CN115745399A - Phase separation glass, preparation method thereof, tempered glass, glass cover plate and electronic equipment - Google Patents
Phase separation glass, preparation method thereof, tempered glass, glass cover plate and electronic equipment Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 200
- 238000005191 phase separation Methods 0.000 title claims abstract description 39
- 239000005341 toughened glass Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 238000002834 transmittance Methods 0.000 claims abstract description 20
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 9
- 239000006064 precursor glass Substances 0.000 claims description 45
- 239000006058 strengthened glass Substances 0.000 claims description 20
- 239000012798 spherical particle Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000013003 hot bending Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000013001 point bending Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
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- 238000005496 tempering Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 12
- 238000003426 chemical strengthening reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000011534 incubation Methods 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 6
- 229910001947 lithium oxide Inorganic materials 0.000 description 6
- 229910052810 boron oxide Inorganic materials 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006025 fining agent Substances 0.000 description 3
- 239000006132 parent glass Substances 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 239000006112 glass ceramic composition Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 238000007493 shaping process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
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- 238000007667 floating Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000006133 sodium aluminosilicate glass Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Glass Compositions (AREA)
Abstract
The invention relates to phase separation glass, a preparation method thereof, tempered glass, a glass cover plate and electronic equipment. The phase-splitting glass comprises a silicon-rich lithium phase and a phosphorus-rich phase, and comprises the following components in percentage by mass: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O 5％～17％、Na 2 O 0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -8% and ZrO 2 0.1% -10%, wherein (Na) 2 O+K 2 O)≤Li 2 O/10, and the phase-separated glass does not contain TiO 2 . The phase-splitting glassHas high transmittance and ion exchange performance.
Description
Technical Field
The invention relates to the field of glass, in particular to phase separation glass, a preparation method of the phase separation glass, tempered glass, a glass cover plate and electronic equipment.
Background
With the development of mobile electronic devices such as notebook computers, portable navigators, smart phones, etc. toward the trend of being more portable and more powerful, people have increasingly high dependence on them. The increase in frequency of use in turn places higher demands on the packaging or casing material of the electronic device, and it is a research direction of researchers in this field how to make the packaging or casing material lighter and thinner, and harder and stronger.
Currently, ion-exchange strengthened soda-aluminosilicate glasses are commonly used as encapsulation or housing materials. The microcrystalline glass containing a large amount of crystals can also be strengthened in the same way, and the microcrystalline glass after ion exchange strengthening has more excellent comprehensive mechanical properties compared with the sodium aluminosilicate glass after ion exchange strengthening. However, the first step of the microcrystalline glass production process usually includes two steps of nucleation and crystallization, which increases the energy consumption of the production, thereby increasing the production cost of the microcrystalline glass. Secondly, the microcrystalline glass contains a large amount of crystals, which makes it extremely difficult to grind and polish during deep processing. In addition, ion exchange of the glass ceramics requires higher temperature and longer time due to the presence of a large amount of crystals. These greatly reduce the production and processing efficiency of the chemically strengthened glass ceramics.
Therefore, researchers have proposed an ion-exchangeable phase-separated glass by introducing TiO into a glass composition, aiming at the characteristics of microcrystalline glass such as high energy consumption, difficult processing and high ion exchange temperature 2 Can prepare glass with phase separation characteristic, and avoids the defects of microcrystalline glass. However, trace amounts (50 ppm to 1000 ppm) of TiO 2 The transmittance of the glass in the range of 360nm to 780nm is slightly lowered, and (a) is slightly more>0.1%) of TiO 2 Can even result in a yellowish to amber color visible to the naked eye, making the glass (0.7 mm) less than 87% or even lower in transmittance, which limits the application of phase-separated glass as a protective material for end device panels. Furthermore, the ion exchange Depth (DOL) of the above-mentioned phase-separated glass is generally less than 100 μm, and the central tensile stress (CT) is generally less than 80MPa, which is a limit to the improvement of the strength of the product.
Disclosure of Invention
Based on the above, it is necessary to provide a phase-separated glass with high transmittance and ion exchange performance and a preparation method thereof, wherein the ion exchange depth of the phase-separated glass after ion exchange is not less than 100 μm, the central tensile stress is not less than 80MPa, and the strength of the phase-separated glass is improved.
In addition, a need exists for a strengthened glass, a glass cover plate and an electronic device.
A phase-separated glass comprising a silicon-rich lithium phase and a phosphorus-rich phase, the phase-separated glass comprising, by mass percent: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O 5％～17％、Na 2 O0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -8% and ZrO 2 0.1% -10%, wherein (Na) 2 O+K 2 O)≤Li 2 O/10, and the phase-separated glass does not contain TiO 2 。
In one embodiment, the phase separated glass satisfies at least one of the following conditions:
(1)SiO 2 the mass percentage of the component (A) is 65-75%;
(2)Na 2 the mass percent of O is 0-0.25%; and
(3)K 2 the mass percent of O is 0-0.25%.
In one embodiment, the phase-separated glass comprises the following components in percentage by mass: siO 2 2 65％～75％、Al 2 O 3 6％～12％、Li 2 O 9％～13％、Na 2 O 0～0.25％、K 2 O 0～0.25％、B 2 O 3 0～5％、CaO0～3％、BaO 0～3％、P 2 O 5 2% -4% and ZrO 2 4.5％～6.5％。
In one embodiment, the silicon-rich lithium phase is dispersed in the phosphorus-rich phase in the form of spherical particles having an average particle size of 100nm or less.
