WO2019153845A1 - 玻璃用组合物、低夹杂物含量的玻璃及其制备方法和应用 - Google Patents
玻璃用组合物、低夹杂物含量的玻璃及其制备方法和应用 Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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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
- C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Definitions
- the invention relates to the field of glass manufacturing, in particular to a glass composition, a low inclusion content glass, a preparation method and application thereof.
- Handheld display devices such as mobile phones, have a mainstream pixel density of more than 200 ppi, 300 ppi or even 400 ppi; fixed display devices, such as LCD TVs, have resolutions exceeding 2K, 4K or even 8K.
- the trend of high definition puts higher and higher requirements on the fineness of the panel process, and then needs to upgrade the thermal stability and quality of the supporting substrate glass.
- the glass suitable for display substrate belongs to alkali-free high alumina silicate glass system, which has the characteristics of high strain point, high temperature viscosity and large surface tension. The manufacturing difficulty is obviously higher than that of ordinary soda lime glass, and it is difficult to remove residual gaseous inclusions at high temperature. Excluded, and finally cured on the surface or inside of the glass, forming a bad point, resulting in product waste.
- One method is to reduce the viscosity of the high temperature glass melt.
- the lower viscosity melt has a higher temperature, which is beneficial to the reduction of the chemical solubility of common gaseous substances in most glass (such as SO 3 , CO 2 , O 2 ), and is beneficial for the residual gaseous inclusions to stick when rising inside the melt.
- the hysteresis resistance is reduced, which is favorable for the ascending and combined overflow, and the glass homogenate having the residual gaseous inclusion content satisfying the requirements is obtained.
- the substrate glass has the characteristics of high temperature viscosity and large surface tension.
- the viscosity of the glass melt used to exclude residual gaseous inclusions in the above glass melt is generally about 100 poise, and the corresponding temperature at the viscosity often reaches 1650 ° C. At 1700 ° C or even above 1750 ° C, reducing the viscosity of the high temperature glass melt again will lead to a further increase in temperature, resulting in an increase in the reaction between the glass and the refractory material, which in turn poses a great challenge to the temperature resistance and service life of the supporting refractory material;
- the smelting vessel of the above glass melt is often composed of high zirconium bricks having a ZrO 2 content of more than 80%, and high temperature corrosion and spalling refractories (for example, zirconia) become a potential risk source for solid inclusions inside the glass.
- Another method is to increase the chemical clarifying agent content.
- This method has problems such as increasing residual solid inclusions or eliminating residual gaseous inclusions.
- the above high-viscosity glass melt is often subjected to a chemical clarifying agent at the time of high-temperature melting, and is, for example, at least one of As 2 O 3 , Sb 2 O 3 , SnO 2 , BaSO 4 , Ba(NO 3 ) 2 or the like.
- SnO 2 is currently more used as a clarifying agent in an amount of between about 0.1 and 1% by weight.
- the object of the present invention is to overcome the problem of difficulty in removing inclusions existing in the prior art, and to provide a composition for glass having a low inclusion content, a simple preparation process, and a low preparation cost. Etc.
- an aspect of the invention provides a composition for glass comprising 50-64 wt% of SiO 2 , 14-24 wt% of Al 2 O 3 , 0-7 wt% of B 2 O 3 +P 2 O 5 , 0.5-7 wt% of MgO, 1-10 wt% of CaO, 0-9 wt% of SrO, 0.1-14 wt% of BaO, 0.1-5 wt% of ZnO, 0.1-4 wt% of TiO 2 , 0.1-7 wt % Y 2 O 3 +La 2 O 3 +Nd 2 O 3 , ⁇ 0.05 wt% R 2 O, wherein R 2 O is the sum of Li 2 O, Na 2 O, K 2 O content, and the combination
- the material satisfies the following conditions: (1) a viscosity of 100 poise corresponding to a temperature T 100 of 1730 ° C or more; (2) a surface tension of 1300 ° C of less than 420 mN /
- the composition further satisfies: (3) the liquidus temperature T L is less than 1180 °C.
- the composition further satisfies: (4) the strain point T st is 710 ° C or higher.
