WO2018192380A1 - 玻璃用组合物、碱土铝硅酸盐玻璃及其制备方法和应用 - Google Patents

玻璃用组合物、碱土铝硅酸盐玻璃及其制备方法和应用 Download PDF

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WO2018192380A1
WO2018192380A1 PCT/CN2018/082339 CN2018082339W WO2018192380A1 WO 2018192380 A1 WO2018192380 A1 WO 2018192380A1 CN 2018082339 W CN2018082339 W CN 2018082339W WO 2018192380 A1 WO2018192380 A1 WO 2018192380A1
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Prior art keywords
glass
mol
alkaline earth
mgo
bao
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PCT/CN2018/082339
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English (en)
French (fr)
Inventor
张广涛
王俊峰
李刚
田鹏
闫冬成
王丽红
郑权
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东旭科技集团有限公司
东旭集团有限公司
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Application filed by 东旭科技集团有限公司, 东旭集团有限公司 filed Critical 东旭科技集团有限公司
Priority to US16/606,449 priority Critical patent/US11407674B2/en
Priority to JP2019556807A priority patent/JP6921989B2/ja
Priority to KR1020197033900A priority patent/KR102282396B1/ko
Priority to EP18787904.4A priority patent/EP3613710B1/en
Publication of WO2018192380A1 publication Critical patent/WO2018192380A1/zh

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    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • 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
    • 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
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/02—Annealing glass products in a discontinuous way

Definitions

  • the invention relates to the field of glass manufacturing, in particular to a composition for glass, an alkaline earth aluminosilicate glass and a preparation method and application thereof.
  • AMLCD active matrix liquid crystal display
  • OLED organic light emitting diode
  • LTPS TFT- LCD low temperature polysilicon technology
  • Mainstream silicon-based TFTs can be classified into amorphous silicon (a-Si) TFTs, polycrystalline silicon (p-Si) TFTs, and single crystal silicon (SCS) TFTs, of which amorphous silicon (a-Si) TFTs are now mainstream TFT-LCDs.
  • a-Si amorphous silicon
  • p-Si polycrystalline silicon
  • SCS single crystal silicon
  • amorphous silicon (a-Si) TFT technology the processing temperature in the production process can be completed at 300-450 ° C temperature.
  • LTPS polysilicon (p-Si) TFT needs to be processed multiple times at higher temperature during the process.
  • the substrate must not be deformed during multiple high-temperature processing, which puts higher requirements on the performance index of the substrate glass.
  • the strain point is higher than 650 ° C, more preferably higher than 670 ° C, 700 ° C, 720 ° C, so that the substrate has as little heat shrinkage as possible in the panel process.
  • the expansion coefficient of the glass substrate needs to be close to the expansion coefficient of silicon, and the stress and damage are minimized. Therefore, the preferred linear thermal expansion coefficient of the substrate glass is between 28 and 40 ⁇ 10 -7 /°C.
  • the glass used as the display substrate should have a lower melting temperature and molding temperature.
  • a transparent conductive film, an insulating film, a semiconductor (polysilicon, amorphous silicon, etc.) film and a metal film on the surface of the underlying substrate glass by sputtering, chemical vapor deposition (CVD), or the like, and then pass through Photo-etching technology forms various circuits and patterns. If the glass contains alkali metal oxides (Na 2 O, K 2 O, Li 2 O), alkali metal ions diffuse into the deposited semiconductor material during heat treatment, causing damage.
  • alkali metal oxides Na 2 O, K 2 O, Li 2 O
  • the strain point of most silicate glass increases with the increase of the content of the glass forming body and the content of the modifier, but on the one hand, the melting and clarification temperature zone will simultaneously cause high temperature melting and clarification difficulties, resulting in intensified refractory erosion.
  • the liquidus temperature rises in the molding temperature zone, and the probability of occurrence of solid defects such as crystallization is greatly increased, thereby reducing the stability of glass formation, which is not conducive to industrialization and manufacturing, thereby reducing The practicality of the glass frit. Therefore, by improving the composition, the viscosity of the low temperature is increased while ensuring that the high temperature viscosity does not increase greatly, the liquidus temperature is effectively controlled, and the glass formation stability is improved, which is the best breakthrough for improving the strain point.
  • the substrate glass is placed horizontally, and the glass has a certain degree of sagging under the action of its own weight.
  • the degree of sagging is proportional to the density of the glass and inversely proportional to the elastic modulus of the glass.
  • the composition should therefore be designed so that the substrate glass has the lowest possible density and the highest possible modulus of elasticity.
  • the substrate glass should have as high a Vickers hardness as possible.
  • the display panel is developing in the direction of light and thin, ultra-high-definition display, and the panel process technology is developing to higher processing temperature; at the same time, the single-piece glass is processed by process, and the thickness is 0.25mm, 0.2mm, 0.1mm. Even thinner.
  • the way to thin the glass is mainly chemical thinning. Specifically, the glass substrate is etched using hydrofluoric acid or hydrofluoric acid buffer. The thinning principle is as follows:
  • RO+2H + R 2+ +H 2 O (R stands for alkaline earth metal, etc.)
  • the chemical thinning process and the surface quality of the glass substrate after thinning have a certain relationship with the basic glass composition.
  • the "pit" and “bump point” frequently appear in the process of chemical thinning, increasing Production costs.
  • Glass with high chemical stability has better surface quality after thinning, so the development of high chemical stability TFT-LCD substrate glass can reduce production costs such as secondary polishing, improve product quality and yield, for large scale Industrial production has great benefits.
  • k is a constant
  • ⁇ is the density
  • E is the elastic modulus
  • l is the support interval
  • t is the thickness of the glass substrate.
  • ( ⁇ /E) is the reciprocal of the specific modulus.
  • the specific modulus refers to the ratio of the elastic modulus of the material to the density, also known as the "specific modulus of elasticity" or "specific stiffness", which is one of the important requirements of structural design for materials.
  • a higher specific modulus means that the material is lighter in weight at the same stiffness or more rigid at the same mass. It can be seen from the above formula that when l and t are constant, ⁇ becomes smaller and E can increase the sag amount.
  • the substrate glass should have the lowest density and the highest modulus of elasticity, that is, have the largest possible modulus. .
  • the thinned glass has a mechanical strength reduction due to a sharp decrease in thickness, and is more easily deformed. Reducing the density, increasing the specific modulus and strength, and reducing the glass brittleness become a key factor for glass producers.
  • appropriately increasing the refractive index of the glass substrate is advantageous for the light extraction efficiency of the OLED illumination or the display device.
  • a clear gas is used to drive out the gas generated during the glass reaction from the glass melt, and in the case of homogenization and melting, it is necessary to reuse the generated clear gas to increase the bubble diameter. It floats up, thereby taking out the tiny bubbles involved.
  • the glass melt used as the glass substrate for flat panel displays has a high viscosity and needs to be melted at a relatively high temperature.
  • a vitrification reaction is usually caused at 1300 to 1500 ° C, and defoaming and homogenization are performed at a high temperature of 1500 ° C or higher. Therefore, in the clarifying agent, As 2 O 3 capable of generating a clear gas over a wide temperature range (range of 1300-1700 ° C) is widely used.
  • As 2 O 3 is very toxic, and it may pollute the environment and cause health problems in the manufacturing process of glass or the treatment of waste glass, and its use is being limited. Some workers have tried to use cockroach clarification instead of arsenic clarification.
  • the object of the present invention is to overcome the problems of the prior art and to provide a composition for glass, an alkaline earth aluminosilicate glass, a preparation method and application thereof.
  • the present invention provides a composition for glass comprising 68-73 mol% of SiO 2 and 11.5-based on the total moles of the components, based on the oxide. 15 mol% of Al 2 O 3 , 2-6 mol% of MgO, 2.5-7.5 mol% of CaO, 0-3 mol% of SrO, 2-7 mol% of BaO, 0-4 mol% of ZnO, and 0.05-1.5 mol% TiO 2 .
  • the content of each component in the composition is calculated to have a value of greater than 0, more preferably from 0.5 to 50, still more preferably from 0.59 to 33.85, based on the total moles of the components. Further preferably, it is 0.59 to 21.6, and still more preferably 2-13.5, wherein the I value is calculated by the following formula:
  • I [SiO 2 -P 1 ⁇ Al 2 O 3 -P 2 ⁇ BaO-P 3 ⁇ (MgO+ZnO)-P 4 ⁇ (CaO+SrO)-P 5 ⁇ TiO 2 ] ⁇ 100,
  • SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, TiO 2 each represent a mole percentage of the total composition of the component.
  • 0.8 ⁇ (MgO + BaO) / R'O ⁇ 0.34, further preferably, 0.75 ⁇ (MgO + BaO) / R'O ⁇ 0.45, based on the total moles of each component. Further preferably, 0.7 ⁇ (MgO + BaO) / R'O ⁇ 0.5, wherein R'O MgO + CaO + SrO + BaO + ZnO.
  • 0.6 ⁇ Al 2 O 3 /R'O ⁇ 1 in terms of mole percent based on the total moles of each component; further preferably, 0.65 ⁇ Al 2 O 3 / R'O ⁇ 0.95; Further preferably, 0.7 ⁇ Al 2 O 3 /R'O ⁇ 0.85; still more preferably, 0.7 ⁇ Al 2 O 3 /R'O ⁇ 0.8, wherein R'O MgO+CaO+SrO+BaO+ZnO .