In one embodiment, the ratio of the volume of the silicon-rich lithium phase to the total volume of the phase-separated glass is greater than or equal to 40%.
In one embodiment, the average transmittance of the phase-separated glass is more than or equal to 89% in the wavelength range of 360nm to 780 nm.
A preparation method of phase separation glass comprises the following steps:
weighing corresponding raw materials according to the mass percent of each oxide, mixing and melting to obtain precursor glass, wherein the precursor glass comprises the following components in percentage by mass: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O5％～17％、Na 2 O 0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -8% and ZrO 2 0.1％～10％，(Na 2 O+K 2 O)≤Li 2 O/10, and the precursor glass does not contain TiO 2 (ii) a And
and carrying out heat treatment on the precursor glass to obtain the phase-separated glass, wherein the phase-separated glass comprises a silicon-rich lithium phase and a phosphorus-rich phase.
In one embodiment, the heat treatment is performed in a manner selected from any one or a combination of the following manners:
(1) Preserving the temperature of the precursor glass at Tg + 30-Tg +100 ℃ for 1-8 h;
(2) Reducing the precursor glass from the melting temperature to Tg at a rate of 0.5 ℃/min to 20 ℃/min; and
(3) The precursor glass is raised from Tg +30 ℃ to Tg +100 ℃ at a rate of 0.5 ℃/min to 20 ℃/min.
In one embodiment, the method further comprises the following steps: and 3D hot bending and forming the phase-separated glass or the precursor glass, wherein the temperature of the 3D hot bending and forming is less than or equal to 850 ℃.
A tempered glass is obtained by chemically tempering phase-separated glass, wherein the phase-separated glass is the phase-separated glass or the phase-separated glass prepared by the preparation method of the phase-separated glass.
In one embodiment, the strengthened glass satisfies at least one of the following conditions:
(1) The average surface compressive stress of the tempered glass is more than or equal to 100MPa;
(2) The ion exchange depth of the strengthened glass is more than or equal to 100 mu m;
(3) The central tensile stress of the tempered glass is more than or equal to 80MPa; and
(4) The four-point bending strength of the tempered glass is more than or equal to 400MPa.
The glass cover plate is obtained by processing the phase separation glass or the strengthened glass.
An electronic device comprises the phase separation glass, the tempered glass or the glass cover plate.
The phase-separated glass does not contain titanium dioxide and is prepared by introducing P 2 O 5 And adjusting glass components to cause phase separation of the glass, wherein the phase-separated glass is colorless and transparent, and has an average transmittance of more than or equal to 89% in a spectral range of 360-780 nm. After chemical strengthening, the ion exchange Depth (DOL) is more than or equal to 100 mu m, the central tensile stress (CT) is more than or equal to 80MPa, and the four-point bending strength (4 PB) is more than or equal to 400MPa, so that the ion exchange effect is effectively improved on the premise of ensuring phase separation.
Drawings
FIG. 1 is an SEM image of the precursor glass of example 2 after incubation for 8h at Tg +30 ℃;
FIG. 2 is an SEM image of the precursor glass of example 2 after incubation for 4h at Tg +50 ℃;
FIG. 3 is an SEM image of the precursor glass of example 2 after incubation for 1h at Tg +100 ℃;
FIG. 4 is an XRD pattern of the precursor glasses of examples 1-8 after 4h incubation at Tg +50 ℃;
FIG. 5 is a TEM image and element distribution of the precursor glass of example 2 after incubation for 4h at Tg +50 ℃.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments described herein. It will be apparent, however, to one skilled in the art, that the embodiments may be practiced without some or all of these specific details. In other instances, well-known features or processes have not been described in detail in order not to obscure the invention. Further, similar or identical reference numbers may be used to identify common or similar parts. Furthermore, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions herein, will control.
Although other methods and materials may be used in the practice or testing of embodiments of the present invention, some suitable methods and materials are described below.
Disclosed are materials, compounds, compositions, and components that can be used for, can be used in conjunction with, can be used in preparation for, or are embodiments of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein.
Thus, if a class of substituents a, B, and C is disclosed as well as a class of substituents D, E, and F and examples of combined embodiments a-D are also disclosed, each is individually and collectively contemplated. Thus, in this example, each of the following combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated, and should be considered to be taken from A, B, and/or C; D. e and/or F; and example combinations a-D. Likewise, any subset or combination of subsets of the above is specifically contemplated and disclosed. Thus, for example, the sub-groups of A-E, B-F, and C-E are specifically contemplated and should be considered to be derived from A, B, and/or C; D. e and/or F; and example combinations a-D. This concept applies to all aspects of this disclosure including, but not limited to, any component of the compositions and steps in methods of making and using the disclosed compositions. In particular, the exemplary compositional ranges set forth herein are considered to be part of the specification and are further considered to provide exemplary numerical range endpoints that are equivalent in all respects to their inclusion in the text and that all combinations are specifically contemplated and disclosed. Further, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed by any specific embodiment or combination of embodiments of the disclosed methods and that each such combination is specifically contemplated and should be considered disclosed.
