CN116282926A - High-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and preparation method thereof - Google Patents
High-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and preparation method thereof Download PDFInfo
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- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052912 lithium silicate Inorganic materials 0.000 title claims abstract description 25
- 239000006017 silicate glass-ceramic Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 103
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 73
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 22
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000006121 base glass Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- 238000002425 crystallisation Methods 0.000 claims description 34
- 230000008025 crystallization Effects 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 239000010453 quartz Substances 0.000 claims description 19
- 238000002834 transmittance Methods 0.000 claims description 16
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 9
- 238000005728 strengthening Methods 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 7
- 239000004110 Zinc silicate Substances 0.000 claims description 4
- 235000019352 zinc silicate Nutrition 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- 239000006112 glass ceramic composition Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 4
- 229910001423 beryllium ion Inorganic materials 0.000 abstract description 2
- 239000012780 transparent material Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 54
- 239000011787 zinc oxide Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 12
- 239000011734 sodium Substances 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- -1 lithium aluminum silicon Chemical compound 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910000174 eucryptite Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003103 lithium disilicate glass Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 239000006124 glass-ceramic system Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000005398 lithium aluminium silicate glass-ceramic Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a high-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and a preparation method thereof. The reinforced high-strength transparent zinc lithium silicate glass ceramic comprises the following components in percentage by mole: siO (SiO) 2 60～70％、Al 2 O 3 5～10％、Na 2 O 2～3％、Li 2 O 14～15％、ZnO 4～15％、P 2 O 5 1～2％、ZrO 2 1 to 3 percent. The main crystal phase of the microcrystalline glass prepared by the invention is Li 2 ZnSiO 4 The glass ceramic has excellent mechanical properties and transparency, and can be ion exchanged to obtain additional mechanical strength, and at the same time, has low Li 2 The O content is low, the melting point is low, the molding processability is excellent, the application prospect is wide, and the high-strength wear-resistant transparent material can be applied to preparation of high-strength wear-resistant transparent materialThe glass ceramic glaze can also be applied to the preparation of mobile phone panels; the preparation method of the invention is simple and easy to implement, has low melting temperature and has great popularization value.
Description
Technical Field
The invention relates to the technical field of glass ceramic materials, in particular to a high-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and a preparation method thereof.
Background
Along with the arrival of the intelligent age, the intellectualization of various products is rapidly popularized, and is as large as houses, automobiles, furniture, as small as sound equipment, remote controllers, drinking water devices and the like. The screen control is a basic part of most intelligent equipment, so that the screen control is suitable for various use environments of products, and the screen control is used as a screen protection material, so that the characteristics of acid and alkali resistance, temperature impact resistance, mechanical impact resistance and the like of the screen are required to be further improved, and the requirements of various shapes and certain transparency are required to be met.
At present, although the high-alumina glass has good transmittance, the strength is still not high enough, so that the high-alumina glass still has the limit on being used as an appearance protection material of mobile electronic equipment, while the ceramic material has the advantage of high strength, but the transmittance of the ceramic material is still too low, the processing difficulty is high, and the large-scale production is difficult, so that the high-alumina glass has high cost and is limited to be used in the mobile electronic equipment. The lithium aluminum silicon glass ceramic has higher hardness, impact resistance and scratch resistance, thereby being widely applied to cover plate protection materials of touch display products. In addition, after the lithium aluminum silicon glass ceramic is chemically strengthened, the mechanical property of the lithium aluminum silicon glass ceramic can be further improved. The traditional lithium aluminum silicon glass ceramic system at present mainly comprises lithium disilicate glass ceramic, quartz solid solution glass ceramic and eucryptite glass ceramic. Due to Li in the lithium disilicate glass ceramic 2 The higher O content and the insufficient content of the intermediate oxide lead to poor chemical stability, thereby limiting the application of the intermediate oxide on cover glass of electronic equipment. And the quartz solid solution microcrystalline glass and the eucryptite microcrystalline glass limit the production of the quartz solid solution microcrystalline glass and the eucryptite microcrystalline glass because the melting temperature is higher than 1600 ℃ so that the production energy consumption is increased.
