/mm 2 or more.
  • 32 g of the steel ball falls from the height of 500 mm to the glass-ceramic substrate without breaking, and preferably has a height of 650 mm or more, and more preferably has a height of 800 mm or more.
  • the three-point bending strength is 450 MPa or more, preferably 600 MPa or more, and more preferably 800 MPa or more.
  • a compressive stress layer is formed by ion exchange treatment, and the compressive stress layer has a compressive stress value of 300 MPa or more, preferably 400 MPa or more, and more preferably 500 MPa or more.
  • the compressive stress layer has a thickness of 1 ⁇ m or more, preferably 5 ⁇ m or more, and more preferably 8 ⁇ m or more.
  • a portable electronic device containing the above-described glass ceramics.
  • a portable electronic device comprising the above-described glass-ceramic substrate.
  • the glass fiber of the present invention has a thermal conductivity at room temperature of 2 w/m ⁇ k or more and a Vickers hardness (Hv) after tempering of 600 kgf/mm 2 or more.
  • the glass-ceramic or substrate of the present invention is suitable for protective members such as portable electronic devices and optical devices, especially as a back cover, having high thermal conductivity and strength, transparent or having different personality colors. Since the glass ceramics of the present invention have high thermal conductivity, they can also be used as a heat conductive material, and can also be used for other decorative members such as outer frame members of portable electronic devices having a unique outer shape of glass materials.
  • the glass ceramic of the present invention is a material having a crystal phase and a glass phase, which is different from an amorphous solid.
  • the crystal phase of the glass ceramics can be discriminated by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis and by TEMEDX.
  • the crystal phase contains R 2 SiO 3 , R 2 Si 2 O 5 , R 2 TiO 3 , R 4 Ti 5 O 12 , R 3 PO 3 , RAlSi 2 O 6 , RAlSiO 4 O 10 , R 1 or more of Al 2 Si 2 O 8 , R 4 Al 4 Si 5 O 18 , quartz, and quartz solid solution, wherein R is at least one of Li, Na, and K.
  • the Li 2 Si 2 O 5 crystal phase is a lithium disilicate crystal phase, which is an orthorhombic crystal based on a [Si 2 O 5 ] tetrahedral array, and the shape of the crystal is flat or plate-shaped, in the glass ceramics.
  • the lithium disilicate crystal phase is a random, non-oriented interlocking microstructure, which forces the crack to pass through the crystal, thereby preventing the crack from expanding and improving the strength and toughness of the glass-ceramic.
  • the lithium disilicate crystal phase has a high thermal conductivity, thereby increasing the thermal conductivity of the glass ceramic.
  • the crystal phase of Li 2 Si 2 O 5 accounts for 20 to 40% by weight, preferably 20 to 35%, more preferably 20 to 30%, still more preferably 20 to 25% by weight of the glass ceramics. %.
  • Quartz and quartz solid solution crystal phases belong to the three-way or hexagonal system and exist in the form of spheres in the glass-ceramics, which can further prevent the expansion of micro-cracks and improve the flexural strength and toughness of the glass-ceramics compared to the glass phase, quartz and quartz.
  • the solid solution crystal phase has a high thermal conductivity, thereby increasing the thermal conductivity of the glass ceramic.
  • the crystal phase of the quartz and the quartz solid solution in the glass ceramics accounts for 15 to 30% by weight, preferably 20 to 30%, more preferably 25 to 30% by weight of the glass ceramics.
  • the invention controls the crystallization process and the content of the components, the Li 2 Si 2 O 5 crystal phase and the quartz and the quartz solid solution are the main crystal phases, and the total content thereof accounts for less than the weight % of the glass ceramics in the glass ceramics.
  • 50% the study found that if the content of the main crystalline phase exceeds 50%, the crystal phase content is relatively high in the glass, resulting in poor tempering effect of the glass ceramics, which can not increase the strength of the glass, but will reduce the glass.
  • the strength, preferably, the total content of the Li 2 Si 2 O 5 crystal phase and the quartz and the quartz solid solution is 48% or less, and more preferably 46% or less.
  • Lithium feldspar LiAlSi 4 O 10 is a monoclinic crystal, and a three-dimensional framework structure of a layered structure having a folded Si 2 O 6 layer is connected by Li and Al tetrahedrons, and has a low expansion coefficient, which can be used to increase the crystallized glass.
  • the thermal shock resistance is an auxiliary crystal phase of the glass ceramic, which accounts for no more than 15% by weight of the glass ceramic in the glass ceramic.
  • the inventors of the present invention obtained the present invention at a low cost by repeatedly testing and investigating a specific component constituting the glass ceramics by setting the content and the content ratio to specific values and depositing a specific crystal phase.
  • Glass-ceramic or glass-ceramic substrates Next, the composition range of each component of the glass ceramic of the present invention will be described.
  • the content of each component is expressed by weight% relative to the total amount of the glass material converted to the composition of the oxide, unless otherwise specified.
  • the "composition into an oxide” means that an oxide, a composite salt, a metal fluoride or the like which is used as a raw material of the crystallized glass component of the present invention is all decomposed and converted into an oxide upon melting. In this case, the total amount of the substance of the oxide was taken as 100%.
  • the raw glass before crystallization may be included.
  • SiO 2 is an essential component for forming the glass network structure of the glass ceramic of the present invention, and is also an essential component constituting the crystal phase by heat treatment of the raw glass. If the amount is less than 60%, the obtained glass is inferior in chemical durability and devitrification resistance. Therefore, the lower limit of the SiO 2 content is preferably 60%, more preferably 65%, still more preferably 68%. On the other hand, when the content of SiO 2 is 80% or less, excessive viscosity increase and meltability can be suppressed. Therefore, the upper limit of the SiO 2 content is preferably 80%, more preferably 78%, still more preferably 75%.
  • Al 2 O 3 is the same component as SiO 2 in forming a glass network structure, which is an important component for stabilizing the original glass and improving chemical durability, and further improves the thermal conductivity of the glass, but if it is insufficient 4%, the effect is not good. Therefore, the lower limit of the Al 2 O 3 content is 4%, preferably 5%, more preferably 6%, still more preferably 7%. On the other hand, when the content of Al 2 O 3 exceeds 20%, the meltability and the devitrification resistance are lowered. Therefore, the upper limit of the Al 2 O 3 content is 20%, preferably 18%, and more preferably 15%.
  • Li 2 O is an optional component for improving the low-temperature meltability and formability of the glass, and can also be an essential component for forming a desired crystal phase by heat treatment of the raw glass. However, if the content is less than 6%, the effect is not good. On the other hand, if Li 2 O is excessively contained, it is easy to cause a decrease in chemical durability or an increase in the average coefficient of linear expansion. Therefore, the upper limit of the Li 2 O content is preferably 15%, more preferably 12%, still more preferably 10%. When chemical tempering is performed by ion exchange, if the glass ceramic contains a Li 2 O component, it is very effective in forming a deep compressive stress layer.
  • Na 2 O is an optional component for improving low-temperature meltability and formability, but excessively containing Na 2 O tends to cause a decrease in chemical durability or an increase in an average coefficient of linear expansion, and therefore, the upper limit of the Na 2 O content is preferably 12%. More preferably, it is 10%, and most preferably 8%.
  • the glass ceramic contains a Na 2 O component, and exchange of Na + ions and K + ions in the glass ceramics is very effective in forming a compressive stress layer. Therefore, in the case of chemical tempering by ion exchange, the lower limit of the Na 2 O content is more than 0, preferably 0.5%, further preferably 2%, more preferably 4%, and most preferably more than 5%.
  • P 2 O 5 is capable of forming a crystal nucleus by phase separation in the glass, and is an optional component which contributes to the improvement of the low-temperature melting property of the glass.
  • the lower limit of the P 2 O 5 content is preferably more than 0, more preferably 0.4%, still more preferably 0.8%, and most preferably 1%, but if P 2 O 5 is excessively contained, devitrification resistance is easily generated. Reduce the phase separation of the glass. Therefore, the upper limit of the P 2 O 5 content is preferably 5%, more preferably 3%, and most preferably 2%.
  • ZrO 2 has the function of crystal precipitation to form crystal nuclei, and is an optional component that contributes to the improvement of the chemical durability of the glass.
  • the lower limit of the ZrO 2 content is preferably more than 0, more preferably 0.4%, still more preferably 0.8%, and most preferably 1%.
  • the upper limit of the ZrO 2 content is preferably 5%, more preferably 3%, and most preferably 2%.
  • TiO 2 is an optional component that helps to lower the melting temperature of glass-ceramics and improve chemical durability.
  • the lower limit of the TiO 2 content is preferably greater than 0, more preferably 0.5%, further preferably 1%, and most preferably 1.5%.
  • the upper limit of the TiO 2 content is preferably 6%, more preferably 5%, and most preferably 4%.
  • the total content of ZrO 2 , P 2 O 5 and TiO 2 is controlled, that is, ZrO 2 + P 2 O 5 + TiO 2 is 0.5 to 10%.
  • the lower limit of the value of ZrO 2 + P 2 O 5 + TiO 2 is preferably 0.5%, more preferably 1%, further preferably 2%; ZrO 2 + P 2 O 5 + TiO 2
  • the upper limit of the value is preferably 10%, more preferably 8%, still more preferably 6%.
  • the glass since the total content of Li 2 O and Na 2 O in the glass is large, the glass is easily decrystallized, and after adding TiO 2 , the free oxygen of the glass can be effectively absorbed to become a network forming body, and the liquidus temperature of the glass is lowered.
  • the lower limit of the TiO 2 content is preferably more than 0, more preferably 2%, still more preferably 3%, still more preferably 5%, and most preferably more than 6%.
  • the upper limit of the TiO 2 content is 10%, preferably 9.5%, more preferably 9%, and most preferably 8.5%.
  • the total content of ZrO 2 , P 2 O 5 and TiO 2 is controlled, that is, ZrO 2 + P 2 O 5 + TiO 2 is 1 to 16%.
  • the lower limit of the value of ZrO 2 + P 2 O 5 + TiO 2 is preferably 1%, most preferably 2%; and the upper limit of the value of ZrO 2 + P 2 O 5 + TiO 2 is preferably 16 %, more preferably 12%.
