CN111732336A - Composition for glass, aluminosilicate glass, and preparation method and application thereof - Google Patents
Composition for glass, aluminosilicate glass, and preparation method and application thereof Download PDFInfo
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- CN111732336A CN111732336A CN201910975266.0A CN201910975266A CN111732336A CN 111732336 A CN111732336 A CN 111732336A CN 201910975266 A CN201910975266 A CN 201910975266A CN 111732336 A CN111732336 A CN 111732336A
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- 239000011521 glass Substances 0.000 title claims abstract description 181
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 60
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Chemical group O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 238000003754 machining Methods 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 238000005452 bending Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000005347 annealed glass Substances 0.000 abstract description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000007496 glass forming Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 description 1
- 229910000023 beryllium carbonate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the field of glass manufacturing, and discloses a composition for glass, aluminosilicate glass, and a preparation method and application thereof. The composition for glass contains SiO 58-64 wt% calculated by oxide based on the total weight of the composition for glass218-23 wt% of Al2O30-1.6 wt% of B2O30.001 to 0.3 wt% of ZrO20.0005 to 1.8 wt% of a metal oxide M and 12 to 24 wt% of a metal oxide N; the metal oxide M is selected from BeO and Sc2O3And Y2O3The metal oxide N is selected from one or more of MgO, CaO and SrO. The aluminosilicate glass provided by the invention controls the glass material property and the forming stability in a narrow limited range, is beneficial to controlling the large-scale and light-weight production of glass plates, is beneficial to controlling the bending degree of the annealed glass, and ensures the high yield of the glass.
Description
Technical Field
The invention relates to the field of glass manufacturing, and particularly relates to a composition for glass, aluminosilicate glass, and a preparation method and application thereof.
Background
In the development process of the display industry, Low Temperature Polysilicon (LTPS) technology enables display products to have the characteristics of higher resolution, faster response speed, lighter and thinner appearance, larger display area, and the like.
In the manufacturing process of the display panel, the substrate glass is more prone to deformation and warpage due to heat treatment, and thus the product is poor, and therefore the substrate glass is required to have the characteristics of high temperature resistance, low heat shrinkage and stable high-temperature process. In order to achieve the above purpose, the existing substrate glass mostly adopts high-alumina low-borosilicate glass which is substantially alkali-free, the high-alumina low-borosilicate glass has low thermal shrinkage and glass strain point, but the melting and forming difficulty of the high-alumina low-borosilicate glass is high, especially the glass thinning forming is realized by adjusting the glass frit property through composition, and the bending degree after the glass thinning is difficult to control.
Disclosure of Invention
The invention aims to solve the problems that the existing aluminosilicate glass is difficult to melt and form, difficult to form large plates, easy to bend in the production process and the like, and provides a composition for glass, aluminosilicate glass and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a composition for glass containing 58 to 64 wt% of SiO, calculated as an oxide, based on the total weight of the composition for glass218-23 wt% of Al2O30-1.6 wt% of B2O30.001 to 0.3 wt% of ZrO20.0005 to 1.8 wt% of a metal oxide M and 12 to 24 wt% of a metal oxide N; the metal oxide M is selected from BeO and Sc2O3And Y2O3The metal oxide N is selected from one or more of MgO, CaO and SrO.
Preferably, the composition for glass contains 59 to 62 wt% of SiO in terms of oxide based on the total weight of the composition for glass218-21 wt% of Al2O30.001-1.5 wt% of B2O30.001 to 0.2 wt% of ZrO20.1 to 1.5 wt% of metal oxide M and 16 to 19 wt% of metal oxide N.
Preferably, the total iron content of the glass composition is 100-330ppm based on the total weight of the glass composition.
Preferably, of the total iron, Fe3+The iron content is 80 wt% or less.
Preferably, the content of the alkali metal oxide in the composition for glass is 350ppm or less in terms of oxide based on the total weight of the composition for glass.
Preferably, the SO in the composition for glass is based on the total weight of the composition for glass3The content of (B) is 350ppm or less.
Preferably, the halogen content of the composition for glass is 0.004-0.5 wt% calculated by elementary halogen based on the total weight of the composition for glass.
Preferably, the halogen is F and/or Cl.
Preferably, the metal oxide M contains 0 to 100 wt% BeO based on the total weight of the metal oxide M.
Preferably, the metal oxide M contains 0 to 100 wt.% Sc, based on the total weight of the metal oxide M2O3。
Preferably, the metal oxide M contains 0 to 100 wt% of Y based on the total weight of the metal oxide M2O3。
Preferably, the metal oxide N contains SrO in an amount of 33 to 48 wt% based on the total weight of the metal oxide N.