Therefore, the development of microcrystalline glass and microcrystalline glass products with excellent mechanical properties, low lithium oxide content, higher ion exchange depth and larger surface compressive stress is a target pursued by scientific researchers.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a high-strength transparent zinc lithium silicate glass ceramic capable of being reinforced and a preparation method thereof, which solve the technical problems that the glass ceramic has higher lithium oxide content and cannot achieve both high transparency and high strength in the prior art.
The first aspect of the invention provides a high-strength transparent zinc lithium silicate glass ceramic which comprises the following components in percentage by mole: siO (SiO) 2 60～70％、Al 2 O 3 5～10％、Na 2 O 2～3％、Li 2 O 14～15％、ZnO 4～15％、P 2 O 5 1～2％、ZrO 2 1～3％；
The components of the high-strength transparent zinc lithium silicate glass ceramic are expressed in mole percent, and the contents of the components simultaneously satisfy the following 3 conditions:
①(Li 2 O+Al 2 O 3 +ZnO)/SiO 2 the value of (2) is 0.39-0.52;
②(Al 2 O 3 +ZnO)/SiO 2 0.16 to 0.30;
③P 2 O 5 /ZrO 2 the value of (2) is 0.6 to 0.9.
The second aspect of the invention provides a preparation method of a high-strength transparent zinc lithium silicate glass ceramic, which comprises the following steps:
forming a base glass;
and forming microcrystalline glass by the base glass through a crystallization process.
Compared with the prior art, the invention has the beneficial effects that:
the main crystal phase of the microcrystalline glass prepared by the invention is Li 2 ZnSiO 4 The glass ceramic has excellent mechanical properties and transparency, and can be ion exchanged to obtain additional mechanical strength, and at the same time, has low Li 2 The O content is low, the melting point is low, the molding processability is excellent, the application prospect is wide, and the glass ceramic can be applied to preparing high-strength wear-resistant transparent glass ceramic glaze and also can be applied to preparing mobile phone panels;
the preparation method of the invention is simple and easy to implement, has low melting temperature and has great popularization value.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) chart of the base glass prepared in example 8;
FIG. 2 is an X-ray diffraction pattern (XRD) of the glass ceramic prepared in example 8;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a cross section of a glass-ceramic prepared in example 8;
FIG. 4 is a graph showing the transmittance at wavelengths of 250mm to 800mm of the glass ceramic prepared in example 8 of 1 mm.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The first aspect of the invention provides a high-strength transparent zinc lithium silicate glass ceramic which comprises the following components in percentage by mole: siO (SiO) 2 60～70％、Al 2 O 3 5～10％、Na 2 O 2～3％、Li 2 O 14～15％、ZnO 4～15％、P 2 O 5 1～2％、ZrO 2 1～3％。
The invention reduces the melting temperature of glass on one hand and precipitates Li in the glass on the other hand by introducing ZnO 2 ZnSiO 4 Further improving the performance of the microcrystalline glass and enabling the microcrystalline glass to have wider application. But due to Li 2 ZnSiO 4 The crystal growth speed is high, and grains with larger grain sizes can be easily grown in the glass, so that the glass performance is deteriorated; at the same time due to Li 2 ZnSiO 4 The difference of thermal expansion coefficients between the crystalline phase and the glass phase is large, li 2 ZnSiO 4 Too much crystalline phase content can cause larger stress to crack inside the glass ceramics. The invention limits Li by precipitating quartz crystal phase in glass 2 ZnSiO 4 The crystal phase grows, and the quartz crystal phase has better mechanical property, so that the property of the microcrystalline glass is further improved. The crystalline phases involved in the present invention have not been reported.
The microcrystalline glass prepared by the method contains more network forming body ions, so that the chemical stability of the glass is improved; the microcrystalline glass and the microcrystalline glass product of the invention can obtain proper grain size through reasonable component design, so that the microcrystalline glass and the microcrystalline glass product of the invention have high strength; meanwhile, the microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties.
