CN116282909A - High-alumina silicate glass, and preparation method and application thereof - Google Patents
High-alumina silicate glass, and preparation method and application thereof Download PDFInfo
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- CN116282909A CN116282909A CN202310062423.5A CN202310062423A CN116282909A CN 116282909 A CN116282909 A CN 116282909A CN 202310062423 A CN202310062423 A CN 202310062423A CN 116282909 A CN116282909 A CN 116282909A
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- glass
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- aluminosilicate glass
- alumina silicate
- high aluminosilicate
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000005368 silicate glass Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 239000006059 cover glass Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 74
- 239000005354 aluminosilicate glass Substances 0.000 claims description 53
- 238000005728 strengthening Methods 0.000 claims description 19
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000006058 strengthened glass Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000005341 toughened glass Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000005361 soda-lime glass Substances 0.000 abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 239000011734 sodium Substances 0.000 description 16
- 239000000395 magnesium oxide Substances 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000003426 chemical strengthening reaction Methods 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000000155 melt 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
- 239000006060 molten glass Substances 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
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 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
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133331—Cover glasses
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to high-alumina silicate glass, which comprises the following components in percentage by mass: 58% -63% of SiO 2 16% -20% of Al 2 O 3 12 to 16 percent of Na 2 O, 2-5% K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 3 percent of B 2 O 3 . The high-alumina silicate glass with high mechanical strength, the surface stress of the high-alumina silicate glass is more than or equal to 1000MPa, the stress layer depth of the high-alumina silicate glass is more than or equal to 40 mu m, the ball falling breaking height of the high-alumina silicate glass is more than or equal to 120cm, and the thermal expansion coefficient of the high-alumina silicate glass is (86-92) multiplied by 10 ‑7 ℃ ‑1 Is close to soda-lime glass and can be close toThe soda lime glass is bonded to be used as cover glass.
Description
Technical Field
The application relates to the technical field of glass production and manufacturing, in particular to high-alumina silicate glass and a preparation method and application thereof.
Background
Cover glass for display devices is an easy-to-drop article and needs to have sufficiently high mechanical strength. The soda lime glass has poor mechanical strength, low falling ball crushing height and difficulty in meeting the use requirement. The mechanical strength and ball falling performance of the cover plate glass can be greatly improved by adopting high-alumina silicate glass as the cover plate glass material, and the cost is further reduced by adopting the lime-sodium glass for the part of the cover plate glass which is not subjected to main stress. Traditional high-alumina silicate glass has poor mechanical strength or high thermal expansion coefficient, and is difficult to be adhered with lime-sodium glass.
Therefore, how to obtain a high aluminosilicate glass having both high mechanical strength and low expansion coefficient has been a problem to be solved.
Disclosure of Invention
Based on this, it is necessary to provide a high aluminosilicate glass having both high mechanical strength and low expansion coefficient and a method for producing the same.
In one aspect of the present application, there is provided a high aluminosilicate glass comprising, in mass percent: 58% -63% of SiO 2 16% -20% of Al 2 O 3 12 to 16 percent of Na 2 O, 2-5% K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 3 percent of B 2 O 3 。
In one embodiment, the high aluminosilicate glass comprises the following components in percentage by mass: 58% -60% of SiO 2 18-20% of Al 2 O 3 12 to 15 percent of Na 2 O, 2-3% of K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 2 percent of B 2 O 3 。
In one embodiment, the high aluminosilicate glass comprises the following components in percentage by mass: 58% -59% of SiO 2 18-20% of Al 2 O 3 14 to 15 percent of Na 2 O, 2% -2.5% K 2 O, 3 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 1.5 percent of B 2 O 3 。
In one embodiment, the high aluminosilicate glass has a coefficient of thermal expansion in the range of 50 ℃ to 300 ℃ of (86 to 92). Times.10 -7 ℃ -1 。
In one embodiment, the softening point of the high aluminosilicate glass is 810 ℃ to 825 ℃.
In still another aspect of the present application, there is provided a method for preparing the high aluminosilicate glass, comprising the steps of:
weighing raw materials according to the components, heating and preparing a molten liquid;
and forming and annealing the molten liquid to prepare the high-alumina silicate glass.
In one embodiment, the step of heating includes: heating the raw materials to 1660-1690 ℃, preserving heat for 4-8 hours, cooling to 1620-1650 ℃ and preserving heat for 1-2 hours.