Preferably, the mass ratio of MgO to CaO is between 0.8 and 2.
In a second aspect, the present invention provides a method of making an aluminosilicate glass, the method comprising: the composition for glass of the present invention is subjected to melting treatment, molding treatment, annealing treatment and machining treatment in this order.
In a third aspect, the present invention provides an aluminosilicate glass prepared by the above method.
Preferably, the aluminosilicate glass has a viscosity of 1013The annealing point temperature corresponding to the poise time is 770-820 ℃.
Preferably, the aluminosilicate glass has a melting temperature T corresponding to a viscosity of 200 poise200＜1710℃。
Preferably, the aluminosilicate glass has a density < 2.65g/cm3。
Preferably, the aluminosilicate glass has a coefficient of thermal expansion of (33-41) × 10 in the range of 50-350 ℃-7/℃。
Preferably, the aluminosilicate glass has a viscosity of 10000 poise and a corresponding forming temperature T1wHas a viscosity of 4 × 10 with the aluminosilicate glass7Poise time corresponding to forming temperature T4kwDifference value T of1w-T4kw295 ℃ and 365 ℃.
Preferably, when the thickness of the aluminosilicate glass is 0.5mm, the bending degree is less than or equal to 0.15 percent.
Preferably, the aluminosilicate glass has a thermal conductivity > 1.2W/(mk).
Preferably, the Young's modulus of the aluminosilicate glass is more than or equal to 78 GPa.
Preferably, the aluminosilicate glass has a light transmission > 70% at a wavelength of 308 nm.
In a fourth aspect, the invention provides the use of the composition for glass or aluminosilicate glass of the invention in the preparation of a flat panel display substrate and/or carrier.
According to the invention, through reasonably adjusting the components of the glass composition, the glass material property and the forming stability of the aluminosilicate glass can be controlled within a narrow limited range, which is beneficial to controlling large-scale and light-thin production of glass plates, and on the other hand, the heat conductivity coefficient of the glass is optimized, which is beneficial to controlling the curvature of the annealed glass, so that the high yield of the glass is ensured.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In a first aspect, the present invention provides a composition for glass comprising 58 to 64 wt% of SiO in terms of oxide, based on the total weight of the composition for glass218-23 wt% of Al2O30-1.6 wt% of B2O30.001 to 0.3 wt% of ZrO20.0005 to 1.8 wt% of a metal oxide M and 12 to 24 wt% of a metal oxide N; m is selected from BeO and Sc2O3And Y2O3And N is selected from one or more of MgO, CaO and SrO.
In a preferred embodiment of the present invention, the composition for glass contains 59 to 62 wt% of SiO in terms of oxide based on the total weight of the composition for glass218-21 wt% of Al2O30.001-1.5 wt% of B2O30.001 to 0.2 wt% of ZrO20.1 to 1.5 wt% of metal oxide M and 16 to 19 wt% of metal oxide N.
In the composition for glass of the present invention, SiO2Is a glass network forming body, is a main component of a glass system, and is also a framework of a glass network structure. It can improve thermal stability and reduce thermal expansion coefficient. Therefore, taken together, SiO is calculated as the oxide based on the total weight of the composition for glass2The content of (B) is 58-64 wt%; preferably, SiO2The content of (B) is 59-62 wt%. Specifically, for example, the amount of the organic solvent may be 58 wt%, 58.5 wt%, 59 wt%, 59.5 wt%, 60 wt%, 60.3 wt%, 60.8 wt%, 61 wt%, 61.5 wt%, 62 wt%, 63 wt%, 63.2 wt%, 64 wt%, or any two of these valuesAny value within the range of (a).
In the composition for glass of the present invention, Al2O3The glass is a network intermediate, is another key index for improving the heat resistance, the mechanical strength and the bending resistance of the high-aluminum low-boron alkali-free glass, participates in a glass network, plays a role of a former, and can improve the compactness of a glass structure so as to improve the density and the physical and chemical properties. Therefore, in consideration of the fusion molding, thermal shrinkage and mechanical strength of the glass, Al is contained in terms of oxides based on the total weight of the composition for glass2O3The content of (A) is 18-23 wt%; preferably, Al2O3The content of (B) is 18-21 wt%. Specifically, for example, it may be 18 wt%, 18.5 wt%, 19 wt%, 19.2 wt%, 19.4 wt%, 19.5 wt%, 19.6 wt%, 20 wt%, 20.3 wt%, 20.8 wt%, 21 wt%, 22 wt%, 22.3 wt%, 22.5 wt%, 23 wt%, or any two of these values.