  • the ratio of the content of SiO 2 to the content of Li 2 O is 4 to 10.
  • the lower limit of the value of SiO 2 /Li 2 O is preferably 4, more preferably 4.5, most preferably 5; and the upper limit of the value of SiO 2 /Li 2 O is preferably 10, more preferably 9.5. Most preferably 9.
  • the value of ZrO 2 /Li 2 O is made 0 to 0.5, preferably greater than 0 but less than 0.35, more preferably greater than 0 but less than or equal to 0.30.
  • the content of Al 2 O 3 in order to give the steel a good effect, thus improving the strength of the glass-ceramic substrate, it is necessary to control the content of Al 2 O 3 with respect to the total content ratio 2 O and LiO 2 Na, i.e., Al 2 O 3
  • the lower limit of the value of /(Na 2 O+Li 2 O) is preferably 0.5, more preferably 0.7, most preferably 1; and the upper limit of the value of Al 2 O 3 /(Na 2 O+Li 2 O) is preferably 2, More preferably, it is 1.8, and most preferably it is 1.5.
  • the value of Li 2 O/Na 2 O is 0.8.
  • ⁇ 8 is better.
  • the lower limit of the value of Li 2 O/Na 2 O is preferably 0.8, more preferably 1.5, most preferably 2; and the upper limit of the value of Li 2 O/Na 2 O is preferably 8, more preferably It is 7.5, further preferably 7, and most preferably 6.
  • B 2 O 3 helps to lower the viscosity of the glass, improve the meltability and formability of the glass, and improve the glass tempering properties, so it can be added as an optional component.
  • the upper limit of the B 2 O 3 content is preferably 5%, more preferably 4%, and most preferably less than 2%.
  • K 2 O is an optional component which contributes to the improvement of the low-temperature meltability and formability of the glass.
  • the upper limit of the K 2 O content is preferably 5%, more preferably 4%, and most preferably 3%.
  • the lower limit of the K 2 O content is preferably more than 0, more preferably 0.5%, still more preferably 0.8%, and most preferably 1%.
  • MgO helps to lower the viscosity of the glass and inhibit the crystallization of the original glass during molding, and has the effect of improving the low-temperature melting property. It is an optional component, and the lower limit of the MgO content is preferably greater than 0; however, if the MgO content is too high, it may cause The devitrification resistance is lowered, and undesired crystals are obtained after crystallization, resulting in deterioration of the performance of the glass ceramics. Therefore, the upper limit of the MgO content is preferably 2%.
  • ZnO can improve the melting property of glass and improve the chemical stability of glass. It is an optional component.
  • the lower limit of ZnO content is preferably greater than 0.
  • controlling the upper limit of ZnO content to 2% or less can suppress the devitrification. .
  • CaO is an optional component which contributes to the improvement of the low-temperature melting property of the glass. However, if CaO is excessively contained, the devitrification resistance is easily lowered. Therefore, the upper limit of the CaO content is preferably 5%, more preferably 4%, still more preferably 3%, and most preferably 1%.
  • BaO is an optional component which contributes to the improvement of the low-temperature melting property of the glass. However, if BaO is excessively contained, the devitrification resistance is easily lowered. Therefore, the upper limit of the BaO content is preferably 5%, more preferably 4%, still more preferably 3%, and most preferably 1%.
  • FeO can function as a clarifying agent, it can be contained arbitrarily. However, if FeO is contained too much, it is easy to cause excessive coloring or alloying of platinum in a glass melting apparatus. Therefore, the upper limit of the FeO content is preferably 3%, and more preferably 1%.
  • the lower limit of the SnO 2 content is preferably more than 0, more preferably 0.01%, and most preferably 0.05%; however, if SnO 2 is excessively contained, the devitrification resistance of the glass is easily lowered. Therefore, the upper limit of the SnO 2 content is preferably 2%, more preferably 1%, still more preferably 0.4%, and most preferably 0.2%.
  • SrO is an optional component for improving the low-temperature melting property of glass. However, if SrO is excessively contained, the devitrification resistance is easily lowered. Therefore, the upper limit of the SrO content is preferably 5%, more preferably 3%, and most preferably 1%.
  • La 2 O 3 is an optional component to increase the hardness of the glass ceramic. A small amount of addition can lower the melting temperature of the glass and lower the liquidus temperature to a certain extent, but if it contains too much La 2 O 3 , the devitrification resistance is very high. Easy to lower. Therefore, the content of La 2 O 3 is in the range of 10% or less, preferably 9% or less, more preferably more than 0 but less than or equal to 8%.
  • Y 2 O 3 is an optional component for improving the hardness, chemical stability and thermal conductivity of glass ceramics. A small amount of addition can lower the melting temperature of the glass and lower the liquidus temperature to some extent, but if it contains too much Y 2 O 3 , the resistance to devitrification is easily reduced. Therefore, the content of Y 2 O 3 is 10% or less, preferably 9% or less, more preferably 0 or less but 8% or less.
  • Nb 2 O 5 is an optional component for improving the mechanical strength of the glass ceramic, but if Nb 2 O 5 is excessively contained, the devitrification resistance is easily lowered. Therefore, the upper limit of the Nb 2 O 5 content is preferably 10%, more preferably 8%, and most preferably 5%.
  • Ta 2 O 5 is an optional component for increasing the mechanical strength of the glass, but if Ta 2 O 5 is excessively contained, the devitrification resistance is easily lowered. Therefore, the upper limit of the content of Ta 2 O 5 is preferably 10%, more preferably 8%, and most preferably 5%.
  • WO 3 is an optional component for increasing the mechanical strength of the glass, but if WO 3 is excessively contained, the devitrification resistance is easily lowered. Therefore, the upper limit of the WO 3 content is preferably 5%, more preferably 2%, and most preferably 1%.
  • the clarifying agent As 2 O 3 , Sb 2 O 3 , CeO 2 , and one or more selected from the group consisting of F, Cl, NOx, and SOx may be contained as the clarifying agent.
  • the upper limit of the clarifying agent content is preferably 5%, more preferably 2%, and most preferably 1%.
  • the glass ceramics of the present invention may be added with a certain coloring agent to prepare glass ceramics of different colors.
  • NiO and/or Ni 2 O 3 as a coloring agent for preparing brown or green glass ceramics, the two components may be used singly or in combination, and the content thereof is generally not more than 6%, preferably not more than 4%, and more. Preferably, it is not more than 3%, and the lower limit of the content thereof is 0.1% or more. If NiO and Ni 2 O 3 are used in combination, the total amount of NiO and Ni 2 O 3 is generally not more than 6%, and if the content exceeds 6%, the colorant is used. Not very soluble in glass.
  • Pr 2 O 5 as a green glass composition colorant, used alone, generally not more than 8%, preferably not more than 6%, more preferably not more than 5%, and the lower limit of the content is above 0.4%, such as less than 0.4. %, the color of the glass is not obvious.
  • CoO and/or Co 2 O 3 is used as a coloring agent for preparing blue glass ceramics, and the two colorant components may be used singly or in combination, and the content thereof is generally not more than 2%, preferably not more than 1.8. %, if the content exceeds 2%, the colorant is not well soluble in the glass.
  • the total amount of CoO and Co 2 O 3 is not more than 2%, and the lower limit of the content is respectively 0.05% or more, such as lower than 0.05%, the color of the glass is not obvious.
  • the content is not more than 4%, preferably not more than 3%, if When the content exceeds 4%, the glass is easily decrystallized; the CeO 2 is used alone, and the content is generally not more than 4%, preferably not more than 3%. If the content exceeds 4%, the glass gloss is not good. If the two colorants are used in combination, the total amount thereof is generally not more than 4%, and the lower limit of the content is 0.5% or more.
  • Fe 2 O 3 alone as a colorant; or a colorant used in combination of Fe 2 O 3 and CoO; or a colorant used in combination of Fe 2 O 3 and Co 2 O 3 ; or Fe 2 O 3 , a mixed coloring agent of three kinds of CoO and NiO; or a coloring agent used by mixing three kinds of Fe 2 O 3 , Co 2 O 3 and NiO; or using three kinds of mixing of Fe 2 O 3 , CoO and Co 2 O 3 A colorant used; or a colorant used in a mixture of four kinds of Fe 2 O 3 , CoO, NiO, and Co 2 O 3 to prepare black and soot gray crystallized glass.
  • the pigmentation is carried out using Fe 2 O 3 alone in an amount of not more than 8%, preferably not more than 5%, more preferably not more than 3%.
  • CoO and Co 2 O 3 absorb in visible light and can deepen the blackness of the glass.
  • the content of CoO and Co 2 O 3 is not more than 0.3%, and the total amount of CoO and Co 2 O 3 is measured.
  • the lower limit is 0.2% or more.
  • NiO absorbs in visible light and deepens the blackness of the glass. It is generally less than 1% when mixed.
  • MnO 2 as a coloring agent to prepare purple glass-ceramics is generally not more than 4%, preferably less than 3%, and the lower limit of the content is 0.1% or more. If the content is less than 0.1%, the color of the glass is not obvious.
  • Er 2 O 3 is used as a coloring agent for preparing pink glass ceramics, and the content is generally not more than 8%, preferably within 6%. Since the rare earth element Er 2 O 3 has low coloring efficiency, when the content exceeds 8%, the color of the glass is not further deepened, but the cost of the glass is increased, and the lower limit of the content is 0.4% or more, such as less than 0.4%, the color of the glass. Not obvious.
  • a magenta glass composition is prepared using Nd 2 O 3 as a colorant, and the use amount is generally not more than 8%, preferably within 6%. Since the rare earth element Nd 2 O 3 has low coloring efficiency and the use content exceeds 8%, the color of the glass is not further deepened, but the cost of the glass is increased, and the lower limit of the content is 0.4% or more, such as less than 0.4%, the color of the glass. Not obvious.
  • Red glass microcrystalline glass was prepared by mixing coloring agents of Er 2 O 3 , Nd 2 O 3 and MnO 2 .
