CN117550799A - Composition for glass, alkali-free aluminosilicate glass, and preparation method and application thereof - Google Patents
Composition for glass, alkali-free aluminosilicate glass, and preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 146
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims description 16
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000006025 fining agent Substances 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 238000003754 machining Methods 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 4
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 238000010128 melt processing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000008395 clarifying agent Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000004293 potassium hydrogen sulphite Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
- G09F9/335—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes being organic light emitting diodes [OLED]
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to a composition for glass, alkali-free aluminosilicate glass, and a preparation method and application thereof. Composition for glass, 65-72mol% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 10-14mol% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3-7mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 2-6mol% MgO;4-7mol% of CaO;2-5mol% of SrO;0.1 to 1.5mol% BaO; in mole percent, B is more than or equal to 0.03 2 O 3 /(SiO 2 +Al 2 O 3 ) Less than or equal to 0.08; in terms of mole percentage, baO/(MgO+CaO+SrO+BaO) is more than or equal to 0.02 and less than or equal to0.12. The glass has higher strain point and higher Young modulus through the synergistic effect of the components; meanwhile, the glass melting temperature can be reduced, the production characteristics are better, the chemical stability and the mechanical property of the glass can be enhanced, and the thermal expansion coefficient of the glass can be reduced.
Description
Technical Field
The application relates to the technical field of glass materials, and in particular relates to a composition for glass, alkali-free aluminosilicate glass, a preparation method and application thereof.
Background
Thin Film Transistor (TFT) technology plays a key role in modern liquid crystal display and OLED display fabrication. In these displays, thin film transistors are used to control the on-off state and display of the pixels. LTPS (low temperature polysilicon) and IGZO (indium gallium zinc oxide) are two thin film transistor materials commonly used in TFT technology. LTPS and IGZO have high electron mobility and are suitable for high resolution display panel driving. However, these high performance thin film transistors require a stable, high performance substrate to support and secure their operation. Alkali-free aluminosilicate glasses are novel glass materials having high strain points, high Young's modulus, and being free of alkali oxides (e.g., na 2 O、K 2 O、Li 2 O) and therefore does not damage the thin film transistor material during the heat treatment. Accordingly, alkali-free aluminosilicate glass is an ideal substrate choice for high performance thin film transistor fabrication such as LTPS and IGZO. By using alkali-free glass as a substrate, a stable support structure can be provided and TFT technology can be realizedThe manufacturing process and use show higher performance and reliability.
However, when the conventional alkali-free glass satisfies these requirements, there are often problems in production such as high melting temperature and high liquidus temperature, which leads to an increase in manufacturing cost.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of embodiments of the present application to provide a glass composition that improves the performance and production characteristics of glass substrates.
In a first aspect, embodiments of the present application provide a glass composition comprising, in mole percent: 65-72mol% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 10-14mol% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3-7mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 2-6mol% MgO;4-7mol% of CaO;2-5mol% of SrO;0.1 to 1.5mol% BaO; in mole percent, B is more than or equal to 0.03 2 O 3 /(SiO 2 +Al 2 O 3 ) Less than or equal to 0.08; the mol percent is less than or equal to 0.02 and less than or equal to 0.12 of BaO/(MgO+CaO+SrO+BaO).
The glass has higher strain point and higher Young modulus through the synergistic effect of the components; meanwhile, the glass melting temperature can be reduced, the production characteristics are better, the chemical stability and the mechanical property of the glass can be enhanced, and the thermal expansion coefficient of the glass can be reduced. Wherein B is 2 O 3 Is a good fluxing agent for glass, and can obviously reduce the melting temperature of the glass; when the mole percentage is 0.03.ltoreq.B 2 O 3 /(SiO 2 +Al 2 O 3 ) When the content is less than or equal to 0.08, it can be combined with SiO 2 And Al 2 O 3 The combined action forms a network structure and breaks down the continuous network of silicon oxygen tetrahedra, thereby lowering the glass melting temperature. BaO is also a good fluxing agent, and its addition can reduce the glass melting temperature. By co-compounding with MgO, caO and SrO, and when BaO/(MgO+CaO+SrO+BaO). Ltoreq.0.02 in terms of mole percent, a flux of the glass system can be formed, thereby promoting melting of the glass. Furthermore, by SiO 2 、Al 2 O 3 、B 2 O 3 AndThe cooperation of alkaline earth oxides (MgO, caO, srO and BaO) can provide a glass with a higher strain point and specific modulus.