The crystallinity refers to the degree of complete crystallization, the arrangement of particles in the crystal with complete crystallization is more regular, diffraction lines are strong, sharp and symmetrical, and the half-width of diffraction peaks is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation, so that the diffraction lines have wide peak shapes and are dispersed. The worse the crystallinity, the weaker the diffraction power, the broader the diffraction peak until disappeared in the background.
In some embodiments of the invention, the crystalline phase of the glass-ceramic and glass-ceramic article comprises Li 2 ZnSiO 4 And at least one of quartz and/or a quartz solid solution, provides high strength for the glass ceramics and glass ceramics products of the invention, and the glass ceramics and glass ceramics products become high in hardness.
In some embodiments of the present invention, the components of the high-strength transparent zinc lithium silicate glass ceramic are expressed in mole percent, and the contents of the components simultaneously satisfy the following 3 conditions:
①(Li 2 O+Al 2 O 3 +ZnO)/SiO 2 the value of (2) is 0.39-0.52;
②(Al 2 O 3 +ZnO)/SiO 2 0.16 to 0.30;
③P 2 O 5 /ZrO 2 the value of (2) is 0.6 to 0.9.
The reason why the content of each component is defined numerically will be described below:
SiO 2 ：SiO 2 the network formed body of base glass can be independently formed into glass, and is one of necessary components, mainly formed into network main structure of base glass and microcrystalline glassThe base glass and the microcrystalline glass are endowed with better chemical stability and mechanical property. In the course of base glass microcrystallization, li is formed 2 ZnSiO 4 Providing SiO with a quartz solid solution and a quartz solid phase 2 A source to promote the formation of a sufficient crystalline phase of the base glass at a suitable temperature range, siO 2 The content is at least 60mol%; in the process of microcrystallizing the base glass, the SiO is too high 2 Promote quartz and quartz solid solution to appear in glass microcrystallizing process, siO 2 The content is up to 70mol%. In some embodiments of the invention, the range may be from about 62.5mol% to 66mol%.
Al 2 O 3 ：Al 2 O 3 Belongs to network intermediate oxides. There are two coordination states in the glass, namely tetraligand [ AlO 4 ]And eight coordinated [ AlO 6 ]. Al in the base glass 3+ The ion abstracts non-bridging oxygen and charge balances with alkali metal ions, making most alumina prone to [ AlO ] 4 ]The broken network will be reconnected to form part of the glass network, resulting in improved glass stability and mechanical properties. Al (Al) 2 O 3 The volume of the aluminum oxide tetrahedron formed in the glass is larger than that of the silicon oxide tetrahedron in the glass, and the volume of the glass is expanded, so that the density of the glass is reduced, a strengthening channel is provided for the glass in the ion strengthening process, the ion strengthening of the base glass and the microcrystalline glass is promoted, and the Al in the base glass 2 O 3 The content is at least 3mol%; but Al is 2 O 3 Belongs to extremely refractory oxide, can rapidly improve the high-temperature viscosity of glass, and greatly increases the concentration of bubble defects in the glass; in some embodiments of the invention, the range may be from about 5 to 8mol%.
Na 2 O: belongs to network external oxide, can obviously reduce the viscosity of base glass and lower the crystallization temperature of glass; na (Na) 2 Too high an O content will weaken the glass crystallization ability, leading to an increase in the residual glass phase, and thus Na in the present invention 2 The content of O is 2-3 mol%.
Li 2 O: belongs to the network exosome component, can obviously reduce the viscosity of glass,and simultaneously, the crystallization temperature of the glass can be quickly reduced. High Li 2 O concentration promotes Li in basic microcrystallization process 3 PO 4 Formation, which is helpful for crystallization process; in addition, but too high Li 2 O will make the base glass viscosity too low to obtain a chemically stable glass composition, while causing too low a compressive stress value during ion strengthening and increasing the raw material cost, so in this implementation, li 2 The content of O is 14-15 mol%.