  • the content of ZnO is from 0.4 to 3 mol% based on the total moles of the components.
  • the content of Al 2 O 3 is 11.7-12.8 mol% based on the total moles of the components, based on the oxide.
  • the content of SiO 2 is from 68 to 72.2 mol% based on the total moles of the components.
  • the content of MgO is from 2.35 to 5 mol%, based on the total moles of the respective components, based on the oxide.
  • the CaO content is from 3.4 to 7.3 mol%, based on the total moles of the components, based on the oxide.
  • the content of SrO is from 0 to 2.61 mol% based on the total moles of the components.
  • the BaO content is from 2.3 to 5.8 mol%, based on the total moles of the components, based on the oxide.
  • the content of TiO 2 is from 0.05 to 1.2 mol% based on the total moles of the components.
  • the composition further contains a clarifying agent, preferably at least one of a sulfate, a nitrate, a tin oxide, a stannous oxide, a chloride, and a fluoride; and the total number of moles of each component
  • the clarifying agent is contained in an amount of from 0.04 to 0.15 mol%, based on the oxide.
  • the present invention provides a method of preparing an alkaline earth aluminosilicate glass, the method comprising sequentially subjecting the glass composition of the present invention to a melt treatment, a molding treatment, an annealing treatment, and a mechanical processing.
  • the present invention provides an alkaline earth aluminosilicate glass prepared by the process of the present invention.
  • the alkaline earth aluminosilicate glass has a density of less than 2.67 g/cm 3 .
  • the alkaline earth aluminosilicate glass has a Young's modulus greater than 75 GPa.
  • the alkaline earth aluminosilicate glass has a specific modulus greater than 29 GPa/(g/cm 3 ).
  • the alkaline earth aluminosilicate glass has a refractive index n D greater than 1.53.
  • the alkaline earth aluminosilicate glass has a coefficient of thermal expansion of less than 39 x 10 -7 / ° C at 50-350 ° C.
  • the alkaline earth aluminosilicate glass corresponding time-35000P forming temperature T w is lower than a viscosity of 1320 °C.
  • the alkaline earth aluminosilicate glass viscosity lower than 1650 deg.] C corresponding to the melting temperature when the 200P T m.
  • the alkaline earth aluminosilicate glass liquidus temperature T 1 lower than 1220 °C.
  • the alkaline earth aluminosilicate glass has a strain point T st of 750 ° C or higher.
  • the alkaline earth aluminosilicate glass has an annealing point T a of 790 ° C or higher.
  • the alkaline earth aluminosilicate glass has a glass formation stability factor D of less than 1.0, further preferably from 0.5 to 0.95, still more preferably from 0.59 to 0.84, still more preferably from 0.62 to 0.74, wherein the D value is lower.
  • D glass formation stability factor
  • T m , T 1 , and T a represent a corresponding melting temperature, a glass liquidus temperature, and a glass annealing temperature, respectively, when the glass viscosity is 200P. It should be understood by those skilled in the art that the smaller the D value, the stronger the glass resisting crystallization ability, the higher the glass formation stability, and the lower the manufacturing difficulty; the higher the D value, the weaker the glass resisting crystallization ability, the glass The lower the formation stability, the more difficult it is to manufacture.
  • the alkaline earth aluminosilicate glass has a surface tension of less than 350 mN/m at 1200 °C.
  • the alkaline earth aluminosilicate glass has a Vickers hardness of greater than 6.4 GPa.
  • the number of bubbles having a bubble diameter > 0.1 mm per kg of glass substrate is not visible.
  • the present invention provides the use of the glass composition or alkaline earth aluminosilicate glass of the present invention in the preparation of display devices and/or solar cells.
  • a substrate glass substrate material for preparing a flat panel display product and/or a glass film layer material for screen surface protection a substrate glass substrate material for a flexible display product, and/or a surface mount glass material and/or a glass film for screen surface protection.
  • the glass composition of the present invention belongs to an alkaline earth aluminosilicate glass system and is an environmentally friendly and more perfect high heat resistant glass substrate component design, providing a clarifying agent even without using As 2 O 3 and/or Sb 2 O 3 does not have a formulation of a glass substrate which is a surface defect, and an alkali-free glass is designed.
  • the glass substrate prepared by the formulation meets environmental requirements and does not contain As 2 O 3 or Sb 2 O.
  • the present invention has the following beneficial effects:
  • the present invention is environmentally friendly and does not contain any toxic substances.
  • the clarifying agent uses stannous oxide SnO, which is a readily available substance and is known to have no harmful properties, and is used alone as When the glass clarifier has a high temperature range for generating a clarified gas, it is suitable for the elimination of such glass bubbles.
  • the glass composition contains a specific content of SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO and TiO 2 to control SiO 2 +Al 2 O 3 >80mol%, I value>0, 0.8 ⁇ (MgO+BaO)/R'O ⁇ 0.34, 0.6 ⁇ Al 2 O 3 /R'O ⁇ 1, the prepared glass can have a high strain point at the same time Higher Young's modulus, higher specific modulus, higher Vickers hardness, higher chemical stability, higher glass forming stability, lower molding temperature, lower melting temperature and Excellent characteristics such as lower liquidus temperature, specifically, the obtained alkaline earth aluminosilicate glass has a density of less than 2.67 g/cm 3 , a Young's modulus of more than 75 GPa, and a specific modulus of more than 29 GPa/(g/cm 3 ).
  • the thermal expansion coefficient of 50-350 ° C is less than 39 ⁇ 10 -7 / ° C
  • the refractive index n D is greater than 1.53
  • the corresponding molding temperature T w is lower than 1320 ° C when the viscosity is 35000 P
  • the corresponding melting temperature T m is low when the viscosity is 200 P at 1650 °C
  • liquidus temperature T 1 is less than 1220 °C
  • strain point T st above 750 °C annealing at T a point above 790 °C
  • a surface tension of less than 350mN / m, Vickers hardness greater than 6.4GPa, per kilogram of the glass substrate bulb diameter> 0.1mm number of bubbles are not visible.
  • composition of the composition of the present invention contains a high amount of SiO 2 and Al 2 O 3 combined, and the component does not contain B 2 O 3 , a high strain point is ensured, and a certain proportion of MgO+CaO is matched.
  • +SrO+BaO+ZnO+TiO 2 can effectively reduce the melting temperature, improve the stability of glass formation, reduce the difficulty of glass manufacturing, and bring a large space for the improvement of production line yield, while the production cost of fuel and electricity is reduced.
  • the present invention provides a composition for glass comprising 68-73 mol% of SiO 2 and 11.5-15 mol% of Al 2 based on the total moles of the components, based on the oxide.
  • O 3 2-6 mol% of MgO, 2.5-7.5 mol% of CaO, 0-3 mol% of SrO, 2-7 mol% of BaO, 0-4 mol% of ZnO, and 0.05-1.5 mol% of TiO 2 .
  • alkali-free means that the glass composition or glass does not contain an alkali metal (i.e., six alkali metal elements of Group IA of the Periodic Table of the Elements).
  • SiO 2 +Al 2 O 3 is preferably >80 mol% based on the total moles of the components, based on the oxide.
  • the content of each component in the composition is calculated to satisfy the I value of more than 0, preferably 0.5 to 50, based on the total number of moles of each component in the composition. It is preferably from 0.59 to 33.85, still more preferably from 0.59 to 33.35, still more preferably from 0.59 to 21.6, still more preferably from 2 to 13.5, most preferably from 3.65 to 1.16, wherein the value of I is calculated by the following formula:
  • I [SiO 2 -P 1 ⁇ Al 2 O 3 -P 2 ⁇ BaO-P 3 ⁇ (MgO+ZnO)-P 4 ⁇ (CaO+SrO)-P 5 ⁇ TiO 2 ] ⁇ 100,
  • SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, TiO 2 each represent a mole percentage of the total composition of the component.
  • composition of the present invention preferably 0.8 ⁇ (MgO + BaO) / R'O ⁇ 0.34, further preferably 0.75 ⁇ (MgO + ) based on the total moles of the respective components.
  • BaO) / R'O ⁇ 0.45, still more preferably, 0.7 ⁇ (MgO + BaO) / R'O ⁇ 0.5, wherein R'O MgO + CaO + SrO + BaO + ZnO.
  • SiO 2 is a glass forming body. If the content is too low, it is not conducive to the enhancement of chemical corrosion resistance, the expansion coefficient is too high, and the glass is easily devitrified; increasing the SiO 2 content contributes to glass weight reduction and thermal expansion. The coefficient is reduced, the strain point is increased, the chemical resistance is increased, but the high temperature viscosity is increased, which is not conducive to melting, and the general kiln is difficult to satisfy. Therefore, the content of SiO 2 is 68-73%. Therefore, it is considered that the content of SiO 2 is from 68 to 73 mol%, preferably from 68 to 72.2 mol%, based on the total moles of the respective components, based on the oxide.
  • Al 2 O 3 is used to increase the strength of the glass structure. If the content is less than 11.5 mol%, the heat resistance of the glass is difficult to be improved, and it is also easily corroded by external moisture and chemical agents.
  • the high content of Al 2 O 3 contributes to the increase of the strain point and mechanical strength of the glass. However, when the content is too high, the glass is prone to crystallization and the glass is difficult to be melted. Therefore, considering the total molar amount of each component Based on the number, the content of Al 2 O 3 is from 11.5 to 15 mol%, preferably from 11.7-12.8 mol%, based on the oxide.
