CN116924684A - High-permeability high-strength zinc aluminum silicon microcrystalline glass and preparation method thereof - Google Patents
High-permeability high-strength zinc aluminum silicon microcrystalline glass and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 99
- -1 zinc aluminum silicon Chemical compound 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 13
- 239000006104 solid solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 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
- 238000002834 transmittance Methods 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 238000013001 point bending Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 description 20
- 230000008025 crystallization Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000006121 base glass Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000006132 parent glass Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
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
- C03C10/0036—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 a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of glass ceramics, and provides high-permeability high-strength zinc-aluminum-silicon glass ceramics and a preparation method thereof, wherein the glass ceramics comprises the following compounds in percentage by mole: znO 5-13%, al 2 O 3 12%‑22%，SiO 2 40%‑65%，ZrO 2 0.1%‑1.5%，RE 2 O 3 1%‑8%，Li 2 O 2%‑11%，Na 2 O 0.5%‑2%，TiO 2 1.5%‑4.5%，B 2 O 3 0.1%‑2%、P 2 O 5 0.1%‑1.5%，NaCl 0.1%‑0.8%，Sb 2 O 3 0.1% -0.3%; wherein RE is 2 O 3 Comprising Y 2 O 3 、La 2 O 3 、Gd 2 O 3 One or more of the following. Through the technical scheme, the problems of poor shatter resistance and scratch resistance, high lithium content and poor chemical strengthening capability of the microcrystalline glass in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of glass ceramics, in particular to high-permeability high-strength zinc-aluminum-silicon glass ceramics and a preparation method thereof.
Background
Along with rapid development and iteration of the information age, in order to reduce signal shielding and loss, along with popularization and application of technologies such as 5G communication, wireless charging and the like, requirements on cover plate and back plate glass in the field of mobile terminals are rapidly increased. The chemical tempering (ion exchange) is the main means for reinforcing the current electronic glass, and can generate high compressive stress and stress layer depth on the surface layer of the glass, so that the strength of the glass is obviously improved, but the intrinsic mechanical property of the glass is poor and the comprehensive performance is not ideal.
The transparent glass ceramic is a special glass formed by crystallization heat treatment of glass with a specific matrix at a certain temperature. The glass interior of the glass is subjected to crystallization heat treatment to form a large number of tiny crystals, so that a compact multiphase complex of a microcrystalline phase and a glass phase is formed. The controlled precipitated microcrystalline phase can effectively prevent the diffusion of microcracks in the glass, so that the intrinsic strength of the glass is improved, the glass has the advantages of scratch resistance, impact resistance and the like, and the glass becomes a novel cover plate and back plate material with great potential and is a development trend of the future market.
In recent years, ultra-porcelain crystal panels used for apple mobile phones are nano microcrystals used for flagship machines, and the like, the materials introduce crystals to improve the hardness and the elastic modulus of the materials, improve the puncture resistance, play a good role in preventing crack propagation, are the main direction of the existing high-end machine cover plate materials, but are limited by patent barriers and preparation technology, have higher production cost, use lithium oxide with higher price and high content, have high comprehensive cost and large preparation difficulty, and meanwhile, the glass has unsatisfactory chemical strengthening effect, so that the application range and the field are greatly limited.
Disclosure of Invention
The invention provides high-permeability high-strength zinc aluminum silicon microcrystalline glass and a preparation method thereof, and solves the problems of poor shatter resistance and scratch resistance, high lithium content and poor chemical strengthening capability of microcrystalline glass in the related technology. The patent provides the high-transparency glass ceramics with low lithium content, and has excellent chemical strengthening capability, and the anti-drop performance is remarkably improved.
The technical scheme of the invention is as follows:
the high-permeability high-strength zinc aluminum silicon microcrystalline glass comprises the following compounds in percentage by mole: znO 5-13%, al 2 O 3 12%-22%，SiO 2 40%-65%，ZrO 2 0.1%-1.5%，RE 2 O 3 1%-8%，Li 2 O 2%-11%，Na 2 O 0.5%-2%，TiO 2 1.5%-4.5%，B 2 O 3 0.1%-2%，P 2 O 5 0.1%-1.5%，NaCl 0.1%-0.8%，Sb 2 O 3 0.1% -0.3%; wherein RE is 2 O 3 Comprising Y 2 O 3 、La 2 O 3 、Gd 2 O 3 One or more of the following.
