CN115490428A - Transparent glass ceramics with ultrahigh drop strength and preparation method thereof - Google Patents
Transparent glass ceramics with ultrahigh drop strength and preparation method thereof Download PDFInfo
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 145
- 238000002834 transmittance Methods 0.000 claims abstract description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 15
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 11
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims abstract description 11
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052670 petalite Inorganic materials 0.000 claims abstract description 11
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 10
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
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- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 238000003723 Smelting Methods 0.000 claims description 10
- 238000013001 point bending Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
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- 238000000137 annealing Methods 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 6
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 14
- 210000004940 nucleus Anatomy 0.000 description 11
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- 239000000126 substance Substances 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
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- 238000006124 Pilkington process Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 238000005352 clarification Methods 0.000 description 1
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- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- -1 lithium-aluminum-silicon Chemical compound 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The application discloses transparent glass ceramics with ultrahigh drop strength and a preparation method thereof, belonging to the field of glass manufacturing, wherein the transparent glass ceramics comprises the following components in percentage by mass: siO 2 2 60～78％，Al 2 O 3 3～11％，Li 2 O 8～16％，ZrO 2 2～6％，P 2 O 5 1 to 4 percent of the total weight of the waste water, and 0.1 to 4 percent of clarifying agent. The transparent glass-ceramic has a spherical crystalline phase part and a glass phase part,the spherical crystalline phase part at least comprises lithium disilicate and petalite; the transmittance of the transparent glass ceramics in a visible light wave band range is more than 86%, the haze is less than 0.5%, the falling height of the whole machine sand paper is more than 180cm, and the transparent glass ceramics have high transmittance, high strength, super-strong impact capability and anti-falling performance.
Description
Technical Field
The invention relates to the technical field of glass manufacturing, in particular to transparent glass ceramics with ultrahigh drop strength and a preparation method thereof.
Background
With the development of communication technology, the thinning, large screen and portability of mobile terminal equipment rapidly become the mainstream of the market, and with the increasing popularization of 5G and wireless charging technology, the rear cover glass of mobile communication equipment (such as mobile phones, smart watches and the like) becomes a necessary trend, which puts higher requirements on the front and rear cover glass materials for protecting display devices. How to lighten, thin and enlarge the screen of the glass and improve the mechanical strength of the glass, thereby ensuring that the screen of the mobile communication equipment can not be broken when the mobile communication equipment is collided and impacted by foreign objects or falls from a high place (more than 150 cm) to a rough surface (such as cement ground, gravel, asphalt roads and the like) in the using process, and becoming the key point of research and development of various large original factories and cover plate factories.
The protective glass of the display device adopted in the market at present is usually medium-high alumina glass or lithium-aluminum-silicon glass, after primary strengthening or secondary strengthening, the surface Compressive Stress (CS) can reach 700-800 Mpa, the depth of stress layer (DOL) can reach 40-100 mu m, and the protective glass has better mechanical properties, but the glass is used as a brittle material, a plurality of Griffith cracks exist in the glass, the breaking of the glass is just a result of crack propagation, and although the chemically strengthened surface compressive stress layer can play a certain role in blocking the cracks, the crack propagation resistance is limited (the effect is invalid when the depth of the compressive stress layer is exceeded). Therefore, after the screen is assembled and applied to mobile terminal equipment, the impact resistance and the drop resistance of the whole machine to sharp objects are not enough, and particularly when the screen falls from a high position to a rough surface, the screen breakage rate is greatly increased when the drop height exceeds 120 cm.
Patent CN107207332A discloses a strengthening method of microcrystalline glass, which realizes chemical strengthening by divalent ion exchange, and after the strengthening is carried out by adopting the optimized chemical strengthening method, the surface compressive stress of the microcrystalline glass is not more than 230Mpa at most, and the depth of the compressive stress layer is not more than 10 μm at most.
In patent CN105859143A, a glass-ceramic is described, which precipitates Li 2 SiO 5 And the mechanical properties of crystalline phases such as beta-spodumene are improved to a certain extent, but the light transmittance of the crystalline phases is only 70 percent, the breaking strength is only 380MPa, and the application requirements of the mobile terminal cannot be met.
Therefore, it is urgently needed to develop a microcrystalline glass with high light transmittance, high strength, excellent impact resistance and excellent drop resistance so as to meet the performance requirements of front and rear cover plate materials of an intelligent mobile terminal.