In one embodiment, the annealing conditions include: the annealing temperature is 730-760 ℃ and the annealing time is 2-4 hours.
In yet another aspect of the present application, a strengthened glass is provided, obtained by chemically strengthening the high aluminosilicate glass.
In one embodiment, the step of chemically strengthening treatment comprises: and placing the high-alumina silicate glass into potassium nitrate molten salt, and preserving the heat for 3-6 hours at the temperature of 410-430 ℃.
In one embodiment, the surface compressive stress of the tempered glass is greater than or equal to 1000MPa, and the depth of stress layer is greater than or equal to 40 μm.
In one embodiment, the ball breaking height of the tempered glass is not less than 120cm.
In yet another aspect of the present application, there is provided a cover glass for a display device, comprising the high aluminosilicate glass or the tempered glass.
The high-alumina silicate glass with high mechanical strength, the surface stress of the high-alumina silicate glass is more than or equal to 1000MPa, the stress layer depth of the high-alumina silicate glass is more than or equal to 40 mu m, the ball falling breaking height of the high-alumina silicate glass is more than or equal to 120cm, and the thermal expansion coefficient of the high-alumina silicate glass is (86-92) multiplied by 10 -7 ℃ -1 The glass is close to soda-lime glass and can be bonded with the soda-lime glass to be used as cover glass.
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.
The following provides a high aluminosilicate glass, a preparation method and application thereof.
In one aspect of the present application, there is provided a high aluminosilicate glass comprising, in mass percent: 58% -63% of SiO 2 16% -20% of Al 2 O 3 12 to 16 percent of Na 2 O, 2-5% K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 3 percent of B 2 O 3 。
Silicon dioxide (SiO) 2 ) Is a main component forming a glass skeleton, and can improve the strength of glass, but can increase the viscosity of the glass and reduce the erosion resistance of the glass to etching liquid. When SiO 2 When the content of (2) is less than 58%, the glass forming performance of the glass is poor, and the strength and weather resistance are insufficient; when SiO 2 At a content of more than 63%, the glass melting and refining temperature is high, melting and homogenization are difficult, and crystallization tendency is increased. Among the above-mentioned high aluminosilicate glass components, siO 2 Is 58-63% by mass, specifically SiO 2 Including but not limited to: 58%, 58.6%, 59%, 59.8%, 60%, 60.3%, 61%, 61.6%, 62% or 63%, preferably 58% to 60%, more preferably 58% to 59%.
Alumina (Al) 2 O 3 ) The strength of the glass and the erosion resistance to etching liquid can be improved, and the ion exchange capacity of the glass can be greatly improved, but the viscosity of the glass can be increased, and the clarification difficulty is improved. When Al is 2 O 3 When the mass percentage is less than 16%, the glass is insufficient in etching resistance and ion exchange capacity, and when Al 2 O 3 When the mass percentage is higher than 20%, the viscosity of the glass is too high, clarification is difficult, the melting quality is reduced, and various properties of the glass can be obviously affected. Therefore, among the above-mentioned components of the high aluminosilicate glass, al 2 O 3 Is 16-20% by mass, specifically Al 2 O 3 Including but not limited to: 16%, 16.5%, 17%, 17.4%, 18%, 18.2%, 19%, 19.6% or 20%, preferably 18% to 20%.
Sodium oxide (Na) 2 O) is an essential component for ion exchange of glass, and at the same time, the meltability of glass can be significantly improved. Na (Na) 2 When the O content is less than 12%, the glass has poor meltability and Na 2 When the content of O is more than 16%, the weather resistance of the glass becomes poor. Thus, na is contained in the composition of the high aluminosilicate glass 2 The mass percentage of O is 12-16%, specifically Na 2 The mass percent of O includes, but is not limited to, 12%, 12.6%, 13%, 13.4%, 14%, 14.8%, 15%, 15.2%15.7% or 16%, preferably Na 2 The mass percentage of O is 12-15%. More preferably, na 2 The mass percentage of O is 14-15%.