As a further technical scheme, the crystal phase comprises RE 2 Ti 2 O 7 、RE 2 Zr 2 O 7 、ZnAl 2 O 4 、Al 1.5x Zr 2y O 1.5+2y 、Zr 2x Y 1.5y Ti 2z O 2x+1.5y+2z One or more composite crystalline phases in solid solution of lithium silicate, zirconium oxide and quartz.
As a further technical scheme, (ZnO+Al) 2 O 3 )/SiO 2 From 0.3 to 0.95, preferably from 0.4 to 8.
As a further technical scheme, znO/Al 2 O 3 From 0.25 to 0.8, preferably from 0.4 to 0.75.
As a further technical scheme, (Li) 2 O+Na 2 O)/(RE 2 O 3 +ZnO) of 0.2 to 1.8, preferably 0.3 to 1.7, more preferably 0.4 to 1.5. If the ratio is lower than 0.2, the chemical strengthening effect of the glass ceramics is poor, especially CS50 is lower than 150MPa, DOC is lower than 100 μm, and when the ratio is higher than 1.8, the precipitation of the glass ceramics crystal is affected, even the situation of no crystallization occurs.
As a further technical scheme, na 2 O/Li 2 O≤0.5，Li 2 O+Na 2 O is 2.5% -13%.
By controlling alkali metal compound Li 2 O and Na 2 The introduction amount and the proportion of O can influence the precipitation of the crystalline phase of the microcrystalline glass, and when Li 2 O+Na 2 O is more than 13%, and devitrification of glass ceramics is difficult, even difficult. When Li 2 O+Na 2 When the O content is less than 2.5%, the base glass is difficult to melt, high-quality glass liquid is difficult to obtain, and the later-stage ion exchange chemical strengthening effect of the glass ceramics is not ideal. And when Li 2 When O is excessive, quartz solid stone is easy to be separated out in the crystallization process of glass to reduce transparency and Na 2 O/Li 2 When O is greater than 0.5, DOC is less than 100 μm.
As a further embodiment, zrO is used in the present invention at the same time 2 、TiO 2 、P 2 O 5 As composite crystal nucleus agent, tiO needs to be controlled 2 /ZrO 2 When TiO is the ratio of 2 /ZrO 2 When the temperature is more than or equal to 2.5, the precipitated main crystal phase is ZnAl 2 O 4 When TiO 2 /ZrO 2 At < 2.5, the precipitated primary crystal phase comprises RE 2 Ti 2 O 7 、RE 2 Zr 2 O 7 、Al 1.5x Zr 2y O 1.5+2y 、Zr 2x Y 1.5y Ti 2z O 2x+1.5y+2z One or more complex crystalline phases of lithium silicate, zirconia, quartz solid solutions, and the like.
As a further technical scheme, the main crystal phase is solid solution, the crystallinity of the solid solution is more than or equal to 25%, preferably more than or equal to 30%, more preferably more than or equal to 40%, and most preferably more than or equal to 50%.
The main crystal phase of the microcrystalline glass appears in the form of solid solution, namely, several crystals with similar crystal peak positions exist at the same time, so that the crystallinity of the microcrystalline glass is greatly improved, the high crystallinity is favorable for blocking generated cracks, and the breakage resistance of the microcrystalline glass is improved.
As a further technical scheme, the 550nm transmittance of the glass ceramic with the thickness of 0.7mm is more than or equal to 89%, preferably more than or equal to 90%, and more preferably more than or equal to 91%.
As a further technical scheme, through ion exchange chemical strengthening, the performance of the high-permeability high-strength zinc-aluminum-silicon glass ceramic meets the following conditions: CS50 is more than or equal to 190MPa, CS80 is more than or equal to 100MPa, DOC is more than or equal to 110 mu m,2.5D form complete machine counterweight 200g 80-mesh sand paper is more than or equal to 1.0m, four-point bending strength is more than or equal to 600MPa, and 110g steel ball impact height is more than or equal to 200mm.
