CN111348833A - Glass ceramics and substrate thereof - Google Patents

Glass ceramics and substrate thereof Download PDF

Info

Publication number
CN111348833A
CN111348833A CN202010355184.9A CN202010355184A CN111348833A CN 111348833 A CN111348833 A CN 111348833A CN 202010355184 A CN202010355184 A CN 202010355184A CN 111348833 A CN111348833 A CN 111348833A
Authority
CN
China
Prior art keywords
glass
percent
content
less
sio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010355184.9A
Other languages
Chinese (zh)
Other versions
CN111348833B (en
Inventor
原保平
于天来
聂小兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CDGM Glass Co Ltd
Original Assignee
CDGM Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CDGM Glass Co Ltd filed Critical CDGM Glass Co Ltd
Priority to CN202010355184.9A priority Critical patent/CN111348833B/en
Publication of CN111348833A publication Critical patent/CN111348833A/en
Application granted granted Critical
Publication of CN111348833B publication Critical patent/CN111348833B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C10/0018—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
    • 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
    • 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

Abstract

The invention provides a microcrystalline glass and a substrate thereof, which have low liquid phase temperature and comprise the following components in percentage by weight: SiO 2260～80％；Al2O34～20％；Li2O 0～15％；Na2O is greater than 0 but less than or equal to 12%; k2O 0～5％；ZrO2Greater than 0 but less than or equal to 5%; p2O50～5％；TiO20 to 10% and a crystal phase containing R2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18And quartz solid solution. The microcrystalline glass has a liquid phase temperature below 1450 ℃, a thermal conductivity above 2 w/m.k, and a Vickers hardness of 600kgf/mm2The above is applicable to portable electronic devices and optical devices.