Potassium oxide (K) 2 O) and Na 2 O is the same as alkali metal oxide and has similar function in the glass structure, and is the essential component for ion exchange of glass. 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, thereby improving the surface compressive stress and the stress layer depth after the glass is strengthened. 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, K is a component of the high aluminosilicate glass 2 O is 2-5% by mass, specifically K 2 The mass percent of O includes, but is not limited to, 2%, 2.2%, 3%, 3.4%, 4%, 4.5% or 5%, preferably K 2 O is 2-3% by mass, more preferably K 2 The mass percentage of O is 2-2.5%. When K is 2 When the mass percentage of O is less than 2%, the glass has poor meltability, and the ideal stress layer depth is difficult to reach after strengthening; when K is 2 When the mass percentage of O is more than 5%, the weather resistance of the glass becomes poor and the thermal expansion coefficient becomes excessively large.
Magnesium oxide (MgO) can reduce the viscosity of glass, promote melting and fining of glass, reduce the coefficient of thermal expansion of glass, and increase the surface compressive stress value of glass after strengthening. If the mass percentage of MgO is less than 2%, the glass becomes poor in meltability and it is difficult to achieve an ideal surface compressive stress value after strengthening; if the mass percentage of MgO is more than 5%, the glass is liable to devitrify, and the glass has too short a batch property to be molded. Thus, the high aluminosilicate glass comprises 2% -5% MgO by mass, specifically, 2%, 2.5%, 3%, 3.2%, 3.4%, 3.7%, 4%, 4.3%, 4.8% or 5% MgO by mass, preferably 3% -5% MgO by mass.
Zirconia (ZrO) 2 ) Can improve glassWeather resistance, as well as a reduction in the coefficient of thermal expansion of the glass, are an essential component of the above-mentioned high aluminosilicate glass. If ZrO 2 If the mass percentage of the glass is less than 0.5%, the weather resistance of the glass is insufficient, and the thermal expansion coefficient is too large; if ZrO 2 If the mass percentage is more than 1.5%, the glass becomes poor in meltability. Thus, zrO among the components of the above-mentioned high aluminosilicate glass 2 Is 0.5 to 1.5 mass percent, specifically, zrO 2 Including but not limited to 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5% by mass.
Boron oxide (B) 2 O 3 ) Can reduce the high-temperature viscosity and the thermal expansion coefficient of the glass, but B 2 O 3 Has a blocking effect on ion exchange. When B is 2 O 3 When the content is less than 1%, the glass has poor meltability and an excessively large thermal expansion coefficient; when B is 2 O 3 When the content is more than 3%, the ion exchange performance of the glass is poor. Thus, of the above-mentioned components of the high aluminosilicate glass, B 2 O 3 Is 1-3% by mass, specifically B 2 O 3 Including but not limited to: 1%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.5%, 2.8% or 3%, preferably 1% to 2%, more preferably 1% to 1.5%.
In one example, the high aluminosilicate glass comprises the following components in mass percent: 58% -60% of SiO 2 18-20% of Al 2 O 3 12 to 15 percent of Na 2 O, 2-3% of K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 2 percent of B 2 O 3 。
In one example, the high aluminosilicate glass comprises the following components in mass percent: 58% -59% of SiO 2 18-20% of Al 2 O 3 14 to 15 percent of Na 2 O, 2% -2.5% K 2 O, 3 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 1.5 percent of B 2 O 3 。
In one example, the high aluminosilicate glass has a coefficient of thermal expansion in the range of 50 ℃ to 300 ℃ of (86 to 92). Times.10 -7 ℃ -1 . The main stream soda lime glass has a coefficient of thermal expansion of about 90 x 10 -7 ℃ -1 The thermal expansion coefficient of the high aluminosilicate glass is controlled within the above range, so that the glass can be better bonded with soda lime glass.
In one example, the softening point of the high aluminosilicate glass is 810 to 825 ℃. The temperature of the softening point is higher than 810 ℃ so that the glass can obtain better stress relaxation resistance, the depth of a stress layer can be increased by prolonging the chemical strengthening time, and meanwhile, the attenuation of the surface compressive stress is smaller; the temperature of softening point is lower than 825 ℃, so that glass can be thermally bent at relatively low temperature, the loss of the die is reduced, and the service life of the die is prolonged.
In one example, the high aluminosilicate glass has a melting temperature of < 1700 ℃.
In still another aspect of the present application, a method for preparing the high aluminosilicate glass described above is provided, including the steps of:
weighing raw materials according to the components, heating and preparing a molten liquid;
and forming and annealing the molten liquid to prepare the high-alumina silicate glass.
In one example, the heating step includes: heating the raw materials to 1660-1690 ℃, preserving heat for 4-8 hours, cooling to 1620-1650 ℃ and preserving heat for 1-2 hours.