The invention also provides a preparation method of the high-permeability high-strength zinc aluminum silicon microcrystalline glass, which comprises the following steps: and weighing carbonate or nitrate corresponding to the compound in proportion, melting at high temperature, forming, carrying out heat preservation annealing treatment, cooling along with a furnace, and carrying out heat treatment to obtain the microcrystalline glass.
The microcrystalline glass can be produced by adopting a casting method, a calendaring method, a float method, a down-draw method and other forming processes, and controllable crystal growth is realized through an effective heat treatment system.
As a further technical scheme, the heat treatment is performed for 0.5-18h under 600-700 ℃, and then the temperature is raised to 700-850 ℃ for crystallization for 0.2-12h.
As a further technical scheme, the heat preservation is carried out for 1-5h at 500-550 ℃.
The working principle and the beneficial effects of the invention are as follows:
1. the invention provides a glass material with high transparency and high strength, which is prepared by a controllable microcrystal crystallization process, wherein the glass material with high transparency and high elastic modulus can be used for improving surface stress and ion exchange layer depth through single-step/multi-step chemical strengthening, has CS50 of more than 190MPa, CS80 of more than 100MPa and DOC of more than 110 mu m, plays an effective protective role, improves the breakage resistance of the material, and can be applied to electronic equipment protective shells and mobile terminal touch protective materials.
2. The invention adopts a microcrystal system with high crystallinity which is different from the prior art, realizes the aim of achieving high strength by combining the microcrystal system with high transparency, higher crystallinity and high elastic modulus with a composition with more excellent strengthening performance; the raw material cost is reduced by the design of a basic microcrystalline glass material formula, a melting and forming process.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an electron microscope image of a crystal according to example 8 of the present invention;
FIG. 2 is an electron microscope image of the crystal according to example 10 of the present invention;
FIG. 3 is a crystal diffraction pattern of examples 8 and 10 of the present invention;
wherein A is the crystalline diffraction pattern of example 8 and B is the crystalline diffraction pattern of example 10;
FIG. 4 is a graph showing the stress distribution after chemical strengthening of glass according to example 10 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. In the present specification, unless otherwise specified, the contents of the respective components are expressed in terms of mole percentages of the compounds. In the present specification, the term "glass" refers to a glass precursor before crystallization, and after crystallization, the term "glass ceramic".
The high-permeability high-strength zinc aluminum silicon microcrystalline glass comprises the following compounds in percentage by mole: znO 5-13%, al 2 O 3 12%-22%，SiO 2 40%-65%，ZrO 2 0.1%-1.5%，RE 2 O 3 1%-8%，Li 2 O 2%-11%，Na 2 O 0.5%-2%，TiO 2 1.5%-4.5%，B 2 O 3 0.1%-2%，P 2 O 5 0.1%-1.5%，NaCl 0.1%-0.8%，Sb 2 O 3 0.1% -0.3%; wherein RE is 2 O 3 Comprising Y 2 O 3 、La 2 O 3 、Gd 2 O 3 One or more of the following.
The crystalline phase of the glass ceramic material of the invention comprises RE 2 Ti 2 O 7 、RE 2 Zr 2 O 7 、ZnAl 2 O 4 、Al 1.5x Zr 2y O 1.5+2y 、Zr 2x Y 1.5y Ti 2z O 2x+1.5y+2z One or more composite crystalline phases in solid solution of lithium silicate, zirconium oxide and quartz.
The microcrystalline glass material is a composite material with high transparency and high strength and has a crystalline phase and a glass phase, the crystalline phase of the microcrystalline glass material can be analyzed by X-ray diffraction, and the crystal morphology is measured by SEM. Through continuous experiments and researches, the inventor of the invention controls the specific composition of the microcrystalline glass material through crystallization technology to generate a crystal phase with specific proportion, and the microcrystalline glass material of the invention is obtained at lower cost.
The reason why the glass ceramics of the present invention are limited in composition and content will be described below.