  • MgO has a characteristic of greatly increasing the Young's modulus and hardness of the glass, lowering the viscosity at a high temperature, and making the glass easy to melt.
  • the network exosome Mg 2+ with large electric field intensity is introduced, which tends to cause local accumulation in the structure and increase the short-range order.
  • a large amount of the intermediate oxide Al 2 O 3 is introduced , and when it exists in the [AlO 4 ] state, since these polyhedrons are negatively charged, part of the network external cation is attracted, so that the degree of accumulation of glass and the ability of crystallization are obtained.
  • MgO metal-oxide-semiconductor
  • the introduction of MgO can reconnect the broken silicon tetrahedron and reduce the crystallization ability of the glass. Therefore, pay attention to the ratio of the other components when adding MgO.
  • the presence of MgO results in a lower coefficient of expansion and density, higher chemical resistance, strain point and modulus of elasticity relative to other alkaline earth metal oxides. If MgO is more than 6 mol%, the glass resistance will be deteriorated, and at the same time, the glass is easily devitrified, and the too low MgO content is unfavorable in comparison with the modulus. Therefore, it is considered that the content of MgO is from 2 to 6 mol%, preferably from 2.35 to 5 mol%, based on the total moles of the respective components, based on the oxide.
  • CaO is used to promote melting of glass and to adjust glass moldability. If the calcium oxide content is less than 2.5 mol%, the viscosity of the glass is not easily lowered, and when the content is too large, the glass is liable to be devitrified, and the coefficient of thermal expansion is also greatly increased, which is disadvantageous for subsequent processes. Therefore, it is considered that the content of CaO is from 2.5 to 7.5 mol%, preferably from 3.4 to 7.3 mol%, based on the total moles of the respective components, based on the oxide.
  • SrO is used as a fluxing agent and a component for preventing crystallization of the glass. If the content is too large, the glass density is too high, resulting in a molar excess of the product. Therefore, the content of SrO is from 0 to 3 mol%, preferably from 0 to 2.61 mol%, based on the total moles of the respective components.
  • the content of BaO is from 2 to 7 mol%, preferably from 2.3 to 5.8 mol%, based on the total moles of the respective components, based on the oxide.
  • the divalent metal oxide can be classified into two types according to its influence on the position and the property of the periodic table: one type is an alkaline earth metal oxide located in the main group, and the ion R 2+ has 8 The electronic structure; the second type is located in the subgroup of the periodic table (such as ZnO, CdO, etc.), and its ion R 2+ has 18 outer electronic structures, and the structural state of the two in the glass is different from the influence on the glass properties.
  • ZnO can reduce the high temperature viscosity of the glass (such as 1500 ° C), which is beneficial to eliminate bubbles; at the same time, below the softening point, it has the effect of improving the strength, hardness, increasing the chemical resistance of the glass and reducing the thermal expansion coefficient of the glass.
  • the addition of an appropriate amount of ZnO contributes to inhibition of crystallization and lowers the crystallization temperature.
  • ZnO is introduced into the glass as an extracellular body in the alkali-free glass. It is generally in the form of [ZnO 4 ] at high temperatures, and is more loose than the [ZnO 6 ] glass structure, and is the same as the glass without ZnO.
  • the ZnO-containing glass Compared with the high temperature state, the ZnO-containing glass has a smaller viscosity, a higher atomic motion velocity, and cannot form a crystal nucleus. It is necessary to further lower the temperature to favor the formation of the crystal nucleus, thereby lowering the crystallization maximum temperature of the glass. Too much ZnO content will greatly reduce the strain point of the glass. Therefore, it is considered that the content of ZnO is from 0 to 4 mol%, preferably from 0.4 to 3 mol%, based on the total moles of the respective components, based on the oxide.
  • TiO 2 is used to promote the melting of glass and to improve the stability of glass formation, and can effectively increase the refractive index of the glass and reduce the expansion coefficient.
  • the content of TiO 2 is from 0.05 to 1.5 mol%, preferably from 0.05 to 1.2 mol%, based on the total moles of the respective components, based on the oxide.
  • the composition further contains a clarifying agent, and the clarifying agent is preferably at least one of a sulfate, a nitrate, a tin oxide, a stannous oxide, a chloride, and a fluoride; wherein, in the glass component, oxidation may preferably be added.
  • Stannous SnO acts as a fining agent or defoaming agent for glass melting to increase the melting mole of glass. If the content is too large, the glass substrate is devitrified. Therefore, the content of the clarifying agent is preferably 0.04 to 0.15 mol% based on the total moles of the respective components, based on the oxide.
  • the composition containing SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO and TiO 2 means that the composition contains a Si-containing compound.
  • Al-containing compound, Mg-containing compound, Ca-containing compound, Sr-containing compound, Ba-containing compound, Zn-containing compound, and Ti-containing compound such as carbonate, nitrate, sulfate, phosphate, basic type containing each of the foregoing elements Carbonate, oxide, etc., and the content of each of the aforementioned components is based on the oxide of each element, specific carbonate, nitrate, sulfate, phosphate, basic carbonate of each element
  • oxides is well known to those skilled in the art and will not be described herein.
  • the reason why the glass has excellent comprehensive properties is mainly attributed to the mutual cooperation between the components in the composition, especially SiO 2 .
  • the complexing action between Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO and TiO 2 is more particularly the interaction between the components of the aforementioned specific content.
  • the present invention provides an alkaline earth aluminosilicate glass comprising 68-73 mol% SiO 2 , 11.5-15 mol % Al 2 O 3 , 2 based on the total moles of each component. -6 mol% of MgO, 2.5-7.5 mol% of CaO, 0-3 mol% of SrO, 2-7 mol% of BaO, 0-4 mol% of ZnO, and 0.05-1.5 mol% of TiO 2 .
  • SiO 2 + Al 2 O 3 is > 80 mol%.
  • the content of each component in the composition is calculated to have a molar ratio of more than 0, more preferably 0.5 to 50, based on the total number of moles of each component in the composition. It is still further preferably 0.59 to 33.85, still more preferably 0.59 to 21.6, still more preferably 2.07-13.29, wherein the I value is calculated by the following formula:
  • I [SiO 2 -P 1 ⁇ Al 2 O 3 -P 2 ⁇ BaO-P 3 ⁇ (MgO+ZnO)-P 4 ⁇ (CaO+SrO)-P 5 ⁇ TiO 2 ] ⁇ 100,
  • SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, TiO 2 each represent a mole percentage of the component in the total composition.
  • the content of ZnO is 0.4 to 3 mol% based on the total moles of the respective components, based on the oxide.
  • the content of Al 2 O 3 is 11.7-12.8 mol% based on the total moles of the respective components, based on the oxide.
  • the content of SiO 2 is 68-72.2 mol% based on the total moles of the respective components, based on the oxide.
  • the content of MgO is from 2.35 to 5 mol% based on the total moles of the respective components, based on the oxide.
  • the content of CaO is 3.4 to 7.3 mol% based on the total moles of the respective components, based on the oxide.
  • the content of SrO is from 0 to 2.61 mol% based on the total moles of the respective components, based on the oxide.
  • the alkaline earth aluminosilicate glass has a BaO content of 2.3 to 5.8 mol% based on the total moles of the respective components, based on the oxide.
  • the content of TiO 2 is from 0.05 to 1.2 mol% based on the total moles of the respective components, based on the oxide.
  • the content of the fining agent is from 0.04 to 0.15 mol%.
  • the present invention provides a method of preparing an alkaline earth aluminosilicate glass, which comprises subjecting the glass composition of the present invention to a melt treatment, a molding treatment, an annealing treatment, and a mechanical treatment in sequence.
  • the conditions of the melt treatment include a temperature lower than 1650 ° C and a time greater than 1 h.
  • a person skilled in the art can determine the specific melting temperature and melting time according to the actual situation, which is well known to those skilled in the art and will not be described herein.
  • the conditions of the annealing treatment include: the temperature is above 790 ° C, and the time is greater than 0.1 h.
  • the conditions of the annealing treatment include: the temperature is above 790 ° C, and the time is greater than 0.1 h.
  • the mechanical processing is not particularly limited, and various mechanical processing methods which are common in the art can be used, for example, the products obtained by annealing treatment can be cut, ground, polished, and the like.
  • the raw materials of the composition including the corresponding mole percentage components of the respective glass substrates are uniformly stirred and mixed, and then the mixed raw materials are melt processed, and the bubbles are stirred and discharged by a platinum rod. And then lowering the temperature to the molding temperature range of the glass substrate required for molding, and forming the thickness of the glass substrate required for the flat display by the annealing principle, and then performing a simple cold working on the formed glass substrate, and finally on the glass substrate. Basic physical characteristics are tested to become qualified products.
  • the present invention provides an alkaline earth aluminosilicate glass prepared by the above method.
  • the alkaline earth aluminosilicate glass of the present invention has a density of less than 2.67 g/cm 3 .
  • the alkaline earth aluminosilicate glass has a Young's modulus greater than 75 GPa.
  • the alkaline earth aluminosilicate glass has a specific modulus greater than 29 GPa/(g/cm 3 ).
  • the alkaline earth aluminosilicate glass has a coefficient of thermal expansion of less than 39 x 10 -7 / ° C at 50-350 ° C.