In the composition for glass of the present invention, the metal oxide M (selected from BeO and Sc)2O3、Y2O3One or more of) is a component for reducing the melting temperature, the forming viscosity and the expansion coefficient of the glass substrate, and can improve the heat conductivity coefficient, the 308 nanometer ultraviolet transmittance, the Young modulus and the like of the glass substrate, wherein the improvement of the heat conductivity of the BeO on the glass is several times of that of alumina, the heat conductivity coefficient of the glass can be obviously improved, the annealing quality of large glass is improved, and the bending degree of the glass substrate after the glass is annealed is reduced. However, as the content of the metal oxide M increases, some properties are not improved any more, and the production cost is increased significantly. Therefore, in general, the content of the metal oxide M is 0.0005 to 1.8% by weight in terms of oxide, based on the total weight of the composition for glass; preferably, the content of the metal oxide M is 0.005 to 1.5 wt%; more preferably, the content of the metal oxide M is 0.1 to 1.5 wt%. Specifically, for example, it may be 0.0005 wt%, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.7 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.5 wt%, 1.8 wt%, and any two values of these valuesAny number within the constituted range.
In the composition for glass of the present invention, preferably, the metal oxide M contains 0 to 100 wt% of BeO based on the total weight of the metal oxide M; more preferably, the metal oxide M contains 1-80 wt% of BeO; further preferably, the metal oxide M contains 1-60 wt% of BeO. Specifically, for example, it may be any of 0 wt%, 10 wt%, 20 wt%, 28.57 wt%, 30 wt%, 33.33 wt%, 37.5 wt%, 40 wt%, 50 wt%, 53.33 wt%, 60 wt%, 66.67 wt%, 70 wt%, 76.92 wt%, 80 wt%, 83.33 wt%, 90 wt%, 100 wt%, and a range formed by any two of these values.
In the composition for glass of the present invention, it is preferable that the metal oxide M contains Sc in an amount of 0 to 100 wt% based on the total weight of the metal oxide M2O3(ii) a More preferably, the metal oxide M contains 0.1 to 80 wt.% Sc2O3(ii) a Further preferably, the metal oxide M contains 0.1 to 60 wt.% Sc2O3. Specifically, for example, it may be 0 wt%, 10 wt%, 13.33 wt%, 20 wt%, 26.67 wt%, 30 wt%, 33.33 wt%, 37.5 wt%, 40 wt%, 41.67 wt%, 42.86 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, or any number in the range of any two of these values.
In the composition for glass of the present invention, preferably, the metal oxide M contains 0 to 100 wt% of Y based on the total weight of the metal oxide M2O3(ii) a More preferably, the metal oxide M contains 0.01 to 50 wt% of Y2O3(ii) a Further preferably, the metal oxide M contains 0.01 to 30 wt% of Y2O3. Specifically, for example, it may be 0 wt%, 6.67 wt%, 10 wt%, 16.67 wt%, 20 wt%, 23.08 wt%, 25 wt%, 28.57 wt%, 30 wt%, 33.33 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, or any number in the range of any two of these values.
In a preferred embodiment of the invention, beryllium oxide is introduced as basic beryllium carbonate, which decomposes at high temperature to generate gas, and can promote bubble discharge of the glass melt and increase the fluidity of the melt, so that the components in the melt are uniformly dispersed.
In the composition for glass of the present invention, B2O3Is a good fluxing agent, and under the condition of high-temperature melting, B2O3The high-temperature viscosity can be reduced, the low-temperature viscosity of the glass can be improved, and the glass can be prevented from crystallizing, but the Young modulus of the substrate glass can be reduced by the boron oxide. Therefore, in general, B is calculated as oxide based on the total weight of the composition for glass2O3The content of (B) is 0-1.6 wt%; preferably, B2O3The content of (B) is 0.001-1.5 wt%; more preferably, B2O3The content of (B) is 0.001-1.1 wt%. Specifically, for example, it may be 0 wt%, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.6 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.6 wt%, or any number in the range of any two of these values.