Unless otherwise indicated in a particular instance, the numerical ranges set forth herein include the upper and lower values and are intended to include the endpoints of the ranges, and all integers and fractions within the ranges. The scope of the invention is not limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is expressed in terms of a range, one or more preferred ranges, or an upper preferred numerical range and a lower preferred numerical range, it is understood that any range by combining any pair of an upper range limit or a preferred numerical value with any lower range limit or a preferred numerical value is specifically disclosed, regardless of whether such a combination is specifically disclosed. Finally, when the term "about" is used to describe a value or an end-point of a range, it is understood that the invention includes the particular value or end-point referenced.
As used herein, the term "about" refers to amounts, sizes, formulations, parameters, and other quantities and characteristics that are not and need not be exact, but may be approximate and/or larger or lower, if desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like. Generally, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximately" whether or not explicitly stated.
As used herein, the term "or" is inclusive, specifically the phrase "a or B" refers to "a, B, or a and B". In this document, for example, an exclusive "or" is specified by terms such as "either a or B" and "one of a or B.
The elements and components of the disclosure will be described using the indefinite articles "a" or "an". The use of these articles means that one or at least one of these elements or components is present. Although these articles are often used to connote a modified noun as a singular noun, the articles "a" or "an" as used herein also include the plural unless otherwise indicated. Similarly, also as used herein, the definite article "the" also indicates that the modified noun may be singular or plural, unless otherwise indicated.
For the purposes of describing embodiments of the present invention, it should be noted that references herein to a variable being a "function" of one parameter or another are not intended to mean that the variable is merely a function of the listed parameter or variable. In contrast, a "function" as referred to herein where a variable is a listed parameter is open ended, such that the variable may be a single parameter or a function of multiple parameters.
It is noted that terms such as "preferably," "commonly," and "typically" are not utilized herein to limit the scope of the invention or to imply that certain features are critical, or even essential to the structure or function of the described embodiments of the invention. Rather, these terms are merely intended to identify particular aspects of an embodiment of the present invention or to emphasize alternative or additional features that may or may not be utilized in a particular embodiment of the present invention.
It is to be noticed that one or more of the claims should use the term 'characterized in' as a transitional phrase. For the purposes of defining the invention, it is noted that the term is used in the claims as an open transition phrase to bring out a description of a series of structural features, which should be interpreted similar to the more commonly used open introductory phrases "comprising".
As a result of the raw materials and/or equipment used to produce the glass composition, certain impurities or components may be present in the final glass composition that are not intentionally added. Such materials are present in small amounts in glass or glass ceramic compositions and are referred to herein as "fugitive materials".
As used herein, the inclusion of 0 wt.% of a compound in a glass or glass ceramic composition is defined as the absence of the intentional addition of the compound, molecule or element to the composition, but the composition may still include the compound, usually in indeterminate amounts or trace amounts. Similarly, "titanium-free," "iron-free," "sodium-free," "lithium-free," "zirconium-free," "alkaline earth metal-free," "heavy metal-free," and the like are defined as the absence of deliberate addition of the compound, molecule or element to the composition, but the composition may still include titanium, iron, sodium, lithium, zirconium, alkaline earth metal, or heavy metal, and the like, but in near indeterminate amounts or trace amounts.
Unless otherwise indicated, the concentrations of all components cited herein are expressed in mass percent (mass%).
Aiming at the problems of color, opacity and low strength after ion exchange of the surface of the traditional phase-splitting glass, the invention provides the phase-splitting glass which is colorless and transparent and has good ion exchange performance.
Specifically, the phase-separated glass of one embodiment comprises a silicon-rich lithium phase and a phosphorus-rich phase, and the phase-separated glass comprises the following components in percentage by mass: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O 5～17％、Na 2 O 0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -8% and ZrO 2 0.1% -10% of (Na) in the formula 2 O+K 2 O)≤Li 2 O/10, and the phase-separated glass does not contain TiO 2 。
In the present embodiment, the silicon-rich lithium phase means SiO 2 And Li 2 An aggregated phase containing O in an amount larger than that in the mother glass before phase separation, and a phosphorus-rich phase P 2 O 5 An aggregated phase in an amount greater than its amount in the parent glass prior to phase separation.
In some embodiments, the silicon-rich lithium phase also contains other oxides in the glass composition in addition to silica and lithium oxide. The phosphorus-rich phase also contains other oxides in the glass composition besides phosphorus pentoxide.
In some embodiments, the silicon-rich lithium phase is dispersed in the phosphorus-rich phase, which forms the matrix phase. Further, the silicon-rich lithium phase is dispersed in the phosphorus-rich phase in the form of spherical particles. It will be appreciated that there may also be a small number of connections between the spherical particles.
In some embodiments, the spherical particles have an average particle size of 100nm or less. In one embodiment, the spherical particles have an average particle size of 100nm, 90nm, 80nm, 70nm, 60nm, 50nm, 40nm, 30nm, 20nm, 10nm, 5nm, or a range consisting of any two of these values. Further, the average particle diameter of the spherical particles is less than or equal to 80nm. Further, the spherical particles have an average particle size of 60nm or less. Further, the spherical particles have an average particle size of 40nm or less. Further, the spherical particles have an average particle size of 20nm or less. Further, the spherical particles have an average particle diameter of 10nm or less. Too large size of the phase-separated spherical particles will result in the decrease of the transmittance of the phase-separated glass, while too small size of the phase-separated spherical particles will not improve the mechanical properties of the phase-separated glass.
