TW202017881A - Composition for glass, and aluminosilicate glass and preparation method therefor and use thereof - Google Patents

Abstract

A composition for glass, and an aluminosilicate glass and a preparation method therefor and use thereof. The composition for glass comprises, in terms of oxides, 62-69 mol% of SiO2, 11-15 mol% of Al2O3, 0-3 mol% of B2O3, 7-11 mol% of MgO, 2-8 mol% of CaO, 3-8 mol% of SrO, 0-2 mol% of BaO, 0.01-2 mol% of ZnO, 0.02-0.65 mol% of RE2O3, and less than 0.05 mol% of R2O; RE is a rare earth element, and R is an alkali metal. The aluminosilicate glass prepared with the preparation method has the advantages of high thermostability, high ultraviolet transmittance andhigh mechanical stability and is suitable for large industrial production.

Description

Composition for glass, aluminosilicate glass, and preparation method and application thereof

The invention relates to the field of glass manufacturing, in particular to a glass composition, aluminosilicate glass, and preparation method and application thereof.

With the rapid development of the photoelectric industry, the demand for various display devices is growing, such as active matrix liquid crystal display (AMLCD), organic light emitting diode (OLED) and active matrix liquid crystal display (LTPS TFT) using low-temperature polysilicon technology -LCD) devices, these display devices are based on the use of thin-film semiconductor materials to produce thin-film transistor (TFT) technology. Mainstream silicon-based TFTs can be divided 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 The applied technology, amorphous silicon (a-Si) TFT technology, the processing temperature in the production process can be completed at a temperature of 300-450 ℃. LTPS poly-silicon (p-Si) TFTs need to be processed multiple times at higher temperatures during the manufacturing process. The substrate must not be deformed during multiple high-temperature processes, which puts higher requirements on the glass performance of the substrate, and the preferred strain The point is higher than 650°C, more preferably higher than 670°C, 700°C, and 720°C, so that the substrate has as little thermal shrinkage as possible in the panel manufacturing process. At the same time, the expansion coefficient of the glass substrate needs to be close to that of silicon to minimize stress and damage. Therefore, the preferred linear thermal expansion coefficient of the substrate glass is between 28-41×10 ^-7 /℃. In order to facilitate production, the glass used as the display substrate should have a low melting temperature, high temperature surface tension, high temperature volume resistivity, and liquidus temperature.

For the glass substrate used for flat display, it is necessary to form a transparent conductive film, an insulating film, a semiconductor (polycrystalline silicon, amorphous silicon, etc.) film and a metal film on the surface of the underlying substrate glass by sputtering, chemical vapor deposition (CVD), etc. Various circuits and patterns are formed by photo-etching technology. 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 the heat treatment process and damage The characteristics of semiconductor films, therefore, the glass should be free of alkali metal oxides, the first choice is SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , alkaline earth metal oxide RO (RO = Mg, Ca, Sr, BaO), etc. The main component is alkaline earth aluminosilicate glass.

The annealing point and strain point of most silicate glass increase as the content of glass former increases and the content of modifier decreases. But at the same time it will cause difficulties in high temperature melting and clarification, resulting in increased corrosion of refractory materials, increasing energy consumption and production costs. Therefore, through component improvement, the low-temperature viscosity is increased while ensuring that the high-temperature viscosity will not be greatly improved, and even reduced is the best breakthrough to improve thermal stability.

The alkali-free glass used for display has a high viscosity and usually needs to be heated to above 1600°C during melting. The commonly used flame melting technology has shown insufficient in terms of quality and process control of alkali-free glass. Auxiliary electric melting or all electric melting technology must be adopted to achieve efficient melting of glass. The alkali-free glass for display is an electrical insulator at room temperature, with a resistivity of 10 ¹⁹ -10 ²² Ω•cm. When the alkali-free glass for display is heated, its electrical conductivity increases significantly with increasing temperature, usually melting The non-alkali glass liquid used in the state shows a resistivity of 100-300Ω·cm, which is a good conductor of electricity and can be used as a Joule effect heating element. However, relative to the resistivity of high alkali metal silicate glass which is usually less than 10Ω·cm in the molten state, the alkali-free glass used for display still has the problem of high resistivity, which is not conducive to improving thermal efficiency. Electric fluxing or full electric melting technology uses the self-heating characteristics of molten glass liquid at high temperature to convert electrical energy into the form of heat energy, so that the glass heats itself from the inside to increase its internal temperature, reduce the temperature difference between the upper and lower layers of the glass liquid, and improve For the clarification effect, the thermal efficiency is much higher than the heat absorbed by the flame radiation heating, thereby saving energy, greatly increasing the glass melting rate, and improving the quality of the glass liquid. The resistivity of alkali-free glass liquid at high temperature is the key to affect the Joule heating effect of glass. If the high temperature resistivity is too small, it may weaken the Joule heating effect, and its own calorific value can not meet the needs of melting, and it will also cause the deterioration of the high temperature viscosity performance; too high high temperature resistivity will affect the conductivity of the glass liquid, which will cause The current flows to the refractory material and causes high temperature erosion of the refractory material. Therefore, the resistivity of molten glass liquid at high temperature must be controlled within a reasonable range to achieve the purpose of improving the melting efficiency and improving the quality of the glass liquid.

During the processing of the glass substrate, the substrate glass is placed horizontally. Under the effect of its own weight, the glass sags to a certain extent. The degree of sag is proportional to the density of the glass and inversely proportional to the elastic modulus of the glass. With the development of substrate manufacturing in the direction of large size and thinning, the sag of the glass plate in manufacturing must be paid attention to. Therefore, the composition should be designed so that the substrate glass has the lowest possible density and the highest possible elastic modulus.