In some embodiments of the present application, the glass composition includes, in mole percent: 67-71mol% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 11-13.5mol% Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3.5 to 5.5mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3.5 to 5.5mol% MgO;4.5 to 6.2mol percent of CaO;2.5 to 4.5mol% SrO;0.2-1mol% BaO; b is more than or equal to 0.04 and less than or equal to 0mol percent 2 O 3 /(SiO 2 +Al 2 O 3 ) Less than or equal to 0.07; the mol percent is less than or equal to 0.03 and less than or equal to 0.1 of BaO/(MgO+CaO+SrO+BaO).
In some embodiments of the present application, the method further comprises, in mole percent: 0.1 to 1mol% ZnO. ZnO has 18 outer-layer electronic structures, zn relative to alkaline earth metals 2+ Ions are more easily polarized, the viscosity of the glass (such as more than 1400 ℃) can be reduced at high temperature, the viscosity of the glass containing ZnO is smaller, the movement speed of atoms is higher, crystal nuclei are not easy to form, and therefore the crystallization upper limit temperature of the glass is reduced. In addition, zn 2+ And Mg (magnesium) 2+ The charge numbers are the same, the ionic radii are close, and when the charge numbers and the ionic radii are used together, the similar mixed alkaline earth effect can be generated, and the optimal toughness, chemical resistance and dielectric property can be generated.
In some embodiments of the present application, the above composition further comprises 0-1 mole% of a clarifying agent, in mole percent. The clarifier can adsorb and neutralize impurities and metal ions in the glass, so that the impurities in the glass are reduced, and the purity and optical quality of the glass are improved. Bubbles may be generated during the glass melting process. The fining agent helps to reduce the number and size of bubbles, thereby reducing the gas content in the glass and improving the transparency and uniformity of the glass.
In some embodiments of the present application, the above composition further comprises 0.05 to 0.2 mole percent of a clarifying agent, in mole percent.
In some embodiments of the present application, the fining agent includes at least one of sulfate, nitrate, halide, tin oxide, and stannous oxide. The compounds have good clarifying effect in the glass preparation process, and can effectively improve the purity, the transparency and the optical performance of the glass. At the same time, the addition amount of the glass is small, and the performance of the glass is not negatively influenced.
In some embodiments of the present application, the fining agent includes at least one of sodium sulfate, sodium nitrate, potassium nitrate, sodium chloride, strontium chloride, calcium fluoride, tin oxide, and stannous oxide.
In a second aspect, embodiments of the present application provide a method for preparing alkali-free aluminosilicate glass, including: the glass composition is subjected to a melting treatment, a molding treatment, an annealing treatment and a machining treatment in this order.
The preparation method has relatively simple steps, does not need complex equipment and operation, and can be carried out under the condition of a conventional laboratory. Because the preparation method is simple, the required equipment and material cost is relatively low, and the preparation cost is reduced. And the components and the properties of the glass can be better controlled by controlling the proportion of the raw materials and the preparation conditions.
In the present application, the machining treatment is not particularly limited, and various machining methods common in the art may be used, and for example, cutting, grinding, polishing, and the like may be performed on the product obtained by the annealing treatment.
In some embodiments of the present application, the conditions of the melt processing include: the melting temperature is 1550-1650 ℃ and the melting time is 4-8h. In the above temperature range, the raw materials can be sufficiently melted and reacted, which contributes to improving the uniformity and stability of the glass. In the melting time range, the raw materials can be fully reacted and bubbles can be discharged, so that the glass liquid has higher uniformity and purity. At the same time, the method is beneficial to eliminating internal stress in the glass and reducing possible crystallization and fracture risks.
In some embodiments of the present application, the conditions of the annealing treatment include: the annealing temperature is 750-800 ℃, and the annealing time is 1-3h. Stresses may develop within the glass during its manufacture due to temperature changes during melting and cooling. These internal stresses can be helped to be relieved by the annealing process, thereby improving the stability and durability of the glass.
In a third aspect, embodiments of the present application provide an alkali-free aluminosilicate glass produced by a method as described above.
The alkali-free glass prepared from the glass composition has the following characteristics:
(1) The density is less than or equal to 2.54g/cm 3 ；
(2) Coefficient of thermal expansion in the range of 50-350 ℃ is lower than 40 x 10 -7 /℃。
(3) Young's modulus not less than 80GPa, specific modulus not less than 31GPa (g/cm) 3 )。
(4) Strain point T st Is 710-740 ℃.
(5) Liquidus temperature T L ≤1200℃。
(6) The expansion softening temperature Ts is greater than 820 ℃.
(7) The viscosity is 200 poise and the corresponding temperature T200 is less than or equal to 1670 ℃.
