CN116023025A - Aluminoborosilicate glass for ion exchange, preparation method and application thereof - Google Patents
Aluminoborosilicate glass for ion exchange, preparation method and application thereof Download PDFInfo
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- CN116023025A CN116023025A CN202310060596.3A CN202310060596A CN116023025A CN 116023025 A CN116023025 A CN 116023025A CN 202310060596 A CN202310060596 A CN 202310060596A CN 116023025 A CN116023025 A CN 116023025A
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- 239000005407 aluminoborosilicate glass Substances 0.000 title claims abstract description 73
- 238000005342 ion exchange Methods 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title description 4
- 238000002844 melting Methods 0.000 claims abstract description 40
- 230000008018 melting Effects 0.000 claims abstract description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims description 111
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000005388 borosilicate glass Substances 0.000 claims description 10
- 239000005341 toughened glass Substances 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- 239000006058 strengthened glass Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000006059 cover glass Substances 0.000 claims description 3
- 238000005034 decoration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims 2
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 30
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 22
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 19
- 239000000395 magnesium oxide Substances 0.000 description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 19
- 239000011734 sodium Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 239000000292 calcium oxide Substances 0.000 description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 238000005496 tempering Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000008395 clarifying agent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003251 Na K Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004554 molding of glass Methods 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to an aluminoborosilicate glass for ion exchange, comprising, in mole percent: siO (SiO) 2 48％～70％、Al 2 O 3 5％～16％、B 2 O 3 3.5％～12.5％、Na 2 O 3.5％～14.5％、K 2 0 to 2.5 percent of O, 15.01 to 25 percent of MgO, 0 to 4.5 percent of CaO, 0 to 2.5 percent of SrO and ZrO 2 0% -1.5% and does not comprise ZnO. The aluminoborosilicate glass for ion exchange with the components in mole percentage has higher mechanical strength and cold and hot impact resistance, and the surface stress after one-step chemical strengthening is 400 MPa-900The depth of the stress layer is 15-50 μm under the pressure of MPa, the temperature of the cold and hot impact resistance can reach more than 350 ℃, and the melting temperature is lower.
Description
Technical Field
The application relates to the technical field of glass production and manufacturing, in particular to aluminoborosilicate glass for ion exchange and a preparation method and application thereof.
Background
The aluminoborosilicate glass is an important inorganic material, has good physical and chemical properties, and has simple and easily obtained raw materials, so that the aluminoborosilicate glass has wide commercial application in the aspects of daily chemical industry, electronic display, nuclear waste treatment and the like. Although the traditional aluminoborosilicate glass for ion exchange has higher chemical stability, the mechanical strength and the cold and hot impact resistance are poorer, the melting temperature is higher, a platinum channel is needed to be used for melting, the requirement on a kiln is high, the production difficulty is high by adopting a float process, and the smooth production of the glass is not facilitated.
Therefore, it has been a need to solve the problem of how to obtain an aluminoborosilicate glass for ion exchange having both high mechanical strength and cold and hot impact resistance, and a low melting temperature.
Disclosure of Invention
Based on this, there is a need for an aluminoborosilicate glass for ion exchange having both high mechanical strength and cold and hot impact resistance, and having a low melting temperature, and a method for producing the same.
In one aspect of the present application, there is provided an aluminoborosilicate glass for ion exchange, the composition of the aluminoborosilicate glass for ion exchange comprising, in mole percent: siO (SiO) 2 48％～70％、Al 2 O 3 5％～16％、B 2 O 3 3.5％～12.5％、Na 2 O 3.5％～14.5％、K 2 O 0～2.5％、MgO 15.01％～25％、CaO 0-4.5%, srO 0-2.5% and ZrO 2 0% -1.5% and does not comprise ZnO.
In one embodiment, the composition of the aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 56％～66％、Al 2 O 3 6％～12％、B 2 O 3 5％～10％、Na 2 O 4％～10％、K 2 0 to 1 percent of O, 15.01 to 22 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -1% and does not comprise ZnO.
In one embodiment, the composition of the aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 59％～64％、Al 2 O 3 7％～10％、B 2 O 3 6％～9％、Na 2 O 5％～8％、K 2 0 to 0.5 percent of O, 15.01 to 20 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -0.5% and does not comprise ZnO.