  • the alkaline earth aluminosilicate glass has a refractive index n D of more than 1.53, more preferably from 1.534 to 1.545.
  • the alkaline earth aluminosilicate glass corresponding time-35000P forming temperature T w is lower than a viscosity of 1320 °C.
  • the alkaline earth aluminosilicate glass viscosity lower than 1650 deg.] C corresponding to the melting temperature when the 200P T m.
  • the alkaline earth aluminosilicate glass has a liquidus temperature T 1 of less than 1220 ° C, more preferably from 1120-1180 ° C.
  • the alkaline earth aluminosilicate glass has a strain point T st of 750 ° C or higher.
  • the alkaline earth aluminosilicate glass has an annealing point T a of 790 ° C or higher.
  • the alkaline earth aluminosilicate glass has a glass formation stability factor D of less than 1.0, more preferably from 0.5 to 0.95, still more preferably from 0.59 to 0.84, still more preferably from 0.59 to 0.74, still more preferably from 0.62. -0.74, where the D value is calculated by:
  • T m , T 1 , and T a represent the melting temperature at a glass viscosity of 200 poise, the liquidus temperature of the glass, and the annealing temperature of the glass, respectively.
  • the alkaline earth aluminosilicate glass has a surface tension of less than 350 mN/m at 1200 °C.
  • the alkaline earth aluminosilicate glass has a Vickers hardness of greater than 6.4 GPa.
  • the number of bubbles having a bubble diameter > 0.1 mm per kg of glass substrate is not visible.
  • the present invention provides the use of the glass composition or alkaline earth aluminosilicate glass of the present invention in the preparation of display devices and/or solar cells.
  • a substrate glass substrate material for preparing a flat panel display product and/or a glass film layer material for screen surface protection a substrate glass substrate material for a flexible display product, and/or a surface mount glass material and/or a glass film for screen surface protection.
  • the glass density was measured in units of g/cm 3 with reference to ASTM C-693.
  • the coefficient of thermal expansion of the glass at 50-350 ° C was measured using a horizontal dilatometer in accordance with ASTM E-228, in units of 10 -7 /°C.
  • the Young's modulus of the glass was measured using a material mechanics tester in accordance with ASTM C-623, in units of GPa.
  • the Vickers hardness of the glass was measured using a Vickers hardness tester in accordance with ASTM E-384, in units of GPa.
  • the glass annealing point and strain point were measured using an annealing point strain point tester in accordance with ASTM C-336 in °C.
  • the glass high temperature viscosity-temperature curve was measured using a rotary high-temperature viscometer according to ASTM C-965, wherein the melting temperature T m at a viscosity of 200 P is expressed in ° C; and the molding temperature T w corresponding to a viscosity of 35000 P is in ° C.
  • the glass crystallization upper limit temperature (liquidus temperature) was measured by a ladder furnace method in accordance with ASTM C-829.
  • the surface tension at 1200 ° C was measured using a high temperature surface tension meter in mN/m.
  • the refractive index n D at a wavelength of 587.6 nm was measured at room temperature using a WAY-2S Abbe digital refractometer.
  • the number of bubbles with a bubble diameter of >0.1 mm per kg of glass substrate refers to the number of bubbles with a bubble diameter of >0.1 mm per kg of alkaline earth aluminosilicate glass substrate.
  • the method is as follows: weighing the sample glass with an electronic balance with an accuracy of 0.01 g The number of bubbles was counted using an optical microscope, and the number of bubbles having a bubble diameter of >0.1 mm per kg of glass was calculated.
  • the components were weighed as shown in Table 1-4, mixed, and the mixture was poured into a platinum crucible, and then heated in a 1620 ° C resistance furnace for 4 hours, and stirred with a platinum rod to discharge air bubbles.
  • the molten glass liquid was poured into a stainless steel cast iron grinder, formed into a predetermined block glass product, and then the glass product was annealed in an annealing furnace for 2 hours, and the power was turned off and cooled to 25 ° C with the furnace.
  • the glass product is cut, ground, polished, and then cleaned and dried with deionized water to obtain a finished glass product that meets the test requirements.
  • the various properties of each glass finished product were measured, and the results are shown in Table 1-4, respectively.