ZnO: belongs to a network intermediate, zn in glass 2+ With hexacoordinated [ ZnO ] 6 ]And four coordinated [ ZnO ] 4 ]Two states. When the ZnO content is higher, znO belongs to the network modifier and Zn 2+ Hexacoordinated [ ZnO 6 ]The state exists in the glass network. When the ZnO content is low, znO is a network former, zn 2+ Tetradentate [ ZnO 4 ]The state exists in the glass network and is connected with the silica network. When the ZnO content is too high, li is promoted 2 ZnSiO 4 The crystal phase is rapidly separated out, so that the crystal grain size is rapidly increased, and transparent microcrystalline glass is difficult to prepare. In some embodiments of the invention, the ZnO content is in the range of 4 to 12 mol%.
P 2 O 5 : mainly as a crystal nucleus agent to be introduced into a glass system, P 5+ The ions have large field intensity, strong oxygen capturing capability and small accumulation effect. Due to P 5+ Ion field strength greater than Si 4+ Ions, P 5+ Ions are easily combined with alkali metal ions to be separated from a network to form crystal nuclei, and the crystal nuclei are the most effective nucleating agent in the base glass; when the content of the base glass is not contained or is too low, the base glass is not wholly crystallized in the microcrystallizing process, so that atomization appears on the surface, and even microcrystalline glass is difficult to crystallize. In some embodiments of the invention, P 2 O 5 The content is in the range of 1.3 to 1.8mol%, more preferably 1.3 to 1.5mol%.
ZrO 2 : zrO is introduced into the glass system mainly as a nucleating agent 2 Can reduce the formation crystallization of the base glass and P 2 O 5 Can cooperate with each other, widen the crystallization temperature range of glass, improve the nucleation of microcrystalline glass and reduceHaze of glass ceramics and glass ceramics products. In the present invention, the ZrO is contained by 1.2mol% or more 2 To obtain the above effects, it is preferable to contain ZrO in an amount of 1.7 to 2.5mol% 2 On the other hand, if ZrO is contained excessively 2 The glass is difficult to melt, so that inclusions are easily formed in the glass, and the strength and the transmittance of the glass are reduced.
In some embodiments of the invention, the method is performed by reacting (Li 2 O+Al 2 O 3 +ZnO)/SiO 2 The value of (2) is 0.39-0.52, the crystal grains of the microcrystalline glass can be thinned, the crystal phase variety in the microcrystalline glass is increased, and the crystallinity and the strength of the microcrystalline glass are improved. But if (Li) 2 O+Na 2 O 2 +MgO)/(Al 2 O 3 +zno) exceeds 0.52, the properties of the base glass and the glass ceramics deteriorate; (Li 2 O+Al 2 O 3 +ZnO)/SiO 2 The value of (2) is preferably between 0.39 and 0.49.
In some embodiments of the invention, if (Al 2 O 3 +ZnO)/SiO 2 Above 0.30, the crystallinity of the glass ceramics and glass ceramics products is reduced, the grain size is enlarged, and transparent glass ceramics are difficult to prepare; if (Al) 2 O 3 +ZnO)/SiO 2 The value is in the range of 0.16-0.25, the devitrification degree of the microcrystalline glass and the microcrystalline glass product is improved, and the strength is improved. (Al) 2 O 3 +ZnO)/SiO 2 The value of (2) is preferably 0.18 to 0.25.
In some embodiments of the invention, the method is performed by causing P to be 2 O 5 /ZrO 2 The value of (2) is in the range of 0.6-0.9, the forming property of the base glass can be optimized, the processing property of the microcrystalline glass and microcrystalline glass products can be optimized, the crystallinity of the microcrystalline glass can be improved, and the transmittance of the microcrystalline glass can be improved. P (P) 2 O 5 /ZrO 2 The value of (2) is preferably 0.6 to 0.75.
In some embodiments of the present invention, the components of the reinforced high-strength transparent zinc lithium silicate glass ceramic further include, in mole percent: mgO 0-2 mol%. When MgO is contained, the crystallization degree of the glass is reduced to less than 30%, and the hardness is reduced to less than 7.1GPa. When MgO is not contained, the crystallization degree of the glass is higher and is more than 70%, and the hardness of the glass is also higher and is more than 6.9GPa. Therefore, the MgO content is preferably 0.