  • the Er ions in the glass were absorbed at 400-500 nm, the Mn ions were mainly absorbed at 500 nm, and the Nd ions were mainly at 580 nm. Strong absorption, mixing of three substances, can prepare red glass composition, because Er 2 O 3 and Nd 2 O 3 are rare earth coloring, the coloring ability is weak, Er 2 O 3 is used within 6%, Nd 2
  • the amount of O 3 used is within 4%, the coloring of Mn ions is strong, the amount of MnO 2 used is in the range of 2%, and the lower limit of the total amount of mixed colorants used is 0.9% or more.
  • Cr 2 O 3 as a green glass composition coloring agent, used alone, generally not more than 4%, preferably not more than 3%, more preferably not more than 2%, and the lower limit of the content is above 0.2%, if the content is lower than 0.2%, the color of the glass is not obvious.
  • V 2 O 5 as a yellow-green glass composition colorant, used alone, generally not more than 4%, preferably not more than 3%, more preferably not more than 2%, and the lower limit of the content is above 0.2%, such as lower 0.2%, the color of the glass is not obvious.
  • the glass composition may be composed only of the above components, but other components may be added insofar as the characteristics of the glass are not seriously impaired.
  • components such as TeO 2 , Bi 2 O 3 , and GeO 2 may be added.
  • the glass ceramic of the present invention has the following characteristics.
  • the glass ceramics of the present invention have higher resistance to devitrification and, more specifically, have a lower liquidus temperature. That is, the upper limit of the glass liquidus temperature of the present invention is preferably 1450 ° C, more preferably 1400 ° C, still more preferably 1380 ° C, and most preferably 1320 ° C. Thereby, even if the molten glass flows out at a low temperature, devitrification at the time of forming glass from a molten state can be reduced. Further, since the glass can be molded even if the melting temperature of the glass is lowered, deterioration of the platinum device and the mold can be suppressed, and energy consumed during glass forming can be reduced, and the production cost of the glass can be reduced.
  • the lower limit of the liquidus temperature of the glass of the present invention is not particularly limited, and the lower limit of the liquidus temperature of the glass produced by the present invention is preferably 1000 ° C, more preferably 1100 ° C, and most preferably 1200 ° C.
  • the liquidus temperature is an index of resistance to devitrification.
  • the value measured by the following method is used as the liquidus temperature.
  • a 30 cc glass-like glass sample was placed in a platinum crucible having a capacity of 50 ml, and kept at 1500 ° C to be completely molten; then, after cooling to a predetermined temperature for 12 hours, it was taken out of the furnace. After cooling, the presence or absence of crystals on the surface of the glass and the glass was observed, and the observation was carried out in units of 10 ° C up to 1200 ° C. At this predetermined temperature, the lowest temperature at which crystals were not observed was taken as the liquidus temperature.
  • the glass ceramic of the present invention has a thermal conductivity of 2 W/m ⁇ k or more.
  • a compressive stress layer can be formed by ion exchange treatment, and chemical tempering can be performed.
  • the compressive stress layer preferably has a compressive stress value of 300 MPa or more.
  • the compressive stress value of the compressive stress layer of the glass-ceramic substrate of the present invention is preferably 300 MPa or more, more preferably 400 MPa or more, and most preferably 500 MPa or more.
  • the thickness of the compressive stress layer of the glass-ceramic substrate of the present invention is preferably 1 ⁇ m or more. Since the compressive stress layer has such a thickness, even if a deep crack is generated on the glass ceramic substrate, crack propagation or substrate breakage can be suppressed. Therefore, the thickness of the compressive stress layer is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and most preferably 8 ⁇ m or more.
  • the Vickers hardness (Hv) of the glass-ceramic substrate of the present invention is preferably 600 or more. Since such hardness is obtained, it is possible to suppress occurrence of scratches and to improve mechanical strength. Therefore, the glass ceramics (Hv) of the glass ceramic of the present invention is preferably 600 or more, more preferably 650 or more, and most preferably 700 or more.
  • the glass ball does not break even when 32 g of the steel ball falls from a height of 500 mm to the glass-ceramic substrate. Since it has such impact resistance, it can withstand an impact at the time of falling or collision when it is used as a protective member. Therefore, even if the 32 g steel ball is dropped, the falling height of the glass ceramic substrate is not broken, and the height is preferably 500 mm or more, more preferably 650 mm or more, and most preferably 800 mm or more.
  • the three-point bending strength of the glass-ceramic substrate of the present invention is preferably 450 MPa. Due to such a three-point bending strength, the glass does not break when subjected to sufficient pressure. Therefore, the three-point bending strength is preferably 450 MPa or more, more preferably 600 MPa or more, and most preferably 800 MPa or more.
  • the glass ceramics of the present invention can be prepared by uniformly mixing the raw materials according to the composition ratio range, and placing the homogeneous mixture in a crucible made of platinum or quartz, in accordance with the ease of melting of the glass composition, in an electric furnace or gas.
  • the furnace is melted in a temperature range of 1250 to 1550 ° C for 5 to 24 hours, stirred to make it uniform, then lowered to an appropriate temperature and cast into a mold, and slowly cooled.
  • the raw glass of the glass ceramic of the present invention can be molded by a well-known method.
  • the raw glass of the glass ceramics of the present invention is subjected to crystallization treatment after molding or after molding, and crystals are uniformly precipitated inside the glass.
  • the crystallization treatment may be carried out in one stage or in two stages, but it is preferred to carry out 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 treatment performed at the first temperature is referred to as a first crystallization treatment
  • the crystallization treatment performed at the second temperature is referred to as a second crystallization treatment.
  • the preferred heat treatment conditions are:
  • the above-described crystallization treatment is performed in one stage, and the core formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization treatment temperature, and after the heat treatment temperature is reached, the temperature is maintained for a certain period of time, and then the temperature is lowered.
  • the temperature of the crystallization treatment is preferably 500 to 700 ° C, more preferably 550 to 680 ° C in order to precipitate a desired crystal phase, and the holding time at the crystallization treatment temperature is preferably 0 to 8 h, more preferably 1 to 6h.
  • the first temperature is preferably 500 to 700 ° C
  • the second temperature is preferably 650 to 850 ° C.
  • the holding time at the first temperature is preferably 0 to 24 hours, and most preferably 2 to 15 hours.
  • the holding time at the second temperature is preferably 0 to 10 h, and most preferably 2 to 5 h.
  • the above holding time of 0 points means that the temperature is lowered or increased in less than one minute after reaching the temperature.
  • a glass molded body can be produced by a method such as grinding or polishing. By processing the glass molded body into a thin plate shape, the glass ceramic substrate having the glass ceramics of the present invention as a base material can be obtained.
  • the method of producing a glass molded body is not limited to these methods.
  • the glass-ceramic substrate of the present invention can be prepared into various shapes by a method such as hot bending or pressing at a certain temperature, wherein the temperature of the hot bending temperature and the molding type is lower than the temperature of the crystallization.
  • a method such as hot bending or pressing at a certain temperature, wherein the temperature of the hot bending temperature and the molding type is lower than the temperature of the crystallization.
  • the method of producing various shapes of glass is not limited to these methods.
  • the glass ceramic of the present invention can also obtain higher strength by forming a compressive stress layer.
  • the method for forming the compressive stress layer is a chemical tempering method in which an alkaline component present in the surface layer of the glass-ceramic substrate is exchange-reacted with an alkaline component having a larger ionic radius, and a compressive stress layer is formed on the surface layer.
  • the glass ceramics and the glass-ceramic substrate of the invention are suitable for the protection cover of portable electronic devices such as mobile phones, tablet PCs and watches, and are therefore suitable for use in portable electronic devices such as mobile phones and tablet PCs.
  • the glass ceramics and glass-ceramic substrates of the present invention are also suitable for use in various optical instruments.
  • the examples (Tables 1 to 8) of the present invention are prepared by the following methods: First, as raw materials of various components, respective oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, and the like are selected. For raw materials such as hydroxides and metaphosphoric acid compounds, the raw materials are uniformly mixed according to the composition ratio range, and a uniform mixture is placed in a crucible made of platinum or quartz, and in an electric furnace or a gas furnace according to the ease of melting of the glass composition. The mixture is melted in a temperature range of 1,250 to 1,550 ° C for 5 to 24 hours, stirred to be uniform, then lowered to an appropriate temperature and cast into a mold, and slowly cooled to obtain a raw glass.
  • a one-stage or two-stage heat treatment is separately performed to produce a glass ceramic, in which Examples 15, 18, 20, and 22 are subjected to one-stage heat treatment, and other examples A two-stage heat treatment is performed.
  • Tables 1 to 8 the heat treatment conditions of the first stage are recorded in the column of "nucleation process", and the heat treatment conditions of the second stage are recorded in the column of "crystallization process", the temperature of the heat treatment and the maintenance at the temperature thereof. The time is as described in the table.
  • the crystal phase of the glass ceramics before chemical tempering was analyzed by an X-ray diffraction analyzer to analyze the crystal phase in the glass-ceramic substrate by the angle of the peak displayed on the X-ray diffraction pattern.
  • the prepared glass ceramics were cut and ground to obtain a 36 ⁇ 29 ⁇ 0.7 mm size sheet, and the opposite surfaces were polished in parallel, and then the polished glass ceramics were immersed in a KNO 3 molten salt for chemical tempering to obtain micro Crystal glass substrate.
  • the temperature of the soaked molten salt and the soaking time are as described in the column "Chemical tempering conditions" in the table.
  • the compressive stress value of the surface of the glass-ceramic substrate subjected to chemical tempering and the thickness of the compressive stress layer were measured by a glass surface stress meter FSM-6000.
  • the measurement conditions were calculated such that the refractive index of the sample was 1.53 and the optical elastic constant was 28.5 [(nm/cm)/Mpa].
  • the Vickers hardness of the glass-ceramic substrate in the embodiment is calculated by dividing the load (N) when the pyramidal indenter is pressed into the pyramid-shaped depression on the test surface by a diamond quadrangular indenter having an opposite surface angle of 136° divided by the length of the depression. The value of the surface area (mm 2 ) is expressed.
  • the test load was set to 100 (N) and the holding time was 15 (seconds).