Disclosure of Invention
The invention discloses transparent glass ceramics with ultrahigh drop strength and a preparation method thereof, which aim to solve the problems.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in view of the above objects, the present invention discloses a transparent glass-ceramic with ultra-high drop strength, which has a spherical crystalline phase portion and a glass phase portion, wherein the spherical crystalline phase portion at least comprises lithium disilicate and petalite; the transmittance of the transparent glass ceramics in the visible light wave band range is more than 86 percent, the haze is less than 0.5 percent, and the falling height of the whole machine sand paper is more than 160cm;
the transparent glass ceramics comprises the following oxides in percentage by mass: siO 2 2 60～78％，Al 2 O 3 3～11％，Li 2 O 8～16％，ZrO 2 2～6％，P 2 O 5 1 to 4 percent of the total weight of the waste water, and 0.1 to 4 percent of clarifying agent;
wherein, zrO 2 +P 2 O 5 The value of (b) is 3 to 9.5%.
Go to oneIn a preferred embodiment of the present invention, the oxide of the transparent glass-ceramic satisfies SiO 2 +Al 2 O 3 +Li 2 The value of O is 85 to 95%.
Further, in a preferred embodiment of the present invention, the transparent glass-ceramic further includes, in terms of mass percent of oxides: na (Na) 2 O 0～2％，K 2 O 0～2％，MgO 0～1％，TiO 2 0～0.5％。
Further, in a preferred embodiment of the present invention, the spherical crystalline phase portion further includes at least one of lithium metasilicate, β -quartz, and β -quartz solid solution crystals, and the size of the spherical crystalline phase is 1 to 100nm.
Further, in a preferred embodiment of the present invention, the transparent glass-ceramic has a spherical crystalline phase portion of 50 to 93% of the entire glass.
Further, in a preferred embodiment of the present invention, the compressive stress at a position of 30 μm from the surface of the transparent glass-ceramic is greater than 90Mpa, and the depth of the compressive stress layer is greater than 100 μm; vickers hardness of 650kgf/mm 2 The four-point bending strength is above 650 MPa; the impact strength is more than 0.25J.
The invention also discloses a preparation method of the transparent glass ceramics with ultrahigh drop strength, which is characterized by comprising the following steps:
mixing the raw materials according to the mass percentage of the oxide, and carrying out smelting, forming and annealing to obtain a glass substrate;
sequentially carrying out nucleation and crystallization on the glass substrate to obtain microcrystalline glass; and
chemically strengthening the microcrystallized glass.
Further, in a preferred embodiment of the present invention, in the above-mentioned process for preparing the microcrystallized glass, the nucleation temperature is 520-600 ℃ and the nucleation time is 1-10 h; the crystallization temperature is 620-720 ℃, and the crystallization time is 0.2-5 h;
further, in a preferred embodiment of the present invention, in the above-mentioned process for preparing a glass substrate, the melting step includes: melting the mixed raw materials at 1300-1350 ℃ for 1-4 h, and clarifying at 1350-1400 ℃ for 2-8 h.
Further, in a preferred embodiment of the present invention, the chemical strengthening is a secondary strengthening, which includes:
at 380-450 deg.C and at least contains Na + Carrying out primary ion exchange in the molten salt for 1-4 h; and
pure KNO at 360-440 DEG C 3 Carrying out secondary ion exchange in the molten salt for 0.5-3 h.
Compared with the prior art, the invention has the following beneficial effects:
the transparent glass ceramics provided by the invention is used for preparing a glass substrate suitable for crystallization and strengthening by controlling the composition and the proportion of oxides, and then is used for preparing the transparent glass ceramics with high transmittance and ultrahigh drop strength suitable for chemical strengthening by controlling the crystal phase type and crystallization degree of the glass under specific nucleation and crystallization conditions.
The transparent glass ceramics prepared by the technical scheme of the invention has the light transmittance of over 86 percent and the haze of less than 0.5 percent in the visible light (380-780 nm) range; under the dual functions of crystallization and chemical reinforcement, the falling height of the whole sand paper reaches more than 180 cm. The transparent glass ceramics prepared by the invention has ultrahigh drop strength, excellent other mechanical properties, light transmittance of more than 86%, and high transmittance, high strength, super-strong impact capability and drop resistance of the transparent glass ceramics.
Drawings
FIG. 1 is an XRD pattern of a microcrystallized glass in example 1 of the present invention;
FIG. 2 is a transmittance chart of a crystallized glass in example 1 of the present invention
Detailed Description
Embodiments of the present invention will be described in detail with reference to the following examples, but those skilled in the art will understand that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention, and that the specific conditions not specified in the examples are carried out according to conventional conditions or conditions suggested by the manufacturer, and that the reagents or equipment used are not specified by the manufacturer, and are all conventional products available through commercial purchase.