The microcrystalline glass of the invention not only improves mechanical properties through precipitation crystallization, but also can obtain higher strength through forming a compressive stress layer, thereby preparing microcrystalline glass products.
In some embodiments of the invention, the base glass or glass-ceramic may be processed into a sheet, shaped, polished and/or polished, and then strengthened by a chemical strengthening process.
The performance of the glass ceramics prepared by the invention can be further improved after chemical strengthening, and meanwhile, the ion exchange depth and the surface compressive stress intensity are improved compared with the traditional transparent LAS glass ceramics.
The chemical strengthening is ion exchange method. During ion exchange, smaller alkali ions in the base glass or glass-ceramic are replaced or "exchanged" with larger alkali ions of the same valence state in close proximity to the base glass or glass-ceramic. And replacing smaller ions with larger ions to construct compressive stress in the base glass or the microcrystalline glass, so as to form a compressive stress layer.
In some embodiments of the invention, the glass-ceramic or glass-ceramic article has a crystallinity of 15% or more, preferably 17 to 90%, more preferably 60 to 90%, and most preferably 87.5%.
The grain size of the glass ceramics or glass ceramics products of the invention can influence the transmittance of the glass ceramics or glass ceramics products, namely the light transmittance is influenced, and the smaller the grain size is, the higher the transmittance is. In some embodiments, the glass-ceramic or glass-ceramic article has a grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less. On the other hand, it has been found through studies that the smaller the refractive index difference between the crystalline phase and the glass phase in the glass-ceramic, the higher the transparency of the glass-ceramic or glass-ceramic product.
In some embodiments of the invention, the high strength transparent lithium zinc silicate glass-ceramic or glass-ceramic article described above exhibits high transmittance in the visible range (i.e., the glass-ceramic or glass-ceramic article is transparent). In some embodiments, the light transmittance of a 1mm thick glass-ceramic article or glass-ceramic at 550nm is 45% or greater, preferably 85% or greater, and more preferably 89% or greater.
In some embodiments of the present invention, the vickers hardness of the glass-ceramic product before strengthening the high-strength transparent zinc lithium silicate glass-ceramic is in the range of 6.0-7.6 GPa, most preferably 7.6GPa; the vickers hardness of the reinforced microcrystalline glass product ranges from 7.1GPa to 8.4GPa, and is most preferably 8.4GPa; the surface stress of the glass ceramic product after strengthening is 220-325 MPa, and most preferably 325MPa; and/or the ion exchange layer depth ranges from 100 to 165 μm, most preferably 165 μm.
The base glass or the glass ceramic of the present invention may be a glass molded product of a sheet material manufactured by a method such as grinding or polishing, but the method for manufacturing the glass molded product is not limited to these methods.
The second aspect of the invention provides a preparation method of a high-strength transparent zinc lithium silicate glass ceramic, which comprises the following steps:
forming a base glass; wherein the components of the base glass are expressed in mole percent and contain SiO 2 60～70％、Al 2 O 3 5～10％、Na 2 O 2～3％、Li 2 O 14～15％、ZnO 4～15％、P 2 O 5 1～2％、ZrO 2 1～3％；
And forming microcrystalline glass by the base glass through a crystallization process.
In some embodiments of the present invention, the melting temperature is 1500 to 1600 ℃ and the melting time is 2 to 4 hours according to the melting difficulty of the glass composition in the process of forming the base glass. In some more specific embodiments of the invention, the melting temperature is 1550 ℃ and the melting time is 2 hours.
The base glass of the present invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated in the glass.
The crystallization treatment of the present invention may be performed in 1 stage or 2 stages, and preferably, the crystallization treatment is 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 treatment performed at the 1 st temperature is referred to as a 1 st crystallization treatment, and the crystallization treatment performed at the 2 nd temperature is referred to as a 2 nd crystallization treatment.