  • the present invention utilizes a glass prepared from a glass composition containing a specific content of SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, and TiO 2 , especially when In the glass composition, in terms of mole percent, SiO 2 + Al 2 O 3 > 80 mol%, I value > 0, 0.8 ⁇ (MgO + BaO) / R'O ⁇ 0.34, 0.6 ⁇ Al 2 O 3 / R' When O ⁇ 1, the prepared glass can have higher strain point, higher Young's modulus, higher specific modulus, higher Vickers hardness, higher chemical stability and higher.
  • Excellent properties such as glass formation stability, lower molding temperature, lower melting temperature and lower liquidus temperature.
  • the density of the obtained alkaline earth aluminosilicate glass is less than 2.67 g/cm 3 , Yang
  • the modulus is greater than 75 GPa, the specific modulus is greater than 29 GPa/(g/cm 3 ), the thermal expansion coefficient at 50-350 ° C is less than 39 ⁇ 10 -7 /° C, the refractive index n D is greater than 1.53, and the corresponding molding temperature is 35000 P.
  • T w is lower than 1320 °C, when the viscosity of the corresponding 200P melting temperature T m lower than 1650 °C, liquidus temperature T 1 is less than 1220 °C, strain point T st above 750 °C, annealing T a surface above 790 °C, glass forming stability factor D is smaller than the tension of less than 1.0,1200 °C 350mN / m, Vickers hardness greater than 6.4GPa, per kilogram of the glass substrate bulb diameter> 0.1mm number of bubbles are not visible.

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Abstract

一种玻璃用组合物、碱土铝硅酸盐玻璃及其制备方法和应用。以各组分的总摩尔数为基准，以氧化物计，该组合物含有68‑73mol％的SiO 2、11.5‑15mol％的Al 2O 3、2‑6mol％的MgO、2.5‑7.5mol％的CaO、0‑3mol％的SrO、2‑7mol％的BaO、0‑4mol％的ZnO和0.05‑1.5mol％的TiO 2。玻璃具有较高的应变点、杨氏模量、比模数、维氏硬度、化学稳定性、折射率和玻璃形成稳定性，具有较低的成型温度、熔化温度、热膨胀系数、表面张力和密度，且玻璃制造难度低。

Description

玻璃用组合物、碱土铝硅酸盐玻璃及其制备方法和应用 技术领域
本发明涉及玻璃制造领域，具体涉及一种玻璃用组合物、碱土铝硅酸盐玻璃及其制备方法和应用。
背景技术
随着光电行业的快速发展，对各种显示器件的需求正在不断增长，比如有源矩阵液晶显示(AMLCD)、有机发光二极管(OLED)以及应用低温多晶硅技术的有源矩阵液晶显示(LTPS TFT-LCD)器件，这些显示器件都基于使用薄膜半导体材料生产薄膜晶体管(TFT)技术。主流的硅基TFT可分为非晶硅(a-Si)TFT、多晶硅(p-Si)TFT和单晶硅(SCS)TFT，其中非晶硅(a-Si)TFT为现在主流TFT-LCD应用的技术，非晶硅(a-Si)TFT技术，在生产制程中的处理温度可以在300-450℃温度下完成。LTPS多晶硅(p-Si)TFT在制程过程中需要在较高温度下多次处理，基板必须在多次高温处理过程中不能发生变形，这就对基板玻璃性能指标提出更高的要求，优选的应变点高于650℃，更优选的是高于670℃、700℃、720℃，以使基板在面板制程中具有尽量小的热收缩。同时玻璃基板的膨胀系数需要与硅的膨胀系数相近，尽可能减小应力和破坏，因此基板玻璃优选的线性热膨胀系数在28～40×10 -7/℃之间。为了便于生产，降低生产成本，作为显示器基板用的玻璃应该具有较低的熔化温度和成型温度。
用于平面显示的玻璃基板，需要通过溅射、化学气相沉积(CVD)等技术在底层基板玻璃表面形成透明导电膜、绝缘膜、半导体(多晶硅、无定形硅等)膜及金属膜，然后通过光蚀刻(Photo-etching)技术形成各种电路和图形，如果玻璃含有碱金属氧化物(Na 2O、K 2O、Li 2O)，在热处理过程中碱金属离子扩散进入沉积半导体材料，损害半导体膜特性，因此，玻璃应不含碱金属氧化物，首选的是以SiO 2、Al 2O 3、碱土金属氧化物RO(RO＝Mg、Ca、Sr、Ba)等为主成分的碱土铝硅酸盐玻璃。
大多数硅酸盐玻璃的应变点随着玻璃形成体含量的增加和改性剂含量的减少而增高，但是一方面在熔融澄清温度区会同时造成高温熔化和澄清困难，造成耐火材料侵蚀加剧，增加能耗和生产成本；另一方面在成型温度区会造成液相线温度升高，析晶等固态缺陷出现的几率大大增加，由此降低玻璃形成稳定性，不利于工业化推广制造，从而降低玻璃料方的实用性。因此，通过组分改良，使得低温粘度增大的同时还要保证高温 粘度不会出现大的提升、液相线温度得到有效控制、玻璃形成稳定性得以提高才是提高应变点的最佳突破口。
在高铝无碱硅酸盐玻璃体系中，添加氧化硼B 2O 3可以带来良好的助熔效果，同时有利于提升玻璃耐化性。但是在低温粘度区，B 2O 3却使得玻璃应变点显著降低，如何同时提高玻璃基板的耐化性和应变点温度成为长期困扰本领域技术人员的一道难题。
在玻璃基板的加工过程中，基板玻璃是水平放置的，玻璃在自重作用下，有一定程度的下垂，下垂的程度与玻璃的密度成正比、与玻璃的弹性模量成反比。随着基板制造向着大尺寸、薄型化方向的发展，制造中玻璃板的下垂必须引起重视。因此应设计组成，使基板玻璃具有尽可能低的密度和尽可能高的弹性模量。另一方面，为了减小玻璃基板在运输、传送、制造、使用过程中的表面擦划伤，基板玻璃应具有尽可能高的维氏硬度。
随着智能手机与平板电脑的普及，开启了智能移动的时代。以往的手机局限在通讯功能，但目前包括智能手机与平板电脑的智能设备的性能已与笔记本接近，使得让人们凭借无线通信的方便性无时无刻不在执行及享受较高层次的商务及娱乐活动。在这样的趋势下，对显示器性能要求也不断提高，尤其是对移动智能设备的画面质量、在户外的可视性能要求也正在提升，同时为了减轻手持式设备的使用负担，重量变轻、厚度变薄成为不可避免的大趋势。在这种发展潮流引导下，显示面板正在向轻薄化、超高清显示的方向发展，面板制程工艺向更高处理温度发展；同时单片玻璃经过工艺处理，厚度达到0.25mm、0.2mm、0.1mm甚至更薄。使玻璃变薄的方式目前主要是化学减薄，具体的说，使用氢氟酸或氢氟酸缓冲液对玻璃基板进行腐蚀，其薄化原理如下：
主要化学反应：4HF+SiO 2＝SiF 4+2H 2O
次要化学反应：RO+2H +＝R 2++H 2O(R代表碱土金属等)
化学减薄工艺及玻璃基板减薄后的表面质量与基础玻璃组成有一定关系，现有TFT-LCD基板玻璃在化学减薄过程中频繁出现“凹坑”、“凹凸点”等不良欠点，增加了生产成本。具有高的化学稳定性的玻璃在减薄后具有更好的表面质量，因此研发高化学稳定性的TFT-LCD基板玻璃，可以减少二次抛光等生产成本，提升产品品质和良品率，对于大型工业化生产有较大益处。
随着轻薄化趋势的发展，在G5代、G6代、G7代、G8代等更高世代玻璃基板生产中，水平放置的玻璃基板由于自重产生的下垂、翘曲成了重要研究课题。对玻璃基板生产者而言，玻璃板材成型后要经过退火、切割、加工、检验、清洗等多种环节，大尺寸玻璃基板的下垂将影响在加工点之间运送玻璃的箱体中装入、取出和分隔的能力。对面 板制造商来讲，类似的问题同样存在。较大的垂度或翘曲会导致碎片率提高以及CF制程工艺报警，严重影响产品良率。如果在两端支撑基板两边时，玻璃基板的最大下垂量(S)可以下述公式(I)表示：
Figure PCTCN2018082339-appb-000001
k为常数，ρ为密度，E为弹性模量，l为支撑间隔，t为玻璃基板厚度。其中，(ρ/E)为比模数的倒数。比模数是指材料弹性模量与密度的比值，亦称为“比弹性模量”或“比刚度”，是结构设计对材料的重要要求之一。比模数较高说明相同刚度下材料重量更轻，或相同质量下刚度更大。由上式可见，当l、t一定时，ρ变小E加大后可以降低下垂量，因此应该使基板玻璃具尽量低的密度和尽量高的弹性模量，即具有尽量大的比模数。减薄后的玻璃由于厚度的急剧减小而出现机械强度降低，更容易变形。降低密度、增大比模数及强度，降低玻璃脆性成为玻璃生产者需要重点考虑的因素。
同时，在不显著增加制造成本的前提下，适当提高玻璃基板的折射率，有利于OLED照明或显示器件的光取出效率。
为了得到无泡的无碱玻璃，利用澄清气体，从玻璃熔液中驱逐玻璃反应时产生的气体，另外在均质化熔化时，需要再次利用产生的澄清气体，增大泡层径，使其上浮，由此取出参与的微小泡。
可是，用作平板显示器用玻璃基板的玻璃熔液的粘度高，需用较高的温度熔化。在此种的玻璃基板中，通常在1300-1500℃引起玻璃化反应，在1500℃以上的高温下脱泡、均质化。因此，在澄清剂中，广泛使用能够在宽的温度范围(1300-1700℃范围)产生澄清气体的As 2O 3。但是，As 2O 3的毒性非常强，在玻璃的制造工序或废玻璃的处理时，有可能污染环境和带来健康的问题，其使用正在受到限制。有工作者曾尝试用锑澄清来替代砷澄清。然而，锑本身存在引起环境和健康方面的问题。虽然Sb 2O 3的毒性不像As 2O 3那样高，但是Sb 2O 3仍然是有毒的。而且与砷相比，锑产生澄清气体的温度较低，除去此种玻璃气泡的有效性较低。