In a fourth aspect, embodiments of the present application provide a composition as described above or an alkali-free aluminosilicate glass as described above for use in the field of display panels. The display panel can be used as a liquid crystal display substrate and a semiconductor device.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes a composition for glass, alkali-free aluminosilicate glass, a preparation method thereof and an intelligent equipment protection cover plate.
The embodiment of the application provides alkali-free aluminosilicate glass, which is prepared from the following components in percentage by mole: 65-72mol% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 10-14mol% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3-7mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 2-6mol% MgO;4-7mol% of CaO;2-5mol% of SrO;0.1 to 1.5mol% BaO; the method comprises the steps of carrying out a first treatment on the surface of the 0.1-1mol% ZnO and 0-1mol% clarifying agent.
In the above composition, siO 2 Is an essential component constituting a glass network structure. By adding 65-72mol% of SiO 2 The heat resistance and chemical stability of the glass can be improved, so that the glass can obtain higher strain point, can work at high temperature and resist chemical attack. This is very important for TFT liquid crystal displays because the display needs to operate at different temperatures for a long time, while high temperature stability performance guarantees the performance and lifetime of the display. At the same time, siO in this mole percent range 2 And the mechanical strength and hardness of the glass are improved, so that the glass is more durable and scratch-resistant, and damage caused by external force is reduced.
Al 2 O 3 The glass composition plays a role of a network forming body, promotes the connection integrity of a glass network structure, and ensures that the glass has higher mechanical stability and heat resistance. At the same time Al 2 O 3 The thermal expansion coefficient of the glass can be reduced, the dimensional stability of the glass is increased, and the requirement of the liquid crystal display field on the dimensional stability can be met.
B 2 O 3 Is a glass-forming oxide that enhances the chemical stability and mechanical properties of the glass while reducing the coefficient of thermal expansion and dielectric constant of the glass. At the same time B 2 O 3 And the glass is also good fluxing agent, so that the glass melting temperature can be greatly reduced, and the glass is easier to melt and form in the production process.
MgO, caO, srO and BaO are both alkaline earth oxides, wherein MgO is a network exosome oxide, and its addition can improve the thermal stability of the glass, so that the glass remains structurally intact at high temperatures, reducing the risk of devitrification and phase separation. MgO is an alkaline earth metal oxide, and its addition can effectively reduce the high-temperature viscosity of the glass, so as to improve the meltability and formability of the glass, and can increase the strain point of the glass. MgO also has a high specific modulus, which contributes to the improvement of mechanical strength and dimensional stability of the glass. The addition of CaO and SrO is helpful to optimize the chemical and mechanical properties of the glass, and simultaneously adjust the physical properties of the glass to meet the requirements of the liquid crystal display field on high-performance glass. The addition of BaO helps to reduce the dielectric constant of the glass, thereby reducing the influence of electron migration in liquid crystal display and improving the performance of the display panel.
ZnO has 18 outer-layer electronic structures, zn relative to alkaline earth metals 2+ Ions are more easily polarized, the viscosity of the glass (such as more than 1400 ℃) can be reduced at high temperature, the viscosity of the glass containing ZnO is smaller, the movement speed of atoms is higher, crystal nuclei are not easy to form, and therefore the crystallization upper limit temperature of the glass is reduced. In addition, zn 2+ And Mg (magnesium) 2+ The charge numbers are the same, the ionic radii are close, and when the charge numbers and the ionic radii are used together, the similar mixed alkaline earth effect can be generated, and the optimal toughness, chemical resistance and dielectric property can be generated. The fining agent includes at least one of sulfate, nitrate, halide, tin oxide, and stannous oxide. Such as sodium sulfate, sodium nitrate, potassium nitrate, sodium chloride, strontium chloride, calcium fluoride, tin oxide, stannous oxide, and the like. Sulfate (e.g., sodium sulfate) adsorbs and neutralizes metal ions during the glass melting process, decontaminates the glass, and helps to remove bubbles. The addition amount of the sulfate is small, so that the transparency and the optical performance of the glass can be effectively improved. Nitrates (such as sodium nitrate and potassium nitrate) decompose at high temperatures to produce oxygen, which can help to remove bubbles and impurities and clean the glass. In addition, nitrate can promote the release of gas in the glass, thereby improving the uniformity of the glass. The addition of halides (such as sodium chloride and strontium chloride) helps to remove some metal oxides and impurities and improve the optical quality of the glass. They also allow the refractive index of the glass to be adjusted. Tin oxide and stannous oxide can undergo a reduction reaction at high temperature to adsorb and remove bubbles and impurities in the glass. Their addition helps to improve the transparency and optical properties of the glass. Illustratively, the mole percent of clarifying agent includes, but is not limited to, 0 mole%, 0.1 mole%, 0.2 mole%, 0.3 mole%, 0.4 mole%, 0.5 mole%, 0.6 mole%, 0.7 mole%, 0.8 mole%, 0.9 molel％、1.0mol％。