In one embodiment, the composition of the aluminoborosilicate glass for ion exchange further comprises, in mole percent, 0% to 0.5% chloride and 0% to 0.2% CeO 2 。
In one embodiment, the melting temperature of the aluminoborosilicate glass used for ion exchange is 1560 ℃ to 1620 ℃.
In still another aspect of the present application, there is provided a method for preparing the ion-exchanged aluminoborosilicate glass, comprising the steps of:
weighing raw materials according to the components, heating to a melting temperature of 1560-1620 ℃, and preserving heat for 4-8 hours to prepare a melt;
and forming the melt, and annealing at 600-680 ℃ to prepare the aluminum borosilicate glass for ion exchange.
In yet another aspect of the present application, there is provided a tempered glass obtained by chemically tempering the aluminoborosilicate glass for ion exchange, the step of chemically tempering comprising: and placing the aluminoborosilicate glass for ion exchange into potassium nitrate molten salt, and preserving the temperature for 2-8 hours at 390-460 ℃.
In one embodiment, the surface stress of the tempered glass is 400MPa to 900MPa.
In one embodiment, the stress layer depth of the tempered glass is 15 μm to 50 μm.
In yet another aspect of the present application, there is provided the use of said aluminoborosilicate glass for ion exchange or said tempered glass as curtain wall glass, fire protection glass, ovenware glass, home decoration glass, pharmaceutical glass, automotive glass, solar collector glass or cover glass for display devices.
The aluminum borosilicate glass for ion exchange with the components in mole percentage has higher mechanical strength and cold and hot impact resistance, the surface stress is 400-900 MPa after one-step chemical strengthening, the stress layer depth is 15-50 mu m, the cold and hot impact resistance temperature can reach more than 350 ℃, and the melting temperature is lower.
Detailed Description
In order to facilitate an understanding of the invention, the present application will be described more fully below. Preferred embodiments of the present application are given below. This application may, however, be embodied in many different forms and is not limited to the embodiments described 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 application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Al in the composition of conventional high borosilicate glasses 2 O 3 Less than or equal to 3wt% of Na 2 O is less than or equal to 4 weight percent, which is not beneficial to K-Na ions with molten salt in the chemical strengthening processExchanging; in addition, the conventional high borosilicate glass has higher melting temperature, and the glass is 10 percent 2 The temperature corresponding to dPa.S viscosity is above 1700 ℃, the forming temperature is above 1330 ℃, the melting temperature and the forming temperature are high, the production technology difficulty is high, the requirements on a kiln are high, the platinum channel is needed, the glass production difficulty is high by adopting a float process, and the smooth production is not facilitated. Based on this, there is a need for an aluminoborosilicate glass for ion exchange having both high mechanical strength and cold and hot impact resistance, and having a low melting temperature, and a method for producing the same.
An aluminoborosilicate glass for ion exchange, a method for preparing the same, and applications thereof are provided herein.
In one aspect of the present application, there is provided an aluminoborosilicate glass for ion exchange, the composition of the aluminoborosilicate glass for ion exchange comprising, in mole percent: siO (SiO) 2 48％～70％、Al 2 O 3 5％～16％、B 2 O 3 3.5％～12.5％、Na 2 O 3.5％～14.5％、K 2 0 to 2.5 percent of O, 15.01 to 25 percent of MgO, 0 to 4.5 percent of CaO, 0 to 2.5 percent of SrO and ZrO 2 0% -1.5% and does not comprise ZnO.
Silicon dioxide (SiO) 2 ) The glass is a network forming body oxide of glass and is a component necessary for forming a glass network framework, so that the strength and chemical stability of the glass can be improved, the strain point of the glass can be improved, and the thermal expansion coefficient of the glass can be reduced. Of the above components for ion-exchanged aluminoborosilicate glass, siO 2 Is 48 to 70 mole percent, specifically SiO 2 Including but not limited to: 48%, 50%, 53%, 55%, 58%, 59%, 60%, 62%, 64%, 65%, 66%, 67%, 68%, 69% or 70%, preferably 56% to 66%, and more preferably 59% to 64%. When SiO 2 The content of (2) is too low, the thermal expansion coefficient is increased, the molding and chemical stability are poor, and the crystallization tendency is caused; when SiO 2 The content of (2) is too high, the glass melting and clarifying temperature is high, the viscosity of the glass melt is increased, the glass is difficult to homogenize, and the glass is not beneficialAnd (5) manufacturing the glass by a molding process.