- the composition contains 56-63 wt% SiO 2 , 17-22 wt% Al 2 O 3 , 0-5.2 wt% B 2 O 3 + P 2 O 5 , 1-5 wt% MgO, 2- 8 wt% CaO, 0-8 wt% SrO, 1-12 wt% BaO, 0.3-4 wt% ZnO, 0.2-3 wt% TiO 2 , 0.1-4 wt% Y 2 O 3 + La 2 O 3 + Nd 2 O 3 , ⁇ 0.05 wt% of R 2 O, wherein R 2 O is the sum of the contents of Li 2 O, Na 2 O, and K 2 O.
- the composition contains from 0 to 5% by weight of B 2 O 3 and from 0 to 7% by weight of P 2 O 5 , preferably from 0 to 5% by weight.
- the composition contains 0 to 2 wt% of Y 2 O 3 , 0 to 3 wt % of La 2 O 3 , and 0 to 3 wt% of Nd 2 O 3 .
- the composition contains Li 2 O of 0.01% by weight or less, Na 2 O of 0.01% by weight or less, and K 2 O of 0.01% by weight or less.
- the composition further contains a chemical clarifying agent.
- the chemical fining agent is preferably tin oxide.
- the clarifying agent is contained in an amount of not more than 1% by weight based on the total weight of the composition.
- the raw material is uniformly mixed with NH 4 NO 3 by the above-mentioned composition for the glass composition, and then melt-treated, and then the gaseous inclusions are removed in a viscosity range of 210 to 500 poise, and the molding treatment and the annealing treatment are sequentially performed.
- the glass obtained afterwards satisfies: the content of gaseous inclusions having an equivalent spherical diameter (D.EQ.) of more than 0.02 mm is less than 0.5/Kg of glass.
- a low inclusion content glass which is prepared by using the above glass composition of the present invention.
- the low inclusion content glass is prepared by uniformly mixing the raw material with NH 4 NO 3 by the above composition for the glass composition, and then performing the melt treatment to remove the gaseous inclusions in a viscosity range of 210-500 poise. Then, molding processing and annealing treatment are sequentially performed.
- a third aspect of the present invention provides a method for producing a glass having a low inclusion content, which comprises mixing a raw material with NH 4 NO 3 by a ratio of the above composition for glass, and then performing a melt treatment, and then having a viscosity of 210- Gaseous inclusions are removed within 500 poise.
- the NH 4 NO 3 is used in an amount of 0.2 to 10% by weight, preferably 1 to 8% by weight, more preferably 2.5 to 5% by weight, based on the raw material of the composition for glass.
- the gaseous inclusions are removed in the range of from 220 to 350 poise; more preferably, the gaseous inclusions are removed in the range of from 250 to 300 poise.
- the method further comprises sequentially performing a forming treatment, an annealing treatment, and a mechanical processing on the product after removing the gaseous inclusions.
- the method further comprises: subjecting the product obtained by the mechanical processing to a secondary melting and thinning treatment.
- the prepared glass has a thickness of less than 0.1 mm by the mechanical processing or the secondary fusion thinning treatment.
- a low inclusion content glass prepared by the above preparation method.
- the low inclusion content glass satisfies the following conditions:
- the low inclusion content glass satisfies the following conditions:
- the low inclusion content glass satisfies the following conditions: a density lower than 2.7 g/cm 3 , a thermal expansion coefficient in the range of 50-350 ° C lower than 40 ⁇ 10 -7 /° C., and a Young's modulus higher than 80 GPa
- the transmittance at a wavelength of 308 nm is 50% or more, and the heat shrinkage at 600 ° C / 10 min is less than 15 ppm.
- the use of the low inclusion content glass in a display device, a solar cell substrate glass, a safety glass, a bulletproof glass, a smart car glass, an intelligent traffic display, a smart window or a smart card ticket is provided.
- the inventors of the present invention conducted intensive studies on glass having a low inclusion content and found that by appropriately controlling the composition and properties of the composition for glass, the operating temperature for removing inclusions in the preparation of high-viscosity glass can be lowered, and inclusions can be made. It is easier to eliminate, thereby greatly reducing the content of gaseous inclusions and/or solid inclusions in the produced glass, and reasonably reducing the glass manufacturing cost.