In the composition for glass, the material property of the glass is regulated and controlled by metal oxide N (one or more selected from MgO, CaO and SrO), wherein SrO has the best fluxing effect, can obviously reduce the melting temperature of the glass and prevent the glass from generating crystallization, but the content is too high, the density of the glass is larger, the thermal expansion coefficient is increased, and the chemical stability is poor; if the content of CaO is too low, the viscosity of the high-temperature glass cannot be reduced efficiently, the content is too high, the glass is easy to crystallize, the forming temperature range is reduced, and the thermal expansion coefficient is also greatly increased; the existence of MgO brings lower expansion coefficient and density and higher chemical resistance, strain point and elastic modulus to adjust various performance indexes of the substrate glass. Therefore, in general, the content of the metal oxide N is 12 to 24 wt% in terms of oxide, based on the total weight of the composition for glass; preferably, the content of metal oxide N is 14 to 22 wt%; more preferably, the content of the metal oxide N is 16 to 19 wt%. Specifically, for example, it may be 12 wt%, 13 wt%, 15 wt%, 16.2 wt%, 16.9 wt%, 17 wt%, 17.1 wt%, 17.5 wt%, 17.9 wt%, 18 wt%, 18.3 wt%, 19 wt%, 20 wt%, 22 wt%, 24 wt%, or any two of these values.
In the composition for glass of the present invention, preferably, the metal oxide N contains SrO in an amount of 33 to 48 wt% based on the total weight of the metal oxide N; more preferably, the metal oxide N contains 36-42 wt% SrO. Specifically, for example, it may be 34 wt%, 34.9 wt%, 35 wt%, 35.3 wt%, 36 wt%, 37 wt%, 38 wt%, 38.3 wt%, 39 wt%, 40 wt%, 40.2 wt%, 40.9 wt%, 41 wt%, 41.2 wt%, 42 wt%, 43 wt%, 44 wt%, 44.4 wt%, 45 wt%, 45.9 wt%, 46 wt%, 48 wt%, or any number in the range of any two of these values.
In the composition for glass of the present invention, preferably, the mass ratio of MgO to CaO is 0.8 to 2; more preferably, the mass ratio of MgO to CaO is between 0.9 and 1.75. Specifically, for example, the numerical value may be 0.8, 0.82, 0.83, 0.9, 0.91, 0.95, 1%, 1.02, 1.04, 1.1, 1.2, 1.22, 1.3, 1.33, 1.4, 1.44, 1.5, 1.55, 1.6, 1.7, 1.75, 1.8, 1.9, 2, or any two of these values.
In the composition for glass of the present invention, ZrO2The intermediate oxide can improve the chemical stability of the glass, reduce the expansion coefficient of the glass, increase the content, is difficult to melt and is easy to crystallize. Thus, in general, ZrO is calculated as oxides based on the total weight of the composition for glass2The content of (B) is 0.001-0.3 wt%; preferably, ZrO2The content of (B) is 0.001-0.2 wt%. Specifically, for example, it may be 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.005 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, or any value in a range of any two of these values.
SiO introduced into high-aluminum low-boron alkali-free glass system2Using high-purity quartz sand, whichLarge dosage and high production cost, and the total iron content and Fe content of the main impurity-ferric oxide in the high-purity quartz sand are introduced into the glass3+The influence on the light transmittance of 308nm is most obvious, so that in order to enhance the market competitiveness of products and reduce the production cost, the total iron content in the glass composition is 100-330ppm based on the total weight of the composition for glass; preferably, the total iron content of the glass composition is 160-250ppm, based on the total weight of the composition for glass.
In the composition for glass of the present invention, preferably, Fe is contained in the total iron3+The iron content is less than 80 wt%; more preferably, of the total iron, Fe3+The iron content is less than 70 wt%; further preferably, of the total iron, Fe3+The iron content is 65 wt% or less.
In the composition for glass of the present invention, the content of the alkali metal oxide in the composition for glass is preferably 350ppm or less in terms of oxide based on the total weight of the composition for glass.
In the composition for glass of the present invention, it is preferable that SO in the composition for glass is contained in an amount of SO based on the total weight of the composition for glass3The content of (B) is 350ppm or less.
In the composition for glass of the present invention, preferably, the composition for glass contains a fining agent. The content of the refining agent is not particularly limited, and the content of the refining agent is less than or equal to 0.5 wt% calculated by oxide based on the total weight of the composition for glass, and the chemical refining agent is preferably selected from one or more of strontium sulfate, calcium sulfate, strontium nitrate and stannous oxide.
In the composition for glass of the present invention, preferably, the content of halogen in the composition for glass is 0.004 to 0.5 wt% in terms of elemental halogen based on the total weight of the composition for glass.