Description

Glass ceramics and substrate thereof
The application is a divisional application of Chinese patent application with the application date of 2017, 12 and 01, application number of 201711248375.X and the invention name of microcrystalline glass and a substrate thereof.
Technical Field
The present invention relates to a glass ceramic and a substrate using the glass ceramic as a base material, and more particularly, to a glass ceramic and a substrate having high thermal conductivity and high strength, which are suitable for a protective member such as a portable electronic device or an optical device.
Background
For portable electronic devices such as smart phones, tablet PCs, and other optical devices, a back cover is used to protect the internal electronics. These protective materials for the back cover, particularly for electronic devices that require wireless signals, are required to have high thermal conductivity, different individual colors, and high strength, to be able to be used in harsh environments, and to have good processability. In the past, metal is generally used as a rear cover protection material, but the metal rear cover can seriously affect the signal acceptance, only can be designed into a sectional type, and the metal rear cover cannot be used along with the development of a 5G signal.
As a ceramic material which does not affect signals, the ceramic material has good texture and higher thermal conductivity, but has poorer processability and higher cost compared with glass. At present, the common glass has low thermal conductivity and low strength, and the use of the common glass as a rear cover material of electronic equipment is limited.
Glass ceramics are also called glass ceramics, and are materials in which crystals are precipitated inside glass by heat treatment of glass. The crystallized glass can have physical properties that cannot be obtained in glass due to crystals dispersed therein. For example, the mechanical strength such as Young's modulus and fracture toughness, the etching characteristics with an acidic or alkaline chemical solution, the thermal properties such as the thermal expansion coefficient, and the increase and decrease of the glass transition temperature. The microcrystalline glass has higher mechanical properties, and the heat conductivity of the glass can be improved because the microcrystalline glass is formed in the glass, but the conventional microcrystalline glass is not suitable for the protective material because the heat conductivity and the strength are poor. In addition, conventional glass ceramics have low productivity because of high viscosity and high devitrification of the base glass, and thus are difficult to be used for the protective material.
Japanese patent application laid-open No. 2014-114200 discloses a crystallized glass substrate for an information recording medium, which cannot obtain a sufficient compressive stress value after chemical tempering and cannot form a deep stress layer.
With SiO2-Li2O-Al2O3-K2O-ZnO-P2O5-ZrO2Lithium disilicate glass ceramics developed for a system have lithium disilicate crystals uniformly distributed in a glass matrix to form an interlocking plate-shaped crystal microstructure, so that crack propagation can be prevented, the strength and fracture toughness of the material can be obviously improved, and better optical properties are kept.
The lithium disilicate glass ceramic has better strength and toughness, can generate better microcrystalline glass strength effect by chemical rigidization or physical strengthening, and can be used for protecting cover plates of portable electronic equipment such as smart phones, flat-plate PCs and other optical equipment.
Disclosure of Invention
The invention aims to provide microcrystalline glass and a substrate thereof, which have low liquid phase temperature.
The technical scheme adopted by the invention for solving the technical problem is as follows: the microcrystalline glass comprises the following components in percentage by weight: SiO 2260～80％；Al2O34～20％；Li2O 0～15％；Na2O is greater than 0 but less than or equal to 12%; k2O 0～5％；ZrO2Greater than 0 but less thanOr equal to 5%; p2O50～5％；TiO20 to 10% and a crystal phase containing R2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18And quartz solid solution, wherein R is at least 1 selected from Li, Na and K.
Further, the method also comprises the following steps: b is2O30 to 5 percent; and/or MgO 0-2%; and/or 0-2% of ZnO; and/or 0-5% of CaO; and/or 0-5% of BaO; and/or 0-3% of FeO; and/or SnO20-2%; and/or 0-5% of SrO; and/or La2O30 to 10 percent; and/or Y2O30 to 10 percent; and/or Nb2O50 to 10 percent; and/or Ta2O50 to 10 percent; and/or WO30～5％。
The microcrystalline glass comprises the following components in percentage by weight: SiO 2260～80％；Al2O34～20％；Li2O 0～15％；Na2O is greater than 0 but less than or equal to 12%; ZrO (ZrO)2Greater than 0 but less than or equal to 5%; p2O50～5％；TiO20～10％；B2O30～5％；K2O 0～5％；MgO 0～2％；ZnO 0～2％；CaO 0～5％；BaO 0～5％；FeO 0～3％；SnO20～2％；SrO 0～5％；La2O30～10％；Y2O30～10％；Nb2O50～10％；Ta2O50～10％；WO30 to 5 percent; 0-5% of a clarifying agent, and the crystal phase contains R2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18And quartz solid solution, wherein R is at least 1 selected from Li, Na and K.
Further, SiO265-78%; and/or Al2O35-18%; and/or Li20-12% of O; and/or Na20.5-10% of O; and/or ZrO20.4-3%; and/or P2O50.4-3%; and/or TiO22-9.5%; and/or B2O30 to 4 percent; and/or K20.5-4% of O; and/or MgO is 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 0-4% of CaO; and/or 0-4% of BaO; and/or 0-1% of FeO; and/or SnO20.01-1%; and/or 0-3% of SrO; and/or La2O30 to 9 percent; and/or Y2O30 to 9 percent; and/or Nb2O50-8%; and/or Ta2O50-8%; and/or WO30-2%; and/or the fining agent comprises As2O3、Sb2O3、CeO2And 0 to 5% of one or more selected from the group consisting of F, Cl, NOx and SOx.
Further, SiO2/Li2O is 4-10; and/or ZrO2/Li2O is 0 to 0.5; and/or Al2O3/(Na2O+Li2O) is 0.5 to 2; and/or Li2O/Na2O is 0.8 to 8; and/or ZrO2+P2O5+TiO21 to 16%.
Further, SiO268-75%; and/or Al2O36-15%; and/or Li26-10% of O; and/or Na2O2-8%; and/or ZrO20.8-2%; and/or P2O50.8-2%; and/or TiO23-9%; and/or B2O30 to less than 2 percent; and/or K20.8-3% of O; and/or 0-3% of CaO; and/or 0-3% of BaO; and/or SnO20.05-0.4%; and/or 0-1% of SrO; and/or La2O3Greater than 0 but less than or equal to 8%; and/or Y2O3Greater than 0 but less than or equal to 8%; and/or Nb2O50 to 5 percent; and/or Ta2O50 to 5 percent; and/or WO30 to 1 percent; and/or 0-2% of a clarifying agent.
Further, SiO2/Li2O is 4.5 to 9.5; and/or ZrO2/Li2O is greater than 0 but less than 0.35; and/or Al2O3/(Na2O+Li2O) is 0.7 to 1.8; and/or Li2O/Na2O is 1.5 to 7.5; and/or ZrO2+P2O5+TiO2Is 2 to 12.
Further, Na2O4-8%, preferably more than 5% but less than or equal to 8%; and/or Al2O37-15%; and/or ZrO21-2%; and/or P2O51-2%; and/or TiO25-8.5%; and/or K21-3% of O; and/or 0-1% of CaO; and/or 0-1% of BaO; and/or SnO20.05-0.2%; and/or 0-1% of a clarifying agent; and/or SiO2/Li2O is 5-9; and/or ZrO2/Li2O is greater than 0 but less than or equal to 0.30; and/or Al2O3/(Na2O+Li2O) is 1 to 1.5; and/or Li2O/Na2O is 2 to 7, preferably Li2O/Na2O is 2 to 6.
Further, NiO and/or Ni is contained2O3The total amount is not more than 6%, preferably not more than 4%, more preferably not more than 3%, and the lower limit of the total amount is not less than 0.1%; or contains Pr2O5The content is not more than 8%, preferably not more than 6%, more preferably not more than 5%, and the lower limit of the content is more than 0.4%; or containing CoO and/or Co2O3The total amount is not more than 2%, preferably not more than 1.8%, and the lower limit of the total amount is not less than 0.05%; or containing Cu2O and/or CeO2The total amount is not more than 4%, preferably not more than 3%, and the lower limit of the total amount is not less than 0.5%; or containing Fe2O3In an amount not exceeding 8%, preferably not exceeding 5%,more preferably not more than 3%; or containing Fe2O3And CoO, CoO not exceeding 0.3%; or containing Fe2O3And Co2O3，Co2O3Not more than 0.3%; or containing Fe2O3CoO and NiO; or containing Fe2O3、Co2O3And NiO; or containing Fe2O3CoO and Co2O3Wherein, CoO and Co2O3The lower limit of the total amount is more than 0.2 percent; or containing Fe2O3CoO, NiO and Co2O3(ii) a Or containing MnO2The content is not more than 4 percent, preferably within 3 percent, and the lower limit of the content is more than 0.1 percent; or containing Er2O3The content is not more than 8 percent, preferably within 6 percent, and the lower limit of the content is more than 0.4 percent; or containing Nd2O3The content is not more than 8 percent, preferably within 6 percent, and the lower limit of the content is more than 0.4 percent; or containing Er2O3、Nd2O3And MnO2，Er2O3Content within 6% of Nd2O3Content within 4%, MnO2The content is within 2 percent, and the lower limit of the total amount is more than 0.9 percent; or containing Cr2O3The content is not more than 4%, preferably not more than 3%, more preferably not more than 2%, and the lower limit of the content is more than 0.2%; or contain V2O5The content is not more than 4%, preferably not more than 3%, more preferably not more than 2%, and the lower limit of the content is not less than 0.2%.
Further, Li2Si2O5The content of the crystalline phase in the microcrystalline glass is 20 to 40 wt%, preferably 20 to 35 wt%, more preferably 20 to 30 wt%, and still more preferably 20 to 25 wt%.
Furthermore, the weight percent of the crystal phase of quartz and quartz solid solution in the microcrystalline glass is 15-30%, preferably 20-30%, and more preferably 25-30%.