Alumina (Al) 2 O 3 ) Can participate in the formation of glass network, reduce the crystallization tendency of glass, improve the chemical stability, thermal stability, mechanical strength and hardness of glass, and is also an essential component for improving the elastic modulus of glass. Al in glass 3+ Tending to form an AlO tetrahedral network 4 ]Specific silicon oxygen tetrahedron [ SiO ] 4 ]The network skeleton has much larger gap and larger gap can be used as a channel for ion diffusion, so that higher Al 2 O 3 The content can promote the migration and displacement rate of alkali metal ions, and is beneficial to ion exchange. Al (Al) 2 O 3 When the content is low, the gaps of the network space become smaller, which is unfavorable for ion migration and seriously affects the efficiency of chemical enhancement. But Al is 2 O 3 Can increase the high-temperature viscosity of the glass, cause the defects of overhigh melting temperature, increased energy consumption, adverse control of bubbles, stones and the like in the production process, and if Al 2 O 3 When the content of (C) is too high, it is difficult to obtain a glass having a long batch property, and the glass is difficult to mold. Thus, of the above components of the aluminoborosilicate glass for ion exchange, al 2 O 3 5-16 mol percent, specifically Al 2 O 3 Including but not limited to: 5%, 10%, 11%, 12%, 13%, 14%, 15% or 16%, preferably 6% to 12%, more preferably 7% to 10%.
Boron oxide (B) 2 O 3 ) Is one of the main components of borosilicate glass, and is a forming body oxide of a glass structure. B (B) 2 O 3 Can reduce the thermal expansion coefficient of the glass and improve the thermal stability and chemical stability of the aluminosilicate glass. But when B 2 O 3 When the content is too high, the viscosity of the melt is reduced at high temperature, the volatilization of boron is serious, and B 2 O 3 Too high content can also narrow the forming temperature of the glass, which brings difficulty to the precision control of the wall thickness and the pipe diameter in the process of forming the aluminum borosilicate glass drawing pipe, in addition, B 2 O 3 When the content is too high, the boron-oxygen triangle body [ BO 3 ]The expansion coefficient of the aluminoborosilicate glass increases abnormally，B 2 O 3 Too high a content can also result in a significant decrease in the ion exchange capacity of the glass; b (B) 2 O 3 Too low a content does not significantly lower the melting temperature and thermal expansion coefficient of the glass, and therefore, B is contained in the above-mentioned components for ion-exchanged aluminoborosilicate glass 2 O 3 Is 3.5 to 12.5 mole percent, specifically B 2 O 3 Including but not limited to: 5%, 7%, 8%, 9%, 10%, 11%, 12% or 12.5%, preferably 5% to 10%, more preferably 6% to 9%.
Sodium oxide (Na) 2 O) is an exo-oxide of the aluminoborosilicate glass network, and can provide free oxygen to break Si-O bonds, thereby reducing the viscosity and melting temperature of the aluminoborosilicate glass. Na (Na) 2 When the O content is too high, the thermal expansion coefficient of the glass increases, the chemical stability decreases, and Na 2 The increased volatilization of O can lead to non-uniform components of the aluminoborosilicate glass; na (Na) 2 The content of O is too low, which is not beneficial to melting and molding of glass and chemical exchange of Na ions and K ions, so that the formation of a compressive stress layer on the surface of the glass is affected, and the purpose of enhancing the mechanical strength of the glass cannot be achieved. Thus, na in the composition of the aluminoborosilicate glass for ion exchange 2 The mole percentage of O is 3.5-14.5%, specifically Na 2 The mole percent of O includes, but is not limited to, 4%, 6%, 7%, 8%, 9%, 11%, 12%, 13%, 14% or 14.5%, preferably Na 2 The mol percentage of O is 4-10%. More preferably, na 2 The mol percentage of O is 5-8%.
Potassium oxide (K) 2 O) and Na 2 O is an alkali oxide and has a similar effect in the glass structure. Will K 2 O and Na 2 O is compounded, can exert the effect of mixed alkali, improves the glass performance, can be used for improving the melting property of glass, and improves the ion exchange rate in chemical strengthening so as to obtain the required surface compressive stress and stress layer depth. But K is 2 If the O content is too high, the weather resistance is lowered, and the ion exchange performance of the glass is lowered. Thus, the aluminoborosilicate glass for ion exchangeAmong the components, K 2 O is 0-2.5 mol percent, specifically K 2 The mole percent of O includes, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 1%, 1.5%, 2% or 2.5%, preferably K 2 O is 0 to 1 mol%, more preferably K 2 The mole percentage of O is 0-0.5%.