SiO 2 Is an essential component of the glass of the present invention, is one of the main components forming crystals after heat treatment, if SiO 2 The content of (2) is 40% or less, the glass forming property of the glass is deteriorated, the chemical stability is unstable, and the base glass tends to be easy to phase-separate. Thus, siO 2 The lower limit of the content is preferably 40%, preferably 45%. If SiO 2 The content is above 65%, the melting temperature is high, clarification and homogenization are difficult, and the precipitation of crystals and SiO are not easy 2 The upper limit of the content is preferably 65%, more preferably 60%. In some embodiments, about 40%, 45%, 49%, 50%, 52%, 54%, 56%, 60%, 65% SiO may be included 2 。
Al 2 O 3 The glass is necessary components for forming a glass network structure, is very beneficial to improving the structure and chemical stability of the glass, can refine grains in heat treatment, controls the crystallization speed, is beneficial to improving the ion exchange capacity of the glass ceramics by chemical strengthening, but if the content of the glass ceramics is less than 12 percent, the crystallization is very unfavorable, the crystallization speed is difficult to control, the crystal size is enlarged, aluminum is difficult to enter the crystal, the crystallinity is reduced, the elastic modulus of the glass material is reduced, and the chemical strengthening characteristic stress value such as CS50 is influenced. Thus, al 2 O 3 The lower limit of the content is 12%, preferably 18%. On the other hand, if Al 2 O 3 If the content exceeds 22%, melting of the glass becomes difficult and precipitation of crystals is inhibited, so that Al 2 O 3 The upper limit of the content is 22%, preferably 20%. In some embodiments, about 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22% Al may be included 2 O 3 。
Li 2 O is an essential component in the glass composition, and can reduce the viscosity of the mother glass and promote crystal formation, is also an essential component in the ion exchange process, and is combined with Na + 、K + The component to be displaced can increase the depth of the compressive stress of chemical strengthening, but if the content is less than 2%, on the one hand, the glass melting effect is affected and on the other hand, a deeper stress layer is difficult to obtain, and therefore, li 2 The lower limit of the O content is 2%, preferably 4%. If too much Li is contained 2 O, the chemical stability of glass becomes poor, and it is difficult to control during crystallization, and lithium-containing crystals such as quartz solid solution phase, spodumene and the like are easily produced, and the glass-ceramic transparency is lowered. Thus Li 2 The upper limit of the O content is 11%, preferably 10%, more preferably 9%. In some embodiments, about 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% of Li may be included 2 O。
Na 2 O is used as an essential component in the invention, and is low in Na with common microcrystalline glass 2 The O content is obviously different, na 2 O is taken as an external body of a glass network, mainly plays a role in breaking network to provide free oxygen, has a stronger function of inhibiting crystal precipitation, and is common microcrystalline glass Na 2 The low O content is beneficial to crystallization, if Na is used in the invention 2 When the O content is low, the precipitated crystal is petalite crystal, and in addition, na 2 Too low O, na in the glass ceramics during ion exchange + And K is equal to + Insufficient exchange content, low surface compressive stress value, and strength influence, thus Na 2 The lower limit of the O content is 0.5%, and the preferred lower limit is 1%. Excessive glass containing Na 2 O, the glass expansion coefficient becomes large, the thermal stability is poor, annealing is difficult, the risk of cracking is easy to occur, and the crystal precipitation is inhibited, so Na 2 The upper limit of the O content is 2%, preferably 1.5%. In some embodiments, about 0.5%, 1%, 1.5%, 2% Na may be included 2 O。
ZrO 2 The invention is an essential component, and the functions of the invention are mainly as follows: firstly, the glass is used as a crystal nucleus agent to enable the glass to be uniformly crystallized, so that the precipitation of crystals and the size of the crystals can be effectively controlled, and the influence on the optical performance caused by overlarge crystal size is avoided; second, can be in Li + The chemical stability of the mother glass or the microcrystalline glass is improved under the condition of higher content. In the course of experimental investigation, zrO 2 And the devitrification risk of the matrix glass in the forming process is effectively reduced. To achieve the effects of the present invention, zrO 2 The lower limit of the content is preferably 0.1%, more preferably 0.3%, further preferably 0.5%; but if too much ZrO is contained 2 The melting temperature of the glass is increased, which makes melting difficult, and excessive high temperature can inhibit precipitation of target crystalline phase, which makes crystallization uncontrollable, so ZrO 2 The upper limit of the content is 1.5%, preferably 1.2%, more preferably 1.0%. In some embodiments, zrO may be included at about 0.1%, 0.3%, 0.5%, 1.0%, 1.2%, 1.5% 2 。
TiO 2 Is the main crystal nucleus agent of the glass composition of the invention, can effectively promote the precipitation of crystals and TiO 2 And ZrO(s) 2 The compound crystal nucleus agent is inseparable and plays a role in mutual influence. TiO (titanium dioxide) 2 The lower limit of the content is preferably 1.5%, more preferably 2%, further preferably 2.5%; but if too much TiO is contained 2 Then easily and Li + The interaction leads the parent glass to generate phase separation, the devitrification in the crystallization process is uncontrollable, the mechanical property of the microcrystalline glass can be reduced, and in addition, excessive glass is easy to cause yellow color, and the chromaticity is influenced. Thus, tiO 2 The upper limit of the content is 4.5%, preferably 4%, more preferably 3.5%. In some embodiments, about 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% TiO may be included 2 。
ZnO is an essential component in the invention, improves the material property and the thermal property of the parent glass, is favorable for refining grains in the crystallization process, improves the optical property of the microcrystalline glass, and has the lower limit of 5 percent, and other crystals can be obtained after crystallization when the content is higher than 13 percent, thereby influencing the mechanical property and the optical property. Therefore, the upper limit of the ZnO content is 13%, preferably 12%. In some embodiments, about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% ZnO may be included.