- the strong oxidant NH 4 NO 3 promotes the variable-price chemical clarifying agent to remain in a high-priced state, avoiding premature reaction failure before the intense oxygen releasing section;
- the N 2 decomposed by NH 4 NO 3 dissolves and saturates in the glass and then enters the gaseous inclusions.
- the partial pressure of N 2 gas increases, it promotes O 2 , CO 2 , etc.
- gaseous inclusions and/or solid inclusions in the glass can be further reduced by adding NH 4 NO 3 and removing gaseous inclusions in a specific viscosity range. content.
- any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values are understood to include values that are close to the ranges or values.
- the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values.
- the scope should be considered as specifically disclosed herein.
- the present invention provides a composition for glass comprising 50-64 wt% of SiO 2 , 14-24 wt% of Al 2 O 3 , 0-7 wt% of B 2 O 3 + P 2 O 5 , 0.5- 7 wt% of MgO, 1-10 wt% of CaO, 0-9 wt% of SrO, 0.1-14 wt% of BaO, 0.1-5 wt% of ZnO, 0.1-4 wt% of TiO 2 , 0.1-7 wt% of Y 2 O 3 +La 2 O 3 +Nd 2 O 3 , ⁇ 0.05 wt% of R 2 O, wherein R 2 O is the sum of the contents of Li 2 O, Na 2 O, K 2 O, and the composition satisfies the following conditions: 1) The viscosity T 100 corresponds to a temperature T 100 of 1730 ° C or more; (2) 1300 ° C surface tension is less than 420 mN / m.
- the composition satisfies: (2) a surface tension of less than 400 mN/m at 1300 °C.
- the composition further satisfies: (3) a liquidus temperature T L of less than 1180 °C.
- the composition further satisfies: (4) the strain point T st is 710 ° C or higher.
- the temperature T 100 corresponding to a viscosity of 100 poise is determined by referring to ASTM C-965, wherein the 100 P viscosity corresponds to a temperature T 100 in units of ° C; and the 1300 ° C surface tension is measured using a high temperature surface tension meter ( Beijing Xuhui Xinrui Technology Co., Ltd., model ZLXS-II); liquidus temperature T L is determined by the ladder furnace method with reference to ASTM C-829; strain point T st is determined by reference to ASTM C-336.
- the glass composition can be subjected to the removal of residual gaseous inclusions in the glass melt at a high viscosity (e.g., 210-500 poise).
- a high viscosity e.g., 210-500 poise.
- the melt of the composition for glass of the present invention exhibits a "boiling" effect at an appropriate stage, which not only greatly reduces the content of residual gaseous inclusions, but also promotes the homogenization process of the melt, while simultaneously promoting the melt homogenization process.
- the process belt is widened to reduce the production difficulty.
- the present invention can make the gaseous inclusions easier to remove by controlling the surface tension of the glass, and further reduce the content of inclusions in the produced glass.
- the composition contains 56-63 wt% SiO 2 , 17-22 wt% Al 2 O 3 , 0-5.2 wt% B 2 O 3 + P 2 O 5 , 1 -5 wt% of MgO, 2-8 wt% of CaO, 0-8 wt% of SrO, 1-12 wt% of BaO, 0.3-4 wt% of ZnO, 0.2-3 wt% of TiO 2 , 0.1-4 wt% of Y 2 O 3 + La 2 O 3 + Nd 2 O 3 , ⁇ 0.05 wt% of R 2 O, wherein R 2 O is the sum of the contents of Li 2 O, Na 2 O, and K 2 O.
- the composition contains from 0 to 5% by weight of B 2 O 3 and from 0 to 7% by weight of P 2 O 5 , preferably from 0 to 5% by weight.
- B 2 O 3 is 0-4.7 wt% and/or P 2 O 5 is 0-1.5 wt%.
- the composition contains 0 to 2 wt% of Y 2 O 3 , 0 to 3 wt % of La 2 O 3 , and 0 to 3 wt% of Nd 2 O 3 .
- Y 2 O 3 is 0-1 wt%
- La 2 O 3 is 0-1.7 wt%
- Nd 2 O 3 is 0-2 wt%.