In some embodiments, the volume of the silicon-rich lithium phase is ≧ 10% by volume of the total volume of the phase-separated glass. In a particular example, the volume of the silicon-rich lithium phase relative to the total volume of the phase-separated glass is 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or a range consisting of any two of these values. Furthermore, the volume ratio of the silicon-rich lithium phase to the total volume of the phase-separated glass is more than or equal to 40 percent. The higher the proportion of the silicon-rich lithium phase in the phase-separated glass is, the higher the strength of the phase-separated glass is. Further, the volume of the silicon-rich lithium phase is 10% to 90% of the total volume of the phase-separated glass, and preferably the volume of the silicon-rich lithium phase is 50% to 90% of the total volume of the phase-separated glass.
In some embodiments, the hardness of the silicon-rich lithium phase is greater than the hardness of the phosphorus-rich phase.
In some embodiments, the silica is present in the phase-separated glass in an amount of 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 80.5% by mass or in a range consisting of any two of these values. A mass percentage of silica lower than 60% will result in poor chemical stability and mechanical properties of the phase-separated glass, and a mass percentage of silica higher than 80.5% will result in an excessively high melting temperature and difficulty in phase separation. Further, the mass percent of the silicon dioxide is 65-75%.
In some embodiments, the mass percent of alumina in the phase separated glass is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or a range consisting of any two of these values. The mass percent of the aluminum oxide is lower than 2 percent, so that the split-phase glass can be quickly devitrified; the mass percentage of the alumina is higher than 20%, which narrows the phase separation area and increases the control difficulty of the phase separation heat treatment. Further, the mass percent of the alumina is 3% -19%. Furthermore, the mass percent of the alumina is 4-18%. Furthermore, the mass percent of the alumina is 5-17%. Furthermore, the mass percent of the alumina is 6-14%. Furthermore, the mass percent of the alumina is 6-12%.
In some embodiments, the mass percent of lithium oxide in the phase-separated glass is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, or a range consisting of any two of these values. The mass percent of the lithium oxide is less than 5 percent, which causes the melting temperature to be increased and the parent glass is not easy to phase separate; a mass percentage of lithium oxide higher than 17% will result in a decrease in chemical stability and a decrease in transmittance due to the difficulty in controlled phase separation of the parent glass. Further, the mass percent of the lithium oxide is 8-14%. Further, the mass percent of the lithium oxide is 9-13%.
In some embodiments, the mass percent of sodium oxide in the phase separated glass is 0, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, or a range consisting of any two of these values. The mass percent of the sodium oxide is more than 0.5 percent, which causes difficult ion exchange and can not effectively improve the mechanical property of the phase separation glass through chemical strengthening. Further, the mass percent of the sodium oxide is 0-0.25%.
In some embodiments, the potassium oxide is present in the phase separated glass in an amount of 0, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5% by mass or in a range consisting of any two of these values. The mass percent of the potassium oxide is more than 0.5 percent, which causes difficult ion exchange and can not effectively improve the mechanical property of the phase-separated glass through chemical strengthening. Further, the mass percent of the potassium oxide is 0-0.25%.
In some embodiments, the boron oxide is present in the phase separated glass in a mass percent of 0, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, or a range consisting of any two of these values. Boron oxide greater than 10% by mass will produce more boron-oxygen tetrahedral units ([ BO)] 4 ) This will suppress the occurrence of phase separation. Further, the mass percent of the boron oxide is 0-7.5%. Further, the mass percent of the boron oxide is 0-5%. Further, the mass percent of the boron oxide is 0-2.5%.
In some embodiments, (Na) 2 O+K 2 O)≤Li 2 And (4) O/10. If Na 2 O+K 2 O>Li 2 O/10, which causes difficulty in ion exchange and failure to passThe mechanical property of the split-phase glass is effectively improved by chemical strengthening. Further, na 2 O+K 2 O is less than or equal to 0.5 percent. For example, na 2 O+K 2 The mass percentage of O is 0, 0.25%, 0.5% and the like.
In some embodiments, the percentage by mass of calcium oxide in the phase-separated glass is 0, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.5%, 5% or a range consisting of any two of these values. The mass percent of the calcium oxide is more than 5 percent, on one hand, the occurrence of phase separation can be inhibited, on the other hand, the ion exchange is difficult, and the mechanical property of the phase separation glass can not be effectively improved through chemical strengthening. Further, the mass percent of the calcium oxide is 0-3%.
In some embodiments, the mass percent of barium oxide in the phase-separated glass is 0, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.5%, 5% or a range consisting of any two of these values. The mass percent of the barium oxide is more than 5 percent, on one hand, the occurrence of phase separation can be inhibited, on the other hand, the ion exchange is difficult, and the mechanical property of the phase separation glass can not be effectively improved through chemical strengthening. Further, the mass percent of the barium oxide is 0-3%.
In some embodiments, the phosphorus pentoxide is present in the phase-separated glass at 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% by mass or in a range consisting of any two of these values. The mass percent of the phosphorus pentoxide is less than 0.5%, and the precursor glass is not easy to phase separate; the mass percent of the phosphorus pentoxide is more than 8 percent, and the transparent phase-separated glass is not easy to obtain because the phase separation rate of the precursor glass is too high. Further, the mass percent of the phosphorus pentoxide is 1-6%. Furthermore, the mass percent of the phosphorus pentoxide is 2-5%. Furthermore, the mass percent of the phosphorus pentoxide is 2-4%.