Further, the Li2Si2O5The crystal phase and quartz solid solution are main crystal phases, and the total content of the crystal phase and the quartz solid solution accounts for the weight of the microcrystalline glassThe amount% is less than 50%, preferably 48% or less, more preferably 46% or less.
Further, LiAlSi4O10The crystal phase accounts for no more than 15 percent of the weight of the microcrystalline glass.
Further, the upper limit of the glass liquidus temperature is 1450 ℃, preferably 1400 ℃, more preferably 1380 ℃, and most preferably 1320 ℃.
Further, the glass has a thermal conductivity of 2 w/m.k or more at room temperature (25 ℃ C.).
The microcrystalline glass substrate is prepared by chemically toughening the microcrystalline glass.
Further, the Vickers hardness (Hv) is 600kgf/mm2Above, preferably 650kgf/mm2Above, more preferably 700kgf/mm2The above.
Further, the 32g steel ball is dropped from a height of 500mm toward the glass-ceramic substrate without breaking, and the height is preferably 650mm or more, more preferably 800mm or more.
Further, the three-point bending strength is 450MPa or more, preferably 600MPa or more, and more preferably 800MPa or more.
Further, a compressive stress layer having a compressive stress value of 300Mpa or more, preferably 400Mpa or more, and more preferably 500Mpa or more is formed by ion exchange treatment.
Further, the thickness of the compressive stress layer is 1 μm or more, preferably 5 μm or more, and more preferably 8 μm or more.
The invention has the beneficial effects that: the microcrystalline glass of the present invention has a liquidus temperature of 1450 ℃ or lower, a thermal conductivity of 2 w/m.k or higher at room temperature, and a Vickers hardness (Hv) of 600kgf/mm after tempering2The above. The microcrystalline glass or the substrate is suitable for protective components of portable electronic equipment, optical equipment and the like, particularly used as a rear cover plate, has high heat conductivity and strength, and is transparent or can have different individual colors. The glass ceramics of the present invention can be used as a heat conductive material because of its high heat conductivity, and can be used for other members such as an outer frame member of a portable electronic device having a specific outer shape of a glass materialAnd (6) decorating.
Detailed Description
The crystallized glass 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 crystallized glass can be discriminated by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis, and by TEMEDX. The crystallized glass of the present invention contains R in the crystal phase2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18And quartz solid solution, wherein R is more than 1 of Li, Na and K.
Wherein the above Li2Si2O5The crystal phase is a lithium disilicate crystal phase and is based on [ Si ]2O5]The crystal is flat or platy, the lithium disilicate crystal phase is a random non-oriented interlocking microstructure inside the microcrystalline glass, a path is bent when a crack passes through the crystal, so that the crack is prevented from expanding, the strength and the toughness of the microcrystalline glass are improved, and compared with the glass phase, the lithium disilicate crystal phase has high thermal conductivity, so that the thermal conductivity of the microcrystalline glass is improved. In the microcrystalline glass of the present invention, Li2Si2O5The content of the crystalline phase in the microcrystalline glass is 20 to 40 wt%, preferably 20 to 35 wt%, more preferably 20 to 30 wt%, and still more preferably 20 to 25 wt%.
The crystal phase of the quartz and the quartz solid solution belongs to a trigonal or hexagonal system, exists in the microcrystalline glass in a spherical form, can further prevent the expansion of microcracks, and improves the bending strength and toughness of the microcrystalline glass. The weight percentage of the crystal phase of quartz and quartz solid solution in the microcrystalline glass is 15-30%, preferably 20-30%, and more preferably 25-30%.
The invention controls the crystallization process and the content of the components, and Li2Si2O5The crystal phase and quartz solid solution are main crystal phases, and the total content of the crystal phases and the quartz solid solution accounts for less than 50 percent of the weight of the glass ceramics in the glass ceramics, and researches show that if the content of the main crystal phase exceeds 50 percent, the crystal phase content is higher in the glass, so that the glass ceramics have poor toughening effect, cannot play a role in increasing the strength of the glass, but can reduce the strength of the glass, preferably, Li2Si2O5The total content of the crystal phase, quartz and quartz solid solution is 48% or less, and more preferably 46% or less.
Petalite LiAlSi4O10Is a monoclinic crystal with folded Si connected by Li and Al tetrahedra2O6The three-dimensional framework structure of the layered structure of the layers has a low coefficient of expansion, can be used for improving the thermal shock resistance of the glass-ceramic, and is an auxiliary crystalline phase of the glass-ceramic, wherein the auxiliary crystalline phase accounts for not more than 15% of the weight of the glass-ceramic in the glass-ceramic.
The inventors of the present invention have made extensive experiments and studies, and have obtained a glass ceramic or a glass ceramic substrate of the present invention at a low cost by specifying the content and content ratio of specific components constituting the glass ceramic to specific values and precipitating specific crystal phases. The compositional ranges of the respective components of the glass ceramics of the present invention will be explained below. In the present specification, the contents of the respective components are all expressed in wt% with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition in terms of oxide" means that when all of the oxides, complex salts, metal fluorides, and the like used as the raw materials of the glass-ceramic composition component of the present invention are decomposed and converted into oxides at the time of melting, the total amount of the oxides is 100%. In the present specification, the term "glass" may include raw glass before crystallization.
SiO2Is an essential component for forming the glass network structure of the glass ceramics of the present invention, and is also an essential component which can be converted into a compositional crystal phase by heat treatment of the original glass. If the amount is less than 60%, the resulting glass is inferior in chemical durability and resistance to devitrification. Thus, SiO2The lower limit of the content is preferably 60%, more preferably 65%, and still more preferably 68%. On the other hand, by using SiO2The content of (b) is 80% or less, and excessive increase in viscosity and decrease in meltability can be suppressed. Thus, SiO2The upper limit of the content is preferably 80%, more preferably 78%, and still more preferably 75%.
Al2O3With SiO2Also, a component forming a network structure of glass, which is an important component contributing to stabilization of raw glass and improvement of chemical durability, may further improve the thermal conductivity of glass, but if the content thereof is less than 4%, the effect is not good. Thus, Al2O3The lower limit of the content is 4%, preferably 5%, more preferably 6%, and still more preferably 7%. On the other hand, if Al2O3When the content of (b) exceeds 20%, the meltability and devitrification resistance are lowered. Thus, Al2O3The upper limit of the content is 20%, preferably 18%, more preferably 15%.
Li2O is an optional component for improving the low-temperature melting property and the formability of the glass, and can 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 is contained excessively2O, a decrease in chemical durability or an increase in the average linear expansion coefficient is likely to occur. Thus, Li2The upper limit of the O content is preferably 15%, more preferably 12%, and still more preferably 10%. When chemical tempering is performed by ion exchange, if Li is contained in the microcrystalline glass2The O component is very effective in forming a deep compressive stress layer.
Na2O is an optional component for improving low-temperature melting property and moldability, and Na is excessively contained2O is liable to cause a decrease in chemical durability or an increase in the average linear expansion coefficient, and therefore, Na2The upper limit of the O content is preferably 12%, more preferably 10%, most preferably 8%. When chemically tempered by ion exchange, the microcrystalline glass contains Na2O component, Na in the glass ceramics+Ion and K+Ion exchange is very effective in forming the compressive stress layer. Thus, in chemical tempering by ion exchange, Na2The lower limit of the O content is more than 0, preferably 0.5%, more preferably 2%, still more preferably 4%, and most preferably more than 5%.
P2O5The ability to phase separate in the glass to form nuclei is an optional component that contributes to the improvement in the low-temperature melting properties of the glass. P2O5The lower limit of the content is preferably more than 0, more preferably 0.4%, further preferably 0.8%, most preferably 1%, but if P is contained excessively2O5The deterioration of devitrification resistance and phase separation of the glass are easily caused. Thus, P2O5The upper limit of the content is preferably 5%, more preferably 3%, and most preferably 2%.