- the composition contains Li 2 O of 0.01% by weight or less, Na 2 O of 0.01% by weight or less, and K 2 O of 0.01% by weight or less.
- the glass composition of the present invention may further contain a chemical clarifying agent as needed.
- the chemical clarifying agent is not particularly limited, and may be a conventional chemical clarifying agent which can be used for glass, for example, one or more of tin oxide, arsenic oxide, cerium oxide, barium sulfate, and cerium nitrate.
- the chemical fining agent is preferably tin oxide.
- the content of the chemical clarifying agent is preferably 100% by weight based on the total weight of the composition, and the clarifying agent is contained in an amount of not more than 1% by weight, preferably 0.1% to 0.8% by weight, more preferably 0.2% to 0.4% by weight.
- the melt treatment in order to reduce the inclusion content of the glass composition, it is preferred to carry out the melt treatment by uniformly mixing the raw material with NH 4 NO 3 by using the above composition for the glass composition, and then having a viscosity of 210-
- the gas inclusions are removed in the range of 500 poise, and the glass obtained after the molding treatment and the annealing treatment in sequence satisfies: the content of gaseous inclusions having an equivalent spherical diameter (D.EQ.) of more than 0.02 mm is less than 0.5/Kg of glass.
- the raw material is uniformly mixed with NH 4 NO 3 by the above-mentioned composition for the glass composition, and then melt-treated, and then the gaseous inclusions are removed in the range of 210-500 poise, and sequentially
- the glass obtained after the molding treatment and the annealing treatment also satisfies: the N 2 content in the gaseous inclusion component is ⁇ 50 vol.% based on the volume percentage.
- the present invention also provides a low inclusion content glass which is prepared using the above glass composition of the present invention.
- the above low inclusion content glass can be carried out by any conventional method for glass preparation.
- the low inclusion content glass is prepared by mixing the raw material with NH 4 NO 3 and melting it by using the above composition for the glass composition of the present invention.
- the treatment removes gaseous inclusions in a viscosity range of 210-500 poise, and then performs molding processing and annealing treatment in sequence.
- the present invention also provides a method for preparing a glass having a low inclusion content, wherein the method comprises mixing a raw material with NH 4 NO 3 by a ratio of the above composition for glass, and then performing a melt treatment, and then having a viscosity of 210- Gaseous inclusions are removed within 500 poise.
- the glass composition of the present invention contains SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, TiO 2 , Y 2 O 3 , La 2 O 3 and Nd. 2 O 3
- a raw material for preparing the above-mentioned composition for glass composition means using a carbonate, a nitrate, a sulfate, a phosphate, a basic carbonate, an oxide, or the like containing each of the above elements, and The content of each component mentioned above is based on the oxide of each element, and the specific carbonate, nitrate, sulfate, phosphate, basic carbonate, oxide of each element is selected in the art. It is well known to the person and will not be described here.
- the obtained product is not greatly reduced.
- the content of gaseous inclusions and/or solid inclusions in the glass can simultaneously reduce the glass manufacturing cost.
- the amount of the NH 4 NO 3 to be used is not particularly limited, and the effect of eliminating gaseous inclusions can be achieved.
- the NH 4 NO 3 is used in an amount of 0.2 to 10% by weight, preferably 1 to 8% by weight, more preferably 2.5-%, based on the raw material of the composition for glass composition. 5wt%.
- the present invention it is preferred to remove gaseous inclusions in the range of from 220 to 350 poise; more preferably, to remove gaseous inclusions in the range of from 250 to 300 poise.
- the present invention can be at a lower level than the removal of gaseous inclusions in the viscosity range of conventional 100 poise and below.
- the operation of removing gaseous inclusions is performed at a temperature, thereby reducing manufacturing energy consumption and cost.
- the conditions of the melt treatment are not particularly limited, and conventional conditions which can be used for the melt treatment of the glass composition can be employed.
- the conditions of the melt treatment include: a temperature lower than 1680 ° C, a time greater than 1 h, such as a temperature of 1600-1650 ° C, and a time of 2-50 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 method further comprises sequentially subjecting the product after removing the gaseous inclusions to a forming treatment, an annealing treatment, and a mechanical processing.