In some flat display manufacturing processes, it is necessary to use ultraviolet light as energy to separate the display unit from the substrate glass in contact with it. In order to reduce the cost of separation and increase the probability of success, it is necessary for the glass substrate to have a high and stable transmittance in the ultraviolet region. For example, for a glass substrate with a thickness of 0.5 mm, the transmittance at a wavelength of 308 nm is required to be higher than 50 %, and the transmission rate between different glass substrates in the batch is extremely poor within 1%. However, due to unavoidable factors, SO ₃ , Fe ₃ O ₄ and other components that have strong absorption in the ultraviolet region are always introduced too much and too little in the manufacturing process of glass substrates, so various impurities are strictly controlled in the manufacturing process of glass substrates The content of the components is beneficial to the manufacture of 308nm high-transmittance glass substrates.

Therefore, the purpose of the present invention is to overcome the problems of the existing aluminosilicate glass that the display substrate glass is difficult to melt and the transmittance at 308 nm is low, to provide a glass composition, aluminosilicate glass and preparation thereof Method and application, the aluminosilicate glass has high thermal stability, high ultraviolet transmittance and high mechanical stability.

In order to achieve the above object, the first aspect of the present invention provides a glass composition, based on the total moles of the glass composition, based on the oxide, the glass composition contains 62-69mol% SiO ₂ , 11-15mol% Al ₂ O ₃ , 0-3mol% B ₂ O ₃ , 7-11mol% MgO, 2-8mol% CaO, 3-8mol% SrO, 0-2mol% BaO, 0.01 -2mol% ZnO, 0.02-0.65mol% RE ₂ O ₃ and less than 0.05mol% R ₂ O, where RE is a rare earth element and R is an alkali metal.

Preferably, based on the total moles of the glass composition, the glass composition contains 65-68 mol% SiO ₂ , 11.5-14.5 mol% Al ₂ O ₃ , 0-1.5 in terms of oxides mol% B ₂ O ₃ , 7.5-9mol% MgO, 3-6mol% CaO, 4.5-6mol% SrO, 0.1-0.9mol% BaO, 0.05-1.9mol% ZnO, 0.1-0.46mol% RE ₂ O ₃ and less than 0.05mol% R ₂ O.

Preferably, it is characterized in the form of Fe ₂ O ₃ based on the total moles of the glass composition, and the glass composition contains Fe ₂ O _{3 of} 150 ppm or less.

Preferably, based on the total moles of the glass composition as a basis, it is characterized in the form of elemental halogen, and the glass composition contains 0.01-0.6 mol% of halogen; wherein, the halogen is F and Cl.

Preferably, the content of each component in the composition for glass satisfies 0<Z≦1 in terms of mole percent, where Z is calculated by the following formula: Z=-10.31+(16.04×SiO ₂ +6 ×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO); Among them, SiO ₂ , Al ₂ O ₃ , MgO, CaO, SrO, BaO and ZnO each represent the mole percentage of the component in the glass composition.

Preferably, the content of each component in the glass composition satisfies 0.1<Y≤0.67 in terms of mole percent, wherein the Y value is calculated by the following formula: Y=-10.31+(16.04×SiO ₂ + 6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO-102.7×RE ₂ O ₃ ); Among them, SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO, RE ₂ O ₃ each represent the mole percentage of the component in the glass composition.

Preferably, the content of each component in the glass composition satisfies R=0.05-0.48 in terms of mole percent, where the R value is calculated by the following formula: R=-10.31+(16.04×SiO ₂ + 6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO-102.7×RE ₂ O ₃ -39.6×(F+Cl)); Among them, SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO, RE ₂ O ₃ , F, Cl each represent the mole percentage of the component in the glass composition .

Preferably, in terms of mole percent, (MgO+ZnO+SrO)/(MgO+CaO+SrO+BaO+ZnO)≥0.5.

Preferably, (MgO+SrO)/(1-MO)≥0.6, wherein, based on the total moles of the glass composition, MO stands for SiO ₂ , Al ₂ O ₃ , B in the glass composition The sum of the molar percentages of all components except ₂ O ₃ .

Preferably, the RE is yttrium and lanthanide, and the R is Li, Na and K.

Preferably, the RE is one or more of Y, La, Nd and Lu.

Preferably, the glass composition further contains a clarifying agent, and the content of the clarifying agent is less than or equal to 0.5 mol% based on the total moles of each component.

In a second aspect, the present invention provides a method for preparing an aluminosilicate glass, which includes sequentially performing melting treatment, molding treatment, annealing treatment, and mechanical processing treatment on the glass composition of the present invention.

Preferably, the method further includes adding fluoride and/or chloride to the glass composition.

Preferably, based on the total weight of the mixture, the amount of the fluoride added is 0.02-0.7wt%.

Preferably, based on the total weight of the mixture, the added amount of the chloride is 0.02-0.7wt%.

In a third aspect, the present invention provides aluminosilicate glass prepared by the above method.

Preferably, the resistivity of the glass melt at 1600°C of the aluminosilicate glass is ≤100Ω•cm.

Preferably, the viscosity of the glass melt is ≤300 poise at 1600°C.

Preferably, the liquidus viscosity of the glass melt η _L ≥ 20000 poise.

Preferably, the viscosity of the glass melt is the corresponding temperature T ₂₀₀ ≤1630°C at ₂₀₀ poises.

Preferably, the viscosity at 35000 poises corresponds to a temperature T ₃₅₀₀₀ ≤ 1240°C.

Preferably, the corresponding annealing point at a viscosity of 10 ¹³ poise is ≥770°C.

Preferably, the temperature corresponding to a viscosity of 10 ^4.5 poise is ≤1250°C; the liquidus temperature T _L ≤1250°C; the difference between the temperature corresponding to a viscosity of 10 ^4.5 poise and the liquidus temperature T _L is ≥-20°C.

Preferably, the elemental sulfur content in the form of elemental sulfur S in the aluminosilicate glass is ≤500 ppm.

Preferably, the hydroxyl content in the aluminosilicate glass is ≤0.3/mm.

Preferably, the density of the aluminosilicate glass is less than 2.7g/cm ³ ; the coefficient of thermal expansion in the range of 50-350°C is less than 40×10 ^-7 /°C; Young's modulus ≥83GPa; specific modulus ≥32GPa/ (g×cm ^-3 ).