Magnesium oxide (MgO) is a network external oxide of glass, can reduce the melting point of the glass, can reduce the viscosity of the glass at high temperature, promotes the melting and clarification of the glass, improves the uniformity and enhances the hydrolysis resistance. MgO can also enable the glass to be at a temperature, enhance the durability of the glass, prevent the glass from crystallizing, inhibit the movement of alkali metal ions in the glass, and improve the elastic modulus of the glass at the same time, thereby improving the cold and hot impact resistance of the glass. MgO can enhance the stability of the glass network space at low temperature, can reduce the thermal expansion coefficient of the glass to a certain extent, but has an effect of blocking ion exchange. Thus, in the composition of the aluminoborosilicate glass for ion exchange, the mole percentage of MgO is 15.01% -25%, specifically, the mole percentage of MgO includes, but is not limited to, 16%, 17%, 18%, 19%, 20%, 22% or 25%, preferably, the mole percentage of MgO is 15.01-22%, more preferably, the mole percentage of MgO is 15.01-20%.
Calcium oxide (CaO) can make silicon oxygen tetrahedron [ SiO ] 4 ]The network structure is loosened and broken, so that the melting property of the glass at high temperature is improved, and the glass is not easy to devitrify; however, too high a CaO content affects the weather resistance of the aluminosilicate glass and seriously hinders the progress of ion exchange. Thus, in the composition of the aluminoborosilicate glass for ion exchange, the mole percentage of CaO is 0% to 4.5%, specifically, the mole percentage of CaO includes, but is not limited to, 1%, 2%, 3%, 4% or 4.5%, preferably, the mole percentage of CaO is 0 to 2%.
Strontium oxide (SrO) and CaO are similar, can reduce the high-temperature viscosity of the glass, and is beneficial to glass melting. However, since the ion radius is large and the exchange process of Li-Na-K ions is not hindered in the glass structure, a small amount of SrO can be used instead of part of MgO. In the composition for ion-exchanged aluminoborosilicate glass, the mole percentage of SrO is 0% to 2.5%, specifically, the mole percentage of SrO includes, but is not limited to, 0.2%, 0.5%, 1%, 1.5%, 2% or 2.5%, preferably, the mole percentage of SrO is 0 to 1%.
Zirconia (ZrO) 2 ) In silicate glass essentially in the form of cubes [ ZrO 8 ]The coordination form exists, the ion radius is larger, the ion belongs to a network exosome in the glass structure, the solubility of the ion in the glass is smaller, the thermal expansion coefficient of the glass can be reduced, the acid-base resistance and the refractive index of the glass can be improved, but the excess ZrO 2 The viscosity of the glass is significantly increased, so that the addition amount thereof is not more than 3%. Of the components of the aluminoborosilicate glass for ion exchange, zrO 2 0 to 1.5 mole percent, in particular ZrO 2 Including but not limited to 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 1.0%, 1.2% or 1.5%, preferably ZrO 2 Is 0 to 1% by mole, more preferably ZrO 2 The mole percentage of (2) is 0-0.5%.
Further, the components of the aluminoborosilicate glass used for ion exchange do not comprise zinc oxide (ZnO), so that the crystallization tendency of the glass can be avoided, and the devitrification and whitening of the glass can be avoided.
In one example, the composition of the aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 56％～66％、Al 2 O 3 6％～12％、B 2 O 3 5％～10％、Na 2 O 4％～10％、K 2 0 to 1 percent of O, 15.01 to 22 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -1% and does not comprise ZnO.
In one example, the composition of the aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 59％～64％、Al 2 O 3 7％～10％、B 2 O 3 6％～9％、Na 2 O 5％～8％、K 2 0 to 0.5 percent of O, 15.01 to 20 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -0.5% and does not comprise ZnO.
In one example, the composition of the aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 60％～64％、Al 2 O 3 7％～10％、B 2 O 3 6％～8％、Na 2 O 5％～8％、K 2 0 to 0.5 percent of O, 15.01 to 20 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -0.5% and does not comprise ZnO.