Preferably, the halogen is F and/or Cl.
In a second aspect, the present invention provides a method of making an aluminosilicate glass, the method comprising: the composition for glass of the present invention is subjected to melting treatment, molding treatment, annealing treatment and machining treatment in this order.
In the method of the present invention, for the specific definition of the composition for glass, reference is made to the corresponding description above, and details are not repeated here.
The method for producing the aluminosilicate glass is not particularly required, and for example, the method may include: the raw materials of the composition for glass are fully and uniformly mixed, and are kept warm for 7 to 24 hours in a platinum rhodium crucible at 1630-. And then pouring the melted glass liquid on a stainless steel mold for molding, annealing at the temperature of 800 ℃, and then carrying out mechanical processing to obtain the aluminosilicate glass.
The mechanical processing treatment is not particularly limited, and various mechanical processing methods commonly used in the art may be used, and for example, the product obtained by the annealing treatment may be cut, ground, polished, or the like.
In a third aspect, the present invention provides an aluminosilicate glass prepared by the above method.
The thickness of the above aluminosilicate glass may vary within a wide range, and may be a thickness of a high-alumina low-boron alkali-free glass known to those skilled in the art, for example, a thickness of 0.05 to 1.2mm, or a selection range may be appropriately expanded according to the thickness requirement of the glass substrate.
The aluminosilicate glass of the present invention preferably has a viscosity of 1013The annealing point temperature corresponding to poise is 770-820 ℃; more preferably, the viscosity is 1013The annealing point temperature at poise is 780-815 ℃.
In the float glass forming process, the control of the temperature drop curve is one of the key technologies for producing high-quality glass, the change of the temperature drop curve in the thinning area directly influences the change of the transverse thickness distribution of the glass ribbon, the temperature drop speed after the glass ribbon is drawn out of the thinning area directly determines the warping formation and the glass cutting quality, the natural temperature reduction process of the glass ribbon in the forming area is closely related to the material property of the glass, the reasonable control of the material property temperature is favorable for ensuring the glass quality,the design and manufacturing cost of the forming and annealing equipment are reduced, therefore, the aluminosilicate glass of the invention preferably has a forming temperature T corresponding to a viscosity of 10000 poises1wAnd a viscosity of 4 × 107Poise time corresponding to forming temperature T4kwThe difference value of 295-365 ℃; more preferably, the forming temperature T corresponds to a viscosity of 10000 poise1wAnd a viscosity of 4 × 107Poise time corresponding to forming temperature T4kwThe difference value of the temperature difference is 300-360 ℃; further preferably, the molding temperature T corresponds to a viscosity of 10000 poise1wAnd a viscosity of 4 × 107Poise time corresponding to forming temperature T4kwThe difference is 305-355 ℃.
The aluminosilicate glass of the present invention preferably has a melting temperature T corresponding to a viscosity of 200 poise200(iii) less than 1710 ℃; more preferably, the melting temperature T corresponds to a viscosity of 200 poise200(iii) less than 1700 ℃; further preferably, the melting temperature T corresponds to a viscosity of 200 poise200＜1690℃。
The aluminosilicate glass of the present invention preferably has a density of < 2.65g/cm3(ii) a More preferably, the aluminosilicate glass has a density of < 2.63g/cm3(ii) a Further preferably, the aluminosilicate glass has a density < 2.62g/cm3。
The aluminosilicate glass of the present invention preferably has a thermal expansion coefficient of (33-41) × 10 in the range of 50-350 DEG C-7/. degree.C., more preferably (35-40) × 10-7Further preferred is (35-39) × 10/. degree.C-7/℃。
By utilizing the principle that the physical characteristics of adjacent areas of the flat glass are consistent or similar, two adjacent glass strips are cut on the flat glass, the upper surfaces of the two pieces of glass are oppositely overlapped with the upper surfaces or the lower surfaces of the two pieces of glass are oppositely overlapped with the lower surfaces, the heads and the tails of the two pieces of glass are kept consistent, and the curvature is calculated by measuring the maximum gap between the two pieces of glass. The bending degree is an important functional index considering the glass, and the bending degree of the aluminosilicate glass is preferably less than or equal to 0.15 percent when the thickness of the aluminosilicate glass is 0.5 mm; more preferably, the aluminosilicate glass has a tortuosity < 0.12% at a thickness of 0.5 mm; further preferably, the aluminosilicate glass has a bow of < 0.1% at a thickness of 0.5 mm.