ZrO2Has the function of crystallization precipitation to form crystal nucleus, and is also an optional component which contributes to the improvement of the chemical durability of the glass. ZrO (ZrO)2The lower limit of the content is preferably more than 0, more preferably 0.4%, further preferably 0.8%, most preferably 1%, but if ZrO is contained excessively2The resistance to devitrification of the glass is easily lowered. Thus, ZrO2The upper limit of the content is preferably 5%, more preferably 3%, and most preferably 2%.
TiO2Is an optional component which is helpful for reducing the viscosity of the microcrystalline glass, improving the chemical durability and reducing the liquid phase temperature, because Li in the glass2O and Na2The total content of O is high, which causes the glass to be easy to crystallize, and TiO is added2Then the free oxygen of the glass can be effectively absorbed to become a network former, and the liquid phase temperature of the glass is reduced. TiO 22The lower limit of the content is preferably more than 0, more preferably 2%, further preferably 3%, further preferably 5%, most preferably more than 6%. On the other hand, too much TiO2Failure to fully enter the glass network can lead to devitrification of the glass. Thus, TiO2The upper limit of the content is 10%, preferably 9.5%, more preferably 9%, most preferably 8.5%.
In the present invention, in order to obtainTo a desired crystal phase to thereby improve the thermal conductivity and hardness of the glass-ceramic substrate, it is necessary to control SiO2Relative to Li2Ratio of O content, i.e. making SiO2/Li2The value of O is 4 to 10. In order to more easily obtain the effect, SiO2/Li2The lower limit of the value of O is preferably 4, more preferably 4.5, most preferably 5; SiO 22/Li2The upper limit of the value of O is preferably 10, more preferably 9.5, most preferably 9.
In the present invention, in order to obtain uniform fine and more crystal phases in the glass and thereby improve the thermal conductivity and bending strength of the glass-ceramic substrate, it is necessary to control ZrO2Relative to Li2Ratio of O content, i.e. to ZrO2/Li2The value of O is 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.
In the present invention, in order to obtain a good tempering effect and thereby improve the strength of the glass-ceramic substrate, it is necessary to control Al2O3Relative to LiO2And Na2Ratio of total O content, i.e. Al2O3/(Na2O+Li2O) is preferably 0.5, more preferably 0.7, most preferably 1; al (Al)2O3/(Na2O+Li2O) is preferably 2, more preferably 1.8, most preferably 1.5.
In the present invention, in order to improve the devitrification resistance and the meltability and formability during melting, it is necessary to control Li2O relative to Na2Ratio of O, i.e. making Li2O/Na2The value of O is preferably 0.8 to 8. In order to more easily obtain the effect, Li2O/Na2The lower limit of the value of O is preferably 0.8, more preferably 1.5, most preferably 2; li2O/Na2The upper limit of the value of O is preferably 8, more preferably 7.5, still more preferably 7, and most preferably 6.
In the present invention, ZrO is controlled so that uniform crystals can be precipitated2、P2O5And TiO2I.e. ZrO2+P2O5+TiO21 to 16%. In order to more easily obtain the effect, ZrO2+P2O5+TiO2The lower limit of the value of (b) is preferably 1%, most preferably 2%; ZrO (ZrO)2+P2O5+TiO2The upper limit of the value of (b) is preferably 16%, more preferably 12%.
B2O3The glass is beneficial to reducing the viscosity of the glass, improving the melting property and the formability of the glass and improving the toughening property of the glass, so the glass can be added as an optional component. If B is contained excessively2O3The chemical durability of the glass ceramics is likely to be lowered, and the precipitation of desired crystals is likely to be suppressed. Thus, B2O3The upper limit of the content is preferably 5%, more preferably 4%, most preferably less than 2%.
K2O is an optional component for improving the low-temperature melting property and the formability of the glass, but if K is excessively contained, K is excessively contained2O, a decrease in chemical durability and an increase in the average linear expansion coefficient are easily generated. Thus, K2The upper limit of the O content is preferably 5%, more preferably 4%, most preferably 3%. When chemical tempering is performed by ion exchange, if K is contained in the glass ceramics2O is very effective in forming a deep compressive stress layer. Thus, when chemically tempered by ion exchange, K2The lower limit of the O content is preferably more than 0, more preferably 0.5%, further preferably 0.8%, and most preferably 1%.
MgO is an optional component contributing to lowering the viscosity of glass and suppressing devitrification of raw glass during molding, and also has an effect of improving low-temperature meltability, and the lower limit of the MgO content is preferably more than 0; however, if the content of MgO is too high, devitrification resistance may be deteriorated, and undesirable crystals are obtained after crystallization, resulting in deterioration of the performance of the glass ceramics, so that the upper limit of the content of MgO is preferably 2%.
ZnO can improve the melting performance of the glass and improve the chemical stability of the glass, and is an optional component, and the lower limit of the ZnO content is preferably more than 0; on the other hand, the upper limit of the ZnO content is controlled to 2% or less, and the deterioration of the devitrification property can be suppressed.
CaO is an optional component contributing to improvement of the low-temperature melting property of the glass, but if CaO is contained excessively, resistance to devitrification is liable to be lowered. Therefore, the upper limit of the CaO content is preferably 5%, more preferably 4%, further preferably 3%, and most preferably 1%.
BaO is an optional component contributing to improvement of the low-temperature melting property of the glass, but if BaO is excessively contained, resistance to devitrification is easily lowered. Therefore, the upper limit of the BaO content is preferably 5%, more preferably 4%, further preferably 3%, and most preferably 1%.
FeO can be contained arbitrarily because it functions as a refining agent, but if FeO is contained excessively, excessive coloring or alloying of platinum in the glass melting apparatus tends to occur. Therefore, the upper limit of the FeO content is preferably 3%, more preferably 1%.
SnO2Is an optional component capable of exerting the function as a clarifying agent and the function of precipitating crystals to form crystal nuclei. Thus, SnO2The lower limit of the content is preferably more than 0, more preferably 0.01%, most preferably 0.05%; however, if it contains too much SnO2The resistance to devitrification of the glass is easily lowered. Thus, SnO2The upper limit of the content is preferably 2%, more preferably 1%, still more preferably 0.4%, most preferably 0.2%.
SrO is an optional component for improving the low-temperature melting property of the glass, but if SrO is contained excessively, resistance to devitrification is liable to be lowered. Therefore, the upper limit of the SrO content is preferably 5%, more preferably 3%, and most preferably 1%.
La2O3Is an optional component for improving the hardness of the microcrystalline glass, can reduce the melting temperature of the glass by adding a small amount, and can reduce the liquid phase temperature to a certain extent, but if La is excessively contained, the hardness of the microcrystalline glass is improved2O3The resistance to devitrification is liable to be lowered. Thus, La2O3The content range of (B) is 10% or less, preferably 9% or less, more preferably greater than 0 but 8% or less.
Y2O3Is an optional component for improving the hardness, chemical stability and thermal conductivity of the microcrystalline glass, and can reduce the hardness, chemical stability and thermal conductivity of the glass by adding a small amountMelting temperature and lowering liquidus temperature to some extent, but if Y is contained excessively2O3The resistance to devitrification is liable to be lowered. Thus, Y2O3The content of (B) is 10% or less, preferably 9% or less, more preferably greater than 0 but 8% or less.
Nb2O5Is an optional component for improving the mechanical strength of the glass ceramics, but if Nb is contained excessively2O5The resistance to devitrification is liable to be lowered. Thus, Nb2O5The upper limit of the content is preferably 10%, more preferably 8%, most preferably 5%.
Ta2O5Is an optional component for improving the mechanical strength of the glass, but if Ta is contained excessively2O5The resistance to devitrification is liable to be lowered. Thus, Ta2O5The upper limit of the content is preferably 10%, more preferably 8%, most preferably 5%.
WO3Is an optional component for improving the mechanical strength of the glass, but if too much WO is contained3The resistance to devitrification is liable to be lowered. Thus, WO3The upper limit of the content is preferably 5%, more preferably 2%, most preferably 1%.
As may be contained As a fining agent in the glass ceramics of the present invention2O3、Sb2O3、CeO2And one or more selected from the group consisting of F, Cl, NOx, and SOx. However, the upper limit of the content of the clarifying agent is preferably 5%, more preferably 2%, most preferably 1%.
The microcrystalline glass of the invention can be added with a certain coloring agent to prepare microcrystalline glass with different colors.