The heat treatment system, namely the 1 st temperature and the 2 nd temperature of the crystallization process of the base glass, are determined by DSC curves of the base glass. Temperature T1 1 Between the glass transition temperature T g To T g In the range of +60℃, for nucleation, preferably T g +20℃≤T 1 ≤T g +60℃; temperature T of 2 nd 2 Between Li 2 ZnSiO 4 Crystallization temperature T of crystal phase p1 And crystallization temperature T of quartz crystal phase p2 In order to better precipitate Li 2 ZnSiO 4 Crystalline phase and avoidance of Li 2 ZnSiO 4 The crystal phase and quartz crystal phase grow too fast, preferably T p1 +30℃≤T 2 ≤T p1 -10℃。
In some embodiments of the invention, the 1 st temperature is 550 to 650 ℃, preferably 570 to 600 ℃, and the 2 nd temperature is 680 to 800 ℃, preferably 700 to 740 ℃; the holding time at the 1 st temperature is 0 to 4 hours, preferably 4 hours; the holding time at the 2 nd temperature is 2 to 4 hours, preferably 2 hours.
In some embodiments of the present invention, the method for preparing the reinforced high-strength transparent zinc lithium silicate glass ceramic further comprises the following steps:
and forming the microcrystalline glass product by the microcrystalline glass through a chemical strengthening process.
Further, the step of forming the glass-ceramic product from the glass-ceramic through the chemical strengthening process includes: the glass ceramics are immersed in a salt bath of molten 80 to 95 weight percent sodium salt and 5 to 20 weight percent potassium salt at the temperature of 300 to 450 ℃ for 1 to 6 hours.
Still further, sodium salts include, but are not limited to, sodium chloride, sodium nitrate, etc., and potassium salts include, but are not limited to, potassium chloride, potassium nitrate, etc., and may be selected by those skilled in the art according to the actual circumstances. And through a chemical strengthening process, sodium ions replace part of lithium ions in the base glass or the microcrystalline glass, so that a surface compression layer is formed and high mechanical properties are presented.
In some embodiments of the present invention, the chemical strengthening process includes: the glass ceramics were immersed in a salt bath of molten 90wt% sodium salt and 10 wt% potassium salt at a temperature of 400 ℃ for 4 hours.
Examples 1 to 10
The base glass and the glass ceramics of the embodiment can be prepared by the following method:
(1) Uniformly mixing the raw materials according to the component proportions of the table 1, putting the uniform mixture into a platinum-rhodium crucible, and melting the mixture in a furnace at 1550 ℃ for 2 hours to form base glass;
(2) Forming microcrystalline glass by the base glass through a crystallization process; the crystallization treatment was performed in 2 stages, wherein the 1 st temperature was 570 to 600 ℃, the holding time was 4 hours, the 2 nd temperature was 700 to 740 ℃, and the holding time was 2 hours, and the specific results are shown in Table 1.
(3) Immersing the glass ceramics in 90wt% NaNO melted at 400 DEG C 3 And 10% by weight KNO 3 And (5) mixing the molten salt and the glass ceramic in a salt bath for 4 hours to form the microcrystalline glass product.
Control groups 1 to 8
The control groups 1 to 8 differ from the examples only in the raw material content and the partial process, see in particular Table 2.
Test group
The performance indexes of the base glass and/or the microcrystalline glass are tested by adopting the following methods:
[ Crystal grain size ]
And (3) measuring by using an SEM scanning electron microscope, carrying out surface treatment on the microcrystalline glass in HF acid, then carrying out platinum spraying on the surface of the microcrystalline glass, carrying out surface scanning under the SEM scanning electron microscope, and determining the size of crystal grains.
[ transmittance ]
The samples were processed to a thickness of 1mm and subjected to parallel polishing of the opposite faces, and the light transmittance of 200 to 750nm was measured by using a Hitachi U-41000-shaped spectrophotometer.
[ crystallinity ]
The XRD diffraction peaks were compared with the database spectra, and the crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the overall spectrum, and internal calibration was performed by using pure quartz crystals.
[ surface stress ] and [ depth of ion exchange layer ]
Ion exchange layer depth measurements were performed using a glass surface stress meter SLP-2000.