RE 2 O 3 Comprising Y 2 O 3 、La 2 O 3 、Gd 2 O 3 One or more of the following. As the necessary compound component in the invention, the network filler exists in the glass, thus enhancing the network density and the strength of the glass; meanwhile, the fluxing agent also has good fluxing effect. RE (RE) 2 O 3 The invention can also take into crystal structure to form crystal solid solution, promote crystal precipitation, and play a key role in resisting crack expansion. When the content is too high, the refractive index of the glass is larger, the glass is difficult to meet the high-requirement optical performance as an electronic product, particularly a display cover plate, and the transmittance of the glass is also influenced, so that the glass is difficult to reach more than 90%; in addition, too high a dosage results in high material cost, which is not consistent with the direction of cost reduction, thus RE 2 O 3 The content is below 8%, and the content is too low, so that the mechanical property of the glass is not obviously improved, the elastic modulus can not meet the design requirement, and the necessary components of the crystal can not be formed, and the crystallization is not good. RE (RE) 2 O 3 In an amount of 1% -8%, in some embodiments, may comprise about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% RE 2 O 3 . For clarity, Y is used in the examples 2 O 3 Is representative of the description.
P 2 O 5 As a glass network forming body, a triangular body and a tetrahedral structure can be formed in glass, a good fluxing effect can be achieved, and in the invention, the crystal nucleus agent TiO 2 The effect of (2) can lead the color of the glass to be yellow, affect the color balance of the display material, and introduce a proper amount of P 2 O 5 This problem can be effectively alleviated. However, when the content is too high, the chemical stability of the mother glass is lowered, and thus P 2 O 5 The upper limit of the content is 1.5%.
B 2 O 3 As a glass network forming body, the structure of a triangle and a tetrahedron can be formed in glass, the structure can be effectively supplemented, and the glass network forming body can play a good role in fluxing and is suitable forAmount B of 2 O 3 Can play a role in stabilizing the structure of the glass, enlarge the formation interval of the glass and reduce the expansion coefficient. When the glass phase separation is easily caused by the addition of the excessive glass phase separation, the crystallization temperature is low, and the precipitation of crystals is influenced. Thus B 2 O 3 The upper limit of the content is 2%, and the lower limit of the content is 0.1%.
NaCl and Sb 2 O 3 The invention plays a role of clarifying agent, and the NaCl content is 0.1-0.8%; sb (Sb) 2 O 3 The content is 0.1% -0.3%.
The test method applied by the invention comprises the following steps:
1) Crystal morphology
And (3) measuring by using an SEM scanning electron microscope, carrying out surface treatment on the microcrystalline glass in 5wt% of HF acid, then carrying out metal spraying on the surface of the microcrystalline glass, carrying out surface scanning under the SEM scanning electron microscope, and determining the grain size of the microcrystalline glass. Fig. 1 and 2 are electron microscope pictures of the crystals of example 8 and example 10 of the present invention, respectively.