  • the examples having "chemical tempering conditions" were carried out on a substrate after chemical tempering.
  • the height of the falling ball in the embodiment is the maximum falling height of the impact which can be withstood by the two surfaces of the substrate of 36 ⁇ 29 ⁇ 0.8 mm after being polished and placed on the rubber sheet so that the 32 g of the steel ball falls from the predetermined height and the substrate does not break. .
  • the test was carried out from a ball landing height of 650 mm, and the height was changed by 700 mm, 750 mm, 800 mm, 850 mm, and 900 mm without breaking.
  • the substrate after chemical tempering was used as a test object.
  • test data of 900 mm was recorded, indicating that even if the steel ball was dropped from the height of 900 mm, the steel plate did not break and was subjected to impact.
  • the three-point bending strength in Tables 1 to 8 was tested by a microcomputer-controlled electronic universal testing machine CMT6502, glass size 36 ⁇ 29 ⁇ 0.7 mm, and ASTM C 158-2002.
  • the thermal conductivity of the glass ceramics in Tables 1 to 8 was measured using a thermal conductivity tester LFA447.
  • the room temperature (25 ° C) and the sample size is ⁇ 12.7 mm ⁇ 1.5 mm as the measurement conditions, and the "JC/T675-1997 glass material thermal conductivity test method" standard is implemented.
  • the color in the examples is the color of the 36 x 29 x 0.8 mm glass piece observed by the naked eye.
  • the glass ceramic of the present invention has a thermal conductivity of 2 W/m ⁇ k or more at room temperature (25 ° C), has high thermal conductivity, good bending strength and hardness, and good The anti-fall performance, while the glass ceramic of the invention can also have a good personality.
  • the glass-ceramic or substrate obtained by the invention is suitable for protective members such as portable electronic devices and optical devices, especially as a rear cover.

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Abstract

一种微晶玻璃及其基板，其成分按重量％组成含有：SiO260～80％；Al2O34～20％；Li2O 0～15％；Na2O大于0但小于或等于12％；K2O 0～5％；ZrO2大于0但小于或等于5％；P2O50～5％；TiO 20～10％，且晶相含有从R2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18、石英以及石英固溶体中的1种以上。该微晶玻璃的液相温度在1450℃以下，热导率在2w/mk以上，维氏硬度为600kgf/mm2以上,适用于便携式电子设备与光学设备。

Description

微晶玻璃及其基板 技术领域
本发明涉及一种微晶玻璃以及以该微晶玻璃为基材的基板，本发明特别是涉及一种适用于便携式电子设备或光学设备等保护构件的具有高的热导率、较高强度的微晶玻璃以及基板。
背景技术
对于智能手机、平板型PC以及其它光学设备等便携式电子设备，需使用后盖以保护内部电子器件。对于这些用于后盖的保护材料，尤其是用于要求带有无线信号的电子设备，要求具有较高的热导率、不同个性色彩以及较高的强度，能够在恶劣的环境下使用，并且加工性能良好。以往，用于后盖板保护材料通常使用金属，但金属后盖板会严重影响信号的接受，只能设计成分段式，随着5G信号的发展，金属后盖已不能使用。
作为不影响信号的陶瓷材料，具有良好的质感和较高的热导率，但相比玻璃而言，加工性较差，成本较高。目前普通玻璃的热导率较低、强度不够高，限制了其作为电子设备后盖材料的使用。
微晶玻璃也称为玻璃陶瓷，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。微晶玻璃通过在内部分散的结晶，能够具备在玻璃中无法得到的物性值。例如，对于杨氏模量、断裂韧性等机械强度，对酸性或碱性药液的蚀刻特性，热膨胀系数等热性能，玻璃化转变温度的上升以及消失等。微晶玻璃具有更高的机械性能，并且由于在玻璃中形成微晶，可以提高玻璃的热导率，但以往的微晶玻璃由于热导率和强度较差，不适用于上述保护材料。另外，以往的微晶玻璃由于其毛坯玻璃的粘度较高，或失透性较高，因此生产率较低，很难用于上述保护材料。
日本专利文献特开2014-114200公开了一种用于信息记录介质的微晶玻璃基板，该微晶玻璃基板在实施化学钢化后，无法取得足够的压缩应力值，不能形成较深的应力层。
发明内容
本发明所要解决的技术问题是提供一种微晶玻璃及其基板，具有较高 热导率和强度。
本发明解决技术问题所采用的技术方案是：微晶玻璃，其成分按重量％组成含有：SiO 2 60～80％；Al 2O 3 4～20％；Li 2O 0～15％；Na 2O大于0但小于或等于12％；K 2O 0～5％；ZrO 2大于0但小于或等于5％；P 2O 5 0～5％；TiO 2 0～10％，且晶相含有从R 2SiO 3、R 2Si 2O 5、R 2TiO 3、R 4Ti 5O 12、R 3PO 3、RAlSi 2O 6、RAlSiO 4O 10、R 2Al 2Si 2O 8、R 4Al 4Si 5O 18、石英以及石英固溶体中选择的1种以上，其中，R为从Li、Na、K中选择的1种以上。
进一步的，还含有：B 2O 3 0～5％；和/或MgO 0～2％；和/或ZnO 0～2％；和/或CaO 0～5％；和/或BaO 0～5％；和/或FeO 0～3％；和/或SnO 2 0～2％；和/或SrO 0～5％；和/或La 2O 3 0～10％；和/或Y 2O 3 0～10％；和/或Nb 2O 5 0～10％；和/或Ta 2O 5 0～10％；和/或WO 3 0～5％。
微晶玻璃，其成分按重量％组成为：SiO 2 60～80％；Al 2O 3 4～20％；Li 2O 0～15％；Na 2O大于0但小于或等于12％；ZrO 2大于0但小于或等于5％；P 2O 5 0～5％；TiO 2 0～10％；B 2O 30～5％；K 2O 0～5％；MgO 0～2％；ZnO 0～2％；CaO 0～5％；BaO 0～5％；FeO 0～3％；SnO 2 0～2％；SrO 0～5％；La 2O 3 0～10％；Y 2O 3 0～10％；Nb 2O 5 0～10％；Ta 2O 5 0～10％；WO 3 0～5％；澄清剂0～5％，且晶相含有从R 2SiO 3、R 2Si 2O 5、R 2TiO 3、R 4Ti 5O 12、R 3PO 3、RAlSi 2O 6、RAlSiO 4O 10、R 2Al 2Si 2O 8、R 4Al 4Si 5O 18、石英以及石英固溶体中选择的1种以上，其中，R为从Li、Na、K中选择的1种以上。
进一步的，SiO 2 65～78％；和/或Al 2O 3 5～18％；和/或Li 2O 0～12％；和/或Na 2O 0.5～10％；和/或ZrO 2 0.4～3％；和/或P 2O 5 0.4～3％；和/或B 2O 3 0～4％；和/或K 2O 0.5～4％；和/或MgO大于0但小于或等于2％；和/或ZnO大于0但小于或等于2％；和/或CaO 0～4％；和/或BaO 0～4％；和/或FeO 0～1％；和/或SnO 2 0.01～1％；和/或SrO 0～3％；和/或La 2O 3 0～9％；和/或Y 2O 3 0～9％；和/或Nb 2O 5 0～8％；和/或Ta 2O 5 0～8％；和/或WO 3 0～2％；和/或澄清剂含有As 2O 3、Sb 2O 3、CeO 2以及从F、Cl、NOx、SOx的群中选择的一种以上，含量为0～5％。
进一步的，SiO 2/Li 2O为4～10；和/或ZrO 2/Li 2O为0～0.5；和/或Al 2O 3/(Na 2O+Li 2O)为0.5～2；和/或Li 2O/Na 2O为0.8～8。
进一步的，SiO 2 68～75％；和/或Al 2O 3 6～15％；和/或Li 2O 6～10％；和/或Na 2O 2～8％；和/或ZrO 2 0.8～2％；和/或P 2O 5 0.8～2％；和/或TiO 2 1～4％；和/或B 2O 3 0～小于2％；和/或K 2O 0.8～3％；和/或CaO 0～3％；和/或BaO0～3％；和/或SnO 2 0.05～0.4％；和/或SrO 0～1％；和/或La 2O 3大于0但小于或等于8％；和/或Y 2O 3大于0但小于或等于8％；和/或Nb 2O 5 0～5％；和/或Ta 2O 50～5％；和/或WO 3 0～1％；和/或澄清剂0～2％。