The embodiment provides transparent glass ceramics with ultrahigh drop strength, which comprises a spherical crystalline phase part and a glass phase part, wherein the spherical crystalline phase part at least comprises lithium disilicate and petalite. The transparent microcrystalline glass has the following excellent performance characteristics: in the range of 380-780 nm of visible light, the light transmittance is over 86 percent, and the haze is less than 0.5 percent; after secondary strengthening, the depth of the compressive stress layer is more than 100 mu m; under the dual effects of crystallization and chemical strengthening, the falling height of the whole sand paper reaches more than 160cm, the Vickers hardness reaches more than 650kgf/mm < 2 >, the four-point bending strength reaches more than 700Mpa, and the impact strength is more than 0.25J.
To achieve the above-mentioned effects of the present invention, the present embodiment firstly provides a transparent glass-ceramic composition suitable for post crystallization and strengthening, and specifically, li suitable for chemical strengthening 2 O-Al 2 O 3 -SiO 2 The glass-ceramic composition is composed of the following components in percentage by mass of oxides: siO 2 2 60～78％，Al 2 O 3 3～11％，Li 2 O 8～16％，ZrO 2 2～6％，P 2 O 5 1 to 4 percent of ZrO 2 and 0.1 to 4 percent of clarifying agent 2 +P 2 O 5 The value of (A) is 3 to 9.5%.
In order to better understand the design of the material prescription composition of the present invention, the following further explains the relevant compositions:
SiO 2 is the main component forming silica tetrahedron and connected to form glass network structure, and is the basic skeleton of glass. SiO 2 2 The amount added is 60 to 78%, preferably 65 to 75%. When SiO is present 2 When the content of (b) is more than 78%, melting and refining of the glass are difficult, and it is difficult to obtain a transparent and uniform glass-ceramic. If the content is less than 60%, the resulting glass has poor hardness, small devitrification degree and a grain size which is difficult to control.
Al 2 O 3 Is a component of a glass network structure and also is a basic component of a beta-quartz solid solution crystal phase, and can effectively improve glassThe heat resistance and ion exchange properties of the glass and helps stabilize the base glass and create the desired crystalline phase. Al in the glass of the present invention 2 O 3 The content of (B) is in the range of 3 to 11%, preferably 5.5 to 10%. When the content is 3-11%, the uniform nucleation and the control of the grain size are facilitated, and the transparent glass ceramics taking the lithium disilicate and the petalite as main crystal phases are formed.
Li 2 O is an important composition for forming LAS-type glass ceramics, and can improve the melting property and formability of the glass, and a large amount of Li 2 O in turn increases the tendency to crystallize. In addition, the existence of Li ions is beneficial to secondary chemical strengthening, so that the surface of the glass has compressive stress, and the strength is improved. Li in glass of the invention 2 The content of O is in the range of 8 to 16%, preferably 9.5 to 13%.
ZrO 2 Besides being a good composite nucleating agent, the ZrO-based composite nucleating agent also helps to improve the chemical durability and hardness of the glass and reduce the thermal expansion coefficient of the glass, but if ZrO-based composite nucleating agent is used, the ZrO-based composite nucleating agent also helps to improve the chemical durability and hardness of the glass and reduce the thermal expansion coefficient of the glass 2 When too much, the melt property is deteriorated and the molding becomes difficult. ZrO in the glass of the present invention 2 The content of (B) is in the range of 2 to 6%, preferably 3 to 4.5%.
P 2 O 5 Is a glass-forming oxide having good nucleating ability for silicate glass, P 2 O 5 And ZrO 2 The mixture is used as a crystal nucleus agent, so that the nucleation effect of the glass can be improved, the nucleation rate is increased, and the microcrystalline glass with finer grains is obtained. P in the glass of the present invention 2 O 5 The content of (B) is in the range of 1 to 4%, preferably 1.5 to 3.5%.
In particular, in order to precipitate uniform and fine crystal grains and to produce a transparent glass-ceramic, it is necessary to control the ZrO of the crystal nucleus agent 2 And P 2 O 5 In total, i.e. ZrO 2 +P 2 O 5 The value of (b) is 3 to 9.5%, preferably 5 to 8%.
The refining agent is a substance which can promote the elimination of bubbles in the glass melting process and is called as the refining agent, and the refining agent is mainly realized by generating and releasing gas in the glass melting process; in this embodiment, the fining agent is SO 4 2- 、NO 3 - 、Sb 2 O 3 In the range of 0.1 to 4%, preferably 1 to 3%.
Further, in order to improve the performance of the transparent glass ceramics, the transparent glass ceramics also comprises the following components in percentage by mass of oxides: na (Na) 2 O 0～2％，K 2 O 0～2％，MgO 0～1％，TiO 2 0～0.5％。
Wherein, na 2 O is a good co-solvent in the glass component, but the present invention contains a large amount of Li 2 And O, the meltability of the glass is greatly improved. Na in the glass of the present invention 2 The content of O is in the range of 0 to 2%, preferably 0.1 to 1%.