发明内容
本发明的目的是为了克服现有技术存在的述问题，提供一种玻璃用组合物、碱土铝硅酸盐玻璃及其制备方法和应用。
为了实现上述目的，第一方面，本发明提供了一种玻璃用组合物，以各组分的总 摩尔数为基准，以氧化物计，该组合物含有68-73mol％的SiO 2、11.5-15mol％的Al 2O 3、2-6mol％的MgO、2.5-7.5mol％的CaO、0-3mol％的SrO、2-7mol％的BaO、0-4mol％的ZnO和0.05-1.5mol％的TiO 2。
优选地，以各组分的总摩尔数为基准，以氧化物计，SiO 2+Al 2O 3＞80mol％。
优选地，以各组分的总摩尔数为基准，所述组合物中各组分的含量按摩尔百分比计算满足I值大于0，进一步优选为0.5-50，更进一步优选为0.59-33.85，再进一步优选为0.59-21.6，再更进一步优选为2-13.5，其中，I值由下式计算得出：
I＝[SiO 2-P 1×Al 2O 3-P 2×BaO-P 3×(MgO+ZnO)-P 4×(CaO+SrO)-P 5×TiO 2]×100，
其中，P 1＝4，P 2＝-2，P 3＝3.5，P 4＝3，P 5＝-25，
SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO、TiO 2各自代表该组分占总组成的摩尔百分比。
优选地，以各组分的总摩尔数为基准，以摩尔百分数计，0.8≥(MgO+BaO)/R’O≥0.34，进一步优选地，0.75≥(MgO+BaO)/R’O≥0.45，更进一步优选地，0.7≥(MgO+BaO)/R’O≥0.5，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
优选地，以各组分的总摩尔数为基准，以摩尔百分数计，0.6≤Al 2O 3/R’O≤1；进一步优选地，0.65≤Al 2O 3/R’O≤0.95；更进一步优选地，0.7≤Al 2O 3/R’O≤0.85；再进一步优选地，0.7＜Al 2O 3/R’O＜0.8，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
优选地，以各组分的总摩尔数为基准，以氧化物计，ZnO的含量为0.4-3mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，Al 2O 3的含量为11.7-12.8mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，SiO 2的含量为68-72.2mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，MgO的含量为2.35-5mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，CaO的含量为3.4-7.3mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，SrO的含量为0-2.61mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，BaO的含量为2.3-5.8mol％。
优选地，以各组分的总摩尔数为基准，以氧化物计，TiO 2的含量为0.05-1.2mol％。
优选地，所述组合物还含有澄清剂，所述澄清剂优选为硫酸盐、硝酸盐、氧化锡、氧化亚锡、氯化物和氟化物中的至少一种；以各组分的总摩尔数为基准，以氧化物计，所述澄清剂的含量为0.04-0.15mol％。
第二方面，本发明提供了一种制备碱土铝硅酸盐玻璃的方法，该方法包括将本发明所述的玻璃用组合物依次进行熔融处理、成型处理、退火处理和机械加工处理。
第三方面，本发明提供了本发明所述的方法制备得到的碱土铝硅酸盐玻璃。
优选地，所述碱土铝硅酸盐玻璃的密度小于2.67g/cm 3。
优选地，所述碱土铝硅酸盐玻璃的杨氏模量大于75GPa。
优选地，所述碱土铝硅酸盐玻璃的比模数大于29GPa/(g/cm 3)。
优选地，所述碱土铝硅酸盐玻璃的折射率n D大于1.53。
优选地，所述碱土铝硅酸盐玻璃的50-350℃的热膨胀系数小于39×10 -7/℃。
优选地，所述碱土铝硅酸盐玻璃在粘度为35000P时对应的成型温度T w低于1320℃。
优选地，所述碱土铝硅酸盐玻璃在粘度为200P时对应的熔化温度T m低于1650℃。
优选地，所述碱土铝硅酸盐玻璃的液相线温度T 1低于1220℃。
优选地，所述碱土铝硅酸盐玻璃的应变点T st在750℃以上。
优选地，所述碱土铝硅酸盐玻璃的退火点T a在790℃以上。
优选地，所述碱土铝硅酸盐玻璃的玻璃形成稳定性因子D小于1.0，进一步优选为0.5-0.95，更进一步优选为0.59-0.84，再进一步优选为0.62-0.74，其中，D值由下式计算得到：
D＝(T 1-T a)/(T m-T 1)，
其中，T m、T 1、T a分别代表玻璃粘度为200P时对应的熔化温度、玻璃液相线温度、玻璃退火点温度。本领域技术人员应该理解的是，D值越小，表示玻璃抵抗析晶能力越强，玻璃形成稳定性越高，制造难度越低；D值越高，表示玻璃抵抗析晶能力越弱，玻璃形成稳定性越低，制造难度越大。
优选地，所述碱土铝硅酸盐玻璃的1200℃的表面张力小于350mN/m。
优选地，所述碱土铝硅酸盐玻璃的维氏硬度大于6.4GPa。
优选地，每公斤玻璃基板中泡径＞0.1mm的气泡数目不可见。
第四方面，本发明提供了本发明所述的玻璃用组合物或碱土铝硅酸盐玻璃在制备显示器件和/或太阳能电池中的应用。优选为在制备平板显示产品的衬底玻璃基板材料和/或屏幕表面保护用玻璃膜层材料、柔性显示产品的衬底玻璃基板材料和/或表面封装玻璃材料和/或屏幕表面保护用玻璃膜层材料、柔性太阳能电池的衬底玻璃基板材料中的应用。
本发明的玻璃用组合物，属于碱土铝硅酸盐玻璃体系，为一种环境友好型、性能更完美的高耐热性玻璃基板的组分设计，提供了一种澄清剂即使不使用As 2O 3和/或 Sb 2O 3也不存在成为表面缺陷的玻璃基板的配方，设计得到了无碱玻璃，利用该配方制得的玻璃基板符合环保要求，不含As 2O 3、Sb 2O 3及其化合物，也不含碱金属、稀土氧化物和B 2O 3，具有较高的应变点、较高的杨氏模量、较高的比模数、较高的维氏硬度、较高的化学稳定性、较高的折射率、较高的玻璃形成稳定性、较低的成型温度、较低的熔化温度、较低的热膨胀系数、较低的表面张力和较低的密度，符合平板显示行业发展趋势，适合于融合下拉法、浮法等多种成型方式生产制造，制备得到的玻璃可广泛适用于光电显示、照明、光伏器件等行业。
具体地，本发明具有如下有益效果：
(1)本发明具有环境友好性，不含任何有毒物质，根据一种优选的实施方式，澄清剂使用氧化亚锡SnO，SnO是容易得到的物质，且已知无有害性质，单独使用其作为玻璃澄清剂时，有较高的产生澄清气体的温度范围，适合此种玻璃气泡的消除。
(2)根据本发明的一种优选实施方式，玻璃用组合物中含有特定含量的SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO和TiO 2，控制SiO 2+Al 2O 3＞80mol％、I值＞0、0.8≥(MgO+BaO)/R’O≥0.34、0.6≤Al 2O 3/R’O≤1，可使制备得到的玻璃同时具有较高的应变点、较高的杨氏模量、较高的比模数、较高的维氏硬度、较高的化学稳定性、较高的玻璃形成稳定性、较低的成型温度、较低的熔化温度和较低的液相线温度等优良特性，具体地，得到的碱土铝硅酸盐玻璃的密度小于2.67g/cm 3，杨氏模量大于75GPa，比模数大于29GPa/(g/cm 3)，50-350℃的热膨胀系数小于39×10 -7/℃，折射率n D大于1.53，粘度为35000P时对应的成型温度T w低于1320℃，粘度为200P时对应的熔化温度T m低于1650℃，液相线温度T 1低于1220℃，应变点T st在750℃以上，退火点T a在790℃以上，玻璃形成稳定性因子D值小于1.0，1200℃的表面张力小于350mN/m，维氏硬度大于6.4GPa，每公斤玻璃基板中泡径＞0.1mm的气泡数目不可见。
(3)由于本发明的组合物组分中含有较高的SiO 2与Al 2O 3合量，且组分中不含B 2O 3，保证了高应变点，搭配一定比例的MgO+CaO+SrO+BaO+ZnO+TiO 2，可以有效降低熔化温度、提升玻璃形成的稳定性，降低玻璃制造难度，对产线良率提升带来较大空间，同时燃料、电力等生产成本得以降低。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、 各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
第一方面，本发明提供了一种玻璃用组合物，以各组分的总摩尔数为基准，以氧化物计，该组合物含有68-73mol％的SiO 2、11.5-15mol％的Al 2O 3、2-6mol％的MgO、2.5-7.5mol％的CaO、0-3mol％的SrO、2-7mol％的BaO、0-4mol％的ZnO和0.05-1.5mol％的TiO 2。
本发明中，本领域技术人员应该理解的是，“无碱”是指玻璃组合物或玻璃中不含碱金属(即在元素周期表中第IA族的六个碱金属元素)。
本发明的组合物中，优选情况下，以各组分的总摩尔数为基准，以氧化物计，SiO 2+Al 2O 3＞80mol％。
本发明的组合物中，优选情况下，以组成中各组分的总摩尔数为基准，所述组成中各组分的含量按摩尔百分比计算满足I值大于0，优选为0.5-50，进一步优选为0.59-33.85，更进一步优选为0.59-33.35，再进一步优选为0.59-21.6，再更进一步优选为2-13.5，最优选为3.65-11.65，其中，I值由下式计算得出：
I＝[SiO 2-P 1×Al 2O 3-P 2×BaO-P 3×(MgO+ZnO)-P 4×(CaO+SrO)-P 5×TiO 2]×100，
其中，P 1＝4，P 2＝-2，P 3＝3.5，P 4＝3，P 5＝-25，
SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO、TiO 2各自代表该组分占总组成的摩尔百分比。
本发明的组合物中，优选情况下，以各组分的总摩尔数为基准，以摩尔百分数计，0.8≥(MgO+BaO)/R’O≥0.34，进一步优选地，0.75≥(MgO+BaO)/R’O≥0.45，更进一步优选地，0.7≥(MgO+BaO)/R’O≥0.5，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