进一步的，SiO 2/Li 2O为4.5～9.5；和/或ZrO 2/Li 2O为大于0但小于0.35；和/或Al 2O 3/(Na 2O+Li 2O)为0.7～1.8；和/或Li 2O/Na 2O为1.5～7.5。
进一步的，Na 2O 4～8％，优选大于5％但小于或等于8％；和/或Al 2O 3 7～15％；和/或ZrO 2 1～2％；和/或P 2O 5 1～2％；和/或K 2O 1～3％；和/或CaO 0～1％；和/或BaO 0～1％；和/或SnO 2 0.05～0.2％；和/或澄清剂0～1％；和/或SiO 2/Li 2O为5～9；和/或ZrO 2/Li 2O为大于0但小于或等于0.30；和/或Al 2O 3/(Na 2O+Li 2O)为1～1.5；和/或Li 2O/Na 2O为2～7，优选Li 2O/Na 2O为2～6。
进一步的，TiO 2 0.5～5％，优选为TiO 2 1.5～4％；和/或ZrO 2+P 2O 5+TiO 2为0.5～10％，优选为ZrO 2+P 2O 5+TiO 2为1～8％，更优选为ZrO 2+P 2O 5+TiO 2为2～6％。
进一步的，TiO 2 2～9.5％，优选为TiO 2 5～8.5％；和/或ZrO 2+P 2O 5+TiO 2为1～16％，优选为ZrO 2+P 2O 5+TiO 2为2～12％。
进一步的，还含有NiO和/或Ni 2O 3，合计量不超过6％，优选不超过4％，更优选不超过3％，合计量下限在0.1％以上；或含有Pr 2O 5，含量不超过8％，优选不超过6％，更优选不超过5％，含量下限在0.4％以上；或含有CoO和/或Co 2O 3，合计量不超过2％，优选不超过1.8％，合计量下限在0.05％以上；或含有Cu 2O和/或CeO 2，合计量不超过4％，优选不超过3％，合计量下限在0.5％以上；或含有Fe 2O 3，含量不超过8％，优选不超过5％，更优选不超过3％；或含有Fe 2O 3和CoO，CoO不超过0.3％；或含有Fe 2O 3和Co 2O 3，Co 2O 3不超过0.3％；或含有Fe 2O 3、CoO和NiO；或含有Fe 2O 3、Co 2O 3和NiO；或含有Fe 2O 3、CoO和Co 2O 3，其中,CoO和Co 2O 3合计量下限在0.2％以上；或含有Fe 2O 3、CoO、NiO和Co 2O 3；或含有MnO 2，含量不超过4％，优选在3％以内，含量下限在0.1％以上；或含有Er 2O 3，含量不超过8％，优选在6％以内，含量下限在0.4％以上；或含有Nd 2O 3， 含量不超过8％，优选在6％以内，含量下限在0.4％以上；或含有Er 2O 3、Nd 2O 3和MnO 2，Er 2O 3含量在6％以内，Nd 2O 3含量在4％以内，MnO 2含量在2％以内，其合计量的下限在0.9％以上；或含有Cr 2O 3，含量不超过4％，优选含量不超过3％，更优选含量不超过2％，含量下限在0.2％以上；或含有V 2O 5，含量不超过4％，优选含量不超过3％，更优选含量不超过2％，其含量下限在0.2％以上。
进一步的，Li 2Si 2O 5晶相占微晶玻璃的重量％为20～40％，优选为20～35％，更优选为20～30％，进一步优选为20～25％。
进一步的，石英以及石英固溶体晶相占微晶玻璃的重量％为15～30％，优选为20～30％，更优选为25～30％。
进一步的，所述Li 2Si 2O 5晶相和石英以及石英固溶体为主晶相，且其合计含量在微晶玻璃中占微晶玻璃的重量％低于50％，优选为48％以下，更优选为46％以下。
进一步的，LiAlSi 4O 10晶相占微晶玻璃的重量％不超过15％。
进一步的，玻璃液相温度的上限为1450℃，优选为1400℃，更优选为1380℃，最优选为1320℃。
进一步的，玻璃室温(25℃)的热导率在2W/m·k以上。
微晶玻璃基板，采用上述的微晶玻璃经化学钢化制成。
进一步的，维氏硬度(Hv)为600kgf/mm 2以上，优选为650kgf/mm 2以上，更优选为700kgf/mm 2以上。
进一步的，将32g的钢球从500mm的高度落向所述微晶玻璃基板不会发生断裂，优选高度为650mm以上，更优选高度为800mm以上。
进一步的，三点弯曲强度为450Mpa以上，优选为600Mpa以上，更优选为800Mpa以上。
进一步的，通过离子交换处理形成压缩应力层，所述压缩应力层的压缩应力值为300Mpa以上，优选为400Mpa以上，更优选为500Mpa以上。
进一步的，所述压缩应力层的厚度为1μm以上，优选为5μm以上，更优选为8μm以上。
便携式电子设备，含有上述的微晶玻璃。
便携式电子设备，含有上述的微晶玻璃基板。
本发明的有益效果是：本发明的微晶玻璃在室温的热导率在2w/m·k以上，钢化后的维氏硬度(Hv)为600kgf/mm 2以上。本发明的微晶玻璃或基板适用于便携式电子设备与光学设备等保护构件，尤其作为后盖板，具有较高热导率和强度，透明或可具有不同个性色彩。本发明的微晶玻璃由于具有较高的热导率，因此还可以作为导热材料使用，另外，还可以用于具有玻璃材料特有外形的便携式电子设备的外框构件等其他装饰。
具体实施方式
本发明的微晶玻璃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、以及通过TEMEDX进行辨别。本发明的微晶玻璃，晶相含有R 2SiO 3、R 2Si 2O 5、R 2TiO 3、R 4Ti 5O 12、R 3PO 3、RAlSi 2O 6、RAlSiO 4O 10、R 2Al 2Si 2O 8、R 4Al 4Si 5O 18、石英以及石英固溶体中的1种以上，其中，R为Li、Na、K中的1种以上。
其中，上述Li 2Si 2O 5晶相为二硅酸锂晶相，是基于[Si 2O 5]四面体阵列的斜方晶体，晶体的形状是扁平或是板状的，在微晶玻璃的内部，二硅酸锂晶相为无规则无取向的互锁的微观结构，迫使裂纹通过晶体时路径发生弯曲，从而阻止了裂纹的扩展，提高微晶玻璃的强度和韧性，相比玻璃相，二硅酸锂晶相具有高的热导率，从而提高微晶玻璃热导率。本发明的微晶玻璃中，Li 2Si 2O 5晶相占微晶玻璃的重量％为20～40％，优选为20～35％，更优选为20～30％，进一步优选为20～25％。
石英以及石英固溶体晶相属于三方或者是六方晶系，在微晶玻璃中以球状形式存在，可进一步阻止微裂纹的扩展，提高微晶玻璃抗弯强度和韧性，相比玻璃相，石英以及石英固溶体晶相具有高的热导率，从而提高微晶玻璃热导率。微晶玻璃中石英以及石英固溶体晶相占微晶玻璃的重量％为15～30％，优选为20～30％，更优选为25～30％。
本发明通过对晶化工艺和组分含量的控制，Li 2Si 2O 5晶相和石英以及石英固溶体为主晶相，且其合计含量在微晶玻璃中占微晶玻璃的重量％低于50％，研究发现，如该主晶相的含量超过50％，晶相含量在玻璃中比较高，导致微晶玻璃的钢化效果不好，不能起到增加玻璃强度的作用，反而会降低玻璃的强度，优选Li 2Si 2O 5晶相和石英以及石英固溶体合计含量为48％以 下，更优选为46％以下。
透锂长石LiAlSi 4O 10是单斜晶体，通过Li和Al四面体连接具有折叠Si 2O 6层的层状结构的三维框架结构，具有较低的膨胀系数，可以用于提高微晶玻璃的抗热冲击性，为微晶玻璃的辅助晶相，其在微晶玻璃中占微晶玻璃的重量％不超过15％。
本发明的发明人在反复试验和研究，对于构成微晶玻璃的特定成分，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基板。下面，对本发明微晶玻璃的各成分的组成范围进行说明。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玻璃物质总量的重量％表示。在这里，所述“换算成氧化物的组成”是指，作为本发明的微晶玻璃组成成分的原料而使用的氧化物、复合盐、金属氟化物等熔融时全部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，有时包括结晶化前的原玻璃。
SiO 2是形成本发明的微晶玻璃的玻璃网状结构的必要成分，也是通过原玻璃的热处理能够成为组成晶相的必要成分。如果其量不足60％，所得到的玻璃的化学耐久性差，耐失透性也差。因此，SiO 2含量的下限优选为60％，更加优选为65％，进一步优选为68％。另一方面，通过使SiO 2的含量为80％以下，可以抑制过度的粘度升高与熔融性降低。因此，SiO 2含量的上限优选为80％，更加优选为78％，进一步优选为75％。
Al 2O 3与SiO 2同样是形成玻璃网状结构的组分，其是有助于稳定原玻璃、提高化学耐久性的重要成分，还可进一步提高玻璃的热导率，但如果其含量不足4％，则效果不佳。因此，Al 2O 3含量的下限为4％，优选为5％，更优选为6％，进一步优选为7％。另一方面，如果Al 2O 3的含量超过20％，则熔融性与耐失透性降低。因此，Al 2O 3含量的上限为20％，优选为18％，更优选为15％。
Li 2O是提高玻璃的低温熔融性与成形性的可选成分，并通过原玻璃的热处理也能够成为组成所需要晶相的必要成分。但如果其含量不足6％，则效果不佳。另一方面，如果过多地含有Li 2O，则很容易产生化学耐久性的降低或者平均线膨胀系数的升高。因此，Li 2O含量的上限优选为15％，更优 选为12％，进一步优选为10％。在通过离子交换进行化学钢化时，如果微晶玻璃中含有Li 2O成分，则在形成较深的压缩应力层方面非常有效。
Na 2O是提高低温熔融性与成形性的可选成分，但过多地含有Na 2O容易引起化学耐久性降低或平均线膨胀系数升高，因此，Na 2O含量的上限优选为12％，更优选为10％，最优选为8％。在通过离子交换进行化学钢化时，微晶玻璃中含有Na 2O成分，使微晶玻璃中的Na +离子与K +离子交换在形成压缩应力层方面非常有效。因此，在通过离子交换进行化学钢化时，Na 2O含量的下限大于0，优选为0.5％，进一步优选为2％，更优选为4％，最优选为大于5％。
P 2O 5能够在玻璃中进行分相形成晶核，是有助于提高玻璃的低温熔化性的可选成分。P 2O 5含量的下限优选为大于0，更优选为0.4％，进一步优选为0.8％，最优选为1％，但如果过多地含有P 2O 5，则很容易产生耐失透性的降低及玻璃的分相。因此，P 2O 5含量的上限优选为5％，更优选为3％，最优选为2％。