MgO can improve the meltability, strain point and Young's modulus of glass, but MgO reduces the tendency and rate of crystallization of glass, so the content is not preferably more than 3%. The content of MgO in the glass ceramics of the present invention is in the range of 0 to 1%, preferably 0.1 to 0.5%.
K 2 O and Na 2 O has fluxing action as well. Adding a small amount of K 2 O can reduce the tendency to devitrify and increase the transparency and gloss of the glass. K 2 O can reduce the surface tension and hardening speed of the glass, is beneficial to glass forming, and K in the glass 2 The content of O is in the range of 0 to 2%, preferably 0.1 to 1%.
TiO 2 Is an optional component which is helpful for reducing the melting temperature of the glass and improving the chemical stability, the content of the optional component is too high to cause the coloring and the light transmittance of the glass to be reduced, and the TiO in the glass of the invention 2 The content of (b) is in the range of 0 to 0.5%, which makes it easy to control the crystallization process, preferably 0.1 to 0.3%.
In order to further promote the generation of crystalline phase and improve the hardness and light transmittance of the transparent glass ceramics, siO is required 2 、Al 2 O 3 And Li 2 The total content of O is controlled, i.e. SiO is controlled 2 +Al 2 O 3 +Li 2 The value of O is 82 to 95%, preferably 85 to 90%.
The transparent glass-ceramic has spherical crystalline phase part and glass phase partIn the transparent glass ceramics, the spherical crystalline phase part accounts for 50 to 93 percent of the whole glass, and preferably 60 to 90 percent. The spherical crystalline phase portion includes lithium disilicate and petalite, and further includes at least one of lithium metasilicate, β -quartz, and β -quartz solid solution crystals. Wherein the chemical composition of the beta-quartz is SiO 2 The crystal phase of quartz is transformed into beta-quartz at 573-867 ℃; the basic chemical composition of a solid solution of beta-quartz is Li 2 /RO·Al 2 O 3 ·nSiO 2 Wherein R represents Mg 2+ Or Zn 2+ N is 2-10, the crystal can be in SiO 2 Spontaneously in an enriched solid solution.
The transparent glass ceramics has a structure with a large amount of microcrystal phases and a small amount of glass phases, so that the transparent glass ceramics has a functional material with excellent mechanical property, and the microcrystal grains in the glass ceramics can cause the bending and passivation of crack tips, increase the fracture energy, slow down and even prevent cracks from passing through crystal phases and possible interfaces to form a hindered fracture path in the glass, thereby improving the crack propagation resistance and the scratch resistance. And the size of the spherical crystalline phase is 1 to 100nm, preferably 1 to 50nm. The smaller the size of the crystalline phase, the greater the degree of bending and passivation of the crack tips, which is more beneficial to improving the glass properties.
The embodiment also provides a preparation method of the transparent glass ceramics, which comprises the following steps:
step S1: mixing the raw materials according to the mass percentage of the oxide, and carrying out smelting, forming and annealing to obtain a glass substrate;
specifically, the preparation process of the glass substrate comprises the following steps:
(a) Preparing materials: weighing the raw materials according to the weight ratio, pouring the raw materials into a mixer, and uniformly mixing the raw materials to obtain a glass mixture;
(b) Smelting: then putting the mixture into a smelting furnace, melting and clarifying the mixture at high temperature, melting the mixture into high-temperature molten glass, and removing bubbles and foreign matters in the high-temperature molten glass;
(c) Forming and annealing: forming the molten glass liquid at a certain tapping temperature, and then carrying out rough annealing;
wherein the raw material of step (a), wherein Li 2 O、Na 2 O、K 2 O is selected from the group consisting of carbonate,
Introduction in the form of acid or sulphate, P 2 O 5 Introduced in the form of ammonium dihydrogen phosphate and the rest introduced in the form of oxide.
And, the melting of step (b) is: the temperature is 1300-1350 ℃, and the time is 1-4 hours; the clarification is as follows: the temperature is 1350-1400 ℃ and the time is 2-8 hours.
And, the tapping temperature in the step (c) is 1200-1350 ℃; the molding is performed by cooling in a hot mold or by any one of a float method, a rolling method, a pressing method, an overflow method and a drawing-down method.
And the thickness of the glass substrate is 0.3 to 1.8mm, preferably 0.5 to 1.5mm.
Step S2: and (3) carrying out nucleation and crystallization on the glass substrate in sequence to obtain the microcrystalline glass.