本发明的组合物中，优选情况下，以各组分的总摩尔数为基准，以摩尔百分数计，0.6≤Al 2O 3/R’O≤1；进一步优选地，0.65≤Al 2O 3/R’O≤0.95；更进一步优选地，0.7≤Al 2O 3/R’O≤0.85；再进一步优选地，0.7＜Al 2O 3/R’O＜0.8，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
本发明中，SiO 2是玻璃形成体，若含量过低，不利于耐化性腐蚀性的增强，会使膨胀系数太高，玻璃容易失透；提高SiO 2含量有助于玻璃轻量化、热膨胀系数减小、应变点增高、耐化学性增高，但高温粘度升高，这样不利于熔解，一般的窑炉难以满足。所以SiO 2的含量为68-73％。因此，综合考虑，以各组分的总摩尔数为基准，以氧化物计，SiO 2的含量为68-73mol％，优选为68-72.2mol％。
本发明中，Al 2O 3用以提高玻璃结构的强度，若含量低于11.5mol％，玻璃耐热性难以提升，也容易受到外界水气及化学试剂的侵蚀。高含量的Al 2O 3有助于玻璃应变点、机械强度的增高，但过高含量时玻璃容易出现析晶现象，同时会使得玻璃难以熔解，因此，综合考虑，以各组分的总摩尔数为基准，以氧化物计，Al 2O 3的含量为11.5-15mol％，优选为11.7-12.8mol％。
本发明中，MgO具有大幅提升玻璃杨氏模量和硬度、降低高温粘度、使玻璃易于熔化的特点。当无碱硅酸盐玻璃中碱土金属合量较少时，引入电场强度较大的网络外体离子Mg 2+，容易在结构中产生局部积聚作用，使短程有序范围增加。在这种情况下引入较多的中间体氧化物Al 2O 3，以[AlO 4]状态存在时，由于这些多面体带有负电，吸引了部分网络外阳离子，使玻璃的积聚程度、析晶能力下降；当碱土金属合量较多、网络断裂比较严重的情况下，引入MgO，可使断裂的硅氧四面体重新连接而使玻璃析晶能力下降。因此在添加MgO时要注意与其他组分的配合比例。相对于其他碱土金属氧化物，MgO的存在会带来较低的膨胀系数和密度，较高的耐化学性、应变点和弹性模量。如果MgO大于6mol％，玻璃耐化性会变差，同时玻璃容易失透，而过低的MgO含量则对比模数提高不利。因此，综合考虑，以各组分的总摩尔数为基准，以氧化物计，MgO的含量为2-6mol％，优选为2.35-5mol％。
本发明中，CaO用以促进玻璃的熔解和调整玻璃成型性。如果氧化钙含量少于2.5mol％，不易降低玻璃的粘度，而含量过多时玻璃会容易出现析晶，热膨胀系数也会大幅变大，对后续制程不利。因此，综合考虑，以各组分的总摩尔数为基准，以氧化物计，CaO的含量为2.5-7.5mol％，优选为3.4-7.3mol％。
本发明中，SrO作为助熔剂和防止玻璃出现析晶的成分，如果含量过多，玻璃密度会太高，导致产品的摩尔过重。因此，以各组分的总摩尔数为基准，以氧化物计，SrO的含量为0-3mol％，优选为0-2.61mol％。
本发明中，BaO与SrO的作用相似，含量过多，玻璃的密度会变大，且应变点会大幅度降低。因此，以各组分的总摩尔数为基准，以氧化物计，BaO的含量为2-7mol％，优选为2.3-5.8mol％。
本发明中，二价金属氧化物根据它在元素周期表中地位与对性质影响不同，可以分为两类：一类是位于主族的碱土金属氧化物，其离子R 2+具有8个外电子结构；第二类位于周期表副族(如ZnO、CdO等)，其离子R 2+具有18个外层电子结构，在玻璃中两者的结构状态与对玻璃性质影响是不同的。ZnO可以降低玻璃高温粘度(如1500℃)， 有利于消除气泡；同时在软化点以下有提升强度、硬度、增加玻璃的耐化学性，降低玻璃热膨胀系数的作用。在无碱玻璃体系中，添加适量ZnO有助于抑制析晶，可以降低析晶温度。在理论上，ZnO在无碱玻璃中，作为网络外体引入玻璃后，高温下一般以[ZnO 4]的形式存在，较[ZnO 6]玻璃结构更加疏松，与不含ZnO的玻璃处于相同的高温状态下比较，含ZnO的玻璃粘度更小，原子运动速度更大，无法形成晶核，需要进一步降低温度，才有利于晶核的形成，因而，降低了玻璃的析晶上限温度。ZnO含量过多会使玻璃的应变点大幅度降低。因此，综合考虑，以各组分的总摩尔数为基准，以氧化物计，ZnO的含量为0-4mol％，优选为0.4-3mol％。
本发明中，TiO 2用以促进玻璃的熔解和提高玻璃形成稳定性，并且可以有效提高玻璃折射率、降低膨胀系数。含量过多时上述效果增幅显著降低，同时会降低玻璃形成稳定性。因此，综合考虑，以各组分的总摩尔数为基准，以氧化物计，TiO 2的含量为0.05-1.5mol％，优选为0.05-1.2mol％。
本发明中，组合物还含有澄清剂，所述澄清剂优选为硫酸盐、硝酸盐、氧化锡、氧化亚锡、氯化物和氟化物中的至少一种；其中，玻璃成份中可以优选添加氧化亚锡SnO作为玻璃熔解时的澄清剂或除泡剂，以提高玻璃的熔解摩尔。如果含量过多时会导致玻璃基板失透，因此，优选情况下，以各组分的总摩尔数为基准，以氧化物计，所述澄清剂的含量为0.04-0.15mol％。
本领域技术人员应该理解的是，本发明的玻璃用组合物中，组合物含有SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO和TiO 2是指该组合物含有含Si化合物、含Al化合物、含Mg化合物、含Ca化合物、含Sr化合物、含Ba化合物、含Zn化合物和含Ti化合物，如含前述各元素的碳酸盐、硝酸盐、硫酸盐、磷酸盐、碱式碳酸盐、氧化物等，且前述提及的各组分的含量均以各元素的氧化物计，具体的各元素的碳酸盐、硝酸盐、硫酸盐、磷酸盐、碱式碳酸盐、氧化物的选择为本领域技术人员所熟知，在此不再赘述。
本发明的玻璃用组合物中，利用其制备碱土铝硅酸盐玻璃时，之所以能够使得玻璃具有优良的综合性能，主要归功于组合物中各组分之间的相互配合，尤其是SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO和TiO 2之间的配合作用，更尤其是前述特定含量的各组分之间的相互配合。
第二方面，本发明提供了一种碱土铝硅酸盐玻璃，以各组分的总摩尔数为基准，该玻璃含有68-73mol％的SiO 2、11.5-15mol％的Al 2O 3、2-6mol％的MgO、2.5-7.5mol％的CaO、0-3mol％的SrO、2-7mol％的BaO、0-4mol％的ZnO和0.05-1.5mol％的TiO 2。
优选地，碱土铝硅酸盐玻璃中，SiO 2+Al 2O 3＞80mol％。
本发明的组合物中，优选情况下，以组成中各组分的总摩尔数为基准，所述组成中各组分的含量按摩尔百分比计算满足I值大于0，进一步优选为0.5-50，更进一步优选为0.59-33.85，再进一步优选为0.59-21.6，再更进一步优选为2.07-13.29，其中，I值由下式计算得出：
I＝[SiO 2-P 1×Al 2O 3-P 2×BaO-P 3×(MgO+ZnO)-P 4×(CaO+SrO)-P 5×TiO 2]×100，
其中，P 1＝4，P 2＝-2，P 3＝3.5，P 4＝3，P 5＝-25，
SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO、TiO 2各自代表该组分占总组成中的摩尔百分比。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以摩尔百分数计，0.8≥(MgO+BaO)/R’O≥0.34，进一步优选地，0.75≥(MgO+BaO)/R’O≥0.45，更进一步优选地，0.7≥(MgO+BaO)/R’O≥0.5，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以摩尔百分数计，0.6≤Al 2O 3/R’O≤1；进一步优选地，0.65≤Al 2O 3/R’O≤0.95；更进一步优选地，0.7≤Al 2O 3/R’O≤0.85；再进一步优选地，0.7＜Al 2O 3/R’O＜0.8，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，ZnO的含量为0.4-3mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，Al 2O 3的含量为11.7-12.8mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，SiO 2的含量为68-72.2mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，MgO的含量为2.35-5mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，CaO的含量为3.4-7.3mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，SrO的含量为0-2.61mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，BaO的含量为2.3-5.8mol％。
优选地，碱土铝硅酸盐玻璃中，以各组分的总摩尔数为基准，以氧化物计，TiO 2的含量为0.05-1.2mol％。
优选地，碱土铝硅酸盐玻璃中，澄清剂(优选氧化亚锡)的含量为0.04-0.15mol％。
第三方面，本发明提供了一种制备碱土铝硅酸盐玻璃的方法，该方法包括将本发明所述的玻璃用组合物依次进行熔融处理、成型处理、退火处理和机械加工处理。
本发明的方法中，对于玻璃用组合物的具体限定请参见前述相应内容描述，在此不再赘述。
本发明的方法中，优选情况下，熔融处理的条件包括：温度低于1650℃，时间大于1h。本领域技术人员可以根据实际情况确定具体的熔融温度和熔融时间，此为本领域技术人员所熟知，在此不再赘述。
本发明的方法中，优选情况下，退火处理的条件包括：温度在790℃以上，时间大于0.1h。本领域技术人员可以根据实际情况确定具体的退火温度和退火时间，此为本领域技术人员所熟知，在此不再赘述。
本发明的方法中，对于机械加工处理没有特别的限定，可以为本领域常见的各种机械加工方式，例如可以为将退火处理得到的产物进行切割、研磨、抛光等。
具体地，在制备玻璃时，先将包括有上述各玻璃基板对应氧化物摩尔百分比组分的组合物原料均匀搅拌混合后，再将混合原料熔融加工，用铂金棒搅拌排出气泡和使玻璃液均化，然后将其温度降低到成型所需要的玻璃基板成型温度范围，通过退火原理，制作出平面显示器需要的玻璃基板的厚度，再对成型的玻璃基板进行简单的冷加工处理，最后对玻璃基板的基本物理特性进行测试成为合格产品。
第四方面，本发明提供了上述方法制备得到的碱土铝硅酸盐玻璃。
优选情况下，本发明的碱土铝硅酸盐玻璃的密度小于2.67g/cm 3。
优选地，所述碱土铝硅酸盐玻璃的杨氏模量大于75GPa。
优选地，所述碱土铝硅酸盐玻璃的比模数大于29GPa/(g/cm 3)。