ZrO 2具有结晶析出形成晶核的作用，还是有助于提高玻璃的化学耐久性的可选成分。ZrO 2含量的下限优选为大于0，更优选为0.4％，进一步优选为0.8％，最优选为1％，但如果过多地含有ZrO 2，则玻璃的耐失透性很容易降低。因此，ZrO 2含量的上限优选为5％，更优选为3％，最优选为2％。
TiO 2是一种有助于降低微晶玻璃的熔化温度、提高化学耐久性的可选成分。
在一些实施方式中，TiO 2含量的下限优选为大于0，更优选为0.5％，进一步优选为1％，最优选为1.5％。另一方面，通过使TiO 2的含量为6％以下，可以降低微晶玻璃的熔化温度。因此，TiO 2含量的上限优选为6％，更优选为5％，最优选为4％。
在这种情况下，为了可以析出均匀的结晶，控制ZrO 2、P 2O 5和TiO 2的总含量，即，ZrO 2+P 2O 5+TiO 2为0.5～10％。为了更容易取得所述效果，ZrO 2+P 2O 5+TiO 2的值的下限优选为0.5％，更优选为1％，进一步优选为2％；ZrO 2+P 2O 5+TiO 2的值的上限优选为10％，更优选为8％，进一步优选为6％。
在一些实施方式中，由于玻璃中Li 2O和Na 2O总含量较多，导致玻璃容易析晶，加入TiO 2后可有效吸收玻璃的游离氧，成为网络形成体，降低玻璃的液相温度。TiO 2含量的下限优选为大于0，更优选为2％，进一步优选为3％， 更进一步优选为5％，最优选为大于6％。另一方面，过多的TiO 2不能完全进入玻璃网络，会导致玻璃析晶。因此，TiO 2含量的上限为10％，优选为9.5％，更优选为9％，最优选为8.5％。
在这种情况下，为了可以析出均匀的结晶，控制ZrO 2、P 2O 5和TiO 2的总含量，即，ZrO 2+P 2O 5+TiO 2为1～16％。为了更容易取得所述效果，ZrO 2+P 2O 5+TiO 2的值的下限优选为1％，最优选为2％；ZrO 2+P 2O 5+TiO 2的值的上限优选为16％，更优选为12％。
在本发明中，为了得到期望的晶相，从而提高微晶玻璃基板的热导率和硬度，需要控制SiO 2的含量相对于Li 2O含量的比值，即，使SiO 2/Li 2O的值为4～10。为了更容易取得所述效果，SiO 2/Li 2O的值的下限优选为4，更优选为4.5，最优选为5；SiO 2/Li 2O的值的上限优选为10，更优选为9.5，最优选为9。
在本发明中，为了在玻璃中得到均匀细小并且更多的晶相，从而提高微晶玻璃基板的热导率和抗弯强度，有必要控制ZrO 2的含量相对于Li 2O含量的比值，即，使ZrO 2/Li 2O的值为0～0.5，优选为大于0但小于0.35，更优选为大于0但小于或等于0.30。
在本发明中，为了得到很好的钢化效果，从而提高微晶玻璃基板的强度，有必要控制Al 2O 3的含量相对于LiO 2和Na 2O总含量的比值，即，Al 2O 3/(Na 2O+Li 2O)的值的下限优选为0.5，更优选为0.7，最优选为1；Al 2O 3/(Na 2O+Li 2O)的值的上限优选为2，更优选为1.8，最优选为1.5。
在本发明中，为了使熔化时的耐失透性以及熔融性与成形性较佳，需要控制Li 2O相对于Na 2O的比值，即，使Li 2O/Na 2O的值为0.8～8为佳。为了更容易取得所述效果，Li 2O/Na 2O的值的下限优选为0.8，更优选为1.5，最优选为2；Li 2O/Na 2O的值的上限优选为8，更优选为7.5，进一步优选为7，最优选为6。
B 2O 3有助于降低玻璃的粘度，提高玻璃的熔解性与成形性，提高玻璃钢化性能，因此可作为可选组分添加。如果过多地含有B 2O 3，则微晶玻璃的化学耐久性容易降低，很容易抑制所期望的结晶的析出。因此，B 2O 3含量的上限优选为5％，更优选为4％，最优选为小于2％。
K 2O是有助于提高玻璃的低温熔融性与成形性的可选成分，但如果过多地含有K 2O，则很容易产生化学耐久性的降低以及平均线膨胀系数的升高。因此，K 2O含量的上限优选为5％，更优选为4％，最优选为3％。在通过离子交换进行化学钢化时，如果使微晶玻璃中含有K 2O，则在形成较深的压缩应力层方面非常有效。因此，在通过离子交换进行化学钢化时，K 2O含量的下限优选为大于0，更优选为0.5％，进一步优选为0.8％，最优选为1％。
MgO有助于降低玻璃的粘度和成型时抑制原玻璃析晶，还具有提高低温熔化性的效果，是可选成分，MgO含量的下限优选为大于0；但如果MgO含量过高，可能会引起耐失透性下降，在晶化后会得到不理想的晶体，导致微晶玻璃性能下降，因此，MgO含量的上限优选为2％。
ZnO可提高玻璃的熔化性能，改善玻璃的化学稳定性，是可选成分，ZnO含量的下限优选为大于0；另一方面，将ZnO含量的上限控制在2％以下，可以抑制失透性降低。
CaO是有助于提高玻璃的低温熔化性的可选成分，但如果过多地含有CaO，则耐失透性很容易降低。因此，CaO含量的上限优选为5％，更优选为4％，进一步优选为3％，最优选为1％。
BaO是有助于提高玻璃的低温熔化性的可选成分，但如果过多地含有BaO，则耐失透性很容易降低。因此，BaO含量的上限优选为5％，更优选为4％，进一步优选为3％，最优选为1％。
FeO可作为澄清剂发挥作用，因此可以任意含有，但如果过多含有FeO，则容易发生着色过度或者使玻璃熔化装置的铂发生合金化。因此，FeO含量的上限优选为3％，更优选为1％。
SnO 2是能够发挥作为澄清剂的作用以及使结晶析出形成晶核的作用的可选成分。因此，SnO 2含量的下限优选为大于0，更优选为0.01％，最优选为0.05％；但如果过多地含有SnO 2，则玻璃的耐失透性很容易降低。因此，SnO 2含量的上限优选为2％，更优选为1％，进一步优选为0.4％，最优选为0.2％。
SrO是提高玻璃的低温熔化性的可选成分，但如果过多含有SrO，则耐失透性很容易降低。因此，SrO含量的上限优选为5％，更优选为3％，最优选为1％。
La 2O 3是提高微晶玻璃硬度的可选成分，少量加入可以降低玻璃的熔化温度，并在一定程度上降低液相温度，但如果过多含有La 2O 3，则耐失透性很容易降低。因此，La 2O 3的含量范围在10％以下，优选在9％以下，更优选为大于0但小于或等于8％。
Y 2O 3是提高微晶玻璃的硬度、化学稳定性和热导率的可选成分，少量加入可以降低玻璃的熔化温度，并在一定程度上降低液相温度，但如果过多含有Y 2O 3，则耐失透性很容易降低。因此，Y 2O 3的含量在10％以下，优选在9％以下，更优选为大于0但小于或等于8％。
Nb 2O 5是提高微晶玻璃的机械强度的可选成分，但如果过多地含有Nb 2O 5，则耐失透性很容易降低。因此，Nb 2O 5含量的上限优选为10％，更优选为8％，最优选为5％。
Ta 2O 5是提高玻璃的机械强度的可选成分，但如果过多地含有Ta 2O 5，则耐失透性很容易降低。因此，Ta 2O 5含量的上限优选为10％，更优选为8％，最优选为5％。
WO 3是提高玻璃的机械强度的可选成分，但如果过多地含有WO 3，则耐失透性很容易降低。因此，WO 3含量的上限优选为5％，更优选为2％，最优选为1％。
在本发明的微晶玻璃中，作为澄清剂也可以含有As 2O 3、Sb 2O 3、CeO 2以及从F、Cl、NOx、SOx的群中选择的一种或二种以上。但是，澄清剂含量的上限优选为5％，更优选为2％，最优选为1％。
本发明的微晶玻璃可以加入一定的着色剂，制备不同颜色的微晶玻璃。
使用NiO和/或Ni 2O 3为着色剂，用于制备褐色或绿色微晶玻璃，两种组分可以单独使用或者混合使用，其分别含量一般不超过6％，优选不超过4％，更优选不超过3％，其分别的含量下限在0.1％以上，如果NiO和Ni 2O 3混合使用，则NiO和Ni 2O 3的合计量一般不超过6％，如果含量超过6％，着色剂不能很好溶于玻璃中。
使用Pr 2O 5作为绿色玻璃组合物着色剂，单独使用，一般含量不超过8％，优选含量不超过6％，更优选不超过5％，其含量下限在0.4％以上，如含量低于0.4％，则玻璃颜色不明显。
使用CoO和/或Co 2O 3为着色剂，用于制备蓝色微晶玻璃，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不超过2％，优选不超过1.8％，如果含量超过了2％，着色剂不能很好溶于玻璃中，如混合使用时，CoO和Co 2O 3合计量不超过2％，其分别的含量下限在0.05％以上，如低于0.05％，玻璃颜色不明显。
使用Cu 2O和/或CeO 2为着色剂，制备黄色微晶玻璃，两种着色剂组分单独使用或者混合使用，单独使用Cu 2O，含量不超过4％，优选不超过3％，如果含量超过4％，容易使玻璃析晶；单独使用CeO 2，含量一般不超过4％，优选不超过3％，如含量超过4％，玻璃光泽不好。如果两种着色剂混合使用时，其合计量一般不超过4％，含量下限在0.5％以上。
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；或者使用Fe 2O 3、CoO和Co 2O 3三种混合使用的着色剂；或者使用Fe 2O 3、CoO、NiO和Co 2O 3四种混合使用的着色剂，来制备黑色和烟灰色微晶玻璃。单独使用Fe 2O 3着色，含量不超过8％，优选不超过5％，更优选不超过3％。CoO和Co 2O 3在可见光有吸收，可以加深玻璃的黑度，一般与Fe 2O 3混合使用时，CoO与Co 2O 3的含量分别不超过0.3％，CoO和Co 2O 3合计量下限在0.2％以上。NiO在可见光有吸收，可以加深玻璃的黑度，一般混合使用时其含量不超过1％。
使用MnO 2为着色剂，制备紫色微晶玻璃，含量一般不超过4％，优选在3％以内，其含量下限在0.1％以上，如含量低于0.1％，玻璃颜色不明显。
使用Er 2O 3为着色剂，用于制备粉色微晶玻璃，使用含量一般不超过8％，优选在6％以内。由于稀土元素Er 2O 3着色效率低，当使用含量超过8％，也不能使玻璃的颜色进一步的加深，反而增加玻璃的成本，其含量下限在0.4％以上，如低于0.4％，玻璃颜色不明显。
使用Nd 2O 3为着色剂，制备紫红色玻璃组合物，使用含量一般不超过8％，优选在6％以内。由于稀土元素Nd 2O 3着色效率低，使用含量超过了8％，也不能使玻璃的颜色进一步的加深，反而增加玻璃的成本，其含量下限在0.4％以上，如低于0.4％，玻璃颜色不明显。
使用Er 2O 3、Nd 2O 3和MnO 2混合着色剂，制备红色玻璃微晶玻璃，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，可以制备红色玻璃组合物，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，Mn离子着色强，MnO 2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。