2) Transmittance of light
The samples were processed to a thickness of 0.7mm and polished with opposite faces in parallel, and the light transmittance at 550nm was measured using a Lambda 950 uv-vis-nir spectrophotometer.
3) Analysis of crystalline phases
Diffraction peaks of glass ceramics were measured by XRD diffractometer, and crystal types were analyzed by means of the combination of the JADE software and PDF card 2004. Fig. 3 is a crystal diffraction pattern of examples 8 and 10 of the present invention, wherein a is a crystal diffraction pattern of example 8 and B is a crystal diffraction pattern of example 10.
4) Surface stress and ion exchange layer depth
Surface stress (CS 50, CS 80) measurements were performed using a glass surface stress meter FSM-6000 LEUV.
Ion exchange depth of layer (DOC) measurements were performed using a glass surface stress meter SLP-2000.
The measurement conditions were calculated by using a sample having a refractive index of 1.58 and an optical elastic constant of 25.6[ (nm/cm)/MPa ].
FIG. 4 is a graph showing the stress distribution after chemical strengthening of glass according to example 10 of the present invention.
5) Drop test height (i.e. drop impact)
The sample of 157X 65X 0.55mm was polished on both surfaces and placed on a rubber sheet, and a steel ball of 110g was dropped from a predetermined height, and the sample was subjected to a maximum falling ball test height of impact that could be sustained without breaking. Specifically, the test was performed starting from a falling ball test height of 100mm, and the heights were changed in order of 150mm, 200mm, 250mm, 300mm and above without cracking. Test data recorded as 200mm in the examples show that the glass ceramic product is not broken and receives impact even if the steel ball is dropped from a height of 200mm.
6) Drop height of the whole machine (namely, maximum distance of 200g 80-mesh sand paper of 2.5D shape whole machine counterweight)
And (3) polishing two surfaces of a sample with the thickness of 150 multiplied by 57 multiplied by 0.55mm, chemically strengthening, assembling the sample onto a model machine with the weight of 200g, and clamping a mobile phone model by using a dropping machine, so that the glass surface of the whole machine freely drops onto 80-mesh sand paper from a specified height, and the sample is not broken and can bear the maximum drop test height. Specifically, the test was performed starting from a height of 0.4m, and the heights were changed in order by 0.5m, 0.6m, 0.7m, 0.8m, and 0.9m and above without cracking. For the examples having a "drop test height", glass-ceramic articles were the subject of the test. Test data recorded as 1m in the examples indicate that the glass-ceramic article does not break even when dropped from a height of 1 m.
7) Four point bending strength
The microcomputer controlled electronic universal tester CMT6502 is adopted, the glass specification is 150 multiplied by 57 multiplied by 0.55mm, and the test is carried out by taking ASTMC158-2002 as a standard.
8) Vickers hardness of
The transparent glass-ceramic samples were polished to a specular effect, the hardness values of the samples were tested using a vickers durometer (HVS-1000), each sample at least 5 times to reduce errors, the applied load was 200g, the loading time was 10s, and the final results were averaged.
9) Modulus of elasticity
The glass ceramics were cut into strips of 100mm x 20mm x 5mm in size, and the elastic modulus of the samples were tested with a glass material intrinsic mechanical analyzer (BZLX-2013), each sample at least 5 times to reduce errors, and the final results were averaged.
Table 1 compositions and preparation methods of glass-ceramic compounds of examples 1 to 5
Table 2 compositions and preparation methods of glass-ceramic compounds of examples 6 to 10
Table 3 microcrystalline glass compound composition of comparative examples 1-2 and preparation method thereof
TABLE 4 results of test on glass-ceramic Performance of examples 1-5
TABLE 5 results of glass-ceramic Performance test of examples 6-10
Table 6 results of the glass-ceramic Performance test of comparative examples 1 to 2
In Table 6, comparative example 2 was not tested for surface stress and ion exchange layer depth performance because the base glass was split, unusable, and of no research value.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The high-permeability high-strength zinc aluminum silicon microcrystalline glass is characterized by comprising the following compounds in percentage by mole: znO 5-13%, al 2 O 3 12%-22%，SiO 2 40%-65%，ZrO 2 0.1%-1.5%，RE 2 O 3 1%-8%，Li 2 O 2%-11%，Na 2 O 0.5%-2%，TiO 2 1.5%-4.5%，B 2 O 3 0.1%-2%，P 2 O 5 0.1%-1.5%，NaCl 0.1%-0.8%，Sb 2 O 3 0.1% -0.3%; wherein RE is 2 O 3 Comprising Y 2 O 3 、La 2 O 3 、Gd 2 O 3 One or more of the following.