Using NiO and/or Ni2O3For colorants for the preparation of brown or green glass ceramics, the two components can be used individually or in combination, in amounts of generally not more than 6%, preferably not more than 4%, more preferably not more than 3%, respectively, with the lower limit of the respective amounts being above 0.1%, if NiO and Ni are present2O3When mixed, NiO and Ni2O3Is generally not more than 6%, if anyIn amounts exceeding 6%, the colorant does not dissolve well in the glass.
Using Pr2O5As a colorant for green glass compositions, it is used alone, and is generally contained in an amount of not more than 8%, preferably not more than 6%, more preferably not more than 5%, with the lower limit thereof being 0.4% or more, and if the content is less than 0.4%, the color of the glass is not conspicuous.
Using CoO and/or Co2O3For the colorant, for the preparation of blue glass ceramics, the two colorant components may be used alone or in admixture, and both of them are generally contained in an amount of not more than 2%, preferably not more than 1.8%, respectively, and if the content exceeds 2%, the colorant is not well soluble in the glass, such as CoO and Co when used in admixture2O3The total amount is not more than 2%, and the respective contents thereof are limited to 0.05% or more, for example, less than 0.05%, and the color of the glass is not conspicuous.
Using Cu2O and/or CeO2For the colorant, a yellow glass-ceramic is prepared, the two colorant components being used individually or in a mixture, Cu being used alone2O, the content is not more than 4%, preferably not more than 3%, and if the content exceeds 4%, the glass is easily crystallized; using CeO alone2The content is usually not more than 4%, preferably not more than 3%, for example, the content exceeds 4%, and the glass is poor in gloss. When two kinds of colorants are used in combination, the total amount thereof is usually not more than 4% and the lower limit of the content is 0.5% or more.
Use of Fe alone2O3Is a colorant; or using Fe2O3And CoO; or using Fe2O3And Co2O3Two colorants used in combination; or using Fe2O3Three colorants mixed together, CoO and NiO; or using Fe2O3、Co2O3And NiO; or using Fe2O3CoO and Co2O3Three colorants used in combination; or using Fe2O3CoO, NiO and Co2O3Four colorants mixed for use in preparing blackAnd a glass-ceramic having a grayish smoke color. Use of Fe alone2O3Coloring, in an amount not exceeding 8%, preferably not exceeding 5%, more preferably not exceeding 3%. CoO and Co2O3Can increase the blackness of the glass by absorbing visible light, and is generally matched with Fe2O3When used in admixture, CoO with Co2O3Respectively not more than 0.3%, CoO and Co2O3The lower limit of the total amount is more than 0.2 percent. NiO absorbs visible light and can deepen the blackness of the glass, and the content of NiO does not exceed 1 percent when the NiO is mixed for use.
Using MnO2The content of the purple microcrystalline glass prepared by the method as a coloring agent is generally not more than 4 percent, preferably within 3 percent, and the lower limit of the content is more than 0.1 percent, such as the content is less than 0.1 percent, and the color of the glass is not obvious.
Use of Er2O3Is a colorant used for preparing pink microcrystalline glass, and the content of the colorant is generally not more than 8%, and preferably within 6%. Because of rare earth element Er2O3The coloring efficiency is low, when the content exceeds 8 percent, the color of the glass cannot be further deepened, but the cost of the glass is increased, and the lower limit of the content is more than 0.4 percent, such as less than 0.4 percent, and the color of the glass is not obvious.
Using Nd2O3For the colouring agent, a mauve glass composition is prepared, generally in a quantity not exceeding 8%, preferably within 6%. Due to rare earth element Nd2O3The coloring efficiency is low, the use content exceeds 8 percent, the color of the glass cannot be further deepened, the cost of the glass is increased, the lower limit of the content is more than 0.4 percent, such as less than 0.4 percent, and the color of the glass is not obvious.
Use of Er2O3、Nd2O3And MnO2Mixing the colorants to prepare the red glass-ceramic glass, wherein Er ions in the glass have absorption at 400-500nm, Mn ions mainly have absorption at 500nm, Nd ions mainly have strong absorption at 580nm, and the red glass composition can be prepared by mixing the Er ions and the Mn ions2O3And Nd2O3Coloring rare earth, relatively weak coloring ability, Er2O3The usage amount is less than 6 percent, Nd2O3The usage amount is less than 4 percent, the coloring of Mn ions is strong, and MnO is added2The amount of the colorant is within 2%, and the lower limit of the total amount of the colorant mixture is 0.9% or more.
Using Cr2O3As a colorant for green glass compositions, it is used alone, and is generally contained in an amount of not more than 4%, preferably not more than 3%, more preferably not more than 2%, with the lower limit being not less than 0.2%, and if the content is less than 0.2%, the color of the glass is not conspicuous.
Using V2O5As a colorant for a yellow-green glass composition, it is used alone, and is generally contained in an amount of not more than 4%, preferably not more than 3%, more preferably not more than 2%, with the lower limit thereof being 0.2% or more, e.g., less than 0.2%, the color of the glass is not conspicuous.
In the glass ceramics of the present invention, the glass composition may be composed of only the above components, but other components may be added within a range not seriously impairing the glass characteristics. For example, TeO may be added2、Bi2O3、GeO2And the like.
The crystallized glass of the present invention has the following characteristics.
The devitrified glass of the present invention has high devitrification resistance, and more specifically, has a low liquidus temperature. That is, the upper limit of the glass liquidus temperature in the present invention is preferably 1450 ℃, more preferably 1400 ℃, still more preferably 1380 ℃, and most preferably 1320 ℃. This can reduce devitrification when forming glass from a molten state even if the molten glass is discharged at a relatively low temperature. Further, since the glass can be molded even if the melting temperature of the glass is lowered, the deterioration of the platinum device and the mold can be suppressed, and the energy consumption at the time of molding the glass can be reduced, thereby reducing the production cost of the glass.
On the other hand, 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 ℃, more preferably 1100 ℃, and most preferably 1200 ℃.
The liquidus temperature is an index of resistance to devitrification, and in the present specification, a value measured by the following method is used as the liquidus temperature. First, a 30cc glass cullet-like glass sample was placed in a platinum crucible having a capacity of 50ml, and held at 1500 ℃ in a completely molten state; then, after cooling to a predetermined temperature and holding for 12 hours, the glass was taken out of the furnace and cooled, and the presence or absence of crystals on the surface of the glass and in the glass was observed, and the temperature was observed up to 1000 ℃ in units of 10 ℃ and the lowest temperature at which crystals were not observed among the predetermined temperature was taken as the liquidus temperature.
And (3) testing the high-temperature viscosity of the glass composition with the liquid phase temperature lower than 1200 ℃, testing the viscosity of the liquid phase temperature, and according to the SJT11040-1996 standard, after the glass is melted after reaching the highest temperature, descending the rotor by 23mm and entering the glass melt, simultaneously rotating, increasing the viscosity of the glass along with the reduction of the temperature, and automatically stopping the measurement when the torque of the rotor reaches 80% of the set torque, thus obtaining the viscosity of the glass through calculation.
The microcrystalline glass of the present invention has a thermal conductivity of 2W/m.k or more.
The microcrystalline glass substrate can form a compressive stress layer through ion exchange treatment and implement chemical toughening. When the compressive stress layer is formed, the value of the compressive stress layer is preferably 300MPa or more. With such a compressive stress value, it is possible to suppress the extension of cracks and improve the mechanical strength. Therefore, when chemical tempering is performed, the value of the compressive stress layer of the crystallized glass substrate of the present invention is preferably 300Mpa or more, more preferably 400Mpa or more, and most preferably 500Mpa or more.
The thickness of the compressive stress layer of the glass-ceramic substrate of the present invention is preferably 1 μm or more. Since the compressive stress layer has such a thickness, even if a deep crack occurs in the glass-ceramic substrate, crack extension and substrate fracture can be suppressed. Therefore, the thickness of the compressive stress layer is preferably 1 μm or more, more preferably 5 μm or more, and most preferably 8 μm or more.
The microcrystalline glass substrate of the present invention preferably has a vickers hardness (Hv) of 600 or more. With such hardness, occurrence of scratches can be suppressed, and mechanical strength can be improved. Therefore, the microcrystalline glass of the present invention has a vickers hardness (Hv) of preferably 600 or more, more preferably 650 or more, and most preferably 700 or more.