The aluminosilicate glass of the present invention preferably has a thermal conductivity > 1.2W/(mk); more preferably, the aluminosilicate glass has a thermal conductivity > 1.3W/(mk); further preferably, the aluminosilicate glass has a thermal conductivity > 1.35W/(mk).
The aluminosilicate glass of the invention preferably has the Young modulus of more than or equal to 78 GPa; more preferably, the aluminosilicate glass has a Young's modulus > 80 GPa; further preferably, the aluminosilicate glass has a Young's modulus > 82 GPa.
The aluminosilicate glass of the invention preferably has a light transmission of more than 70% at a wavelength of 308 nm; more preferably, the aluminosilicate glass has a light transmission > 72% at a wavelength of 308 nm; further preferably, the aluminosilicate glass has a light transmission > 75% at a wavelength of 308 nm.
The float production process has high glass quality, high yield, homogeneous glass temperature band, sufficient glass annealing stress and capacity of drawing ultrathin electronic display glass continuously and fast. The process comprises the following steps of melting glass raw materials at high temperature in an electric boosting melting furnace with oxy-fuel combustion, clarifying, stirring, homogenizing and cooling the glass raw materials through a platinum channel, then flowing the glass liquid into a tin bath, spreading, flattening and thinning the glass liquid on the tin liquid surface under the combined action of the gravity of the glass liquid, the surface tension and the tension of a transition roller table, and forming the glass liquid into a glass belt with smooth upper and lower surfaces; and (4) conveying the glass to an annealing furnace for annealing through a transition roller table, and cutting to obtain a float glass product. According to the invention, the content of each component in the aluminosilicate glass is adjusted, so that the melting temperature and the high-temperature viscosity are reduced, the glass forming is facilitated, the ultraviolet transmittance is improved, and the heat conduction coefficient is improved; meanwhile, the boron oxide is reduced and the beryllium oxide is increased, so that a good fluxing effect is achieved, the Young modulus is improved, the bending caused by dead weight in the substrate conveying process is avoided, the 308 nanometer ultraviolet transmittance is increased, and the light weight of the glass substrate is realized.
In a fourth aspect, the invention provides the use of the composition for glass or aluminosilicate glass of the invention in the preparation of a flat panel display substrate and/or carrier.
Examples
The following describes in detail specific embodiments of the present invention. It is to be understood that each of the materials specifically described herein in accordance with the present invention are commercially available, unless otherwise specified, in a manner conventional in the art. The embodiments are merely to illustrate and explain the present invention and do not limit the present invention.
The compositions of the glass compositions in examples and comparative examples according to the present invention and the respective measurement results are shown in tables 1 to 3. In addition, glasses in examples and comparative examples were prepared according to the following methods.
According to the embodiment and the comparative example, the components are mixed evenly, the mixed batch is poured into a platinum crucible, then the platinum crucible is heated in a resistance furnace at 1630 ℃ for 15 hours, and the platinum-rhodium alloy stirring rod is used for manual stirring evenly 3 hours before discharging. And pouring the melted glass liquid into a stainless steel mold for molding, then annealing the glass product in an annealing furnace for 2 hours, and turning off a power supply to cool to room temperature along with the furnace. And cutting, grinding and polishing the glass product, cleaning with deionized water and drying to obtain a glass finished product with the thickness of 0.5 mm. The properties of each glass product were measured and the results are shown in Table 1.
According to the invention, the glass density is determined in g/cm with reference to ASTM C-6933。
The coefficient of thermal expansion of the glass at 50-350 ℃ is measured in 10 units using a horizontal dilatometer with reference to ASTM E-228-7/℃。
The Young's modulus of the glass was measured in GPa according to ASTM C-623.
The high temperature viscosity of the glass was measured by a rotary high temperature viscometer with reference to ASTM C-964, and the melting temperature was a temperature T corresponding to the viscosity of 200P20010000P viscosity pairTemperature T of1WTemperature T corresponding to viscosity of 40000000P4KWThe material property interval is T1W-T4KWThe difference in degrees C is given in degrees C.
The glass anneal point was determined using an anneal point strain point tester, in units of ° C, with reference to ASTM C-336.
The light transmittance of the glass was measured by an ultraviolet-visible spectrophotometer, and the thickness of the glass sample was 0.5mm, and the light transmittance at a wavelength of 308nm was taken in%.
The thermal conductivity of the glass at 100 ℃ is measured according to GB/T7962.13 and is expressed in W/(mk).