In one example, the molding temperature is 500 ℃ to 550 ℃.
In one example, the annealing conditions include: the annealing temperature is 730-760 ℃ and the annealing time is 2-4 hours.
In yet another aspect of the present application, a strengthened glass is provided, obtained by chemically strengthening the high aluminosilicate glass described above.
In one example, the step of chemically strengthening treatment includes: and placing the high-alumina silicate glass into potassium nitrate molten salt, and preserving the heat for 3-6 hours at the temperature of 410-430 ℃.
Further, the temperature and the holding time of the above chemical strengthening were determined according to the following table 1, wherein λ= (0.025 SiO) 2 +0.025Al 2 O 3 )^[0.1Al 2 O 3 +1/(0.36MgO+0.64B 2 O 3 )]+0.2ZrO 2 +0.1K 2 O
Wherein each oxide represents the mass percent thereof.
And selecting corresponding chemical strengthening process parameters according to the value range of lambda.
TABLE 1 chemical strengthening Process parameters
| Lambda range | 6.0 or more | 5.0～6.0 | 5.0 or less |
| Strengthening process | 1# | 2# | 3# |
| Molten salt temperature | 430℃ | 420℃ | 410℃ |
| Strengthening time | 3.5h | 4h | 4.5h |
The strengthening performance of the glass can be greatly improved by selecting a proper strengthening process according to the composition.
In one example, the lambda has a value of 4.4 to 6.2.
In one example, the strengthened glass has a surface stress of 1000MPa or more.
In one example, the strengthened glass has a stress layer depth of greater than or equal to 40 μm.
In one example, the ball drop breaking height of the tempered glass is greater than or equal to 120cm.
Further, the stress relaxation coefficient omega of the reinforced glass is more than 1.35, the stress relaxation coefficient omega= (CS 6 x DOL 6)/(CS 3 x DOL 3), wherein CS3 and DOL3 are respectively the surface compressive stress and the stress layer depth of the reinforced glass obtained after the high-alumina silicate glass is placed in potassium nitrate molten salt and is kept at 420 ℃ for 3 hours, and CS6 and DOL6 are respectively the surface compressive stress and the stress layer depth of the reinforced glass obtained after the high-alumina silicate glass is placed in potassium nitrate molten salt and is kept at 420 ℃ for 6 hours.
In one example, the method for preparing the high aluminosilicate glass and the reinforced glass comprises the following steps:
s110: preparing raw materials: based on 1400g of molten glass, the raw materials are calculated and weighed according to the components, ground and fully stirred and mixed.
S120: melting: and placing the mixed raw materials into a crucible for melting. The crucible may be, without limitation, a platinum crucible. The crucible is placed into a lifting furnace, heated to a melting temperature of 1660-1690 ℃, kept for 4-8 hours, cooled to 1620-1650 ℃ and kept for 1-2 hours to prepare the melt.
S130: and (3) forming: pouring the molten liquid into a mould for molding, and curing the molten liquid. The mold may be, without limitation, a rectangular graphite mold having dimensions of 200mm x 120 mm. The temperature of the die is 500-550 ℃ during pouring.
S140: annealing: and (3) placing the molded sample in an annealing furnace at 730-760 ℃ for annealing, and preserving heat for 2-4 hours to prepare the high-alumina silicate glass.
The high aluminosilicate glass was cut into pieces of 155mm by 80mm by 1.1mm in size, double-sided polished, and CNC-machined.
S150: chemical strengthening: and placing the high-alumina silicate glass into potassium nitrate molten salt, and preserving the heat for 3-6 hours at the temperature of 410-430 ℃.
Performance test:
the surface stress value CS and the stress depth DOL of the reinforced glass are tested by using an FSM-6000LE birefringent stress meter and referring to the standard GB/T18144-2008, the photoelastic coefficient adopted during the test is 27.5 nm/(cm.MPa), and the refractive index is 1.51.
Ball drop crushing height test: the center point of the reinforced glass is hit by adopting a steel ball with the mass of 130g, the height is increased by 5cm each time by taking 30cm as the initial height until the glass is broken, and the height during breaking is recorded. The same batch of 20 glass sheets is repeatedly tested, and the value of the falling ball breaking height B10, namely the probability that the breaking height of the glass under the weber distribution is 90% is higher than the value, is determined by adopting weber distribution fitting.