Further, by controlling 0.03.ltoreq.B in terms of mole percent 2 O 3 /(SiO 2 +Al 2 O 3 ) Less than or equal to 0.08, wherein B 2 O 3 Can be used as network forming body oxide in glass, and is helpful for promoting the integrity of network connection and enhancing the chemical stability of the glass. And B is 2 O 3 Is a good fluxing agent, and can greatly reduce the melting temperature of glass, thereby being beneficial to reducing the production cost and energy consumption of the glass. This is important in industrial production, and particularly in a scene where a large number of glass substrates are required for mass production of liquid crystal display panels or the like, the production efficiency can be remarkably improved. At the same time B 2 O 3 The addition of (a) may alter the physical properties of the glass, such as reducing the coefficient of thermal expansion of the glass. This is very important for the manufacture of high-precision products such as liquid crystal display panels, because the matching of thermal expansion coefficients can reduce shape changes and stress concentrations due to temperature changes. Furthermore, B 2 O 3 The addition of (c) can also adjust the optical properties of the glass, such as refractive index. In an optical device such as a liquid crystal display panel, adjustment of refractive index can improve optical effects and display quality. Meanwhile, in terms of mole percent, baO/(MgO+CaO+SrO+BaO) is controlled to be less than or equal to 0.02 and less than or equal to 0.12, the chemical stability of the glass can be influenced by the addition of BaO, and the glass can have proper chemical stability by controlling the content of BaO, so that the dissolution and corrosion of the glass are inhibited, and the durability and the service life of the glass are improved. And the BaO content has a certain influence on the physical properties of the glass, including the density, the thermal expansion coefficient and the like of the glass. By adjusting the content of BaO, a glass having excellent physical properties, such as high density, low thermal expansion coefficient, can be obtained, thereby improving the dimensional stability and temperature resistance of the glass substrate. BaO plays a role of fluxing agent in glass, can reduce the melting temperature of the glass, is beneficial to reducing the preparation temperature and energy consumption of the glass, improves the production efficiency and reduces the production cost. The BaO content has a certain influence on the optical properties such as refractive index and light transmittance of the glass. The refractive index of the glass can be regulated by controlling the content of BaO, thereby generating light transmission and refractionThe influence is helpful to optimize the application performance of the glass in optical devices. In addition, by controlling the content of BaO, the viscosity and fluidity of the glass can be changed, which is beneficial to the forming and processing of the glass and reduces the defect rate and rejection rate of glass products.
The preparation method of the alkali-free aluminosilicate glass comprises the following steps: mixing the components in the composition according to the corresponding proportion to obtain a mixture, pouring the mixture into a platinum crucible, heating the mixture for 4-8 hours in a 1550-1650 ℃ resistance furnace, and stirring the mixture by using a platinum rod to discharge bubbles; pouring the melted glass liquid into a stainless steel cast iron mold, forming a specified blocky glass product, then annealing the glass product in an annealing furnace at 750-800 ℃ for 1-3 hours, closing a power supply, and cooling to 25 ℃ along with the furnace; and then cutting, grinding and polishing the annealed glass product in sequence, and then cleaning with deionized water and drying to obtain a glass finished product with the thickness of 0.7 mm.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1-
The components were weighed according to the instructions shown in Table 1, mixed well, and the mixture was poured into a platinum crucible, then heated in a 1620 ℃ resistance furnace for 5 hours, and stirred using a platinum rod to discharge bubbles. Pouring the melted glass liquid into a stainless steel cast iron grinding tool to form a specified blocky glass product, then annealing the glass product in an annealing furnace for 2 hours at the annealing temperature of 775, and turning off a power supply and cooling to 25 ℃ along with the furnace. Cutting, grinding and polishing the glass product, and then cleaning with deionized water and drying to obtain a glass finished product with the thickness of 0.7 mm.
The preparation methods of the other examples and comparative examples are basically the same as those of example 1, except that the proportions of the components are different, and are shown in Table 1.
TABLE 1
Table 1 (subsequent table)
Table 1 (subsequent table)
Test examples
This test example was conducted for measuring the temperatures corresponding to the density, thermal expansion coefficient, young's modulus, strain point, liquidus temperature and 200P viscosity of the alkali-free aluminosilicate glasses provided in examples 1 to 12 and comparative examples 1 to 6.