使用Cr 2O 3作为绿色玻璃组合物着色剂，单独使用，一般含量不超过4％，优选含量不超过3％，更优选含量不超过2％，其含量下限在0.2％以上，如含量低于0.2％，则玻璃颜色不明显。
使用V 2O 5作为黄绿色玻璃组合物着色剂，单独使用，一般含量不超过4％，优选含量不超过3％，更优选含量不超过2％，其含量下限在0.2％以上，如低于0.2％，则玻璃颜色不明显。
在本发明的微晶玻璃中，作为玻璃组成，可以仅由上述成分组成，但在不严重损害玻璃特性的范围内，也可以添加其他成分。例如，可以添加TeO 2、Bi 2O 3、GeO 2等成分。
本发明的微晶玻璃具有下述特性。
本发明的微晶玻璃耐失透性较高，更具体地说，具有较低的液相温度。即，本发明的玻璃液相温度的上限优选为1450℃，更优选为1400℃，进一步优选为1380℃，最优选为1320℃。由此，即使在较低的温度下流出熔融玻璃，也能够降低从熔融状态形成玻璃时的失透。另外，由于即使降低玻璃的熔解温度也能够使玻璃成形，因此可以抑制铂装置和模具发生劣化，而且还可以减少玻璃成形时耗费的能源，降低玻璃的生产成本。
另一方面，对本发明的玻璃液相温度的下限并没有特殊限定，本发明制得的玻璃的液相温度的下限优选为1000℃，更优选为1100℃，最优选为1200℃。
上述液相温度是耐失透性的指标，在本说明书中，将用以下方法测定的值作为液相温度。首先，向容量为50ml的铂坩埚放入30cc玻璃屑状的玻璃样品，在1500℃下保持，使其处于完全熔融状态；然后，在降温至规定温度并保持12小时之后，取出到炉外进行冷却，观察玻璃表面以及玻璃中 有无结晶，分别以每10℃为单位进行观察直至1200℃，在该规定温度中，以看不到结晶的最低温度作为液相温度。
本发明微晶玻璃的热导率为2W/m·k以上。
本发明的微晶玻璃基板，可以通过离子交换处理形成压缩应力层，实施化学钢化。在形成压缩应力层时，压缩应力层的压缩应力值优选为300Mpa以上。由于具有这样的压缩应力值，可以抑制裂纹的延伸并提高机械强度。因此，在实施化学钢化时，本发明的微晶玻璃基板的压缩应力层的压缩应力值优选为300Mpa以上，更优选为400Mpa以上，最优选为500Mpa以上。
本发明的微晶玻璃基板的压缩应力层的厚度，优选为1μm以上。由于压缩应力层具有这样的厚度，因此即使在微晶玻璃基板上产生较深的裂纹，也能够抑制裂纹延伸或基板断裂。因此，压缩应力层的厚度优选为1μm以上，更优选为5μm以上，最优选为8μm以上。
本发明的微晶玻璃基板的维氏硬度(Hv)优选为600以上。由于具有这样的硬度，因此可以抑制发生划痕，并能够提高机械强度。因此，本发明的微晶玻璃的维氏硬度(Hv)优选为600以上，更优选为650以上，最优选为700以上。
本发明的微晶玻璃基板，优选为，即使将32g的钢球从500mm的高度落向微晶玻璃基板也不会发生断裂。由于具有这样的耐冲击性，因此在作为保护构件使用时能够承受下落或者碰撞时的冲击。因此，即使将32g的钢球下落也不会使微晶玻璃基板发生断裂的下落高度，优选高度为500mm以上，更优选高度为650mm以上，最优选高度为800mm以上。
本发明的微晶玻璃基板的三点弯曲强度，优选为450Mpa。由于具有这样的三点弯曲强度，玻璃在承受足够的压力时，玻璃不会发生断裂。因此，三点弯曲强度优选为450Mpa以上，更优选为600Mpa以上，最优选为800Mpa以上。
本发明的微晶玻璃可以通过如下方法进行制备：按照成分比例范围将原料混合均匀，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1250～1550℃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。
本发明的微晶玻璃的原玻璃可以通过众所周知的方法进行成型。
本发明的微晶玻璃的原玻璃，在成型后或成型加工后进行晶化处理，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，但优选采用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，优选的热处理条件为：
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，在达到热处理温度之后，将其温度保持一定的时间，然后再进行降温。该晶化处理的温度优选为在500～700℃，为了能够析出所期望的晶相，更优选为550～680℃，在晶化处理温度下的保持时间，优选为0～8h，更优选为1～6h。
上述通过2个阶段进行晶化处理时，第1温度优选为500～700℃，第2温度优选为650～850℃。在第1温度下的保持时间，优选为0～24h，最优选为2～15h。在第2温度下的保持时间，优选为0～10h，最优选为2～5h。
上述保持时间0分，是指在达到其温度后不到1分钟又开始降温或升温。
本发明的原玻璃或微晶玻璃，可以采用研磨或抛光加工等方法制造玻璃成形体。通过将玻璃成形体加工成薄板状，可以制得以本发明的微晶玻璃为基材的微晶玻璃基板。但制造玻璃成形体的方法，并不限定于这些方法。
本发明的微晶玻璃基板，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，其中热弯温度和压型的温度小于晶化的温度。但制造玻璃各种形状体的方法，并不限定于这些方法。
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。压缩应力层的形成方法有化学钢化法，即：使微晶玻璃基板的表层存在的碱性成分与比其离子半径大的碱性成分进行交换反应，在表层形成压缩应力层。另外还有向微晶玻璃基板的表层 注入离子的离子注入法，以及对微晶玻璃基板进行加热，然后快速冷却的热钢化法。
本发明的微晶玻璃和微晶玻璃基板适用于制作手机、平板PC、手表等便携式电子设备的保护盖板，因此适用于手机、平板PC等便携式电子设备中。同时，本发明微晶玻璃和微晶玻璃基板也适用于各种光学仪器中。
本发明的实施例(表1～表8)通过如下方法制备：首先，作为各种成分的原料，选择各自相应的氧化物、氢氧化物、碳酸盐、硝酸盐、氟化物、氯化物、氢氧化物以及偏磷酸化合物等原料，按照成分比例范围，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1250～1550℃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，缓慢冷却得到原玻璃。
对于所得到的原玻璃，为了进行核形成以及结晶化，分别实施1阶段或2阶段的热处理制造微晶玻璃，其中，实施例15、18、20和22进行1阶段的热处理，而其他实施例进行2阶段的热处理。在表1～表8中，第1阶段的热处理条件记录在“成核工艺”栏中，第2阶段的热处理条件记录在“晶化工艺”栏中，热处理的温度以及在其温度下的保持时间如表所述。
实施例中化学钢化前的微晶玻璃的晶相，利用X射线衍射分析装置，通过在X射线衍射图案上显示的峰值的角度、分析微晶玻璃基板中晶相。
对所制备的微晶玻璃进行切割以及研磨，得到36×29×0.7mm规格薄片，对相对面进行平行抛光，然后将抛光后的微晶玻璃浸泡在KNO 3熔化盐中进行化学钢化，得到微晶玻璃基板。其中，浸泡熔化盐的温度以及浸泡时间，如表中的“化学钢化条件”栏所述。
实施化学钢化的微晶玻璃基板的表面的压缩应力值与压缩应力层的厚度，利用玻璃表面应力仪FSM-6000进行测定。作为测定条件以样品的折射率为1.53、光学弹性常数为28.5[(nm/cm)/Mpa]进行计算。
实施例中的微晶玻璃基板的维氏硬度，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。对于具有“化学钢化条件”的实施例，是在化学钢化后的基板上进行。
实施例中的落球高度表示，对36×29×0.8mm的基板两表面进行抛光后放置在橡胶片上，使32g的钢球从规定高度落下，基板不发生断裂而能够承受的冲击的最大落球高度。具体地说，试验从落球高度650mm开始实施，在不发生断裂的情况下，通过700mm、750mm、800mm、850mm和900mm改变高度。对于具有“化学钢化条件”的实施例，以化学钢化后的基板为试验对象。在实施例中记录为900mm的试验数据，表示即使从900mm的高度使钢球落下基板也不发生断裂而承受了冲击。
表1～表8中的三点弯曲强度，采用微机控制电子万能试验机CMT6502，玻璃规格36×29×0.7mm，以ASTM C 158-2002为标准进行测试。
表1～表8中的微晶玻璃的热导率，利用热导率测试仪器LFA447进行测定。以室温(25℃)和样品规格是Φ12.7mm×1.5mm作为测定条件，执行《JC/T675-1997玻璃材料导热系数试验方法》标准。
实施例中的颜色是通过肉眼观察36×29×0.8mm玻璃片的颜色。
表1
Figure PCTCN2018116149-appb-000001
Figure PCTCN2018116149-appb-000002
表2
Figure PCTCN2018116149-appb-000003
Figure PCTCN2018116149-appb-000004
表3
Figure PCTCN2018116149-appb-000005
Figure PCTCN2018116149-appb-000006
表4
Figure PCTCN2018116149-appb-000007
Figure PCTCN2018116149-appb-000008
Figure PCTCN2018116149-appb-000009
表5
Figure PCTCN2018116149-appb-000010
Figure PCTCN2018116149-appb-000011
表6
Figure PCTCN2018116149-appb-000012
Figure PCTCN2018116149-appb-000013
表7
Figure PCTCN2018116149-appb-000014
Figure PCTCN2018116149-appb-000015
Figure PCTCN2018116149-appb-000016
表8
Figure PCTCN2018116149-appb-000017
Figure PCTCN2018116149-appb-000018
通过上述实施例可以看出，本发明的微晶玻璃在室温(25℃)的热导率在2W/m·k以上，具有高的热导率、较好的抗弯强度和硬度、良好的抗摔伤性能，同时本发明的微晶玻璃还可具有良好的个性色彩。本发明得到的微晶玻璃或基板，适用于便携式电子设备与光学设备等保护构件，尤其作为后盖板。

Claims (25)