In one example, the composition of the aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 62％～63％、Al 2 O 3 8％～9％、B 2 O 3 7％～9％、Na 2 O 6％～7％、K 2 0.1 to 0.2 percent of O, 15.01 to 16 percent of MgO, 0 to 0.2 percent of CaO, 0 to 0.1 percent of SrO and ZrO 2 0% -0.25% and does not include ZnO. Further, the components of the aluminoborosilicate glass for ion exchange further comprise chloride and CeO 2 As a clarifying agent. When glass is melted, the clarifying agent is added and is not influenced by melting or forming atmosphere, the content of the clarifying agent is controlled within a certain range, and the service life of the kiln is not influenced. The content of chloride is 0% -0.5% by mole, including but not limited to 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, ceO 2 The content of (2) is 0% to 0.2%, including but not limited to 0.1% or 0.2%.
In one example, the chloride is selected from NaCl, naClO 3 NaClO 4 One or more of the following.
In one example, the melting temperature of the aluminoborosilicate glass for ion exchange is 1560 ℃ to 1620 ℃.
In one example, the aluminoborosilicate glass for ion exchange has a coefficient of thermal expansion in the range of 50 ℃ to 300 ℃ of (50 to 90) ×10 -7 ℃ -1 。
In still another aspect of the present application, there is provided a method for preparing the above aluminoborosilicate glass for ion exchange, comprising the steps of:
weighing raw materials according to the components, heating to a melting temperature of 1560-1620 ℃, and preserving heat for 4-8 hours to prepare a melt;
and forming the melt, and annealing at 600-680 ℃ to prepare the aluminum borosilicate glass for ion exchange.
In one example, the method for preparing the ion-exchanged aluminoborosilicate glass comprises the following steps:
s110: preparing raw materials: weighing the raw materials according to the components, and fully stirring and mixing. The raw materials can be oxide, carbonate and the like, and the total mass is more than 500g.
S120: melting: and placing the mixed raw materials into a crucible for melting. The crucible may be, without limitation, a platinum crucible having a volume greater than 400 mL. The crucible is put into a silicon-molybdenum furnace, heated to the melting temperature of 1560-1620 ℃, kept for 4-8 hours and homogenized to prepare the melt.
S130: and (3) forming: and casting the molten liquid into a mould for casting and molding.
S140: annealing: and (3) placing the molded sample into an annealing furnace for annealing at 600-680 ℃ to prepare the aluminoborosilicate glass for ion exchange.
Performance test: the aluminoborosilicate glass for ion exchange was cut into glass sheets having dimensions of 25mm×7mm×0.7mm, and the thermal expansion curve of the glass was measured at a temperature rise rate of 5 ℃/min using a Germany-resistant NETZSCH-DIL 402PC thermal expansion meter with reference to GB/T16920-2015, to obtain a coefficient of thermal expansion CTE (50-300 ℃) of the glass.
In still another aspect of the present application, there is provided a tempered glass obtained by chemically tempering the aluminoborosilicate glass for ion exchange described above, the step of chemically tempering comprising: and (3) placing the annealed sample into potassium nitrate molten salt, and preserving the heat for 2-8 hours at the temperature of 390-460 ℃.
In one example, the surface stress of the tempered glass is 400MPa to 900MPa.
In one example, the strengthened glass has a stress layer depth of 15 μm to 50 μm.
The surface stress value CS and the stress layer depth Dol of the tempered glass were measured using an FSM-6000LE birefringent stress meter, with reference to standard GB/T18144-2008.
Cold and hot impact resistance test: cutting the reinforced glass into glass sheets with the thickness of 50mm multiplied by 6mm by using an STX-1203 wire cutting machine of Shenyang crystal, placing the glass sheets in ovens with different temperatures, preserving the heat for more than 4 hours, taking out the glass sheets, immediately immersing the glass sheets in an ice-water mixture with the temperature of 0 ℃ vertically, and observing whether the glass is good or not after 5 minutes.
It can be understood that the above test method and test equipment are common methods for evaluating glass related properties in the industry, but are only means for characterizing or evaluating the technical scheme and effect of the present invention, and other test methods and test equipment can be used without affecting the final result.
In yet another aspect of the present application, there is provided the use of the above aluminoborosilicate glass for ion exchange as curtain wall glass, fire-resistant glass, ovenware glass, home decoration glass, pharmaceutical glass, automotive glass, solar collector glass or cover glass for display devices.