Testing the high-temperature viscosity of glass by using an Orton RSV-1600 high-temperature viscosimeter to obtain temperature viscosity curve data, fitting the viscosity of the glass at the whole temperature section by using a VFT formula, and determining the melting temperature T of the glass m (viscosity is 10 2.0 dPa.s temperature) and softening point T s (viscosity is 10 7.65 dPa.s temperature);
the high aluminosilicate glass was cut into glass pieces having dimensions of 25mm×7mm×1.1mm, and the thermal expansion coefficient (50 to 300 ℃) of the glass was measured using a relaxation-resistant DIL-402PC horizontal expander, with reference to GB/T16920-2015 standard.
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 still another aspect of the present application, there is provided a cover glass for a display device, comprising the above-described high aluminosilicate glass or tempered glass.
The high-alumina silicate glass with high mechanical strength, the surface stress of the high-alumina silicate glass is more than or equal to 1000MPa, the stress layer depth of the high-alumina silicate glass is more than or equal to 40 mu m, the ball falling breaking height of the high-alumina silicate glass is more than or equal to 120cm, and the thermal expansion coefficient of the high-alumina silicate glass is (86-92) multiplied by 10 -7 ℃ -1 The glass is close to soda-lime glass and can be bonded with the soda-lime glass to be used as cover glass.
The following describes a high aluminosilicate glass and a reinforced glass provided by the invention with reference to specific examples, and a preparation method thereof.
The following are specific examples.
Examples 1 to 9
Examples 1-9 each provide high aluminosilicate glass and strengthened glass. The preparation method comprises the following steps:
1400g of raw materials are calculated and weighed according to the mass percentages of the components in the table 2, and after being ground and uniformly mixed, the raw materials are placed in a platinum crucible, the platinum crucible is placed in a lifting furnace,
calculating and weighing corresponding batch materials based on 1400g of glass liquid, grinding and uniformly mixing, placing the batch materials in a platinum crucible, placing the platinum crucible in a lifting furnace, heating to 1660-1690 ℃ (T1), keeping the temperature for 6 hours, then reducing the temperature to 1620-1650 ℃ (T2), keeping the temperature for 1 hour, pouring the batch materials in a rectangular graphite mold with the size of 200mm multiplied by 120mm and the temperature of 500-550 ℃ (T3), after hardening, transferring the batch materials into an annealing furnace with the temperature of 730-760 ℃ (T4), keeping the temperature for 3 hours, and cooling to room temperature along with the furnace to obtain the high-alumina silicate glass, wherein specific numerical values of the heating temperatures T1, T2, the forming temperature T3 and the annealing temperature T4 are shown in a table 1. In the table:
λ＝(0.025SiO 2 +0.025Al 2 O 3 )^[0.1Al 2 O 3 +1/(0.36MgO+0.64B 2 O 3 )]+0.2ZrO 2 +0.1K 2 o, wherein each oxide represents the mass percent thereof.
TABLE 2 Components and preparation process parameters
And selecting corresponding chemical strengthening process parameters according to the value range of lambda. Specifically, as shown in table 1, when lambda is more than 6.0, adopting a No. 1 strengthening process, placing the high aluminosilicate glass into potassium nitrate molten salt, and preserving heat for 3.5 hours at 430 ℃; when lambda is 5.0-6.0, adopting a No. 2 strengthening process, placing the high-alumina silicate glass into potassium nitrate molten salt, and preserving heat for 4 hours at the temperature of 420 ℃; and when lambda is less than 5.0, adopting a 3# strengthening process, placing the high-alumina silicate glass into potassium nitrate molten salt, and preserving the heat for 4.5 hours at the temperature of 410 ℃.
The high aluminosilicate glasses prepared in examples 1 to 9 were subjected to thermal property test, and the test results are shown in Table 3. Wherein Tm is glass melting temperature in DEG C; ts is the glass softening point temperature in degrees centigrade; CTE is the coefficient of thermal expansion of glass at 50-300 ℃ in x 10 -7 ℃ -1 。
Table 3 high aluminosilicate glass thermal performance test
The strengthening properties of the strengthened glasses prepared in examples 1 to 9 were examined, and the examination results are shown in Table 4. Wherein CS is a surface compressive stress value, and is in MPa; DOL is the maximum stress layer depth in μm; omega is the stress relaxation coefficient; the ball drop height B10 is a value above which the probability of 90% of the broken height of the glass in units of cm is higher in the Weber distribution.