- the molding treatment is not particularly limited, and various molding treatment methods which are common in the art may be used, and for example, it may be an overflow method, a floating method, a pressing method, a blowing method, a drawing method, The rolling method, the casting method, and the like.
- the conditions of the annealing treatment include a temperature higher than 730 ° C, a time greater than 0.1 h, such as a temperature of 770-850 ° C, and a time of 0.5-5 h.
- a person skilled in the art can determine a specific annealing temperature and annealing time according to actual conditions, which are well known to those skilled in the art and will not be described herein.
- the mechanical processing is not particularly limited, and various mechanical processing methods which are common in the art can be used, for example, the product obtained by annealing treatment can be cut, ground, polished, or the like.
- the method further comprises: subjecting the product obtained by the mechanical processing to a secondary fusion thinning process.
- the thickness of the obtained glass can be further reduced by the secondary melting thinning treatment.
- the prepared glass has a thickness of less than 0.1 mm, more preferably 0.01 to 0.08 mm by the mechanical processing or the secondary melting thinning treatment.
- the invention also provides a low inclusion content glass prepared by the above preparation method.
- the low inclusion content glass satisfies the following conditions:
- the low inclusion content glass satisfies the following conditions:
- the low inclusion content glass satisfies the following conditions: the density is less than 2.7 g/cm 3 , and the thermal expansion coefficient in the range of 50-350 ° C is lower than 40 ⁇ 10 -7 /° C.
- the Young's modulus is higher than 80 GPa, the transmittance at a wavelength of 308 nm is 50% or more, and the heat shrinkage is less than 15 ppm at 600 ° C/10 min; preferably, the density is less than 2.7 g/cm 3 , and the range is 50-350 ° C
- the coefficient of thermal expansion is less than 40 ⁇ 10 -7 / ° C
- the Young's modulus is higher than 80 GPa
- the transmittance at a wavelength of 308 nm is 50% or more
- the heat shrinkage at 600 ° C / 10 min is less than 10 ppm.
- the invention also provides the application of the low inclusion content glass in the display device, the solar cell substrate glass, the safety glass, the bulletproof glass, the smart automobile glass, the intelligent traffic display screen and the smart window.
- the low inclusion content glass of the present invention is particularly suitable for preparing a substrate glass substrate material for 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. Glass film material for material and/or screen surface protection, substrate glass substrate material for flexible solar cells, safety glass, bulletproof glass, smart car glass, intelligent traffic display, smart window and smart card ticket, and for other applications requiring high heat stability Application areas of glass materials for sexual and mechanical stability.
- the glass density was measured in accordance with ASTM C-693 in units of g/cm 3 .
- 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 in accordance with ASTM C-623 in units of GPa.
- the glass high temperature viscosity temperature curve is determined in accordance with ASTM C-965, wherein the 100 P viscosity corresponds to a temperature T 100 in ° C; the viscosity is X poe corresponding to a temperature T X in ° C.
- the glass liquidus temperature T L was measured in accordance with ASTM C-829 using a ladder furnace method in °C.
- the glass strain point T st was measured in accordance with ASTM C-336 in °C.
- the surface tension of the glass at 1300 ° C was measured using a high temperature surface tension meter (Beijing Xuhui Xinrui Technology Co., Ltd., model ZLXS-II) in units of mN/m.
- composition and volume percentage of the residual gaseous inclusions in the glass were measured using a bubble analysis mass spectrometer (IPI, Germany, model GIA522) in vol.%.
- the number of gaseous inclusions in the glass was counted in units of /kg glass using a x200-fold polarizing microscope (Olympus, model BX51, the same below).
- the number of solid inclusions in the glass was counted using a x200-fold polarizing microscope in units of /kg glass.
- the content of ZrO 2 in the mixture was measured by X-ray fluorescence spectrometer (PANalytical, Model Magix (PW 2403)), and it was recorded as m 1 in wt%.
- the content of ZrO 2 in the glass was determined by X-ray fluorescence spectrometry.
- m 2 the unit is wt%.
- the glass transmittance was measured using an ultraviolet-visible spectrophotometer (Perkin Elmer, model LAMBDA25), and the thickness of the glass sample was 0.5 mm, and the transmittance at 308 nm was taken in units of %.