The aluminum borosilicate glass for ion exchange with the components in mole percentage has the advantages of low thermal expansion coefficient, high softening point, high mechanical property, 400-900 MPa of surface stress after one-step chemical strengthening, 15-50 mu m of stress layer depth and high cold and hot impact resistance.
The present invention provides an aluminoborosilicate glass for ion exchange and a method for preparing the same, which are described in detail below with reference to specific examples.
The following are specific examples.
Examples 1 to 24
Examples 1-24 all provide aluminoborosilicate glasses for ion exchange. According to the mole percentages of the components in the table 1, the raw materials corresponding to the components are calculated and weighed, fully stirred and mixed, then the raw materials are put into a platinum crucible, the platinum crucible is put into a silicon-molybdenum furnace, the temperature is raised to the melting temperature Tm, and the melting and clarification are carried out for 6 hours, and the raw materials are homogenized and cast into a mould for casting molding, and the molded glass is put into an annealing furnace and annealed at 640 ℃ to obtain the aluminoborosilicate glass for ion exchange.
TABLE 1 Components
The aluminoborosilicate glasses for ion exchange prepared in examples 1 to 24 were examined, and the examination results are shown in Table 2. Wherein Tm is glass melting temperature in DEG C; CTE is the coefficient of thermal expansion of glass at 50-300 ℃ in x 10 -7 ℃ -1 。
The aluminoborosilicate glass for ion exchange was subjected to pure KNO at 420 DEG C 3 And (3) carrying out chemical strengthening on the molten liquid for 5 hours to obtain the strengthened glass. The performance of the tempered glass was examined, and the results are shown in Table 2. Wherein CS is a surface compressive stress value, and is in MPa; dol is the maximum stress layer depth in μm; the cold and hot impact resistant temperature is the highest temperature difference which can be born by the glass under the cold and hot impact, and the unit is the temperature.
TABLE 2 aluminoborosilicate glass Performance test for ion exchange
As can be seen from the data in table 2: the melting temperature Tm of the aluminoborosilicate glasses for ion exchange of examples 1 to 24, which are prepared by the composition ratio of the present application, is 1560 to 1620 ℃, the glass is easier to produce, and the glass has a melting temperature of (54 to 86) x 10 at 50 to 300 DEG C -7 ℃ -1 Is a thermal expansion coefficient of (c). The aluminoborosilicate glasses for ion exchange of examples 1 to 26 were subjected to pure KNO at 420 DEG C 3 After tempering in the molten liquid for 5 hours, the obtained strengthened glass has surface compressive stress CS of more than 500MPa, the composite compressive stress generated by ion exchange is reduced to a stress depth Dol of more than 15 mu m of 0MPa (instrument detection limit), the cold and hot impact resistant temperature is higher than 250 ℃, and the samples are not broken.
Comparative examples 1 to 9
The specific preparation methods of the glasses provided in comparative examples 1 to 9 are the same as in example 1, except that: the molar percentages of the components are different. The mole percentages of the components of comparative examples 1 to 9 are shown in Table 3 below.
TABLE 3 Components
The aluminoborosilicate glasses obtained in comparative examples 1 to 9 were examined, and the examination results are shown in Table 4. Wherein Tm is the melting temperature in DEG C; CTE is the coefficient of thermal expansion of glass at 50-300 ℃ in x 10 -7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the CS is the surface compressive stress value, in MPa; dol is the maximum stress layer depth in μm; the cold and hot impact resistant temperature is the highest temperature difference which can be born by the cold and hot impact of the glassBit c.