In some embodiments, the zirconia may be present in the phase separated glass in an amount of 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% by mass or in a range of any two of these values. The mass percentage of the zirconia is more than 10 percent, which can cause the glass melting temperature to be too high on one hand and can inhibit the occurrence of phase separation on the other hand; does not contain zirconia, so that the size of a phase separation region is not easy to control, and the transmittance of the phase separation glass is reduced and the mechanical property is not obviously improved. Further, the mass percent of the zirconia is 2.5% -10%. Furthermore, the mass percent of the zirconia is 4-10%. Furthermore, the mass percent of the zirconia is 4-8%. Furthermore, the mass percent of the zirconia is 4.5% -6.5%.
In some embodiments, the phase separated glass comprises, in mass percent: siO 2 2 65％～75％、Al 2 O 3 6％～12％、Li 2 O 9％～13％、Na 2 O 0～0.25％、K 2 O 0～0.25％、B 2 O 3 0～5％、CaO 0～3％、BaO 0～3％、P 2 O 5 2% -4% and ZrO 2 4.5％～6.5％。
In some embodiments, the phase-separated glass does not contain titanium dioxide and does not contain any oxides that cause coloration of the glass, such as transition metal oxides and rare earth oxides, e.g., iron oxide, cobalt oxide, nickel oxide, manganese oxide, copper oxide, and the like.
In some embodiments, the phase-separated glass also contains a fining agent, and in one specific example, the fining agent is 0 to 1% by mass. For example, the fining agent can be tin oxide, cerium oxide, chlorides, carbonates, nitrates, sulfates, and the like.
In some embodiments, the phase-separated glass further comprises any impurities introduced during the production process, the mass percent of the impurities being less than 0.08%.
In some embodiments, the phase-separated glass is colorless and transparent. Furthermore, for the phase-separated glass with the thickness of 0.7mm, the average transmittance in the spectral range of 360nm to 780nm is more than or equal to 89 percent. Furthermore, for the phase-separated glass with the thickness of 0.7mm, the average transmittance in the spectral range of 360 nm-780 nm is not less than 90%, further, the average transmittance is not less than 91%, and further, the average transmittance is not less than 92%.
In some embodiments, the average transmittance for a 0.7mm thick phase-separated glass is 85% or more over a spectral range from 360nm to 450nm, further 88% or more, and further 91% or more. The average transmittance in the spectral range of 360 nm-450 nm is not less than 85%, and the requirement of a display screen can be met, so that the split-phase glass can be applied to the display field.
In some embodiments, the haze is ≦ 0.4% for phase separated glass having a thickness of 0.7 mm. Further, the haze is less than or equal to 0.3 percent, further, the haze is less than or equal to 0.2 percent, further, the haze is less than or equal to 0.1 percent.
In some embodiments, the fracture toughness of the phase-separated glass is more than or equal to 0.6 MPa.m 1/2 . Further, the fracture toughness is more than or equal to 0.75 MPa.m 1/2 Further, the fracture toughness is not less than 0.9 MPa.m 1/2 Further, the fracture toughness is not less than 1.05 MPa.m 1/2 . Phase-separated glass is easier to grind and polish than microcrystalline glass, and exhibits higher fracture toughness.
In some embodiments, the phase separated glass is capable of 3D hot roll forming. Furthermore, the 3D forming temperature of the split-phase glass is less than or equal to 850 ℃. For example, the 3D forming temperature of the phase-separated glass is 850 ℃, 820 ℃, 800 ℃, 780 ℃, 750 ℃, 720 ℃, 700 ℃, 680 ℃, 650 ℃ or a range consisting of any two of these values. When the phase separation glass is subjected to 3D forming, the relative size of a phase separation area is hardly changed. By 3D shaping, the phase separated glass may be shaped into a three-dimensional shape or may have a three-dimensional shape.
The strength of the glass is increased by the microcrystalline glass which is produced in a large amount in the glass matrix, but the softening point of the microcrystalline glass is greatly increased, so that the microcrystalline glass is not suitable for 3D hot bending. In contrast, the phase-separated glass of the present embodiment generates phase-separated particles of a silicon-rich lithium phase in a glass matrix, and corresponds to another phase-rich phosphorus phase after phase separation, the softening point of the phosphorus-rich phase is low, which means that hard particles are dispersed in a soft matrix, and the softening point of the whole material is much lower than that of microcrystalline glass, so that the phase-separated glass is suitable for 3D hot bending molding.
In some embodiments, the phase separated glass has a liquidus viscosity of greater than or equal to 2 kpoise (kP), further, a liquidus viscosity of greater than or equal to 5 kpoise (kP), and further, a liquidus viscosity of greater than or equal to 10 kpoise (kP).
In some embodiments, the liquidus temperature of the phase-separated glass is 1400 ℃ or less. Further, the liquidus temperature is less than or equal to 1200 ℃, and further, the liquidus temperature is less than or equal to 1100 ℃.
In some embodiments, the split phase glass has a melting temperature of 1620 ℃ or less, further 1600 ℃ or less, further 1580 ℃ or less, further 1550 ℃ or less.