- the heat shrinkage rate after heat treatment was measured by the following heat treatment method (difference calculation method): the glass was heated from 25 ° C (measured initial length, labeled as L0) to a temperature increase rate of 5 ° C / min to 600 ° C and at 600 ° C After heat preservation for 10 min, then the temperature was lowered to 25 ° C at a cooling rate of 5 ° C / min, the glass length was contracted by a certain amount, and the length was measured again.
- the heat shrinkage rate Y t was expressed as: The final unit is expressed in ppm.
- the glass product is cut, ground, polished, and then cleaned and dried with deionized water to obtain a finished glass product having a thickness of 0.5 mm.
- the various properties of each glass finished product were measured, and the results are shown in Table 1-2, wherein the composition of gaseous inclusions in the glass is shown in Table 3.
- the low inclusion content glass obtained in Examples 1-13 of the present invention greatly reduces the obtained glass by selecting the components and preparation methods of the present invention.
- the content of gaseous inclusions and/or solid inclusions, and the inclusion exclusion process can be performed at a lower temperature, reducing the glass manufacturing cost.
- the obtained glass has a lower liquidus temperature T 1 and a physical property such as a suitable strain point T st , which is more advantageous for the application of the glass.
- Comparative Example 1 the raw materials used in Comparative Example 1 are not within the scope of the present invention, and the obtained physical properties such as strain point and heat shrinkage of the glass are inferior and cannot meet the application requirements; in Comparative Example 2, the inclusions of the present invention are not used. Conditions, while using the higher temperature commonly used inclusions commonly used in the prior art, NH 4 NO 3 was not added in Comparative Example 3 , but the inclusions in the glass obtained in Comparative Examples 2 and 3 were higher, much larger than the present application. The low inclusion content glasses of Examples 1-13.
- the method of the present invention has a significant effect on the problem that the content of gaseous inclusions and solid inclusions in the high viscosity glass such as the substrate glass is too high, and the high viscosity glass obtained by using the glass melt viscosity excluding the gaseous inclusions is simultaneously It has the advantages of relatively low content of gaseous inclusions and solid inclusions, high thermal stability, high stability of glass formation and high mechanical strength.