TABLE 4 test of strengthening Properties of strengthened glass
As can be seen from the data in table 4: use of the components in the present applicationThe high aluminosilicate glass has a thermal expansion coefficient of (86-92) x 10 -7 ℃ -1 The glass is close to soda-lime glass and can be attached to the soda-lime glass to be used as cover glass; after chemical strengthening, the surface stress is more than or equal to 1000MPa, the stress layer depth is more than or equal to 40 mu m, the falling ball crushing height is more than or equal to 120cm, the molten salt temperature in the chemical strengthening process is controlled below 430 ℃, the service life of the molten salt is prolonged, the strengthening time is shortened by more than 0.5 hour compared with the traditional process, and the energy conservation and the processing efficiency improvement are facilitated.
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 mass percentages of the components are different. The mass percentages of the respective components of comparative examples 1 to 9 are shown in Table 5 below.
TABLE 5 Components
The high aluminosilicate glasses and the reinforced glasses obtained in comparative examples 1 to 8 were examined, and the examination results are shown in Table 6.
Table 6 glass performance test
As can be seen from the data in table 6: when Al is 2 O 3 MgO or B 2 O 3 When the content of (C) is too high or too low, the CTE of the glasses prepared in comparative examples 3, 4, 6 and 8 is lower than 86X 10 -7 ℃ -1 Cannot be matched with soda lime glass. And comparative examples 1 to 8 were poor in mechanical strength, and the B10 values were all lower than 120cm. This suggests a strong synergy between the components of the present application, which together bring about the technical effects of the present application as a whole.
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 (13)
1. A high aluminosilicate glass, wherein the high aluminosilicate glass comprises the following components in percentage by mass: 58% -63% of SiO 2 16% -20% of Al 2 O 3 12 to 16 percent of Na 2 O, 2-5% K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 3 percent of B 2 O 3 。
2. The high aluminosilicate glass of claim 1, wherein the high aluminosilicate glass comprises, in mass percent: 58% -60% of SiO 2 18-20% of Al 2 O 3 12 to 15 percent of Na 2 O, 2-3% of K 2 O, 2 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 2 percent of B 2 O 3 。
3. The high aluminosilicate glass of claim 1, wherein the high aluminosilicate glass comprises, in mass percent: 58% -59% of SiO 2 18-20% of Al 2 O 3 14 to 15 percent of Na 2 O, 2% -2.5% K 2 O, 3 to 5 percent of MgO and 0.5 to 1.5 percent of ZrO 2 1 to 1.5 percent of B 2 O 3 。
4. The high aluminosilicate glass according to any one of claims 1 to 3, wherein the high aluminosilicate glass has a coefficient of thermal expansion in a range of 50 ℃ to 300 ℃ of (86 to 92) ×10 -7 ℃ -1 。
5. The high aluminosilicate glass according to any one of claims 1 to 3, wherein the softening point of the high aluminosilicate glass is 810 ℃ to 825 ℃.
6. A method for producing the high aluminosilicate glass according to any one of claims 1 to 5, comprising the steps of:
weighing raw materials according to the components, heating and preparing a molten liquid;
and forming and annealing the molten liquid to prepare the high-alumina silicate glass.
7. The method of making a high aluminosilicate glass according to claim 6, wherein the step of heating comprises: heating the raw materials to 1660-1690 ℃, preserving heat for 4-8 hours, cooling to 1620-1650 ℃ and preserving heat for 1-2 hours.
8. The method of making a high aluminosilicate glass according to any one of claims 6 to 7, wherein the annealing conditions comprise: the annealing temperature is 730-760 ℃ and the annealing time is 2-4 hours.
9. A reinforced glass obtained by chemically strengthening the high alumina silicate glass according to any one of claims 1 to 5.
10. The strengthened glass of claim 9, wherein the step of chemically strengthening comprises: and placing the high-alumina silicate glass into potassium nitrate molten salt, and preserving the heat for 3-6 hours at the temperature of 410-430 ℃.
11. The strengthened glass according to any one of claims 9 to 10, wherein the strengthened glass has a surface compressive stress of at least 1000MPa and a stress layer depth of at least 40 μm.
12. The strengthened glass according to any one of claims 9 to 10, wherein the ball drop breakage height of the strengthened glass is greater than or equal to 120cm.
13. A cover glass for a display device, comprising the high aluminosilicate glass according to any one of claims 1 to 5 or the tempered glass according to any one of claims 9 to 12.
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