Specifically, the microcrystallization step comprises a step of precipitating crystal nuclei at a first temperature (nucleation temperature) of 520 to 600 ℃ and a first time (nucleation time) of 1 to 10 hours, preferably 3 to 7 hours, while maintaining the nucleation temperature, in order to ensure maximum nucleation efficiency and desired crystal size, more preferably 550 to 600 ℃; and a step of performing crystallite growth at a second temperature (crystallization temperature) which is higher than the first temperature and is 620 to 720 ℃, more preferably 640 to 700 ℃, in order to precipitate a desired crystal size, and for a second time (crystallization time) which is 0.2 to 5 hours, preferably 0.1 to 3 hours. The first temperature and the second temperature are both lower than the softening point temperature of the glass substrate, and thus the selection has the advantages that the nucleation and crystallization speed can be effectively controlled during the nucleation and crystallization processes, and the shape of the glass is not changed.
Further, the glass carrier used for the microcrystallization treatment is graphite, and nitrogen, helium, or the like is filled as a protective gas. The graphite is adopted as the carrier, so that the graphite has excellent heat-conducting property, the temperature uniformity in the micro-crystallization treatment process is favorably controlled, and the oxidation of the graphite and the pollution of glass can be reduced by filling nitrogen.
The microcrystallized glass prepared by the microcrystallization treatment step has the crystal phases of mainly lithium disilicate and petalite, and the crystal phase structure has relatively high linear thermal expansion coefficient, high strength, high fracture toughness and low dielectric loss. In some examples, at least one of β -quartz, β -quartz solid solution, lithium metasilicate crystals is also observed. Crystallization degree of 50-93%, crystal size (mean value)<0.1 μm,0.7mm in thickness, and has a light transmittance of over 86% in the visible light range of 380-780 nm and haze<0.5% and a surface hardness of 600kgf/mm 2 The four-point bending strength is above 400 MPa.
And step S3: chemically strengthening the microcrystallized glass.
The chemical strengthening for the microcrystallized glass may be a primary chemical strengthening or a secondary chemical strengthening. In order to further improve the strength of the glass-ceramic, in some preferred embodiments, secondary chemical strengthening is employed.
A secondary chemical strengthening step comprising charging 100% of NaNO into the glass-ceramic obtained as described above 3 Molten salt (or NaNO) 3 With KNO 3 Mixed molten salt of (2) and adding 100% KNO 3 And performing secondary chemical strengthening in the molten salt.
Wherein, the temperature range of the first chemical strengthening is 380-450 ℃, preferably 390-440 ℃, and the strengthening time is 0.5-3.5 h, preferably 1-3 h. The temperature range of the second chemical strengthening is 360-440 ℃, the optimal temperature range is 380-420 ℃, and the strengthening time is 0.5-3 h, the optimal time is 1-2.5 h. And the first chemical strengthening temperature is higher than the second chemical strengthening temperature.
The stress layer depth of the transparent microcrystalline glass after the secondary strengthening>100 μm, preferably>110 μm; the compressive stress at a position 30 mu m away from the surface is 90-150 Mpa, preferably 110-150 Mpa; vickers hardness of 650kgf/mm 2 The above; four-point bending strengthThe temperature is above 700 MPa; the impact strength is more than 0.25J; the falling height of the whole machine sand paper can reach more than 160 cm.
In other embodiments of the present invention, a chemical strengthening process is used to chemically strengthen the microcrystalline glass, specifically, the microcrystalline glass prepared above is preheated and then dipped into NaNO in a proper proportion 3 With KNO 3 The mixed molten salt of (3) is chemically strengthened at a temperature of 380 to 450 ℃, preferably 390 to 440 ℃, for a strengthening time of 1.5 to 10 hours, preferably 3 to 8 hours.
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
The embodiment provides a transparent glass ceramic, and the preparation method comprises the following steps:
(1) First, 72% SiO by weight 2 9% of Al 2 O 3 10.5% of Li 2 O,1.5% Na 2 O,1.5% of K 2 O,0.1% MgO,3.4% ZrO 2 2% of P 2 O 5 Weighing, pouring all the materials into a mixer, and uniformly mixing the materials to obtain a glass mixture;
(2) Then the prepared mixture is put into a smelting furnace, is melted for 4 hours at 1340 ℃, is clarified for 5 hours at 1400 ℃ (the clarifying agent adopts sulfate, carbon powder and nitrate; the mixture is added into a mixer with other raw materials during proportioning), and then the melted glass liquid is taken out of the furnace at 1350 ℃, is shaped by a float method to prepare glass with the thickness of 0.7mm, and is roughly annealed at 510 ℃ in a muffle furnace.
(3) And (3) putting the annealed glass into a high-temperature furnace for microcrystallization treatment, keeping the temperature at 550 ℃ for 5 hours to generate crystal nuclei of the glass as many as possible, and then raising the temperature to 620 ℃ to enter a crystal growth stage for 2.5 hours to obtain microcrystallized glass.