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Abstract
Description
Claims (16)
- 一种玻璃用组合物,其特征在于,该组合物含有50-64wt%的SiO 2、14-24wt%的Al 2O 3、0-7wt%的B 2O 3+P 2O 5、0.5-7wt%的MgO、1-10wt%的CaO、0-9wt%的SrO、0.1-14wt%的BaO、0.1-5wt%的ZnO、0.1-4wt%的TiO 2、0.1-7wt%的Y 2O 3+La 2O 3+Nd 2O 3、<0.05wt%的R 2O,其中,R 2O为Li 2O、Na 2O、K 2O含量的总和,并且该组合物满足如下条件:(1)粘度为100泊对应的温度T 100为1730℃以上;(2)1300℃表面张力小于420mN/m。
- 根据权利要求1所述的玻璃用组合物,其特征在于,该组合物还满足:(3)液相线温度T L低于1180℃;优选地,该组合物还满足:(4)应变点T st为710℃以上。
- 根据权利要求1所述的玻璃用组合物,其特征在于,该组合物含有56-63wt%的SiO 2、17-22wt%的Al 2O 3、0-5.2wt%的B 2O 3+P 2O 5、1-5wt%的MgO、2-8wt%的CaO、0-8wt%的SrO、1-12wt%的BaO、0.3-4wt%的ZnO、0.2-3wt%的TiO 2、0.1-4wt%的Y 2O 3+La 2O 3+Nd 2O 3、<0.05wt%的R 2O,其中,R 2O为Li 2O、Na 2O、K 2O含量的总和。
- 根据权利要求1或3所述的玻璃用组合物,其特征在于,该组合物含有的B 2O 3为0-5wt%,P 2O 5为0-7wt%,优选为0-5wt%;优选地,该组合物含有的Y 2O 3为0-2wt%、La 2O 3为0-3wt%、Nd 2O 3为0-3wt%;优选地,该组合物含有的Li 2O为0.01wt%以下、Na 2O为0.01wt%以下、K 2O为0.01wt%以下。
- 根据权利要求1所述的玻璃用组合物,其特征在于,所述组合物还含有化学澄清剂;优选地,所述化学澄清剂为氧化锡;优选地,以该组合物的总重量为基准,所述澄清剂的含量不大于1wt%。
- 根据权利要求1-5中任意一项所述的玻璃用组合物,其特征在于,通过用所述玻璃用组合物的配比将原料与NH 4NO 3混合均匀后进行熔融处理,然后在粘度为210-500泊范围内除去气态夹杂物,并依次进行成型处理和退火处理后得到的玻璃满足:等效球形直径(D.EQ.)大于0.02mm的气态夹杂物含量小于0.5个/Kg玻璃。
- 一种低夹杂物含量的玻璃,其采用权利要求1-5中任一项所述的玻璃用组合物制备。
- 根据权利要求7所述的低夹杂物含量的玻璃,其特征在于,该低夹杂物含量的玻璃的制备方法为:用权利要求1-5中任意一项所述的玻璃用组合物的配比将原料与NH 4NO 3混合均匀后进行熔融处理,在粘度为210-500泊范围内除去气态夹杂物,然后依次进行成型处理和退火处理。
- 一种低夹杂物含量的玻璃的制备方法,其特征在于,该方法包括用权利要求1-5中任意一项所述的玻璃用组合物的配比将原料与NH 4NO 3混合均匀后进行熔融处理,在粘度为210-500泊范围内除去气态夹杂物,然后依次进行成型处理和退火处理。
- 根据权利要求9所述的低夹杂物含量的玻璃的制备方法,其特征在于,相对于所述玻璃用组合物配比的原料,所述NH 4NO 3的用量为 0.2-10wt%,优选为1-8wt%,更优选为2.5-5wt%;优选地,在粘度为220-350泊范围内除去气态夹杂物;更优选地,在粘度为250-300泊范围内除去气态夹杂物。
- 根据权利要求9所述的低夹杂物含量的玻璃的制备方法,其特征在于,该方法还包括对退火处理后的产物进行机械加工处理;优选地,该方法还包括:对机械加工处理得到的产物进行二次熔融拉薄处理;优选地,通过所述机械加工处理或者二次熔融拉薄处理使制备得到的玻璃厚度小于0.1mm。
- 根据权利要求9-11中任意一项所述的制备方法制备得到的低夹杂物含量的玻璃。
- 根据权利要求7、8和12中任意一项所述的低夹杂物含量的玻璃,其特征在于,所述低夹杂物含量的玻璃满足如下条件:(1)等效球形直径(D.EQ.)大于0.02mm的气态夹杂物含量小于0.5个/Kg玻璃,并且以体积百分比为基准,所述气态夹杂物成分中N 2含量≥50vol.%;(2)ZrO 2含量与高温熔炼前混合料中ZrO 2含量的差值Δ ZrO2≤0.02wt%;(3)大于0.02mm的固态夹杂物含量小于0.5个/kg玻璃。
- 根据权利要求13所述的低夹杂物含量的玻璃,其特征在于,所述低夹杂物含量的玻璃满足如下条件:(1)等效球形直径(D.EQ.)大于0.02mm的气态夹杂物含量小于0.1 个/Kg玻璃,并且以体积百分比为基准,所述气态夹杂物成分中N 2含量≥60vol.%;(2)ZrO 2含量与高温熔炼前混合料中ZrO 2含量的差值Δ ZrO2≤0.015wt%;(3)大于0.02mm的固态夹杂物含量小于0.1个/kg玻璃。
- 根据权利要求12-14中任意一项所述的低夹杂物含量的玻璃,该玻璃满足如下条件:密度低于2.7g/cm 3,50-350℃范围内的热膨胀系数低于40×10 -7/℃,杨氏模量高于80GPa,波长为308nm处透过率为50%以上,600℃/10min条件下热收缩小于15ppm。
- 根据权利要求12-15中任意一项所述的低夹杂物含量的玻璃在显示器件、太阳能电池衬底玻璃、安全玻璃、防弹玻璃、智能汽车玻璃、智能交通显示屏、智能橱窗或者智能卡票中的应用。
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