The split-phase glass of the present embodiment may be subjected to chemical strengthening treatment to improve its mechanical properties. In some embodiments, ions in both the silicon-rich lithium phase and the phosphorus-rich phase in the phase-separated glass can be exchanged. Furthermore, after the phase separation glass is chemically strengthened, the ion exchange Depth (DOL) is more than or equal to 100 μm, the central tensile stress (CT) is more than or equal to 80MPa, and the four-point bending strength (4 PB) is more than or equal to 400MPa.
The phase-separated glass at least has the following advantages:
(1) The phase-separated glass is colorless and transparent, has an average transmittance of more than or equal to 89% in a spectral range of 360-780 nm and a haze of less than or equal to 0.4%, and can be used for display panel protective glass.
(2) The phase-splitting glass comprises a silicon-rich lithium phase and a phosphorus-rich phase, the silicon-rich lithium phase is dispersed in a matrix phase formed by the phosphorus-rich phase by independent or a small amount of connected spherical particles, and the fracture toughness of the phase-splitting glass is more than or equal to 0.6 MPa.m 1/2 The strength of the phase-separated glass can be further improved by adjusting the volume ratio and the average particle size of the silicon-rich lithium phase. In addition, the softening point of the phosphorus-rich phase is low, namely hard particles are dispersed in a soft matrix, and the softening point of the whole material is greatly lower than that of the microcrystalline glass, so that the split-phase glass is suitable for 3D hot bending while the mechanical property of the glass is improved.
(3) The phase-separated glass can be subjected to chemical strengthening treatment. After chemical strengthening, the ion exchange Depth (DOL) is more than or equal to 100 mu m, the central tensile stress (CT) is more than or equal to 80MPa, and the four-point bending strength (4 PB) is more than or equal to 400MPa, so that the ion exchange effect is effectively improved on the premise of ensuring a large amount of phase separation.
The invention also provides a preparation method of the phase-separated glass, which comprises the following steps:
step S110: weighing corresponding raw materials according to the mass percent of each oxide, mixing and melting to obtain precursor glass.
Wherein the mass percent of each oxide is as follows: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O5％～17％、Na 2 O 0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -4% and ZrO 2 0.1％～10％，(Na 2 O+K 2 O)≤Li 2 O/10 and no TiO 2 。
In some embodiments, the temperature of the melting is 1500 ℃ to 1600 ℃. For example, the melting temperature is 1500 ℃, 1510 ℃, 1520 ℃, 1530 ℃, 1540 ℃, 1550 ℃, 1560 ℃, 1570 ℃, 1580 ℃, 1590 ℃, 1600 ℃ or a range consisting of any two of these values.
Step S120: and carrying out heat treatment on the precursor glass to obtain the phase-separated glass.
Wherein the heat treatment mode is selected from any one or combination of the following modes:
(1) Preserving the heat of the precursor glass for 1 to 8 hours at the temperature of Tg +30 to Tg +100 ℃;
(2) Reducing the precursor glass from the melting temperature to Tg at a rate of 0.5 ℃/min to 20 ℃/min; and
(3) The precursor glass is raised from Tg +30 ℃ to Tg +100 ℃ at a rate of 0.5 ℃/min to 20 ℃/min.
In some embodiments, in mode (1), the precursor glass is reduced to Tg +30 ℃ to Tg +100 ℃ at a rate of 0.5 ℃/min to 20 ℃/min and held for 1h to 8h. For example, the cooling rate is 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min, 20 ℃/min or a range consisting of any two of these values.
In the mode (1), the precursor glass is kept at a temperature of Tg +30 ℃, tg +40 ℃, tg +50 ℃, tg +60 ℃, tg +70 ℃, tg +80 ℃, tg +90 ℃, tg +100 ℃ or any two of the temperature ranges for 1h, 2h, 3h, 4h, 5h, 6h, 7h and 8h or any two of the temperature ranges. In one specific example, in mode (1), the precursor glass is cooled to Tg +50 ℃ at a rate of 10 ℃/min and held for 4h, or the precursor glass is cooled to Tg +30 ℃ at a rate of 10 ℃/min and held for 8h, or the precursor glass is cooled to Tg +100 ℃ at a rate of 10 ℃/min and held for 1h.
In the mode (3), the precursor glass is firstly reduced to Tg +30 ℃ at a rate of 0.5 ℃/min to 20 ℃/min and then increased to Tg +100 ℃ at a rate of 0.5 ℃/min to 20 ℃/min. For example, in the mode (3), the temperature decrease rate and the temperature increase rate are each independently selected from the range of 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min, 20 ℃/min or any two of these values.
In some embodiments, the step of heat treating the precursor glass is followed by annealing and cooling to room temperature.
In some embodiments, the method for preparing the phase-separated glass further comprises a step of forming, and the forming mode can be formed by a casting method, a floating method, a rolling method, an overflow method, a downward drawing method, a roll-to-roll method and the like. Further, in some embodiments, the shaping process may also include slicing, grinding, polishing, etc. the phase-separated glass or a precursor glass thereof to obtain a thin glass article.