优选地，所述碱土铝硅酸盐玻璃的50-350℃的热膨胀系数小于39×10 -7/℃。
优选地，所述碱土铝硅酸盐玻璃的折射率n D大于1.53，进一步优选为1.534-1.545。
优选地，所述碱土铝硅酸盐玻璃在粘度为35000P时对应的成型温度T w低于1320℃。
优选地，所述碱土铝硅酸盐玻璃在粘度为200P时对应的熔化温度T m低于1650℃。
优选地，所述碱土铝硅酸盐玻璃的液相线温度T 1低于1220℃，进一步优选为 1120-1180℃。
优选地，所述碱土铝硅酸盐玻璃的应变点T st在750℃以上。
优选地，所述碱土铝硅酸盐玻璃的退火点T a在790℃以上。
优选地，所述碱土铝硅酸盐玻璃的玻璃形成稳定性因子D小于1.0，进一步优选为0.5-0.95，更进一步优选为0.59-0.84，再进一步优选为0.59-0.74，再更进一步优选为0.62-0.74，其中，D值由下式计算得到：
D＝(T 1-T a)/(T m-T 1)，
其中，T m、T 1、T a分别代表玻璃粘度为200泊时的熔化温度、玻璃的液相线温度、玻璃的退火点温度。
优选地，所述碱土铝硅酸盐玻璃的1200℃的表面张力小于350mN/m。
优选地，所述碱土铝硅酸盐玻璃的维氏硬度大于6.4GPa。
优选地，每公斤玻璃基板中泡径＞0.1mm的气泡数目不可见。
第五方面，本发明提供了本发明所述的玻璃用组合物或碱土铝硅酸盐玻璃在制备显示器件和/或太阳能电池中的应用。优选为在制备平板显示产品的衬底玻璃基板材料和/或屏幕表面保护用玻璃膜层材料、柔性显示产品的衬底玻璃基板材料和/或表面封装玻璃材料和/或屏幕表面保护用玻璃膜层材料、柔性太阳能电池的衬底玻璃基板材料中的应用。
实施例
以下将通过实施例对本发明进行详细描述。以下实施例中，如无特别说明，所用的各材料均可通过商购获得，如无特别说明，所用的方法为本领域的常规方法。
以下实施例和对比例中，参照ASTM C-693测定玻璃密度，单位为g/cm 3。
参照ASTM E-228使用卧式膨胀仪测定50-350℃的玻璃热膨胀系数，单位为10 -7/℃。
参照ASTM C-623使用材料力学试验机测定玻璃杨氏模量，单位为GPa。
参照ASTM E-384使用维氏硬度计测定玻璃维氏硬度，单位为GPa。
参照ASTM C-336使用退火点应变点测试仪测定玻璃退火点和应变点，单位为℃。
参照ASTM C-965使用旋转高温粘度计测定玻璃高温粘温曲线，其中，200P粘度时对应的熔化温度T m，单位为℃；35000P粘度对应的成型温度T w，单位为℃。
参照ASTM C-829使用梯温炉法测定玻璃析晶上限温度(液相线温度)。
使用高温表面张力仪测定1200℃的表面张力，单位为mN/m。
使用WAY-2S阿贝数显折射仪，室温下测定波长587.6nm(钠黄光)下的折射率n D。
每公斤玻璃基板中泡径＞0.1mm的气泡数目指每公斤碱土铝硅酸盐玻璃基板中泡径＞0.1mm的气泡数目，测定方法为：使用精度为0.01g的电子天平称量样品玻璃重量，使用光学显微镜统计气泡数量，计算求得每公斤玻璃中泡径＞0.1mm的气泡数目。
实施例1-14、对比例1-13
按照表1-4所示称量各组分，混匀，将混合料倒入铂金坩埚中，然后在1620℃电阻炉中加热4小时，并使用铂金棒搅拌以排出气泡。将熔制好的玻璃液浇注入不锈钢铸铁磨具内，成形为规定的块状玻璃制品，然后将玻璃制品在退火炉中退火2小时，关闭电源随炉冷却到25℃。将玻璃制品进行切割、研磨、抛光，然后用去离子水清洗干净并烘干，制得符合测试要求的玻璃成品。分别对各玻璃成品的各种性能进行测定，结果分别见表1-4。
表1
Figure PCTCN2018082339-appb-000002
表2
Figure PCTCN2018082339-appb-000003
表3
Figure PCTCN2018082339-appb-000004
表4
Figure PCTCN2018082339-appb-000005
通过表1-4的结果可以看出，本发明利用含有特定含量的SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO和TiO 2的玻璃用组合物制备的玻璃，尤其是当玻璃用组合物中，以摩尔百分比计，SiO 2+Al 2O 3＞80mol％、I值＞0、0.8≥(MgO+BaO)/R’O≥0.34、0.6≤Al 2O 3/R’O≤1时，可使制备得到的玻璃同时具有较高的应变点、较高的杨氏模量、较高的比模数、较高的维氏硬度、较高的化学稳定性、较高的玻璃形成稳定性、较低的成型温度、较低的 熔化温度和较低的液相线温度等优良特性，具体地，得到的碱土铝硅酸盐玻璃的密度小于2.67g/cm 3，杨氏模量大于75GPa，比模数大于29GPa/(g/cm 3)，50-350℃的热膨胀系数小于39×10 -7/℃，折射率n D大于1.53，粘度为35000P时对应的成型温度T w低于1320℃，粘度为200P时对应的熔化温度T m低于1650℃，液相线温度T 1低于1220℃，应变点T st在750℃以上，退火点T a在790℃以上，玻璃形成稳定性因子D值小于1.0，1200℃的表面张力小于350mN/m，维氏硬度大于6.4GPa，每公斤玻璃基板中泡径＞0.1mm的气泡数目不可见。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (14)

  1. 一种玻璃用组合物，其特征在于，以各组分的总摩尔数为基准，以氧化物计，该组合物含有68-73mol％的SiO 2、11.5-15mol％的Al 2O 3、2-6mol％的MgO、2.5-7.5mol％的CaO、0-3mol％的SrO、2-7mol％的BaO、0-4mol％的ZnO和0.05-1.5mol％的TiO 2。
  2. 根据权利要求1所述的组合物，其特征在于，以各组分的总摩尔数为基准，以氧化物计，SiO 2+Al 2O 3＞80mol％。
  3. 根据权利要求1或2所述的组合物，其特征在于，以各组分的总摩尔数为基准，所述组合物中各组分的含量按摩尔百分比计算满足I值大于0，优选为0.5-50，进一步优选为0.59-33.85，更进一步优选为0.59-21.6，再进一步优选为2-13.5，其中，I值由下式计算得出：
    I＝[SiO 2-P 1×Al 2O 3-P 2×BaO-P 3×(MgO+ZnO)-P 4×(CaO+SrO)-P 5×TiO 2]×100，
    其中，P 1＝4，P 2＝-2，P 3＝3.5，P 4＝3，P 5＝-25，
    SiO 2、Al 2O 3、MgO、CaO、SrO、BaO、ZnO、TiO 2各自代表该组分占总组成的摩尔百分比。
  4. 根据权利要求1-3中任意一项所述的组合物，其特征在于，以各组分的总摩尔数为基准，以摩尔百分数计，0.8≥(MgO+BaO)/R’O≥≥0.34，优选地，0.75≥(MgO+BaO)/R’O≥≥0.45，进一步优选地，0.7≥(MgO+BaO)/R’O≥0.5，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
  5. 根据权利要求1-4中任意一项所述的组合物，其特征在于，以各组分的总摩尔数为基准，以摩尔百分数计，0.6≤Al 2O 3/R’O≤1；优选地，0.65≤Al 2O 3/R’O≤0.95；进一步优选地，0.7≤Al 2O 3/R’O≤0.85；更进一步优选地，0.7＜Al 2O 3/R’O＜0.8，其中，R’O＝MgO+CaO+SrO+BaO+ZnO。
  6. 根据权利要求1-5中任意一项所述的组合物，其特征在于，以各组分的总摩尔数为基准，以氧化物计，ZnO的含量为0.4-3mol％。
    优选地，以各组分的总摩尔数为基准，以氧化物计，Al 2O 3的含量为11.7-12.8mol％。
    优选地，以各组分的总摩尔数为基准，以氧化物计，SiO 2的含量为68-72.2mol％；
    优选地，以各组分的总摩尔数为基准，以氧化物计，MgO的含量为2.35-5mol％；
    优选地，以各组分的总摩尔数为基准，以氧化物计，CaO的含量为3.4-7.3mol％；
    优选地，以各组分的总摩尔数为基准，以氧化物计，SrO的含量为0-2.61mol％；
    优选地，以各组分的总摩尔数为基准，以氧化物计，BaO的含量为2.3-5.8mol％；
    优选地，以各组分的总摩尔数为基准，以氧化物计，TiO 2的含量为0.05-1.2mol％。
  7. 根据权利要求1-6中任意一项所述的组合物，其特征在于，所述组合物还含有澄清剂，所述澄清剂优选为硫酸盐、硝酸盐、氧化锡、氧化亚锡、氯化物和氟化物中的至少一种；以各组分的总摩尔数为基准，以氧化物计，所述澄清剂的含量为0.04-0.15mol％。
  8. 一种制备碱土铝硅酸盐玻璃的方法，其特征在于，该方法包括将权利要求1-7中任意一项所述的玻璃用组合物依次进行熔融处理、成型处理、退火处理和机械加工处理。
  9. 权利要求8所述的方法制备得到的碱土铝硅酸盐玻璃。
  10. 根据权利要求9所述的碱土铝硅酸盐玻璃，其特征在于，所述碱土铝硅酸盐玻璃的密度小于2.67g/cm 3，杨氏模量大于75GPa，比模数大于29GPa/(g/cm 3)，折射率n D大于1.53。
  11. 根据权利要求9或10所述的碱土铝硅酸盐玻璃，其特征在于，50-350℃的热膨胀系数小于39×10 -7/℃，粘度为35000P时对应的成型温度T w低于1320℃，粘度为200P时对应的熔化温度T m低于1650℃，液相线温度T l低于1220℃，应变点T st在750℃以上，退火点T a在790℃以上。
  12. 根据权利要求9-11中任意一项所述的碱土铝硅酸盐玻璃，其特征在于，玻璃形成稳定性因子D小于1.0，优选为0.5-0.95，进一步优选为0.59-0.84，更进一步优选为0.62-0.74，其中，D值由下式计算得到：
    D＝(T l-T a)/(T m-T l)，
    其中，T m、T l、T a分别代表玻璃粘度为200P时对应的熔化温度、玻璃液相线温度、玻璃退火点温度。
  13. 根据权利要求9-12中任意一项所述的碱土铝硅酸盐玻璃，其特征在于，1200℃的表面张力小于350mN/m，维氏硬度大于6.4GPa，每公斤玻璃基板中泡径＞0.1mm的气泡数目不可见。
  14. 权利要求1-7中任意一项所述的玻璃用组合物或权利要求9-13中任意一项所述的碱土铝硅酸盐玻璃在制备显示器件和/或太阳能电池中的应用，优选为在制备平板显示产品的衬底玻璃基板材料和/或屏幕表面保护用玻璃膜层材料、柔性显示产品的衬底玻璃基板材料和/或表面封装玻璃材料和/或屏幕表面保护用玻璃膜层材料、柔性太阳能电池的衬底玻璃基板材料中的应用。
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