Table 4 glass performance test
As can be seen from the data in table 4: in comparative examples 1 and 2, siO 2 、Al 2 O 3 The content is too low or too high, so that solid infusions can appear during melting, glass state is not formed, glass is opacified, the transmittance is extremely low, and the melting temperature of the glass is too high, so that the industrial production is not facilitated; the comparative example 3 has non-zero ZnO high field intensity ions, which can greatly influence the chemical tempering performance, and the CS of the obtained glass is 402MPa only and dol is 13.2 mu m only; na of comparative example 4 2 Too low an O content also affects ion exchange performance, na 2 The O content was too low and the ion exchange performance was poor, and the CS of the resulting glass was only 302MPa, the dol was only 10.5. Mu.m, and the MgO was too high and B in comparative example 5 2 O 3 Too low, more [ BO ] is generated 3 ]The glass phase separation is caused, solid unmelted matters such as silicon-rich, magnesium-rich and the like appear on the upper surface layer, and the melting temperature of the glass is too high; comparative example 6 belongs to a high borosilicate glass system, the chemical tempering effect of the system is extremely poor, the test value is lower than the lower limit of the detection limit, CS and Dol cannot be tested, and the melting temperature of the glass is too high; na of comparative example 7 2 The O content is too high, so that the thermal expansion coefficient of the glass is too high, and the cold and hot impact resistance is poor; the MgO content of the glasses of comparative examples 8 and 9 was too high or too low, resulting in the occurrence of solid insolubles in the melting of the glass, failure to form a glassy state and opacification of the glass.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. An aluminoborosilicate glass for ion exchange, comprising, in mole percent: siO (SiO) 2 48％～70％、Al 2 O 3 5％～16％、B 2 O 3 3.5％～12.5％、Na 2 O 3.5％～14.5％、K 2 0 to 2.5 percent of O, 15.01 to 25 percent of MgO, 0 to 4.5 percent of CaO, 0 to 2.5 percent of SrO and ZrO 2 0% -1.5% and does not comprise ZnO.
2. The aluminoborosilicate glass for ion exchange of claim 1, wherein said aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 56％～66％、Al 2 O 3 6％～12％、B 2 O 3 5％～10％、Na 2 O 4％～10％、K 2 0 to 1 percent of O, 15.01 to 22 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -1% and does not comprise ZnO.
3. The aluminoborosilicate glass for ion exchange of claim 1, wherein said aluminoborosilicate glass for ion exchange comprises, in mole percent: siO (SiO) 2 59％～64％、Al 2 O 3 7％～10％、B 2 O 3 6％～9％、Na 2 O 5％～8％、K 2 0 to 0.5 percent of O, 15.01 to 20 percent of MgO, 0 to 2 percent of CaO, 0 to 1 percent of SrO and ZrO 2 0% -0.5% and does not comprise ZnO.
4. An aluminoborosilicate glass as claimed in any of claims 1 to 3, which is characterized byCharacterized in that the components of the aluminoborosilicate glass used for ion exchange also comprise 0 to 0.5 percent of chloride and 0 to 0.2 percent of CeO in mole percent 2 。
5. The aluminoborosilicate glass for ion exchange according to any of claims 1 to 3, wherein said aluminoborosilicate glass for ion exchange has a melting temperature of 1560 ℃ to 1620 ℃.
6. A method for producing an aluminoborosilicate glass for ion exchange according to any one of claims 1 to 5, comprising the steps of:
weighing raw materials according to the components, heating to a melting temperature of 1560-1620 ℃, and preserving heat for 4-8 hours to prepare a melt;
and forming the melt, and annealing at 600-680 ℃ to prepare the aluminum borosilicate glass for ion exchange.
7. A strengthened glass obtained by chemically strengthening the aluminoborosilicate glass for ion exchange according to any one of claims 1 to 5, said step of chemically strengthening comprising: and placing the aluminoborosilicate glass for ion exchange into potassium nitrate molten salt, and preserving the temperature for 2-8 hours at 390-460 ℃.
8. The strengthened glass of claim 7, wherein the strengthened glass has a surface stress of 400MPa to 900MPa.
9. The strengthened glass according to any one of claims 7 to 8, wherein the strengthened glass has a stress layer depth of from 15 μιη to 50 μιη.