Wherein the glass density is measured in g/cm with reference to ASTM C-693 3 . The coefficient of thermal expansion of glass at 50-350℃was measured with a horizontal dilatometer in units of 10 with reference to ASTM E-228 -7 and/C. Young's modulus of glass in GPa was measured by reference to ASTM C-623 using a materials mechanics tester. Glass strain points were measured in degrees celsius using an annealing point strain point tester with reference to ASTM C-336. Glass height Wen Nianwen curve is determined with reference to ASTM C-965 using a rotary high temperature viscometer, wherein 200P corresponds to temperature T 1 The unit is in degrees Celsius. Determination of glass liquidus temperature T Using a ladder furnace method with reference to ASTM C-829 L The unit is in degrees Celsius. The detection results of the above items are shown in Table 2.
TABLE 2
Table 2 (subsequent table)
Table 2 (subsequent table)
As can be seen from Table 2, in comparative example 1, when BaO/(MgO+CaO+SrO+BaO) > 0.12, the liquidus temperature of the glass was more than 1200℃and the corresponding temperature of 200P was more than 1670℃and the difficulty in production of the glass was increased and the density was increased. In comparative example 2, when B 2 O 3 /(SiO 2 +Al 2 O 3 ) At > 0.08, the Young's modulus of the glass decreases, resulting in a decrease in the specific modulus of the glass, and the breakage rate of the sample during production, transportation, and processing increases sharply, while the strain point temperature decreases. In comparative example 3, baO/ZnO is more than 3, the corresponding temperature of the glass 200P is more than 1670 ℃, the production difficulty of the glass is increased, and the corresponding production process requirements cannot be matched. In comparative example 4, no ZnO was added to the glass, and the liquidus temperature of the glass increased, and the risk of crystallization became large, which was unfavorable for production. In comparative example 5, the reduction of the strain point of the glass does not satisfy the use requirement without adding BaO. In comparative example 6, the BaO content was higher than 1.5mol%, and the glass density was higher than 2.6g/cm 3 The specific modulus decreases.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Claims (10)
1. A composition for glass comprising, in mole percent:
65-72mol% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 10-14mol% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3-7mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 2-6mol% MgO;4-7mol% of CaO;2-5mol% of SrO;0.1 to 1.5mol% BaO;
in mole percent, B is more than or equal to 0.03 2 O 3 /(SiO 2 +Al 2 O 3 )≤0.08；
The mol percent is less than or equal to 0.02 and less than or equal to 0.12 of BaO/(MgO+CaO+SrO+BaO).
2. The glass composition according to claim 1, comprising, in mole percent:
67-71mol% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 11-13.5mol% Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3.5 to 5.5mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3.5 to 5.5mol% MgO;4.5 to 6.2mol percent of CaO;2.5 to 4.5mol% SrO;0.2-1mol% BaO;
b is more than or equal to 0.04 and less than or equal to 0mol percent 2 O 3 /(SiO 2 +Al 2 O 3 )≤0.07；
The mol percent is less than or equal to 0.03 and less than or equal to 0.1 of BaO/(MgO+CaO+SrO+BaO).
3. The glass composition according to claim 1, further comprising, in mole percent: 0.1-1mol% ZnO;
in terms of mole percent, baO/ZnO is not less than 1 and not more than 3.
4. The glass composition according to any of claims 1 to 3, further comprising 0 to 1mol% of a fining agent in terms of mole percent;
optionally, the glass composition further comprises 0.05 to 0.2 mole percent of a fining agent, in mole percent.
5. The glass composition according to claim 4, wherein the fining agent comprises at least one of sulfate, nitrate, halide, tin oxide, and stannous oxide;
optionally, the fining agent includes at least one of sodium sulfate, sodium nitrate, potassium nitrate, sodium chloride, strontium chloride, calcium fluoride, tin oxide, and stannous oxide.
6. A method for preparing alkali-free aluminosilicate glass, comprising:
the composition for glass according to any one of claims 1 to 5, which is subjected to a melting treatment, a molding treatment, an annealing treatment and a machining treatment in this order.
7. The method according to claim 6, wherein the conditions of the melt processing include: the melting temperature is 1550-1650 ℃ and the melting time is 4-8h.
8. The method according to claim 6, wherein the annealing conditions include: the annealing temperature is 750-800 ℃, and the annealing time is 1-3h.
9. An alkali-free aluminosilicate glass produced by the production process according to any one of claims 6 to 8.
10. Use of the composition of any one of claims 1-5 or the alkali-free aluminosilicate glass of claim 9 in the field of display panels.
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