In some embodiments, the method for producing the phase-separated glass further comprises performing 3D hot bending on the phase-separated glass or a precursor glass thereof to make the phase-separated glass have a three-dimensional shape. Furthermore, the temperature of 3D hot bending molding is less than or equal to 850 ℃. For example, the temperature for 3D hot bending is 850 ℃, 820 ℃, 800 ℃, 780 ℃, 750 ℃, 720 ℃, 700 ℃, 680 ℃, 650 ℃ or a range consisting of any two of these values. When the phase separation glass is subjected to 3D forming, the relative size of a phase separation area is hardly changed.
The preparation method of the phase-separated glass at least has the following advantages:
(1) The preparation method of the phase-splitting glass can obtain the phase-splitting glass which is colorless and transparent, has the average transmittance in the spectral range of 360-780 nm of more than or equal to 89% and the haze of less than or equal to 0.4% by adjusting the proportion of the raw materials and performing certain heat treatment on the precursor glass, and can also perform chemical strengthening, wherein after the chemical strengthening, the ion exchange Depth (DOL) is more than or equal to 100 mu m, the central tensile stress (CT) is more than or equal to 100MPa, and the four-point bending strength (4 PB) is more than or equal to 400MPa, so that the ion exchange effect is effectively improved under the condition of ensuring a large amount of phase-splitting precursors.
(2) The preparation method of the phase-splitting glass can adjust the size and the proportion of spherical particles in the phase-splitting glass by adjusting the heat treatment process, thereby improving the strength of the phase-splitting glass.
The invention also provides the tempered glass of the embodiment, which is obtained by chemically strengthening the phase-separated glass of the embodiment.
In some embodiments, the strengthened glass includes a compressive stress layer (CS layer) extending from a surface of the strengthened glass to a depth within the strengthened glass. The CS layer may be formed by an ion exchange process. As used herein, the term "ion-exchanged" is understood to mean that the phase-separated glass disclosed herein is chemically strengthened by an ion-exchange process. Specifically, the phase separated glass is treated with a heated salt bath containing ions having an ionic radius different from the ions present in the surface of the phase separated glass. Ions in the salt bath replace those ions in the phase separated glass. Phase-separated glass subjected to such ion exchange treatment may be referred to herein as "ion-exchanged (IX) phase-separated glass" or "strengthened glass".
In some embodiments, the strengthened glass has an average surface compressive stress of 100MPa or greater. Further, the average surface compressive stress of the tempered glass is not less than 200MPa, further, the average surface compressive stress is not less than 300MPa, further, the average surface compressive stress is not less than 500MPa.
In some embodiments, the ion exchange Depth (DOL) of the strengthened glass is greater than or equal to 100 μm. Further, the ion exchange depth of the strengthened glass is not less than 120 μm, further, the ion exchange depth of the strengthened glass is not less than 140 μm, and further, the ion exchange depth of the strengthened glass is not less than 160 μm.
In some embodiments, the central tensile stress (CT) of the strengthened glass is greater than or equal to 80MPa. Furthermore, the central tensile stress of the tempered glass is more than or equal to 100MPa. Furthermore, the central tensile stress is more than or equal to 120MPa. Furthermore, the central tensile stress is more than or equal to 140MPa. Furthermore, the central tensile stress is more than or equal to 160MPa.
In some embodiments, the four-point bending strength (4 PB) of the strengthened glass is greater than or equal to 400MPa. Further, the four-point bending strength of the tempered glass is not less than 500MPa, further not less than 600MPa, further not less than 700MPa, further not less than 800MPa.
In some embodiments, the phase-separated glass is chemically strengthened using a one-step or two-step process. In one embodiment, the step of chemically strengthening the phase-separated glass comprises: with 50% KNO 3 :50％ NaNO 3 (mass ratio) the mixed molten salt was ion-exchanged at 430 ℃ for 6 h. It is to be understood that the above list only shows one way of chemical strengthening, but is not limited thereto.
The tempered glass has high surface compressive stress, central tensile stress and four-point bending strength, and can be used as protective glass of electronic equipment.
The invention also provides a glass cover plate of an embodiment, which is obtained by processing the phase separation glass or the strengthened glass.
The invention also provides electronic equipment of an embodiment, which comprises the phase separation glass, the tempered glass or the glass cover plate.
In order to make the objects and advantages of the present invention clearer, the following detailed description of the phase-separated glass and the effects thereof is given in conjunction with the following specific examples, it being understood that the specific examples described herein are only for illustrating the present invention and are not to be construed as limiting the present invention. The following examples are not specifically described, and other components except inevitable impurities are not included. The examples, which are not specifically illustrated, employ drugs and equipment, all of which are conventional in the art. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those described in the literature, in books, or as recommended by the manufacturer.
Examples 1 to 32
The compositions of the phase-separated glasses of examples 1 to 32 are specifically shown in tables 1 to 4 below.
The phase-separated glasses of examples 1 to 32 were prepared as follows:
weighing corresponding raw materials according to the mass percent of each oxide, mixing and melting the raw materials at the melting temperature of 1600 ℃ to obtain the precursor glass. And (3) reducing the melt of the precursor glass to the heat treatment temperature at the speed of 10 ℃/min for heat treatment, wherein the specific heat treatment process is shown in tables 1 to 4, so as to obtain the phase-separated glass. In the following tables, the transmittance refers to the average transmittance in the spectral range of 360nm to 780 nm.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
SEM images of the phase-separated glass prepared in example 2 are shown in FIGS. 1 to 3. FIG. 1 is an SEM image of the precursor glass of example 2 after incubation for 8h at Tg +30 deg.C, FIG. 2 is an SEM image of the precursor glass of example 2 after incubation for 4h at Tg +50 deg.C, and FIG. 3 is an SEM image of the precursor glass of example 2 after incubation for 1h at Tg +100 deg.C.