10. Use of the aluminoborosilicate glass for ion exchange according to any one of claims 1 to 5 or the tempered glass according to any one of claims 7 to 9 as curtain wall glass, fire protection glass, ovenware glass, home decoration glass, pharmaceutical glass, automotive glass, solar collector glass or cover glass for display devices.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910079A (en) * | 2007-11-29 | 2010-12-08 | 康宁股份有限公司 | Glass with improved toughness and scrath resistance |
| CN102730970A (en) * | 2012-06-27 | 2012-10-17 | 华南理工大学 | Red silicate glass and preparation method thereof |
| CN104246883A (en) * | 2012-03-29 | 2014-12-24 | Hoya株式会社 | Glass for magnetic recording medium substrate, and glass substrate for magnetic recording medium and use thereof |
| CN104507885A (en) * | 2012-07-25 | 2015-04-08 | 旭硝子株式会社 | White glass |
| CN107250072A (en) * | 2015-02-24 | 2017-10-13 | 旭硝子株式会社 | The manufacture method of glass and chemically reinforced glass and chemically reinforced glass |
| CN108473369A (en) * | 2016-01-21 | 2018-08-31 | Ａｇｃ株式会社 | The manufacturing method of chemically reinforced glass and chemically reinforced glass |
| CN108473370A (en) * | 2016-01-21 | 2018-08-31 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN109715573A (en) * | 2016-09-21 | 2019-05-03 | Ａｇｃ株式会社 | Chemical strengthening glass and chemically reinforced glass |
| CN110028240A (en) * | 2019-04-16 | 2019-07-19 | 醴陵旗滨电子玻璃有限公司 | A kind of alumina silicate glass and preparation method thereof |
| CN110546115A (en) * | 2017-04-28 | 2019-12-06 | Ａｇｃ株式会社 | Chemically strengthened glass and glass for chemical strengthening |
| CN110770188A (en) * | 2017-07-24 | 2020-02-07 | 日本电气硝子株式会社 | Chemically strengthened glass and method for producing chemically strengthened glass |
| CN110831907A (en) * | 2017-07-04 | 2020-02-21 | Ａｇｃ株式会社 | Glass ball |
-
2023
- 2023-01-19 CN CN202310060596.3A patent/CN116023025A/en active Pending
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910079A (en) * | 2007-11-29 | 2010-12-08 | 康宁股份有限公司 | Glass with improved toughness and scrath resistance |
| CN105776849A (en) * | 2007-11-29 | 2016-07-20 | 康宁股份有限公司 | Glasses Having Improved Toughness And Scratch Resistance |
| CN104246883A (en) * | 2012-03-29 | 2014-12-24 | Hoya株式会社 | Glass for magnetic recording medium substrate, and glass substrate for magnetic recording medium and use thereof |
| CN102730970A (en) * | 2012-06-27 | 2012-10-17 | 华南理工大学 | Red silicate glass and preparation method thereof |
| CN104507885A (en) * | 2012-07-25 | 2015-04-08 | 旭硝子株式会社 | White glass |
| CN107250072A (en) * | 2015-02-24 | 2017-10-13 | 旭硝子株式会社 | The manufacture method of glass and chemically reinforced glass and chemically reinforced glass |
| CN109455926A (en) * | 2016-01-21 | 2019-03-12 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN110255892A (en) * | 2016-01-21 | 2019-09-20 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN109133670A (en) * | 2016-01-21 | 2019-01-04 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN109320098A (en) * | 2016-01-21 | 2019-02-12 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN108473369A (en) * | 2016-01-21 | 2018-08-31 | Ａｇｃ株式会社 | The manufacturing method of chemically reinforced glass and chemically reinforced glass |
| CN115572077A (en) * | 2016-01-21 | 2023-01-06 | Ａｇｃ株式会社 | Chemically strengthened glass and glass for chemical strengthening |
| CN115572076A (en) * | 2016-01-21 | 2023-01-06 | Ａｇｃ株式会社 | Chemically strengthened glass and glass for chemical strengthening |
| CN108473370A (en) * | 2016-01-21 | 2018-08-31 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN110330228A (en) * | 2016-01-21 | 2019-10-15 | Ａｇｃ株式会社 | Chemically reinforced glass and chemical strengthening glass |
| CN109715573A (en) * | 2016-09-21 | 2019-05-03 | Ａｇｃ株式会社 | Chemical strengthening glass and chemically reinforced glass |
| CN110546115A (en) * | 2017-04-28 | 2019-12-06 | Ａｇｃ株式会社 | Chemically strengthened glass and glass for chemical strengthening |
| CN110831907A (en) * | 2017-07-04 | 2020-02-21 | Ａｇｃ株式会社 | Glass ball |
| CN110770188A (en) * | 2017-07-24 | 2020-02-07 | 日本电气硝子株式会社 | Chemically strengthened glass and method for producing chemically strengthened glass |
| CN110028240A (en) * | 2019-04-16 | 2019-07-19 | 醴陵旗滨电子玻璃有限公司 | A kind of alumina silicate glass and preparation method thereof |
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