As a result of XRD examination of the microcrystalline glass, as shown in fig. 1, it was found that the microcrystalline glass had a degree of crystallization of 78% and a grain size of 0.05um, and lithium disilicate and petalite were predominant glass phases, and lithium metasilicate, β -quartz and β -quartz solid solutions were observed in the crystal phases.
(4) The obtained microcrystallized glass is soaked in 100% of NaNO at 440 ℃ after being cleaned, dried and preheated 3 Melting the salt for 2.5 hours to complete the first chemical strengthening; the glass after the first strengthening was salted and then immersed in 100% KNO at 420 ℃ 3 And (5) continuing the molten salt for 2 hours to complete secondary chemical strengthening to obtain the transparent glass ceramics.
The performance of the obtained transparent glass ceramics is detected, and the results are as follows: the depth of the stress layer is 105 μm, the compressive stress at 30 μm from the surface is 125MPa, and the Vickers hardness is 680kgf/mm 2 The four-point bending strength is 750Mpa, the whole sand paper falling height can reach 185cm, and the light transmittance of the 0.7mm microcrystalline glass reaches more than 90% (as shown in figure 2).
Example 2
The embodiment provides a transparent microcrystalline glass, and a preparation method thereof comprises the following steps:
(1) Mixing 73.8% SiO by weight 2 7.5% of Al 2 O 3 11.5% of Li 2 O,0.2% Na 2 O,0.2% of K 2 O,0.1% MgO,4.4% ZrO 2 2.3% of P 2 O 5 Weighing, pouring all the materials into a mixer, and uniformly mixing the materials to obtain a glass mixture;
(2) Then the prepared mixture is put into a smelting furnace, is melted for 4 hours at 1340 ℃, is clarified for 5 hours at 1400 ℃ (the clarifying agent adopts sulfate, carbon powder and nitrate; the mixture and other raw materials are added into a mixer for mixing during the mixing), then the molten glass liquid is discharged at 1350 ℃, is rolled and formed to prepare glass with the thickness of 1.3mm, and is subjected to coarse annealing at 505 ℃ in a muffle furnace.
(3) And (3) putting the annealed glass into a high-temperature furnace for microcrystallization treatment, keeping the temperature at 540 ℃ for 8 hours to generate crystal nuclei of the glass as many as possible, and then raising the temperature to 620 ℃ to enter a crystal growth stage for 2 hours to obtain microcrystallized glass.
XRD detection is carried out on the microcrystalline glass, and the glass is found to have lithium disilicate and petalite as main crystal phases, the crystallization degree is about 85 percent, and the crystal grain size is 0.03um.
(4) The obtained microcrystallized glass is soaked in 100% of NaNO at 440 ℃ after being cleaned, dried and preheated 3 Melting the salt for 2.5 hours to complete the first chemical strengthening; the glass after the first strengthening was salted and then immersed in 100% KNO at 420 ℃ 3 And (5) continuing the molten salt for 2 hours to complete secondary chemical strengthening to obtain the transparent glass ceramics.
The performance of the obtained transparent glass ceramics is detected, and the results are as follows:
the depth of stress layer is 110 μm, the compressive stress at 30 μm from the surface is 135Mpa, and Vickers hardness is 680kgf/mm 2 The four-point bending strength is 780Mpa, the falling height of the whole machine sand paper can reach 190cm, and the light transmittance of 1.3mm microcrystalline glass reaches over 88 percent.
Example 3
The embodiment provides a transparent glass ceramic, and the preparation method comprises the following steps:
(1) Mixing 74.6% SiO by weight 2 7.3% of Al 2 O 3 11.4% of Li 2 O,0.1% Na 2 O,0.1% of K 2 O,4.4% ZrO 2 2.3% of P 2 O 5 Weighing, pouring all the materials into a mixer, and uniformly mixing the materials to obtain a glass mixture;
(2) Then the prepared mixture is put into a smelting furnace, is melted for 4 hours at 1340 ℃, is clarified for 5 hours at 1400 ℃ (the clarifying agent adopts sulfate, carbon powder and nitrate; the mixture is added into a mixer with other raw materials during proportioning), and then the melted glass liquid is taken out of the furnace at 1350 ℃, is pressed and molded to prepare glass with the thickness of 1.1mm, and is roughly annealed at 500 ℃ in a muffle furnace.
(3) And (3) putting the annealed glass into a high-temperature furnace for microcrystallization treatment, keeping the temperature at 550 ℃ for 6 hours to generate crystal nuclei of the glass as many as possible, and then raising the temperature to 630 ℃ to enter a crystal growth stage for 1.5 hours to obtain microcrystallized glass.
XRD detection is carried out on the microcrystalline glass, and the result shows that transparent microcrystalline glass which takes lithium disilicate and petalite as main crystal phases, has the crystallization degree of 90 percent and has the grain size of 0.025um is produced in the glass.