  1. 微晶玻璃，其特征在于，其成分按重量％组成含有：SiO 2 60～80％；Al 2O 3 4～20％；Li 2O 0～15％；Na 2O大于0但小于或等于12％；K 2O 0～5％；ZrO 2大于0但小于或等于5％；P 2O 5 0～5％；TiO 2 0～10％，且晶相含有从R 2SiO 3、R 2Si 2O 5、R 2TiO 3、R 4Ti 5O 12、R 3PO 3、RAlSi 2O 6、RAlSiO 4O 10、R 2Al 2Si 2O 8、R 4Al 4Si 5O 18、石英以及石英固溶体中选择的1种以上，其中，R为从Li、Na、K中选择的1种以上。
  2. 如权利要求1所述的微晶玻璃，其特征在于，还含有：B 2O 3 0～5％；和/或MgO 0～2％；和/或ZnO 0～2％；和/或CaO 0～5％；和/或BaO 0～5％；和/或FeO 0～3％；和/或SnO 2 0～2％；和/或SrO 0～5％；和/或La 2O 3 0～10％；和/或Y 2O 3 0～10％；和/或Nb 2O 5 0～10％；和/或Ta 2O 5 0～10％；和/或WO 3 0～5％。
  3. 微晶玻璃，其特征在于，其成分按重量％组成为：SiO 2 60～80％；Al 2O 3 4～20％；Li 2O 0～15％；Na 2O大于0但小于或等于12％；ZrO 2大于0但小于或等于5％；P 2O 5 0～5％；TiO 2 0～10％；B 2O 30～5％；K 2O 0～5％；MgO 0～2％；ZnO 0～2％；CaO 0～5％；BaO 0～5％；FeO 0～3％；SnO 2 0～2％；SrO 0～5％；La 2O 3 0～10％；Y 2O 3 0～10％；Nb 2O 5 0～10％；Ta 2O 5 0～10％；WO 3 0～5％；澄清剂0～5％，且晶相含有从R 2SiO 3、R 2Si 2O 5、R 2TiO 3、R 4Ti 5O 12、R 3PO 3、RAlSi 2O 6、RAlSiO 4O 10、R 2Al 2Si 2O 8、R 4Al 4Si 5O 18、石英以及石英固溶体中选择的1种以上，其中，R为从Li、Na、K中选择的1种以上。
  4. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，SiO 2 65～78％；和/或Al 2O 3 5～18％；和/或Li 2O 0～12％；和/或Na 2O 0.5～10％；和/或ZrO 2 0.4～3％；和/或P 2O 5 0.4～3％；和/或B 2O 3 0～4％；和/或K 2O 0.5～4％；和/或MgO大于0但小于或等于2％；和/或ZnO大于0但小于或等于2％；和/或CaO 0～4％；和/或BaO 0～4％；和/或FeO 0～1％；和/或SnO 2 0.01～1％；和/或SrO 0～3％；和/或La 2O 3 0～9％；和/或Y 2O 3 0～9％；和/或Nb 2O 5 0～8％；和/或Ta 2O 5 0～8％；和/或WO 3 0～2％；和/或澄清剂含有As 2O 3、Sb 2O 3、CeO 2以及从F、Cl、NOx、SOx的群中选择的一种以上，含量为0～5％。
  5. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，SiO 2/Li 2O为4～10；和/或ZrO 2/Li 2O为0～0.5；和/或Al 2O 3/(Na 2O+Li 2O)为0.5～2；和/或Li 2O/Na 2O为0.8～8。
  6. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，SiO 2 68～75％；和/或Al 2O 3 6～15％；和/或Li 2O 6～10％；和/或Na 2O 2～8％；和/或ZrO 2 0.8～2％；和/或P 2O 5 0.8～2％；和/或TiO 2 1～4％；和/或B 2O 3 0～小于2％；和/或K 2O 0.8～3％；和/或CaO 0～3％；和/或BaO 0～3％；和/或SnO 2 0.05～0.4％；和/或SrO 0～1％；和/或La 2O 3大于0但小于或等于8％；和/或Y 2O 3大于0但小于或等于8％；和/或Nb 2O 5 0～5％；和/或Ta 2O 5 0～5％；和/或WO 3 0～1％；和/或澄清剂0～2％。
  7. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，SiO 2/Li 2O为4.5～9.5；和/或ZrO 2/Li 2O为大于0但小于0.35；和/或Al 2O 3/(Na 2O+Li 2O)为0.7～1.8；和/或Li 2O/Na 2O为1.5～7.5。
  8. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，Na 2O 4～8％，优选大于5％但小于或等于8％；和/或Al 2O 3 7～15％；和/或ZrO 2 1～2％；和/或P 2O 5 1～2％；和/或K 2O 1～3％；和/或CaO 0～1％；和/或BaO 0～1％；和/或SnO 2 0.05～0.2％；和/或澄清剂0～1％；和/或SiO 2/Li 2O为5～9；和/或ZrO 2/Li 2O为大于0但小于或等于0.30；和/或Al 2O 3/(Na 2O+Li 2O)为1～1.5；和/或Li 2O/Na 2O为2～7，优选Li 2O/Na 2O为2～6。
  9. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，TiO 2 0.5～5％，优选为TiO 2 1.5～4％；和/或ZrO 2+P 2O 5+TiO 2为0.5～10％，优选为ZrO 2+P 2O 5+TiO 2为1～8％，更优选为ZrO 2+P 2O 5+TiO 2为2～6％。
  10. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，TiO 2 2～9.5％，优选为TiO 2 5～8.5％；和/或ZrO 2+P 2O 5+TiO 2为1～16％，优选为ZrO 2+P 2O 5+TiO 2为2～12％。
  11. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，还含有NiO和/或Ni 2O 3，合计量不超过6％，优选不超过4％，更优选不超过3％，合计量下限在0.1％以上；或含有Pr 2O 5，含量不超过8％，优选不超过6％，更优选不超过5％，含量下限在0.4％以上；或含有CoO和/或Co 2O 3，合计量不超过 2％，优选不超过1.8％，合计量下限在0.05％以上；或含有Cu 2O和/或CeO 2，合计量不超过4％，优选不超过3％，合计量下限在0.5％以上；或含有Fe 2O 3，含量不超过8％，优选不超过5％，更优选不超过3％；或含有Fe 2O 3和CoO，CoO不超过0.3％；或含有Fe 2O 3和Co 2O 3，Co 2O 3不超过0.3％；或含有Fe 2O 3、CoO和NiO；或含有Fe 2O 3、Co 2O 3和NiO；或含有Fe 2O 3、CoO和Co 2O 3，其中,CoO和Co 2O 3合计量下限在0.2％以上；或含有Fe 2O 3、CoO、NiO和Co 2O 3；或含有MnO 2，含量不超过4％，优选在3％以内，含量下限在0.1％以上；或含有Er 2O 3，含量不超过8％，优选在6％以内，含量下限在0.4％以上；或含有Nd 2O 3，含量不超过8％，优选在6％以内，含量下限在0.4％以上；或含有Er 2O 3、Nd 2O 3和MnO 2，Er 2O 3含量在6％以内，Nd 2O 3含量在4％以内，MnO 2含量在2％以内，其合计量的下限在0.9％以上；或含有Cr 2O 3，含量不超过4％，优选含量不超过3％，更优选含量不超过2％，含量下限在0.2％以上；或含有V 2O 5，含量不超过4％，优选含量不超过3％，更优选含量不超过2％，其含量下限在0.2％以上。
  12. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，Li 2Si 2O 5晶相占微晶玻璃的重量％为20～40％，优选为20～35％，更优选为20～30％，进一步优选为20～25％。
  13. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，石英以及石英固溶体晶相占微晶玻璃的重量％为15～30％，优选为20～30％，更优选为25～30％。
  14. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，所述Li 2Si 2O 5晶相和石英以及石英固溶体为主晶相，且其合计含量在微晶玻璃中占微晶玻璃的重量％低于50％，优选为48％以下，更优选为46％以下。
  15. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，LiAlSi 4O 10晶相占微晶玻璃的重量％不超过15％。
  16. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，玻璃液相温度的上限为1450℃，优选为1400℃，更优选为1380℃，最优选为1320℃。
  17. 如权利要求1-3任一权利要求所述的微晶玻璃，其特征在于，玻璃室温(25℃)的热导率在2W/m·k以上。
  18. 微晶玻璃基板，采用权利要求1-15任一权利所述的微晶玻璃经化学钢化制成。
  19. 如权利要求18所述的微晶玻璃基板，其特征在于，维氏硬度(Hv)为600kgf/mm 2以上，优选为650kgf/mm 2以上，更优选为700kgf/mm 2以上。
  20. 如权利要求18所述的微晶玻璃基板，其特征在于，将32g的钢球从500mm的高度落向所述微晶玻璃基板不会发生断裂，优选高度为650mm以上，更优选高度为800mm以上。
  21. 如权利要求18所述的微晶玻璃基板，其特征在于，三点弯曲强度为450Mpa以上，优选为600Mpa以上，更优选为800Mpa以上。
  22. 如权利要求18所述的微晶玻璃基板，其特征在于，通过离子交换处理形成压缩应力层，所述压缩应力层的压缩应力值为300Mpa以上，优选为400Mpa以上，更优选为500Mpa以上。
  23. 如权利要求18所述的微晶玻璃基板，其特征在于，所述压缩应力层的厚度为1μm以上，优选为5μm以上，更优选为8μm以上。
  24. 便携式电子设备，含有权利要求1-17任一权利要求所述的微晶玻璃。
  25. 便携式电子设备，含有权利要求书18-23任一权利要求所述的微晶玻璃基板。
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