The tortuosity is measured by reference to the black box lattice method specified in GB/T18680 at 9.4. And judging the curvature according to the separation condition of the reflection image and the test image of the same white point. Wherein, when the reflection image with the diameter of the white point of 9.52mm and the test image are two separated circles, the curvature is more than 0.15 percent; when the reflected image with a white dot diameter of 9.52mm and the test image are two intersecting circles, the bow is less than or equal to 0.15%. When the reflection image with the diameter of the white point of 6.35mm and the test image are two intersected circles, the curvature is less than or equal to 0.10 percent; when the overlapping portion of the reflected image with the white dot diameter of 6.35mm and the test image is equal to or more than half, the bow is equal to or less than 0.05%.
TABLE 1
TABLE 2
As can be seen from the examples in tables 1-2, the process of the present invention utilizes a catalyst containing a specific content of SiO2、Al2O3、B2O3M (including BeO and Sc)2O3、Y2O3And combinations thereof), MgO, CaO, SrO, ZrO2The glass prepared from the composition has a molding viscosity of 1 million poise and a glass hardening viscosity of 4 million poise295 plus 365 ℃ is more beneficial to glass forming, in addition, chemical components which have stronger capability of adjusting material property, improve ultraviolet transmittance and improve heat conduction coefficient are added to adjust the material property of the glass, so that the material is more suitable for a float melting forming process, the annealing process is easier to pass, the heat conduction coefficient of the glass is improved, the curvature of the glass is favorably controlled in the annealing process, the curvature is less than or equal to 0.15 percent, and the heat conduction coefficient is more than 1.2W/(mk), so that the display substrate glass with excellent quality is obtained.
TABLE 3
| Oxide composition | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| SiO2(％) | 61.4 | 61.0 | 65.0 | 55.0 | 61.8 |
| Al2O3(％) | 17.0 | 20.0 | 20.0 | 25.0 | 18.0 |
| BeO(％) | 0.0 | 0.0 | 0.0 | 5.0 | 0.0 |
| Y2O3(％) | 0.0 | 1.0 | 0.0 | 0.0 | 0.2 |
| Sc2O3(％) | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| B2O3(％) | 9.0 | 5.0 | 0.0 | 0.0 | 2.8 |
| CaO(％) | 9.5 | 0.0 | 5.0 | 2.0 | 7.0 |
| SrO(％) | 2.0 | 6.0 | 2.0 | 10.0 | 4.5 |
| MgO(％) | 1.0 | 7.0 | 8.0 | 2.7 | 4.5 |
| ZrO2(ppm) | 1500 | 200 | 0 | 3000 | 12000 |
| Total iron (ppm) | 500 | 60 | 300 | 108 | 400 |
| Fe3+Total iron (%) | 90 | 95 | 60 | 50 | 0 |
| Cl(ppm) | 0 | 0 | 200 | 1000 | 0 |
| SO3(ppm) | 100 | 0 | 0 | 200 | 180 |
| M(％) | 0.00 | 1.00 | 0.00 | 5.00 | 0.20 |
| BeO/M(％) | / | 0.00 | / | 100.00 | 0.00 |
| Y2O3/M(％) | / | 100.00 | / | 0.00 | 100.00 |
| Sc2O3/M(％) | / | 0.00 | / | 0.00 | 0.00 |
| N(％) | 12.5 | 13 | 15 | 14.7 | 16 |
| SrO/N(％) | 16 | 46.2 | 13.3 | 68 | 28.1 |
| MgO/CaO(％) | 10.5 | / | 160.0 | 135.0 | 64.3 |
| Density (g/cm)3) | 2.36 | 2.53 | 2.56 | 2.63 | 2.57 |
| Coefficient of thermal expansion (× 10)-7/℃) | 35.71 | 40.12 | 45.69 | 48.86 | 36.51 |
| Young's modulus (GPa) | 70 | 77 | 85 | 74 | 72 |
| T200(℃) | 1656 | 1704 | 1732 | 1684 | 1692 |
| T1W | 1234 | 1315 | 1374 | 1285 | 1307 |
| T4KW | 968 | 985 | 1008 | 994 | 915 |
| Interval of material properties (T)1W-T4KW) | 266 | 330 | 366 | 281 | 292 |
| Annealing Point (. degree.C.) | 718 | 795 | 835 | 818 | 885 |
| Light transmittance at 308nm (%) | 52 | 72 | 57 | 80 | 65 |
| Thermal conductivity W/(mk) | 1.21 | 1.14 | 1.18 | 1.53 | 1.16 |
| Tortuosity (%) | 0.25 | 0.12 | 0.35 | 0.12 | 0.28 |
As can be seen from the comparative examples in table 3, if the range of the present invention or the combination is not satisfactory, the temperature range from 1 million poise of glass forming viscosity to 4 million poise of glass hardening viscosity is likely to exceed the control range of 330 ± 35 ℃, which is not favorable for ensuring the quality of glass, reducing the design and manufacturing cost of forming and annealing equipment, and other properties of the glass substrate are deteriorated, such as uv transmittance, thermal conductivity, bending degree, young's modulus, thermal expansion coefficient, melting temperature, etc., are greatly out of the preferable range, which is not favorable for obtaining display substrate glass with excellent quality.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composition for glass, characterized in that the composition for glass contains 58 to 64 wt% of SiO in terms of oxide based on the total weight of the composition for glass218-23 wt% of Al2O30-1.6 wt% of B2O30.001 to 0.3 wt% of ZrO20.0005 to 1.8 wt% of a metal oxide M and 12 to 24 wt% of a metal oxide N; the metal oxide M is selected from BeO and Sc2O3And Y2O3The metal oxide N is selected from one or more of MgO, CaO and SrO.