(4) The obtained microcrystalline glass is soaked in 100% NaNO at 440 ℃ after being cleaned, dried and preheated 3 Melting the salt for 2.5 hours to complete the first chemical strengthening; the glass after the first strengthening was salted and then immersed in 100% KNO at 420 ℃ 3 And (5) continuing the molten salt for 2 hours to complete secondary chemical strengthening, thereby obtaining the transparent microcrystalline glass.
The performance of the obtained transparent glass ceramics is detected, and the results are as follows:
the depth of the stress layer is 120 μm, the compressive stress at a position 30 μm from the surface is 140MPa, and the Vickers hardness is 680kgf/mm 2 The four-point bending strength is 780Mpa, the falling height of the whole sand paper can reach 200cm, and the light transmittance of 1.1mm microcrystalline glass can reach more than 91 percent.
Example 4
The embodiment provides a transparent glass ceramic, and the preparation method comprises the following steps:
(1) Mixing 68.8% SiO by weight 2 11% of Al 2 O 3 12% of Li 2 O,0.2% Na 2 O,0.2% of K 2 O,1% MgO,4.5% ZrO 2 2.3% of P 2 O 5 Weighing, pouring all the materials into a mixer, and uniformly mixing the materials to obtain a glass mixture;
(2) The prepared mixture is put into a smelting furnace, is melted for 4.5 hours at 1340 ℃, is clarified for 5 hours at 1400 ℃ (the clarifying agent adopts sulfate, carbon powder and nitrate; the mixture is added into a mixer with other raw materials during proportioning), then the molten glass liquid is discharged at 1350 ℃, is molded by an overflow method to prepare glass with the thickness of 0.55mm, and is subjected to rough annealing at 500 ℃ in a muffle furnace.
(3) And (3) putting the annealed glass into a high-temperature furnace for microcrystallization treatment, keeping the temperature at 580 ℃ for 4 hours to generate crystal nuclei of the glass as many as possible, and then raising the temperature to 650 ℃ to enter a crystal growth stage for 1.5 hours to obtain microcrystallized glass.
XRD detection is carried out on the microcrystalline glass, and the transparent microcrystalline glass which takes lithium disilicate and petalite as main crystal phases, has the crystallization degree of 60 percent and the grain size of 0.065um is produced in the glass.
(4) The obtained microcrystalline glass is soaked in 100% NaNO at 440 ℃ after being cleaned, dried and preheated 3 Melting the salt for 2.5 hours to complete the first chemical strengthening; the glass after the first strengthening was salted and then immersed in 100% KNO at 420 ℃ 3 And (5) continuing the molten salt for 2 hours to complete secondary chemical strengthening to obtain the transparent glass ceramics.
The performance of the obtained transparent microcrystalline glass is detected, and the results are as follows:
the depth of the stress layer is 120 μm, the compressive stress at a position 30 μm from the surface is 140MPa, and the Vickers hardness is 680kgf/mm 2 The four-point bending strength is 780Mpa, the falling height of the whole sand paper can reach 200cm, and the light transmittance of the 0.55mm microcrystalline glass can reach more than 91 percent.
Examples 5 to 10
This example provides a transparent glass-ceramic, which is prepared by calculating and weighing raw materials corresponding to each component according to the mixture ratio of each oxide in table 1, and by using a preparation method substantially consistent with that in example 1.
Meanwhile, a summary of the formulations and performance parameters of the transparent glass-ceramic frits provided in examples 1 to 4 is shown in table 1:
TABLE 1 recipes and Performance parameters for examples 1-10
Comparative examples 1 to 5
Comparative examples 1 to 5 provide microcrystalline glasses, which are prepared by calculating and weighing raw materials corresponding to the respective components according to the ratios of the respective oxides in table 2 by a preparation method substantially consistent with that of example 1, and performing performance detection on the prepared microcrystalline glasses:
TABLE 2 recipes and Performance parameters for comparative examples 1 to 5
Comparative examples 6 to 9
Comparative examples 6 to 9 provide microcrystalline glass, the raw materials corresponding to the components are calculated and weighed according to the recipe of comparative example 1, and the microcrystalline glass is prepared by a preparation method basically consistent with that of example 1, except that nucleation temperature and time, crystallization temperature and time are selected during the preparation of microcrystalline glass; and the performance of the prepared microcrystalline glass is detected as follows:
TABLE 3 influence of parameters on the glass Properties during the microcrystallization
By comparing the data in tables 1 to 3 together, it can be found that:
(1) In the present invention, P 2 O 5 And ZrO 2 The content mainly affects the nucleation performance and does not contain P 2 O 5 The time crystallization degree is greatly reduced, the grain size is larger, and a proper amount of P is introduced 2 O 5 Can easily form finer grains, but P 2 O 5 When the dosage is excessive, the glass is easy to lose transparency; using ZrO alone 2 When the glass is used as a crystal nucleating agent, the crystallization degree is low (the number of formed crystal nucleuses is small) and the performance of the glass-ceramics is reduced due to overlarge crystal size; control P 2 O 5 And ZrO 2 The content is in a proper range, so that the microcrystallization process can uniformly nucleate and improve the glass crystallizationThe requirements for degree; the higher the devitrification degree is, the smaller the crystal size is, the higher the vickers hardness of the glass-ceramic is, and the falling height of the sandpaper is also increased.