As can be seen in FIGS. 1-3, the phase-separated glass has one separate phase dispersed in the matrix of another separate phase in an independent spheroidal form, wherein one separate phase is Si-Li rich and the other separate phase is P-rich, and the independent spheroidal phase-separated particles have a diameter of about 40nm or less.
The XRD patterns of the precursor glasses of examples 1 to 8 after incubation at Tg +50 ℃ for 4h are shown in FIG. 4. As can be seen, the phase separated glass did not devitrify, i.e., no diffraction peaks were detected by XRD.
A Transmission Electron Micrograph (TEM) of the precursor glass of example 2 after incubation for 4h at Tg +50 ℃ is shown in FIG. 5, and elemental analysis shows that the phosphorus content outside the spherical phase-separated region is higher than that inside the spherical phase-separated region.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (13)
1. The phase separation glass is characterized by comprising a silicon-rich lithium phase and a phosphorus-rich phase, and the phase separation glass comprises the following components in percentage by mass: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O5％～17％、Na 2 O 0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -8% and ZrO 2 0.1% -10% of (Na) in the formula 2 O+K 2 O)≤Li 2 O/10, and the phase-separated glass does not contain TiO 2 。
2. A phase-separated glass according to claim 1, wherein the phase-separated glass satisfies at least one of the following conditions:
(1)SiO 2 the mass percentage of the component (A) is 65-75%;
(2)Na 2 the mass percent of O is 0-0.25%; and
(3)K 2 the mass percent of O is 0-0.25%.
3. The phase-separated glass according to claim 1, wherein the phase-separated glass comprises, in mass percent: siO 2 2 65％～75％、Al 2 O 3 6％～12％、Li 2 O 9％～13％、Na 2 O 0～0.25％、K 2 O 0～0.25％、B 2 O 3 0～5％、CaO 0～3％、BaO 0～3％、P 2 O 5 2 to 4 percent and ZrO 2 4.5％～6.5％。
4. A phase-separated glass according to any of claims 1 to 3, wherein the silicon-rich lithium phase is dispersed in the phosphorus-rich phase in the form of spherical particles having an average particle size of 100nm or less.
5. An isolated phase glass according to any one of claims 1 to 3, wherein the ratio of the volume of the silicon-rich lithium phase to the total volume of the isolated phase glass is not less than 40%.
6. A phase-separated glass according to any one of claims 1 to 3, wherein the average transmittance in a wavelength range of 360nm to 780nm is not less than 89% for the phase-separated glass having a thickness of 0.7 mm.
7. The preparation method of the phase separation glass is characterized by comprising the following steps:
weighing corresponding raw materials according to the mass percent of each oxide, mixing and melting to obtain precursor glass, wherein the precursor glass comprises the following components in percentage by mass: siO 2 2 60％～80.5％、Al 2 O 3 2％～20％、Li 2 O5％～17％、Na 2 O 0～0.5％、K 2 O 0～0.5％、B 2 O 3 0～10％、CaO 0～5％、BaO 0～5％、P 2 O 5 0.5% -8% and ZrO 2 0.1％～10％，(Na 2 O+K 2 O)≤Li 2 O/10, and the precursor glass does not contain TiO 2 (ii) a And
and carrying out heat treatment on the precursor glass to obtain the phase-separated glass, wherein the phase-separated glass comprises a silicon-rich lithium phase and a phosphorus-rich phase.
8. A method for producing an isolated phase glass according to claim 7, wherein the heat treatment is carried out in a manner selected from any one or a combination of the following manners:
(1) Preserving the temperature of the precursor glass at Tg + 30-Tg +100 ℃ for 1-8 h;
(2) Reducing the precursor glass from the melting temperature to the Tg at a rate of 0.5 ℃/min to 20 ℃/min; and
(3) The precursor glass is raised from Tg +30 ℃ to Tg +100 ℃ at a rate of 0.5 ℃/min to 20 ℃/min.
9. The method for producing a phase-separated glass according to claim 7 or 8, further comprising: and 3D hot bending forming is carried out on the split-phase glass or the precursor glass, wherein the temperature of the 3D hot bending forming is less than or equal to 850 ℃.
10. A tempered glass obtained by chemically tempering an phase-separated glass according to any one of claims 1 to 6 or a phase-separated glass produced by the method for producing an phase-separated glass according to any one of claims 7 to 9.
11. The strengthened glass of claim 10, wherein the strengthened glass satisfies at least one of the following conditions:
(1) The average surface compressive stress of the tempered glass is more than or equal to 100MPa;
(2) The ion exchange depth of the strengthened glass is more than or equal to 100 mu m;
(3) The central tensile stress of the tempered glass is more than or equal to 80MPa; and
(4) The four-point bending strength of the tempered glass is more than or equal to 400MPa.
12. A glass cover sheet obtained by processing the phase-separated glass according to any one of claims 1 to 6 or the strengthened glass according to any one of claims 10 to 11.
13. An electronic device comprising the phase-separated glass according to any one of claims 1 to 6, the tempered glass according to any one of claims 10 to 11, or the glass cover plate according to claim 12.
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