[ Vickers hardness ]
The load (N) of a diamond quadrangular pyramid indenter having an included angle of 136 DEG with respect to the surface of the test surface when the pyramid-shaped recess was pressed into the test surface was divided by the surface area (mm) calculated by the length of the recess 2 ) Is represented by a value of (a). The test load was 1.96 (N) and the holding time was 10 (seconds).
TABLE 1
TABLE 2
As is clear from the comparison of comparative examples 5 to 8, no zinc oxide or less zinc oxide was added, even if P was greatly adjusted 2 O 5 /ZrO 2 After the base glass is crystallized, the glass is still not crystallized, and the microcrystalline glass cannot be obtained.
As can be seen from comparison of comparative examples 1 to 4 and examples 1 to 10, if the contents of the respective components cannot satisfy the following 3 cases at the same time, no glass ceramics can be formed:
①(Li 2 O+Al 2 O 3 +ZnO)/SiO 2 the value of (2) is 0.39-0.52;
②(Al 2 O 3 +ZnO)/SiO 2 0.16 to 0.30;
③P 2 O 5 /ZrO 2 the value of (2) is 0.6 to 0.9.
From the comparison of the data of examples 1 to 10, it can also be seen that (Al 2 O 3 +ZnO)/SiO 2 The ratio of (2) exceeds 0.25, and the transparency is remarkably reduced although the formed glass ceramics still have higher mechanical strength.
Referring to fig. 1, fig. 1 is a Differential Scanning Calorimetry (DSC) chart of a base glass prepared in example 8 of the present invention. As can be seen from FIG. 1, T g For the glass transition temperature, the temperature is usually selected at T g To T g The nucleation treatment is carried out in the range of +60℃, so that the nucleation temperature is selected to be 600 ℃. T (T) p Peak temperature of crystallization peak, T in the figure p1 Corresponding to Li 2 ZnSiO 4 Crystallization temperature of crystal phase, T p2 The crystallization temperature is selected to be 680 to 800 ℃ because the crystallization temperature corresponds to the crystallization temperature of the quartz crystal phase.
Referring to fig. 2, fig. 2 is an X-ray diffraction pattern (XRD) of the glass ceramics prepared in example 8. As can be seen from FIG. 2, the microcrystalline glass prepared in example 8 of the present invention has a crystal phase composition of Li 2 ZnSiO 4 And quartz.
Referring to fig. 3, fig. 3 is a Scanning Electron Microscope (SEM) image of a cross section of the glass-ceramic prepared in example 8. As can be seen from FIG. 3, the crystallite size of the glass ceramics prepared in example 8 of the present invention is less than 100nm, only 30nm.
Referring to FIG. 4, FIG. 4 is a graph showing the transmittance of glass ceramics of example 8 of 1mm at a wavelength of 250mm to 800 mm. As can be seen from FIG. 4, the glass ceramics prepared in example 8 of the present invention has a wavelength transmittance of more than 80% from 300mm to 800mm, and has a very high visible light transmittance.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The reinforced high-strength transparent zinc lithium silicate glass ceramic is characterized by comprising the following components in percentage by mole: siO (SiO) 2 60～70％、Al 2 O 3 5～10％、Na 2 O 2～3％、Li 2 O 14～15％、ZnO 4～15％、P 2 O 5 1～2％、ZrO 2 1～3％；
The components of the high-strength transparent zinc lithium silicate glass ceramic are expressed in mole percent, and the contents of the components simultaneously satisfy the following 3 conditions:
①(Li 2 O+Al 2 O 3 +ZnO)/SiO 2 the value of (2) is 0.39-0.52;
②(Al 2 O 3 +ZnO)/SiO 2 0.16 to 0.30;
③P 2 O 5 /ZrO 2 the value of (2) is 0.6 to 0.9.
2. The strengthened high-strength transparent zinc lithium silicate glass ceramic according to claim 1, wherein the components thereof comprise, in mole percent: siO (SiO) 2 62.5～66％、Al 2 O 3 5～8％、Na 2 O2～3％、Li 2 O 14～15％、ZnO 4～12％、P 2 O 5 1.3～1.5％、ZrO 2 1.7～2.5％。
3. The strengthened high-strength transparent lithium zinc silicate glass ceramic according to claim 1, wherein (Li 2 O+Al 2 O 3 +ZnO)/SiO 2 The value of (C) is 0.39 to 0.49, (Al) 2 O 3 +ZnO)/SiO 2 Has a value of 0.18 to 0.25, P 2 O 5 /ZrO 2 The value of (2) is 0.6 to 0.75.