2. The high-permeability high-strength zinc-aluminum-silicon glass ceramic according to claim 1, wherein the crystalline phase comprises RE 2 Ti 2 O 7 、RE 2 Zr 2 O 7 、ZnAl 2 O 4 、Al 1.5x Zr 2y O 1.5+2y 、Zr 2x Y 1.5y Ti 2z O 2x+1.5y+2z One or more composite crystalline phases in solid solution of lithium silicate, zirconium oxide and quartz.
3. The high-permeability high-strength zinc aluminum silicon glass ceramic according to claim 1, wherein the compound composition satisfies at least one of the following conditions:
(ZnO+Al 2 O 3 )/SiO 2 0.3-0.95;
ZnO/Al 2 O 3 0.25-0.8;
(Li 2 O+Na 2 O)/(RE 2 O 3 +ZnO) of 0.2 to 1.8;
Na 2 O/Li 2 O≤0.5。
4. a high permeability high strength zinc according to claim 1An aluminum silicon glass ceramic is characterized in that when TiO 2 /ZrO 2 When the temperature is more than or equal to 2.5, the precipitated main crystal phase is ZnAl 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the When TiO 2 /ZrO 2 When the ratio is less than 2.5, the precipitated main crystal phase is RE 2 Ti 2 O 7 、RE 2 Zr 2 O 7 、Al 1.5x Zr 2y O 1.5+2y 、Zr 2x Y 1.5y Ti 2z O 2x+1.5y+2z One or more composite crystalline phases in solid solution of lithium silicate, zirconium oxide and quartz.
5. The high-permeability high-strength zinc-aluminum-silicon glass ceramic according to claim 1, wherein the main crystal phase is solid solution, and the crystallinity of the solid solution is more than or equal to 25%.
6. The high-permeability high-strength zinc-aluminum-silicon glass ceramic according to claim 1, wherein the 550nm transmittance of the glass ceramic with the thickness of 0.7mm is more than or equal to 89%.
7. The high-permeability high-strength zinc aluminum silicon glass ceramic according to claim 1, wherein the properties of the glass ceramic are as follows:
CS50 is more than or equal to 190MPa, CS80 is more than or equal to 100MPa, DOC is more than or equal to 110 mu m,2.5D form complete machine counterweight 200g 80-mesh sand paper is more than or equal to 1.0m, four-point bending strength is more than or equal to 600MPa, and 110g steel ball impact height is more than or equal to 200mm.
8. The method for preparing the high-permeability high-strength zinc aluminum silicon microcrystalline glass according to any one of claims 1 to 7, which is characterized by comprising the following steps: and weighing carbonate or nitrate corresponding to the compound in proportion, melting at high temperature, forming, carrying out heat preservation annealing treatment, cooling along with a furnace, and carrying out heat treatment to obtain the microcrystalline glass.
9. The method for preparing high-permeability high-strength zinc-aluminum-silicon glass ceramics according to claim 8, wherein the heat treatment is performed for nucleating at 600-700 ℃ for 0.5-18h, and then the temperature is raised to 700-850 ℃ for crystallizing for 0.2-12h.
10. The method for preparing high-permeability high-strength zinc aluminum silicon microcrystalline glass according to claim 8, wherein the thermal insulation annealing treatment is as follows: and (5) heat preserving at 500-550 ℃ for annealing treatment for 1-5h.
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| CN115490428A (en) * | 2022-09-16 | 2022-12-20 | 四川虹科创新科技有限公司 | Transparent glass ceramics with ultrahigh drop strength and preparation method thereof |
| CN116282926A (en) * | 2022-11-28 | 2023-06-23 | 武汉理工大学 | High-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and preparation method thereof |
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| CN115490428A (en) * | 2022-09-16 | 2022-12-20 | 四川虹科创新科技有限公司 | Transparent glass ceramics with ultrahigh drop strength and preparation method thereof |
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