(2) In the micro crystallization process, nucleation temperature, nucleation time, crystallization temperature and crystallization time influence the formation of crystal nuclei and the growth of crystals. The nucleation temperature is too low (480 ℃), the crystallization degree is still low even if the nucleation time is increased (12 h), the mechanical properties of the glass (hardness, sandpaper falling and the like) are poor, but the transmittance is increased, and the haze is reduced. The nucleation temperature is too high (600 ℃), crystals grow rapidly while the crystal nuclei are formed, the formation of the crystal nuclei is influenced, the crystallization degree is reduced, the size of the crystals with high crystallization temperature (720 ℃) is increased, the mechanical properties (hardness, abrasive paper falling and the like) of the glass are reduced, the transmittance is reduced, and the haze is increased.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. The transparent glass-ceramic with ultrahigh drop strength is characterized by comprising a spherical crystalline phase part and a glass phase part, wherein the spherical crystalline phase part at least comprises lithium disilicate and petalite; the transmittance of the transparent glass ceramics in the visible light wave band range is more than 86%, the haze is less than 0.5%, and the falling height of the whole machine sand paper is more than 160cm;
the transparent glass ceramics comprises the following components in percentage by mass of oxides: siO 2 2 60～78％，Al 2 O 3 3～11％，Li 2 O 8～16％，ZrO 2 2～6％，P 2 O 5 1 to 4 percent of the total weight of the waste water, and 0.1 to 4 percent of clarifying agent;
wherein, zrO 2 +P 2 O 5 The value of (A) is 3 to 9.5%.
2. The ultra-high drop strength transparent glass-ceramic according to claim 1Wherein the oxide of the transparent glass-ceramic satisfies SiO 2 +Al 2 O 3 +Li 2 The value of O is 85 to 95%.
3. The ultra-high drop strength transparent glass-ceramic according to claim 1, further comprising, in mass percent of oxides: na (Na) 2 O 0～2％，K 2 O 0～2％，MgO 0～1％，TiO 2 0～0.5％。
4. The ultra-high drop strength transparent glass-ceramic according to claim 1, wherein the spherical crystalline phase portion further comprises at least one of lithium metasilicate, β -quartz, and β -quartz solid solution crystals, and the size of the spherical crystalline phase is 1 to 100nm.
5. The transparent glass-ceramic with ultrahigh drop strength according to claim 1, wherein the spherical crystalline phase part in the transparent glass-ceramic accounts for 50-93% of the whole glass.
6. The transparent glass-ceramic with ultrahigh drop strength according to claim 1, wherein the compressive stress of the transparent glass-ceramic at a position 30 μm away from the surface is more than 90Mpa, and the depth of the compressive stress layer is more than 100 μm; vickers hardness of 650kgf/mm 2 The four-point bending strength is above 650 MPa; the impact strength is more than 0.25J.
7. A method for producing a transparent glass-ceramic according to any one of claims 1 to 6, comprising:
mixing the raw materials according to the mass percentage of the oxide, and carrying out smelting, forming and annealing to obtain a glass substrate;
sequentially carrying out nucleation and crystallization on the glass substrate to obtain microcrystalline glass; and
chemically strengthening the microcrystallized glass.
8. The method for preparing transparent glass-ceramic according to claim 7, wherein in the process of preparing the microcrystallized glass, the nucleation temperature of the nucleation is 520-600 ℃, and the nucleation time is 1-10 h; the crystallization temperature is 620-720 ℃, and the crystallization time is 0.2-5 h.
9. The method for preparing transparent glass-ceramic according to claim 7, wherein in the process of preparing the glass substrate, the smelting step comprises: melting the mixed raw materials at 1300-1350 ℃ for 1-4 h, and clarifying at 1350-1400 ℃ for 2-8 h.
10. The method for preparing transparent glass-ceramic according to claim 7, wherein the chemical strengthening is a secondary strengthening comprising:
at 380-450 deg.C and at least contains Na + Carrying out primary ion exchange in the molten salt for 1-4 h; and
pure KNO at 360-440 DEG C 3 Carrying out secondary ion exchange in the molten salt for 0.5-3 h.
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