4. The high-strength-strengthened transparent zinc lithium silicate glass ceramic according to claim 1, wherein the components of the high-strength-strengthened transparent zinc lithium silicate glass ceramic, in mole percent, further comprise: mgO 0-2 mol%.
5. The high strength, transparent lithium zinc silicate glass ceramic of claim 1, wherein the high strength, transparent lithium zinc silicate glass ceramic is chemically strengthened by a chemical strengthening process to form a glass ceramic article.
6. The high-strength-capable transparent zinc lithium silicate glass ceramic according to claim 1, wherein the high-strength-capable transparent zinc lithium silicate glass ceramic has a crystallinity of 15% or more, a grain size of 50nm or less, and a light transmittance of 45% or more at 550nm of a 1 mm-thick glass ceramic product or glass ceramic; the vickers hardness of the microcrystalline glass product before strengthening is 6.0-7.6 GPa, the vickers hardness of the microcrystalline glass product after strengthening is 7.1-8.4 GPa, the surface stress of the microcrystalline glass product after strengthening is 220-325 MPa, and the depth of the ion exchange layer is 100-165 mu m.
7. The high strength glass-ceramic composition according to claim 1, wherein the crystalline phase of the glass-ceramic and glass-ceramic product contains Li 2 ZnSiO 4 And at least one of quartz and/or a quartz solid solution.
8. A method for preparing the strengthened high-strength transparent zinc lithium silicate glass ceramics according to any one of claims 1 to 7, which comprises the following steps:
forming a base glass;
and forming microcrystalline glass by the base glass through a crystallization process.
9. The method for preparing the strengthened high-strength transparent zinc lithium silicate glass ceramics according to claim 8, wherein in the process of forming the base glass, the melting temperature is 1500-1600 ℃ and the melting time is 2-4 hours;
in the crystallization process, crystallization treatment is carried out through 2 stages; temperature T1 1 Between the glass transition temperature T g To T g In the range of +60℃, the 2 nd temperature T 2 Between Li 2 ZnSiO 4 Crystallization temperature T of crystal phase p1 And crystallization temperature T of quartz crystal phase p2 Between them.
10. The method for preparing the high-strength strengthened transparent zinc lithium silicate glass ceramic according to claim 8, further comprising the steps of:
and forming the microcrystalline glass product by the microcrystalline glass through a chemical strengthening process.
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| CN116924683A (en) * | 2023-09-19 | 2023-10-24 | 河北省沙河玻璃技术研究院 | Magnesium aluminum silicon microcrystalline glass with high transparency and high strength and preparation method thereof |
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| JP2002203310A (en) * | 2000-11-09 | 2002-07-19 | Minolta Co Ltd | Crystallized glass substrate for information recording medium |
| JP2002203311A (en) * | 2000-11-09 | 2002-07-19 | Minolta Co Ltd | Crystallized glass substrate for information recording medium |
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| CN116924684A (en) * | 2023-09-19 | 2023-10-24 | 河北省沙河玻璃技术研究院 | High-permeability high-strength zinc aluminum silicon microcrystalline glass and preparation method thereof |
| CN116924683A (en) * | 2023-09-19 | 2023-10-24 | 河北省沙河玻璃技术研究院 | Magnesium aluminum silicon microcrystalline glass with high transparency and high strength and preparation method thereof |
| CN116924683B (en) * | 2023-09-19 | 2023-12-22 | 河北省沙河玻璃技术研究院 | Magnesium aluminum silicon microcrystalline glass with high transparency and high strength and preparation method thereof |
| CN116924684B (en) * | 2023-09-19 | 2023-12-22 | 河北省沙河玻璃技术研究院 | High-permeability high-strength zinc aluminum silicon microcrystalline glass and preparation method thereof |
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