In the glass ceramic substrate of the present invention, it is preferable that the glass ceramic substrate is not broken even if 32g of steel balls are dropped from a height of 500mm to the glass ceramic substrate. Since the protective member has such impact resistance, it can withstand an impact when dropped or collided when used as a protective member. Therefore, the falling height at which the glass-ceramic substrate is not broken even when 32g of the steel ball is dropped is preferably 500mm or more, more preferably 650mm or more, and most preferably 800mm or more.
The three-point bending strength of the crystallized glass substrate of the present invention is preferably 450 Mpa. With such three-point bending strength, the glass will not break when subjected to sufficient pressure. Therefore, the three-point bending strength is preferably 450MPa or more, more preferably 600MPa or more, and most preferably 800MPa or more.
The microcrystalline glass of the present invention can be prepared by the following method: the raw materials are uniformly mixed according to the proportion range of the components, the uniform mixture is put into a crucible made of platinum or quartz, the melting is carried out for 5 to 24 hours in an electric furnace or a gas furnace within the temperature range of 1250 to 1550 ℃ according to the melting difficulty of the glass composition, the mixture is stirred to be uniform, then the temperature is reduced to proper temperature and the mixture is cast into a mould, and the mixture is slowly cooled to obtain the glass.
The glass of the glass ceramics of the present invention can be molded by a known method.
The glass-ceramic of the present invention is obtained by subjecting the glass raw material to crystallization treatment after molding or after molding processing, and uniformly precipitating crystals in the glass. The crystallization may be performed in 1 stage or 2 stages, but the crystallization is preferably performed in 2 stages. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization process performed at the 1 st temperature is referred to as a 1 st crystallization process, and the crystallization process performed at the 2 nd temperature is referred to as a 2 nd crystallization process.
In order to obtain desired physical properties of the glass ceramics, preferred heat treatment conditions are:
the above-mentioned crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after reaching the heat treatment temperature, 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 ℃, and the holding time at the crystallization treatment temperature is preferably 550 to 680 ℃, and is preferably 0 to 8 hours, and more preferably 1 to 6 hours, in order to precipitate a desired crystal phase.
When the crystallization is performed in 2 stages, the 1 st temperature is preferably 500 to 700 ℃, and the 2 nd temperature is preferably 650 to 850 ℃. The holding time at the temperature of 1 st is preferably 0 to 24 hours, and most preferably 2 to 15 hours. The holding time at the 2 nd temperature is preferably 0 to 10 hours, and most preferably 2 to 5 hours.
The above-mentioned holding time of 0 minutes means that the temperature is lowered or raised less than 1 minute after the temperature is reached.
The glass or glass ceramics of the present invention can be produced into a glass molded product by a method such as grinding or polishing. The glass-ceramic substrate based on the glass-ceramic of the present invention can be produced by processing a glass molded product into a thin plate. However, the method for producing the glass shaped material is not limited to these methods.
The microcrystalline glass substrate can be prepared into various shapes by adopting methods such as hot bending or pressing at a certain temperature, wherein the hot bending temperature and the pressing temperature are lower than the crystallization temperature. However, the method for producing various glass shapes is not limited to these methods.
The crystallized glass of the present invention can improve mechanical properties by precipitation crystallization and can obtain higher strength by forming a compressive stress layer. The formation method of the compression stress layer comprises a chemical toughening method, namely: an alkali component present in the surface layer of the glass-ceramic substrate is subjected to an exchange reaction with an alkali component having a larger ionic radius than the alkali component, thereby forming a compressive stress layer in the surface layer. There are also an ion implantation method for implanting ions into the surface layer of the glass-ceramic substrate and a thermal tempering method for heating and then rapidly cooling the glass-ceramic substrate.
Examples of the invention (tables 1 to 8) were prepared by the following method: firstly, selecting raw materials of various components, respectively corresponding oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and other raw materials, uniformly mixing the raw materials according to the component proportion range, putting the uniform mixture into a crucible made of platinum or quartz, melting the mixture in an electric furnace or a gas furnace at 1250-1550 ℃ for 5-24 hours according to the melting difficulty of glass composition, stirring the mixture uniformly, cooling the mixture to a proper temperature, casting the mixture into a mold, and slowly cooling the mixture to obtain raw glass.
The obtained raw glass was subjected to heat treatment in 1 stage or 2 stages for core formation and crystallization, respectively, to produce glass ceramics, in which examples 15, 18, 20 and 22 were subjected to heat treatment in 1 stage, and the other examples were subjected to heat treatment in 2 stages. In tables 1 to 8, the heat treatment conditions of the 1 st stage are recorded in the column of "nucleation process", the heat treatment conditions of the 2 nd stage are recorded in the column of "crystallization process", and the temperature of the heat treatment and the holding time at the temperature thereof are as shown in the tables.
In the examples, the crystal phase of the crystallized glass before chemical tempering was analyzed by an X-ray diffraction analyzer from the angle of the peak shown on the X-ray diffraction pattern.
Cutting and grinding the prepared glass ceramics to obtain 36 × 29 × 0.7.7 mm specification slices, polishing the opposite surfaces in parallel, and soaking the polished glass ceramics in KNO3And carrying out chemical toughening in the molten salt to obtain the microcrystalline glass substrate. Wherein, the temperature for soaking the molten salt and the soaking time are shown in the column of 'chemical toughening conditions' in the table.
And (3) measuring the compressive stress value of the surface of the microcrystalline glass substrate subjected to chemical tempering and the thickness of the compressive stress layer by using a glass surface stress meter FSM-6000. 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 crystallized glass substrate in the examples was calculated by dividing the load (N) when a diamond quadrangular pyramid indenter having an included angle of 136 degrees with respect to the opposing surface was pressed into a pyramid-shaped indentation on the test surface by the surface area (mm) calculated from the length of the indentation2) The values of (b) indicate (a). The test load was set to 100(N) and the holding time was set to 15 (sec). For the example with "chemical tempering conditions", this is done on the substrate after chemical tempering.
Specifically, the test was conducted from a ball drop height of 650mm, and the height was changed by 700mm, 750mm, 800mm, 850mm and 900mm without breaking, in the case of the example having "chemical tempering conditions", the substrate after chemical tempering was used as a test object, and the test data recorded as 900mm in the example shows that the substrate was subjected to the impact without breaking even if the steel ball was dropped from a height of 900 mm.
The three-point bending strength in tables 1 to 8 was measured by using a microcomputer controlled electronic universal tester CMT6502, a glass specification of 36 × 29 × 0.7.7 mm, and ASTM C158-.
The thermal conductivity of the microcrystalline glasses in tables 1 to 8 was measured by a thermal conductivity measuring instrument LFA 447. the standard JC/T675-1997 test method for thermal conductivity of glass materials was carried out under the measurement conditions of room temperature (25 ℃) and a sample specification of phi 12.7mm × 1.5.5 mm.
The color in the examples is the color of a 36 × 29 × 0.8.8 mm glass sheet observed by the naked eye.
TABLE 1
Figure BDA0002473190340000131
Figure BDA0002473190340000141
TABLE 2
Figure BDA0002473190340000142
Figure BDA0002473190340000151
TABLE 3
Figure BDA0002473190340000152
Figure BDA0002473190340000161
TABLE 4
Figure BDA0002473190340000162
Figure BDA0002473190340000171
Figure BDA0002473190340000181
TABLE 5
Figure BDA0002473190340000182
Figure BDA0002473190340000191
TABLE 6
Figure BDA0002473190340000192
Figure BDA0002473190340000201
Figure BDA0002473190340000211
TABLE 7
Figure BDA0002473190340000212
Figure BDA0002473190340000221
TABLE 8
Figure BDA0002473190340000222
Figure BDA0002473190340000231
The above examples show that the heat conductivity of the microcrystalline glass of the invention at room temperature (25 ℃) is more than 2W/m.k, the microcrystalline glass has high heat conductivity, better bending strength and hardness, and good anti-falling damage performance, and meanwhile, the microcrystalline glass of the invention also has good individual color. The microcrystalline glass or the substrate obtained by the invention is suitable for protection components of portable electronic equipment, optical equipment and the like, and is particularly used as a rear cover plate.