2. The composition for glass according to claim 1, wherein the composition for glass contains 59 to 62 wt% of SiO in terms of oxide based on the total weight of the composition for glass218-21 wt% of Al2O30.001-1.5 wt% of B2O30.001 to 0.2 wt% of ZrO20.1 to 1.5 wt% of metal oxide M and 16 to 19 wt% of metal oxide N.
3. The composition for glass as defined in claim 1, wherein the total iron content of the glass composition is 100-330ppm based on the total weight of the composition for glass;
preferably, of the total iron, Fe3+The iron content was 80 wt.% based onThe following steps of (1);
preferably, the content of alkali metal oxide in the composition for glass is 350ppm or less in terms of oxide based on the total weight of the composition for glass;
preferably, the SO in the composition for glass is based on the total weight of the composition for glass3The content of (B) is less than 350 ppm;
preferably, the content of halogen in the composition for glass is 0.004-0.5 wt% calculated by elementary halogen based on the total weight of the composition for glass;
preferably, the halogen is F and/or Cl.
4. The composition for glass according to any one of claims 1 to 3, wherein the metal oxide M contains 0 to 100 wt% of BeO based on the total weight of the metal oxide M;
preferably, the metal oxide M contains 0 to 100 wt.% Sc, based on the total weight of the metal oxide M2O3；
Preferably, the metal oxide M contains 0 to 100 wt% of Y based on the total weight of the metal oxide M2O3。
5. The composition for glass according to any one of claims 1 to 3, wherein the metal oxide N contains SrO in an amount of 33 to 48 wt% based on the total weight of the metal oxide N;
preferably, the mass ratio of MgO to CaO is between 0.8 and 2.
6. A method of making an aluminosilicate glass, the method comprising: the composition for glass according to any one of claims 1 to 5 is subjected to melting treatment, molding treatment, annealing treatment and machining treatment in this order.
7. The aluminosilicate glass produced by the method of claim 6.
8. The aluminosilicate glass of claim 7, wherein the aluminosilicate glass has a viscosity of 1013The annealing point temperature corresponding to poise is 770-820 ℃;
preferably, the aluminosilicate glass has a melting temperature T corresponding to a viscosity of 200 poise200＜1710℃；
Preferably, the aluminosilicate glass has a density < 2.65g/cm3；
Preferably, the aluminosilicate glass has a coefficient of thermal expansion of (33-41) × 10 in the range of 50-350 ℃-7/℃；
Preferably, the aluminosilicate glass has a viscosity of 10000 poise and a corresponding forming temperature T1wHas a viscosity of 4 × 10 with the aluminosilicate glass7Poise time corresponding to forming temperature T4kwDifference value T of1w-T4kw295 ℃ and 365 ℃.
9. The aluminosilicate glass of claim 7, wherein the curvature is 0.15% or less when the aluminosilicate glass is 0.5mm thick;
preferably, the aluminosilicate glass has a thermal conductivity > 1.2W/(mk);
preferably, the Young modulus of the aluminosilicate glass is more than or equal to 78 GPa;
preferably, the aluminosilicate glass has a light transmission > 70% at a wavelength of 308 nm.
10. Use of a composition for glass according to any of claims 1 to 5 or an aluminosilicate glass according to any of claims 7 to 9 for the preparation of a substrate and/or a carrier for a flat panel display.
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