Preferably, the transmittance at a wavelength of 308 nm is ≥73%; the transmittance at a wavelength of 550 nm is ≥92%.

Preferably, the heat shrinkage at 600°C/30min is <20ppm.

In a fourth aspect, the present invention provides the use of the glass composition or aluminosilicate glass according to the present invention in the preparation of display devices and/or solar cells.

The aluminosilicate glass of the present invention has high thermal stability, high ultraviolet transmittance and excellent mechanical stability, and can be used for preparing display devices and/or solar cells, especially suitable for preparing substrate glass substrate materials for flat panel display products and/or Or glass film material for screen surface protection, carrier glass material for flexible display products and/or surface encapsulation glass material and/or glass film material for screen surface protection, base glass substrate material for flexible solar cells, safety glass, Bulletproof glass, smart car glass, smart traffic display screens, smart shop windows and smart card tickets, and other applications that require high thermal stability, high UV transmittance and mechanical stability glass materials.

The specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

In the first aspect, the present invention provides a composition for glass, based on the total moles of the composition for glass, based on oxide, the composition for glass contains 62-69 mol% of SiO ₂ and 11-15 mol % Al ₂ O ₃ , 0-3mol% B ₂ O ₃ , 7-11mol% MgO, 2-8mol% CaO, 3-8mol% SrO, 0-2mol% BaO, 0.01-2mol% ZnO, 0.02-0.65 mol% RE ₂ O ₃ and less than 0.05 mol% R ₂ O, where RE is a rare earth element and R is an alkali metal.

In a preferred embodiment of the present invention, based on the total moles of the glass composition, the glass composition contains 65-68 mol% of SiO ₂ and 11.5-14.5 mol% of Al _{2 in} terms of oxides. O ₃ , 0-1.5mol% B ₂ O ₃ , 7.5-9mol% MgO, 3-6mol% CaO, 4.5-6mol% SrO, 0.1-0.9mol% BaO, 0.05-1.9mol% ZnO , 0.1-0.46mol% RE ₂ O ₃ and less than 0.05mol% R ₂ O.

In the glass composition of the present invention, SiO ₂ is a glass-forming body, if the content is too low, it is not conducive to the enhancement of thermal stability, the expansion coefficient is too high, and the glass is easily devitrified; increasing the SiO ₂ content helps the glass Lightweight, the coefficient of thermal expansion is reduced, the strain point is increased, and the chemical resistance is increased, but the high temperature viscosity is increased, which is not conducive to melting, and it is difficult for ordinary kilns to meet their melting needs. Therefore, considering the total number of moles of the glass composition as a basis, the content of the SiO ₂ is 62-69 mol%, preferably 65-68 mol%, specifically, for example, 62 mol, based on the oxide %, 62.2mol%, 62.95mol%, 63.8mol%, 64.6mol%, 64.9mol%, 65mol%, 65.4mol%, 65.7mol%, 66mol%, 66.8mol%, 66.9mol%, 67.08mol%, 67.9mol %, 67.95 mol%, 68 mol%, 68.5 mol%, 68.9 mol%, 69 mol%, and any value in the range formed by any two of these values.

In the glass composition of the present invention, Al ₂ O _{3 is} used to increase the strength of the glass structure. If the content is less than 11 mol%, the glass is easy to devitrify and is easily eroded by external moisture and chemical reagents. A high content of A1 ₂ O ₃ contributes to the increase of glass strain point and flexural strength, but excessively high glass is prone to devitrification. Therefore, considering the total number of moles of the glass composition as a basis, the content of the Al ₂ O ₃ is 11-15 mol%, preferably 11.5-14.5 mol%, specifically, for example, Can be 11mol%, 11.5mol%, 11.6mol%, 11.9mol%, 12mol%, 12.2mol%, 12.6mol%, 12.69mol%, 13.1mol%, 13.2mol%, 13.4mol%, 13.5mol%, 13.8mol %, 14.4 mol%, 14.5 mol%, 14.7 mol%, 14.9 mol%, 15 mol%, and any value in the range formed by any two of these values.

In the glass composition of the present invention, B ₂ O ₃ can form glass alone and is a very good flux. It is difficult to form B ₂ O ₃ under high-temperature melting conditions [BO ₄ ], which can reduce the viscosity at high temperature and B at low temperature. There is a tendency to capture free oxygen to form [BO ₄ ], which makes the structure tend to be tight, improve the low-temperature viscosity of the glass, and prevent the occurrence of crystallization. However, too much B ₂ O ₃ will greatly reduce the strain point of the glass. Therefore, considering the total moles of the glass composition as a basis, the content of the B ₂ O ₃ is 0-3 mol%, preferably 0-1.5 mol%, more preferably 0, based on the oxide , Specifically, for example, it can be 0, 0.1mol%, 0.36mol%, 0.71mol%, 0.9mol%, 1.3mol%, 1.5mol%, 1.7mol%, 1.8mol%, 2mol%, 2.1mol%, 2.37mol %, 2.8mol%, 3mol% and any mass percentage between any two adjacent mass percentages.

In the glass composition of the present invention, MgO has the characteristics of greatly increasing the Young's modulus and specific modulus of the glass, lowering the high-temperature viscosity, and making the glass easy to melt. When the content of alkaline earth metal in the glass is small, the introduction of the ion Mg ²⁺ outside the network with a large electric field strength is likely to cause local accumulation in the structure, which increases the short-range order range. In this case, the introduction of more intermediate oxide Al ₂ O ₃ in the state of [AlO ₄ ], because these polyhedrons are negatively charged, attract some cations outside the network, so that the degree of glass accumulation and crystallization The ability is reduced; when the content of alkaline earth metal is large and the network fracture is serious, the introduction of MgO can make the broken silicon tetrahedron reconnect and reduce the crystallization ability of the glass. Therefore, when adding MgO, pay attention to the mixing ratio with other components. Compared with other alkaline earth metal oxides, the presence of MgO will bring lower expansion coefficient and density, higher chemical resistance, strain point and elastic modulus. If MgO is greater than 11 mol%, the glass resistance will deteriorate, and at the same time, the glass will be easily devitrified. Therefore, considering the total moles of the glass composition as a reference, the content of the MgO is 7-11 mol%, preferably 7.5-9 mol%, specifically, for example, 7 mol%, based on the oxide , 7.1mol%, 7.5mol%, 7.6mol%, 7.8mol%, 7.9mol%, 8mol%, 8.1mol%, 8.2mol%, 8.5mol%, 8.9mol%, 9mol%, 9.1mol%, 9.8mol% , 10.2 mol%, 10.4 mol%, 11 mol%, and any two of these values constitute any value in the range.

In the composition for glass of the present invention, CaO is used to promote melting of glass and adjust glass formability. If the content of calcium oxide is less than 2 mol%, it is not easy to reduce the viscosity of the glass. If the content is too large, the glass will be prone to devitrification, the coefficient of thermal expansion will also be greatly increased, and the brittleness will increase, which is detrimental to the subsequent process. Therefore, considering the total number of moles of the glass composition as a basis, the content of the CaO is 2-8 mol%, preferably 3-6 mol%, specifically, for example, 2 mol% , 2.7mol%, 3mol%, 3.3mol%, 3.9mol%, 4mol%, 4.1mol%, 4.4mol%, 4.65mol%, 4.9mol%, 5mol%, 5.7mol%, 6mol%, 6.6mol%, 7mol %, 7.4mol%, 7.95mol%, 8mol%, and any value in the range formed by any two of these values.

In the glass composition of the present invention, SrO can be used as a flux and a component to prevent the glass from devitrification. If the content is too much, the glass density will be too high, resulting in a decrease in the specific modulus of the product. Sr ²⁺ is a divalent metal ion with a large ionic radius and has a high coordination number. It is often filled in the gap of the tetrahedral network skeleton in alkali-free glass, which has the characteristics of improving chemical stability and mechanical stability. However, too much content will increase the density and increase the incidence of cracks, devitrification and phase separation. Therefore, considering the total number of moles of the glass composition as a reference, the content of the SrO is 3-8 mol%, preferably 4.5-6 mol%, specifically, for example, 3 mol%, based on the oxide , 3.6mol%, 4.04mol%, 4.2mol%, 4.5mol%, 4.6mol%, 4.7mol%, 4.85mol%, 4.9mol%, 5mol%, 5.2mol%, 5.3mol%, 5.6mol%, 5.85mol %, 6 mol%, 6.1 mol%, 6.9 mol%, 7.63 mol%, 8 mol%, and any value in the range formed by any two of these values.

In the composition for glass of the present invention, BaO serves as a flux and a component for preventing crystallization of glass. If the content is too large, the high-temperature volume resistivity of the glass will increase, the density will be too high, and the specific modulus of the product will decrease. Therefore, considering the total number of moles of the glass composition as a basis, the content of the BaO is 0-2 mol%, preferably 0.1-0.9 mol%, specifically, for example, 0 , 0.08mol%, 0.1mol%, 0.11mol%, 0.2mol%, 0.27mol%, 0.36mol%, 0.4mol%, 0.5mol%, 0.85mol%, 0.9mol%, 1.02mol%, 1.33mol%, 1.7 mol%, 2mol%, and any value in the range formed by any two of these values.

In the glass composition of the present invention, the divalent metal oxide can be divided into two categories according to its position in the periodic table of the elements and its effect on properties: one is an alkaline earth metal oxide located in the main group, and its ion R ^{2 +} Has 8 external electronic structures; the second type is located in the subgroup of the periodic table (such as ZnO, CdO, etc.), and its ion R ²⁺ has 18 external electronic structures. The structural state of both in glass and the effect on glass properties are different. ZnO can reduce the high-temperature viscosity of the glass (such as 1500 ℃), which is conducive to eliminating bubbles; at the same time, it can improve the strength and hardness, increase the chemical resistance of the glass below the softening point, and reduce the coefficient of thermal expansion of the glass. In non-alkali glass or low-alkali glass systems, adding an appropriate amount of ZnO helps to suppress crystallization and can reduce the crystallization temperature. In theory, ZnO in alkali-free glass or low-alkali glass is introduced into the glass as the outer body of the network, and generally exists in the form of [ZnO ₄ ] at high temperature, which is more loose than the glass structure of [ZnO ₆ ], and does not contain ZnO Compared with the glass at the same high temperature, the glass containing ZnO has a lower viscosity and a faster atomic movement speed, and cannot form crystal nuclei. It is necessary to further reduce the temperature to facilitate the formation of crystal nuclei, thus reducing the crystallization of the glass Upper limit temperature. Too much ZnO content will greatly reduce the strain point of the glass. Therefore, considering the total number of moles of the glass composition as a basis, the content of the ZnO is 0.01-2 mol%, preferably 0.05-1.9 mol%, specifically, for example, 0.01 mol%, 0.02mol%, 0.05mol%, 0.1mol%, 0.13mol%, 0.4mol%, 0.5mol%, 0.79mol%, 0.9mol%, 0.99mol%, 1mol%, 1.43mol%, 1.49mol%, 1.2 mol%, 1.27 mol%, 1.43 mol%, 1.48 mol%, 1.5 mol%, 1.6 mol%, 1.9 mol%, 2 mol%, and any value in the range formed by any two of these values.

In the glass composition of the present invention, the rare earth oxide RE ₂ O ₃ has a unique ability to improve certain properties of the glass, such as the flexural strength, elastic modulus, strain point and other properties of the glass. After being added, it will increase sharply, which will reduce the brittleness of the glass, increase the fracture toughness greatly, and reduce the high-temperature viscosity and high-temperature volume resistivity of the glass. convenient. After the network outer body such as alkaline earth metal and ZnO is introduced into the glass composition, the excess oxygen atoms break the bridge oxygen bonds in the glass structure to generate non-bridge oxygen. The presence of these non-bridge oxygen significantly reduces the bending strength of the glass. The addition of RE ₂ O ₃ causes the internal structure of the glass to change. The generated Si-O-RE chemical bond reconnects the island-like network elements in the glass, which can improve the network structure of the glass, which can greatly improve the glass's resistance. Bending strength, elastic modulus, strain point, chemical stability, and low temperature volume resistivity. However, when RE ₂ O ₃ is further increased, due to the decrease in the amount of unbridged oxygen available for adjustment, excessive RE ₂ O ₃ has little effect on the above properties of the glass. Therefore, from the comprehensive consideration of other properties such as absorption spectrum, the content of the RE ₂ O ₃ is 0.02-0.65 mol% based on the total moles of the glass composition as an oxide, preferably 0.1-0.46 mol%, the RE is yttrium and lanthanide. In a specific embodiment of the present invention, preferably, the RE is Lu or Lu and at least one of Y, La, and Nd, and the content of Lu is ≥0.05 mol%. Specifically, RE ₂ O ₃ may be, for example, 0.02mol%, 0.05mol%, 0.1mol%, 0.12mol%, 0.19mol%, 0.20mol%, 0.23mol%, 0.24mol%, 0.3mol%, 0.39mol%, Any value within the range of 0.4 mol%, 0.46 mol%, 0.59 mol%, 0.65 mol%, and any two of these values.

In the glass composition of the present invention, a small amount of iron oxide inevitably introduced through the inherent impurities of raw materials, production process contact, etc. will lead to a decrease in the transmittance of the glass in the ultraviolet spectral region (for example, at a wavelength of 308 nm). The laser lift-off technology (LLO) in the manufacturing process of flexible OLED panels has an adverse effect. Therefore, reducing the introduction of iron oxides in various raw materials is conducive to improving the UV transmittance, but excessive reduction will lead to a substantial increase in the cost of raw materials. After introducing a certain amount of fluoride (such as calcium fluoride) in the glass manufacturing process, it can be used as a high-temperature flux to effectively reduce the viscosity of the glass melt, high-temperature surface tension and high-temperature volume resistivity. It has a certain clarification when used in combination with sulfate Effect; on the other hand, the addition of fluorine can increase the transmittance of the glass at 308nm without deliberately reducing the content of iron oxides, and improve the transmittance of the ferrous glass at 308nm in the ultraviolet region, but too much content can easily lead to glass phase separation Or precipitation, causing opacification or crystallization. Therefore, considering, to the total number of moles of the glass composition as a reference, characterized in a Fe ₂ O ₃ form, the content of the ₂ O ₃ Fe ≤150ppm, preferably ≤100ppm, more preferably 80 ppm, more It is preferably ≤50 ppm. Based on the total moles of the glass composition as a basis, it is characterized in the form of elemental halogen, and the content of the halogen is 0.01-0.6 mol%, wherein the halogen is F and Cl, preferably 0.1-0.55 mol%. Specifically, for example, it may be 0.01 mol%, 0.02 mol%, 0.06 mol%, 0.09 mol%, 0.1 mol%, 0.15 mol%, 0.21 mol%, 0.3 mol%, 0.36 mol%, 0.44 mol%, 0.42 mol%, 0.48 mol%, 0.52 mol%, 0.55 mol%, 0.6 mol%, and any value in the range formed by any two of these values.

In the glass composition of the present invention, it is inevitable that a small amount of alkali metal oxide will be introduced through the inherent impurities of the raw materials, which has an adverse effect on the high-temperature panel process, so the alkali content should be strictly controlled. Based on the total moles of the composition for glass, based on the oxide, the alkali metal oxide R ₂ O>0.05mol%, where R ₂ O is the content of Li ₂ O, Na ₂ O, K ₂ O sum.

In a specific embodiment of the present invention, a certain amount of sulfates, such as inorganic sulfates such as calcium sulfate and strontium sulfate, may be added as components for eliminating gaseous inclusions. However, from the perspective of spectral absorption in the ultraviolet region, in order to obtain high transmittance in the ultraviolet region, it is preferred that the residual sulfur element content in the form of elemental sulfur S in the glass be ≤500 ppm, and further preferably ≤100 ppm.

Preferably, the content of each component in the glass composition satisfies 0<Z≤1 in terms of mole percent, preferably 0.5-0.9, further preferably 0.55-0.85, and more preferably 0.6-0.8, wherein , Z is calculated by the following formula: Z=-10.31+(16.04×SiO ₂ +6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+ 3.77×SrO+26.65×BaO-7.82 ×ZnO); wherein, SiO ₂ , Al ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO each represent the mole percentage of the component in the glass composition.

Preferably, in terms of mole percent, the content of each component in the glass composition satisfies 0.1<Y≤0.67, preferably 0.33-0.37, where the Y value is calculated by the following formula: Y=-10.31 +(16.04×SiO ₂ +6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO-102.7×RE ₂ O ₃ ); where , SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO, RE ₂ O ₃ each represent the mole percentage of the component in the glass composition.

Preferably, the content of each component in the glass composition satisfies R=0.05-0.48, preferably 0.23-0.48 in terms of mole percent, where R value is calculated by the following formula: R=-10.31 +(16.04×SiO ₂ +6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO-102.7×RE ₂ O ₃ -39.6× (F+Cl)); wherein, SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO, RE ₂ O ₃ , F, Cl each represent the component accounted for the glass Molar percentage in the composition.

Preferably, in terms of mole percent, (MgO+ZnO+SrO)/(MgO+CaO+SrO+BaO+ZnO)≥0.5.

Preferably, in terms of percent moles, (MgO+SrO)/(1-MO) ≥ 0.6, where, based on the total moles of the glass composition, MO stands for SiO _{2 in the} glass composition. , Al ₂ O ₃ , B ₂ O ₃ excluding the total molar percentage of all components.

In the composition for glass of the present invention, the composition for glass further contains a clarifying agent, the content of the clarifying agent is ≤0.5 mol% based on the total moles of each component, and the chemical clarifying agent is preferably It is at least one of strontium sulfate, calcium sulfate, strontium nitrate, and stannous oxide.

In a second aspect, the present invention provides a method for preparing an aluminosilicate glass, which includes sequentially performing melting treatment, molding treatment, annealing treatment, and mechanical processing treatment on the glass composition of the present invention.

In the method of the present invention, preferably, the method further includes adding fluoride and/or chloride to the glass composition; further preferably, based on the total weight of the mixture, the fluorine The added amount of the compound is 0.02-0.7wt%; more preferably, based on the total weight of the mixture, the added amount of the chloride is 0.02-0.7wt%. In the specific embodiment of the present invention, a mixture of calcium fluoride and strontium chloride is selected, and the content of the mixture of calcium fluoride and strontium chloride is 0.05-1 wt% based on the total weight of the mixture. The weight ratio of calcium fluoride and strontium chloride is 1:1-5. Among them, fluoride such as calcium fluoride is a high-temperature flux, which has the effect of reducing the viscosity of the glass melt, high-temperature surface tension and high-temperature volume resistivity. It has a certain clarifying effect when used in combination with sulfate; on the other hand, fluorine can improve the iron content The transmittance of glass; chloride, such as strontium chloride as a high-temperature flux, has the effect of reducing the high-temperature surface tension and high-temperature volume resistivity of the glass melt, and it has a certain clarifying effect when used in combination with sulfate; on the other hand, chloride It can react with the hydroxyl OH groups in the glass, reduce the hydroxyl content of the glass, and strengthen the glass network structure, so as to achieve the effect of improving the thermal stability of the glass. However, excessive amounts of fluoride and/or chloride are likely to separate or precipitate in the glass, causing opacification or crystallization.

In the method of the present invention, preferably, the mixture is melted at a high temperature through a continuous melting pool kiln; further preferably, the mixture is melted at a high temperature using electric heating and/or gas heating; further preferably, the Heating provides more than 60% of the total energy of the molten glass; the electric heating refers to heating the mixture and the glass liquid directly through multiple pairs of electrodes to promote the completion of silicate reaction, glass formation, clarification and homogenization, etc. In the process, the electrode may be a tin oxide electrode, a molybdenum oxide electrode, and/or a platinum electrode.

In the method of the present invention, for the specific limitation of the composition for glass, please refer to the corresponding description in the foregoing, which will not be repeated here.

In the method of the present invention, preferably, the conditions of the melt treatment include: the temperature is lower than 1700°C and the time is longer than 1h. Those 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 repeated here.

In the method of the present invention, preferably, the conditions of the annealing treatment include: the temperature is higher than 780°C and the time is longer than 0.1h. Those skilled in the art can determine the specific annealing temperature and annealing time according to the actual situation, which is well known to those skilled in the art and will not be repeated here.

In the method of the present invention, the machining process is not particularly limited, and may be various machining processes common in the art. For example, the product obtained by the annealing process may be cut, polished, and polished.

Preferably, the method further includes: performing a secondary melting and thinning treatment on the product obtained by the mechanical processing treatment.

Preferably, the conditions of the mechanical processing process or the secondary melt thinning process are controlled to prepare glass with a thickness of less than 0.1 mm.

In a third aspect, the present invention provides aluminosilicate glass prepared by the above method.

In the aluminosilicate glass of the present invention, the resistivity of the glass melt at 1600°C is ≤100 Ω·cm, preferably ≤90 Ω·cm, and more preferably ≤80 Ω·cm.

In the aluminosilicate glass of the present invention, the viscosity of the glass melt at 1600°C is ≤300 poise, preferably ≤250 poise, and more preferably ≤230 poise.

Aluminosilicate glass according to the present invention, the liquidus viscosity of the glass melt η _L ≥20000 poise, preferably η _L ≥60000 poise.

The aluminosilicate glass of the present invention has a viscosity T ₂₀₀ ≤1630°C at a viscosity of 200 poises, preferably T ₂₀₀ ≤1620°C.

The aluminosilicate glass of the present invention has a temperature T ₃₅₀₀₀ ≤1240°C, preferably ≤1230°C at a viscosity of 35000 poises.

The aluminosilicate glass of the present invention has an annealing point ≥770°C, preferably ≥780°C, and more preferably ≥790°C at a viscosity of 10 ¹³ poises.

The aluminosilicate glass of the present invention has a viscosity corresponding to a temperature of 10 ^4.5 Poise ≤ 1250 ℃, preferably ≤ 1240 ℃, further preferably ≤ 1230 ℃; liquidus temperature T _{L ≤} 1250 ℃, preferably T _L ≤ 1240 ℃, further Preferably T _L ≤1200°C; the difference between the temperature corresponding to the viscosity of 10 ^4.5 poise and the liquidus temperature T _L is ≥-20°C, preferably the difference is ≥0°C.

In a specific embodiment of the present invention, a certain amount of sulfates, such as inorganic sulfates such as calcium sulfate and strontium sulfate, can be added as components for eliminating gaseous inclusions. However, from the perspective of spectral absorption in the ultraviolet region, in order to obtain high transmittance in the ultraviolet region, it is preferred that the residual sulfur element content in the form of elemental sulfur S in the glass be ≤500 ppm, preferably ≤100 ppm.

The content of hydroxyl groups in the aluminosilicate glass of the present invention is ≤0.3/mm, preferably ≤0.26/mm.

Preferably, the density of the aluminosilicate glass of the present invention is <2.7 g/cm ³ , preferably <2.65 g/cm ³ ; the coefficient of thermal expansion in the range of 50-350°C is <40×10 ^-7 /°C, preferably <39 ×10 ^-7 /°C; Young's modulus ≥83 GPa, preferably ≥83.5 GPa; specific modulus ≥32 GPa/(g×cm ^-3 ), preferably ≥33 GPa/(g×cm ^-3 ).

The aluminosilicate glass of the present invention has a transmittance ≥73% at a wavelength of 308 nm, preferably ≥74%; and a transmittance at a wavelength of 550 nm preferably ≥92%.

The aluminosilicate glass of the present invention has a thermal shrinkage under the condition of 600°C/30min<20ppm, preferably<16ppm.

In a fourth aspect, the application of the glass composition or aluminosilicate glass according to the present invention in the preparation of display devices and/or solar cells is provided.

The aluminosilicate glass of the invention has the advantages of high thermal stability, high ultraviolet transmittance and high mechanical stability. It can be used to prepare display devices and/or solar cells, and is particularly suitable for preparing substrate glass substrate materials for flat panel display products and/or glass film materials for screen surface protection, carrier glass materials for flexible display products and/or surface encapsulation glass Materials and/or glass film materials for screen surface protection, glass substrate materials for flexible solar cells, safety glass, bulletproof glass, smart car glass, smart traffic display screens, smart windows and smart card tickets, and other applications requiring high heat Application fields of glass materials with stability, high UV transmittance and mechanical stability.

Examples

The present invention will be described in detail below through examples. In the following embodiments, unless otherwise specified, the materials used can be obtained commercially. Unless otherwise specified, the methods used are conventional methods in the art.

The glass density was measured with reference to ASTM C-693 in g/cm ³ .

Refer to ASTM E-228 and use a horizontal dilatometer to measure the thermal expansion coefficient of glass in the range of 50-350°C, in units of 10 ^-7 /°C.

The Young's modulus of glass is measured with reference to ASTM C-623 in GPa.

Refer to ASTM C-965 to measure the high-temperature viscosity-temperature curve of glass using a rotating high-temperature viscometer. Among them, the viscosity corresponding to 1600℃ is η ₁₆₀₀ in units of P; the viscosity is X corresponding to the temperature T _X in ℃.

According to ASTM C-829, the temperature of the liquidus of the glass, T _L , is measured using a ladder furnace method in °C.

Referring to ASTM C-336 T _a measuring glass annealing point and the strain point T _st annealing point using strain point tester, in units of deg.] C.

Shimadzu UV-2600 ultraviolet-visible spectrophotometer UV-visible spectrophotometer was used to determine the glass transmittance. The thickness of the glass sample was 0.5mm, and the transmittance at 308nm and 550nm was taken as the unit.

。Use the thermoelectric iCAP 6300MFC type inductively coupled plasma emission spectrometer (ICP) to test the iron content (characterized in the form of Fe ₂ O ₃ ) and the fluorine and chlorine content in the glass in mol% or ppm; use the CS-9900 infrared carbon and sulfur The analyzer measures the sulfur content in the glass, which is characterized by the form of S, and the unit is ppm; refer to the test method for the high temperature resistivity of the glass melt disclosed in the patent application CN201710796764.X to determine the resistivity of the melt at 1600 ℃, the unit is Ω • cm; use the following heat treatment method (difference calculation method) to determine the heat shrinkage rate after heat treatment: the glass is heated from 25°C (measured the initial length, marked as L ₀ ) to 600°C at a heating rate of 5°C/min Incubate at 600°C for 30 minutes, and then reduce the temperature to 25°C at a cooling rate of 5°C/min. The glass length shrinks by a certain amount. Measure the length again and mark it as L _t , then the thermal shrinkage rate Y _{t is} expressed as:

.

The following method was used to determine the content of hydroxyl OH in glass: the SPECTRUM TWO Fourier infrared spectrometer of PE company was used to test the transmittance in the range of wave number 400-4000cm ^-1 , and the content of β-OH in glass was calculated by the following formula, the unit is /mm: β-OH=(1/D)*log ₁₀ (T ₁ /T ₂ ), where D: glass thickness (mm); T ₁ : transmittance (%) at the reference wavelength of 3846 cm ^-1 (2600nm); T ₂ : minimum transmittance (%) in the vicinity of the hydroxyl absorption wavelength of 3600 cm ^-1 (2800 nm).

Examples 1-8

Weigh each component as shown in Table 1, mix well, pour the mixture into a high-zirconium brick crucible (ZrO ₂ >85wt%), then heat in a resistance furnace at 1630℃ for 24 hours, and use platinum-rhodium alloy (80wt %Pt+20wt%Rh) Stirrer stir slowly at a uniform speed. The molten glass is poured into a stainless steel mold to form a specified block glass product, and then the glass product is annealed in an annealing furnace for 2 hours, and the power is turned off to cool to 25°C with the furnace. The glass products are cut, ground and polished, and then cleaned with deionized water and dried to obtain a glass product with a thickness of 0.5mm. The performance of each glass product was measured separately, and the results are shown in Table 1.

Examples 9-15

According to the method of Example 1, the difference is that the mixture composition (corresponding to the glass composition) and the performance measurement results of the obtained product are shown in Table 2.

Comparative Example 1-11

According to the method of Example 1, the difference is that the mixture composition (corresponding to the glass composition) and the performance measurement results of the obtained product are shown in Table 3-4.

Comparing the examples in Table 1-2 with the comparative data in Table 3-4, it can be seen that the method of the present invention has the problems of obtaining high ultraviolet transmittance, high strain point (high heat resistance), and low temperature resistivity at high temperature Obvious effect, the aluminosilicate glass obtained by the composition, limited ratio, limited Z/Y/R numerical range and manufacturing method provided by the present invention has higher heat resistance stability, lower high temperature volume resistivity, High UV-Vis spectral transmittance, high Young's modulus, low melting temperature and liquidus temperature, low surface tension, suitable for large-scale industrial manufacturing, suitable for some or all energy sources The molten glass liquid prepared by electric heating is suitable for the application in the preparation of display devices and/or solar cells. Particularly suitable for preparing substrate glass substrate materials for flat panel display products and/or glass film materials for screen surface protection, carrier glass materials for flexible display products and/or surface encapsulating glass materials and/or glass film layers for screen surface protection Materials, substrate materials for flexible solar cells, safety glass, bulletproof glass, smart car glass, smart traffic display screens, smart windows and smart card tickets, and other applications that require high thermal stability, high UV transmittance and mechanical stability Application areas of glass materials.

Table 1

Table 2

table 3

Table 4

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the contents disclosed in the present invention. It belongs to the protection scope of the present invention.

no.

Claims (15)

A composition for glass, comprising: based on the total moles of the composition for glass, based on oxides, the composition for glass contains 62-69 mol% SiO ₂ and 11-15 mol% Al ₂ O ₃ , 0-3mol% B ₂ O ₃ , 7-11mol% MgO, 2-8mol% CaO, 3-8mol% SrO, 0-2mol% BaO, 0.01-2mol% ZnO, 0.02-0.65mol % RE ₂ O ₃ and less than 0.05 mol% R ₂ O, where RE is a rare earth element and R is an alkali metal. The composition for glass according to claim 1, wherein the glass composition contains 65-68 mol% of SiO ₂ and 11.5-14.5, based on the total moles of the glass composition, based on oxides mol% Al ₂ O ₃ , 0-1.5mol% B ₂ O ₃ , 7.5-9mol% MgO, 3-6mol% CaO, 4.5-6mol% SrO, 0.1-0.9mol% BaO, 0.05- 1.9mol% ZnO, 0.1-0.46mol% RE ₂ O ₃ and less than 0.05mol% R ₂ O. The composition for glass according to claim 1 or 2, wherein the composition for glass contains Fe ₂ O ₃ or less based on the total moles of the glass composition, and the composition for glass contains 150 ppm or less of Fe ₂ O ₃ . The composition for glass according to any one of claims 1 to 3, wherein the composition for glass contains 0.01 to 0.6 mol based on the total moles of the composition for glass and is characterized in the form of elemental halogen. % Halogen; Wherein, the halogen is F and Cl. The composition for glass according to any one of claims 1 to 4, wherein the content of each component in the composition for glass satisfies 0<Z≦1 in terms of mole percent, where Z is determined by the following The formula calculates: Z=-10.31+(16.04×SiO ₂ +6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO) ; Among them, SiO ₂ , Al ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO each represents the mole percentage of the component in the glass composition. The composition for glass according to any one of claims 1 to 4, wherein the content of each component in the glass composition satisfies 0.1<Y≤0.67 in terms of mole percent, wherein the Y value is The following formula is calculated: Y=-10.31+(16.04×SiO ₂ +6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO -102.7×RE ₂ O ₃ ); wherein, SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO, RE ₂ O ₃ each represent the composition of the glass composition Molar percentage in The composition for glass according to any one of claims 1 to 4, wherein the content of each component in the glass composition satisfies R=0.05-0.48 in terms of mole percent, and the R value is determined by The formula calculates: R=-10.31+(16.04×SiO ₂ +6×Al ₂ O ₃ +3.29×B ₂ O ₃ -5.47×MgO-5.43×CaO+3.77×SrO+26.65×BaO-7.82×ZnO- 102.7×RE ₂ O ₃ -39.6×(F+Cl)); SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO, RE ₂ O ₃ , F, Cl Represents the mole percentage of this component in the glass composition. The composition for glass according to any one of claims 1-4, wherein (MgO+ZnO+SrO)/(MgO+CaO+SrO+BaO+ZnO)≥0.5 in terms of mole percent; preferably , (MgO+SrO)/(1-MO)≥0.6; where, based on the total moles of the glass composition, MO stands for SiO ₂ , Al ₂ O ₃ and B ₂ O in the glass composition The sum of the mole percentages of all components except ₃ . The composition for glass according to any one of claims 1 to 8, wherein the RE is yttrium and lanthanide, and the R is Li, Na and K; The RE is one or more of Y, La, Nd, and Lu. A method for preparing aluminosilicate glass, comprising: sequentially performing the melting treatment, the forming treatment, the annealing treatment and the mechanical processing treatment on the glass composition according to any one of claims 1-9. The method for preparing aluminosilicate glass according to claim 10, further comprising adding fluoride and/or chloride to the glass composition; Preferably, based on the total weight of the mixture, the amount of the fluoride added is 0.02-0.7wt%; Preferably, based on the total weight of the mixture, the added amount of the chloride is 0.02-0.7wt%. An aluminosilicate glass is prepared by the method for preparing aluminosilicate glass according to claim 10 or 11. The aluminosilicate glass according to claim 12, wherein the resistivity of the glass melt at 1600°C is ≤100Ω•cm; preferably, the viscosity of the glass melt at 1600°C is ≤300 Poise; Preferably, the liquidus viscosity of the glass melt η _L ≥20000 poise; Preferably, the viscosity of the glass melt is 200 Poise corresponding temperature T ₂₀₀ ≤1630 ℃; Preferably, the viscosity is 35000 Poise corresponding Temperature T ₃₅₀₀₀ ≤1240℃; Preferably, the corresponding annealing point ≥770℃ when the viscosity is 10 ¹³ poises; Preferably, the corresponding temperature ≤1250℃ when the viscosity is 10 ^4.5 poises; Liquidus temperature T _L ≤1250℃; Viscosity 10 The difference between the corresponding temperature at ^4.5 poise and the liquidus temperature T _L is ≥-20°C; preferably, the elemental sulfur content in the form of elemental sulfur S in the aluminosilicate glass is ≤500ppm; preferably, the The hydroxyl content in the aluminosilicate glass is ≤0.3/mm. The aluminosilicate glass according to claim 12 or 13, wherein the density of the aluminosilicate glass is <2.7 g/cm ³ ; the coefficient of thermal expansion in the range of 50-350°C is less than 40×10 ^-7 /°C ; Young's modulus ≥83GPa; specific modulus ≥32GPa/(g×cm ^-3 ); preferably, the transmittance at wavelength 308nm ≥73%; the transmittance at wavelength 550nm ≥92%; preferably, Thermal shrinkage under 600℃/30min<20ppm. An application of the glass composition according to any one of claims 1-9 or the aluminosilicate glass according to any one of claims 12-14 in the preparation of display devices and/or solar cells.