Claims (21)

1. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2260～80％；Al2O34～20％；Li2O 0～15％；Na2O is greater than 0 but less than or equal to 12%; k2O 0～5％；ZrO2Greater than 0 but less than or equal to 5%; p2O50～5％；TiO20 to 10% and a crystal phase containing R2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18And quartz solid solution, wherein R is at least 1 selected from Li, Na and K.
2. The glass-ceramic according to claim 1, further comprising: b is2O30 to 5 percent; and/or MgO 0-2%; and/or 0-2% of ZnO; and/or 0-5% of CaO; and/or 0-5% of BaO; and/or 0-3% of FeO; and/or SnO20-2%; and/or 0-5% of SrO; and/or La2O30 to 10 percent; and/or Y2O30 to 10 percent; and/or Nb2O50 to 10 percent; and/or Ta2O50 to 10 percent; and/or WO30～5％。
3. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2260～80％；Al2O34～20％；Li2O0～15％；Na2O is greater than 0 but less than or equal to 12%; ZrO (ZrO)2Greater than 0 but less than or equal to 5%; p2O50～5％；TiO20～10％；B2O30～5％；K2O 0～5％；MgO 0～2％；ZnO 0～2％；CaO 0～5％；BaO 0～5％；FeO 0～3％；SnO20～2％；SrO 0～5％；La2O30～10％；Y2O30～10％；Nb2O50～10％；Ta2O50～10％；WO30 to 5 percent; 0-5% of a clarifying agent, and the crystal phase contains R2SiO3、R2Si2O5、R2TiO3、R4Ti5O12、R3PO3、RAlSi2O6、RAlSiO4O10、R2Al2Si2O8、R4Al4Si5O18And quartz solid solution, wherein R is selected from Li, Na and KMore than 1.
4. The glass-ceramic according to any one of claims 1 to 3, wherein SiO is SiO265-78%; and/or Al2O35-18%; and/or Li20-12% of O; and/or Na20.5-10% of O; and/or ZrO20.4-3%; and/or P2O50.4-3%; and/or TiO22-9.5%; and/or B2O30 to 4 percent; and/or K20.5-4% of O; and/or MgO is 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 0-4% of CaO; and/or 0-4% of BaO; and/or 0-1% of FeO; and/or SnO20.01-1%; and/or 0-3% of SrO; and/or La2O30 to 9 percent; and/or Y2O30 to 9 percent; and/or Nb2O50-8%; and/or Ta2O50-8%; and/or WO30-2%; and/or the fining agent comprises As2O3、Sb2O3、CeO2And 0 to 5% of one or more selected from the group consisting of F, Cl, NOx and SOx.
5. The glass-ceramic according to any one of claims 1 to 3, wherein SiO is SiO2/Li2O is 4-10; and/or ZrO2/Li2O is 0 to 0.5; and/or Al2O3/(Na2O+Li2O) is 0.5 to 2; and/or Li2O/Na2O is 0.8 to 8; and/or ZrO2+P2O5+TiO21 to 16%.
6. The glass-ceramic according to any one of claims 1 to 3, wherein SiO is SiO268-75%; and/or Al2O36-15%; and/or Li26-10% of O; and/or Na2O2-8%; and/or ZrO20.8-2%; and/or P2O50.8-2%; and/or TiO23-9%; and/or B2O30 to less than 2 percent; and/or K20.8-3% of O; and/or 0-3% of CaO; and/or 0-3% of BaO; and/or SnO20.05-0.4%; and/or 0-1% of SrO; and/or La2O3Greater than 0 but less than or equal to 8%; and/or Y2O3Greater than 0 but less than or equal to 8%; and/or Nb2O50 to 5 percent; and/or Ta2O50 to 5 percent; and/or WO30 to 1 percent; and/or 0-2% of a clarifying agent.
7. The glass-ceramic according to any one of claims 1 to 3, wherein SiO is SiO2/Li2O is 4.5 to 9.5; and/or ZrO2/Li2O is greater than 0 but less than 0.35; and/or Al2O3/(Na2O+Li2O) is 0.7 to 1.8; and/or Li2O/Na2O is 1.5 to 7.5; and/or ZrO2+P2O5+TiO22 to 12 percent.
8. The microcrystalline glass according to any of claims 1-3, characterised in that Na is present2O4-8%, preferably more than 5% but less than or equal to 8%; and/or Al2O37-15%; and/or ZrO21-2%; and/or P2O51-2%; and/or TiO25-8.5%; and/or K21-3% of O; and/or 0-1% of CaO; and/or 0-1% of BaO; and/or SnO20.05-0.2%; and/or 0-1% of a clarifying agent; and/or SiO2/Li2O is 5-9; and/or ZrO2/Li2O is greater than 0 but less than or equal to 0.30; and/or Al2O3/(Na2O+Li2O) is 1 to 1.5; and/or Li2O/Na2O is 2 to 7, preferably Li2O/Na2O is 2 to 6.
9. The glass-ceramic according to any one of claims 1 to 3, further comprising NiO and/or Ni2O3The total amount is not more than 6%, preferably not more than 4%, more preferably not more than 3%,the lower limit of the total amount is more than 0.1 percent; or contains Pr2O5The content is not more than 8%, preferably not more than 6%, more preferably not more than 5%, and the lower limit of the content is more than 0.4%; or containing CoO and/or Co2O3The total amount is not more than 2%, preferably not more than 1.8%, and the lower limit of the total amount is not less than 0.05%; or containing Cu2O and/or CeO2The total amount is not more than 4%, preferably not more than 3%, and the lower limit of the total amount is not less than 0.5%; or containing Fe2O3The content is not more than 8%, preferably not more than 5%, more preferably not more than 3%; or containing Fe2O3And CoO, CoO not exceeding 0.3%; or containing Fe2O3And Co2O3，Co2O3Not more than 0.3%; or containing Fe2O3CoO and NiO; or containing Fe2O3、Co2O3And NiO; or containing Fe2O3CoO and Co2O3Wherein, CoO and Co2O3The lower limit of the total amount is more than 0.2 percent; or containing Fe2O3CoO, NiO and Co2O3(ii) a Or containing MnO2The content is not more than 4 percent, preferably within 3 percent, and the lower limit of the content is more than 0.1 percent; or containing Er2O3The content is not more than 8 percent, preferably within 6 percent, and the lower limit of the content is more than 0.4 percent; or containing Nd2O3The content is not more than 8 percent, preferably within 6 percent, and the lower limit of the content is more than 0.4 percent; or containing Er2O3、Nd2O3And MnO2，Er2O3Content within 6% of Nd2O3Content within 4%, MnO2The content is within 2 percent, and the lower limit of the total amount is more than 0.9 percent; or containing Cr2O3The content is not more than 4%, preferably not more than 3%, more preferably not more than 2%, and the lower limit of the content is more than 0.2%; or contain V2O5The content is not more than 4%, preferably not more than 3%, more preferably not more than 2%, and the lower limit of the content is not less than 0.2%.
10. The microcrystalline glass according to any of claims 1-3, characterised in that Li2Si2O5The content of the crystalline phase in the microcrystalline glass is 20 to 40 wt%, preferably 20 to 35 wt%, more preferably 20 to 30 wt%, and still more preferably 20 to 25 wt%.
11. A glass-ceramic according to any one of claims 1-3, characterized in that the quartz and quartz solid solution crystalline phases constitute 15-30%, preferably 20-30%, more preferably 25-30% by weight of the glass-ceramic.
12. The microcrystalline glass according to any of claims 1-3, characterised in that said Li2Si2O5The crystal phase and quartz solid solution are the main crystal phases, and the total content thereof is less than 50%, preferably 48% or less, more preferably 46% or less, in the weight% of the glass ceramics.
13. The glass-ceramic according to any one of claims 1 to 3, wherein LiAlSi is used4O10The crystal phase accounts for no more than 15 percent of the weight of the microcrystalline glass.
14. A glass-ceramic according to any one of claims 1-3, characterized in that the upper limit of the liquidus temperature of the glass is 1450 ℃, preferably 1400 ℃, more preferably 1380 ℃, most preferably 1320 ℃.
15. A glass-ceramic according to any one of claims 1 to 3, characterized in that the glass has a thermal conductivity of 2 w/m-k or more at room temperature (25 ℃).
16. A glass-ceramic substrate, which is made by chemically toughening the glass-ceramic according to any one of claims 1 to 15.
17. The crystallized glass substrate according to claim 16, wherein the vickers hardness (Hv) is 600kgf/mm2Above, preferably 650kgf/mm2Above, more preferably 700kgf/mm2The above.
18. The glass-ceramic substrate according to claim 16, wherein 32g of steel balls are dropped from a height of 500mm toward the glass-ceramic substrate without breaking, preferably the height is 650mm or more, and more preferably the height is 800mm or more.
19. A crystallized glass substrate according to claim 16, wherein the three-point bending strength is 450Mpa or more, preferably 600Mpa or more, more preferably 800Mpa or more.
20. The crystallized glass substrate according to claim 16, wherein a compressive stress layer having a compressive stress value of 300Mpa or more, preferably 400Mpa or more, more preferably 500Mpa or more is formed by an ion exchange treatment.
21. A crystallized glass substrate according to claim 20, wherein the thickness of the compressive stress layer is 1 μm or more, preferably 5 μm or more, and more preferably 8 μm or more.
CN202010355184.9A 2017-12-01 2017-12-01 Glass ceramics and substrate thereof Active CN111348833B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010355184.9A CN111348833B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711248375.XA CN107902909B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof
CN202010355184.9A CN111348833B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201711248375.XA Division CN107902909B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof

Publications (2)

Publication Number Publication Date
CN111348833A true CN111348833A (en) 2020-06-30
CN111348833B CN111348833B (en) 2022-04-08

Family

ID=61849526

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201711248375.XA Active CN107902909B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof
CN202010355184.9A Active CN111348833B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201711248375.XA Active CN107902909B (en) 2017-12-01 2017-12-01 Glass ceramics and substrate thereof

Country Status (1)

Country Link
CN (2) CN107902909B (en)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019105250A1 (en) * 2017-12-01 2019-06-06 成都光明光电股份有限公司 Glass-ceramic and substrate thereof
CN108793734B (en) * 2018-06-20 2019-11-22 醴陵旗滨电子玻璃有限公司 The preparation method of glass composition, sillico aluminate glass and sillico aluminate glass
CN111417602A (en) * 2018-07-16 2020-07-14 康宁股份有限公司 Glass-ceramic articles having increased crush resistance and methods of making the same
WO2020018393A1 (en) * 2018-07-16 2020-01-23 Corning Incorporated Glass ceramic articles having improved properties and methods for making the same
WO2020018285A1 (en) 2018-07-16 2020-01-23 Corning Incorporated Methods of ceramming glass articles having improved warp
CN115403256A (en) 2018-07-16 2022-11-29 康宁股份有限公司 Method for ceramizing glass by using nucleation and growth density and viscosity change
CN111099825B (en) * 2018-10-26 2021-02-02 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN112456806B (en) * 2018-10-26 2022-04-12 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
TWI752849B (en) 2018-11-05 2022-01-11 美商康寧公司 Methods of making three dimensional glass ceramic articles
WO2020112468A1 (en) 2018-11-30 2020-06-04 Corning Incorporated Black beta-spodumene lithium silicate glass ceramics
JP7347449B2 (en) * 2019-02-08 2023-09-20 Ａｇｃ株式会社 Crystallized glass, chemically strengthened glass, and semiconductor support substrates
CN113544103A (en) * 2019-03-06 2021-10-22 株式会社小原 Inorganic composition product and crystallized glass
CN110104954B (en) * 2019-05-28 2022-08-23 科立视材料科技有限公司 Low-temperature crystallized ion-exchangeable glass ceramic
CN110143759B (en) * 2019-06-13 2022-06-14 科立视材料科技有限公司 High-strength transparent glass-ceramic
WO2021035586A1 (en) * 2019-08-28 2021-03-04 重庆鑫景特种玻璃有限公司 Strengthened glass ceramic having low surface compressive stress, and raw sheet glass
CN112441746B (en) * 2019-08-28 2023-11-10 重庆鑫景特种玻璃有限公司 Reinforced glass ceramic with low surface compressive stress and raw sheet glass
CN112939472B (en) * 2019-12-11 2022-04-26 四川旭虹光电科技有限公司 Microcrystalline glass and preparation method and application thereof
CN111087175B (en) * 2019-12-17 2021-06-11 重庆鑫景特种玻璃有限公司 Rare earth doped reinforced glass ceramic and preparation method and application thereof
CN110981206B (en) * 2019-12-20 2022-04-05 重庆鑫景特种玻璃有限公司 Polycrystalline core composite transparent glass ceramic and preparation method thereof
CN111018356B (en) * 2019-12-30 2022-05-10 重庆鑫景特种玻璃有限公司 Microcrystalline glass with high crystal content and preparation method thereof
EP4049981A1 (en) * 2021-02-24 2022-08-31 Ivoclar Vivadent AG Glass ceramic with quartz mixed crystal phase
CN112919809A (en) * 2021-03-09 2021-06-08 山东国瓷功能材料股份有限公司 Glass ceramic and preparation method thereof
CN112919810B (en) * 2021-03-23 2022-02-18 成都光明光电股份有限公司 Glass-ceramic, glass-ceramic article and method for producing same
CN113562977B (en) * 2021-09-27 2021-12-24 武汉理工大学 Glass ceramic and preparation method thereof
CN114671618B (en) * 2022-04-24 2023-11-07 清远南玻节能新材料有限公司 Microcrystalline glass, reinforced glass, preparation method and application thereof
WO2023206002A1 (en) * 2022-04-25 2023-11-02 清远南玻节能新材料有限公司 Glass ceramic, tempered glass, and preparation method therefor and use thereof
WO2023206009A1 (en) * 2022-04-25 2023-11-02 清远南玻节能新材料有限公司 Glass ceramic and preparation method therefor

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1467459A (en) * 1975-10-10 1977-03-16 English Electric Co Ltd Glass ceramics and to the coating of metal articles with glass-ceramic
EP0205262A1 (en) * 1985-06-10 1986-12-17 Corning Glass Works Strengthened glass articles and method for making
CN101279818A (en) * 2007-04-06 2008-10-08 株式会社小原 Inorganic composition article
CN101462829A (en) * 2007-12-21 2009-06-24 株式会社小原 Glass-ceramics and method for manufacturing the same
CN101659518A (en) * 2009-06-16 2010-03-03 北京盛康宁科技开发有限公司 Microcrystalline glass with high transparency and high heat resistance and preparation method thereof
JP2010150117A (en) * 2008-11-26 2010-07-08 Ohara Inc Crystallized glass and process for producing same
JP2012056786A (en) * 2010-09-08 2012-03-22 Ohara Inc Method for producing crystallized glass and crystallized glass article
US20130302618A1 (en) * 2011-01-28 2013-11-14 Kornerstone Materials Technology Co., Ltd. High-strength alkali-aluminosilicate glass
CN103476723A (en) * 2011-04-20 2013-12-25 斯特劳曼控股公司 Process for preparing a glass-ceramic body
CN105683109A (en) * 2013-09-06 2016-06-15 康宁公司 High strength glass-ceramics having lithium disilicate and beta-spodumene structures

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391914A (en) * 1982-06-14 1983-07-05 Corning Glass Works Strengthened glass-ceramic article and method
US20090286058A1 (en) * 2006-05-19 2009-11-19 Noriaki Shibata Crystal Glass Article
DE102010032113B9 (en) * 2010-07-23 2017-06-22 Schott Ag Transparent or transparent colored lithium aluminum silicate glass-ceramic with adjustable thermal expansion and its use
TWI808375B (en) * 2014-10-08 2023-07-11 美商康寧公司 High strength glass-ceramics having petalite and lithium silicate structures

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1467459A (en) * 1975-10-10 1977-03-16 English Electric Co Ltd Glass ceramics and to the coating of metal articles with glass-ceramic
EP0205262A1 (en) * 1985-06-10 1986-12-17 Corning Glass Works Strengthened glass articles and method for making
CN101279818A (en) * 2007-04-06 2008-10-08 株式会社小原 Inorganic composition article
US20080248316A1 (en) * 2007-04-06 2008-10-09 Ohara Inc. Inorganic composition article
CN101462829A (en) * 2007-12-21 2009-06-24 株式会社小原 Glass-ceramics and method for manufacturing the same
JP2010150117A (en) * 2008-11-26 2010-07-08 Ohara Inc Crystallized glass and process for producing same
CN101659518A (en) * 2009-06-16 2010-03-03 北京盛康宁科技开发有限公司 Microcrystalline glass with high transparency and high heat resistance and preparation method thereof
JP2012056786A (en) * 2010-09-08 2012-03-22 Ohara Inc Method for producing crystallized glass and crystallized glass article
US20130302618A1 (en) * 2011-01-28 2013-11-14 Kornerstone Materials Technology Co., Ltd. High-strength alkali-aluminosilicate glass
CN103476723A (en) * 2011-04-20 2013-12-25 斯特劳曼控股公司 Process for preparing a glass-ceramic body
CN105683109A (en) * 2013-09-06 2016-06-15 康宁公司 High strength glass-ceramics having lithium disilicate and beta-spodumene structures

Also Published As

Publication number Publication date
CN107902909A (en) 2018-04-13
CN107902909B (en) 2020-04-28
CN111348833B (en) 2022-04-08

Similar Documents

Publication Publication Date Title
CN111348833B (en) Glass ceramics and substrate thereof
CN111517656B (en) Glass ceramics and substrate thereof
CN109867447B (en) Glass ceramics and substrate thereof
CN107840578B (en) Glass ceramics and substrate thereof
CN111727176B (en) Glass ceramics, glass ceramics product and manufacturing method thereof
JP6765748B2 (en) Crystallized glass and crystallized glass substrate
JP7079851B2 (en) Crystallized glass and its substrate
KR102609966B1 (en) Microcrystalline glass product and microcrystalline glass for electronic equipment cover plate
CN107963815A (en) Devitrified glass and its substrate
CN111099828B (en) Glass ceramics, glass ceramics product and manufacturing method thereof
US20230069922A1 (en) Glass material, and preparation method and product thereof
CN114671619B (en) Glass ceramics and glass ceramics products
CN113402172B (en) Glass ceramic and glass ceramic article

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant