Composition for glass, aluminosilicate glass, and preparation method and application thereof
Technical Field
The invention relates to the technical field of glass production, in particular to a composition for glass, aluminosilicate glass, and a preparation method and application thereof.
Background
With the development of modern display technologies, a great number of electronic display products have emerged in the last 10 years, and advanced flat panel display products are emerging, such as: mobile phone, handheld game machine, liquid crystal television, liquid crystal display (such as notebook liquid crystal display), cash dispenser, flat advertisement media machine, multimedia information inquiry machine, etc.
At present, touch technology is applied to small-size products such as mobile phones, PDAs, MP4 and digital cameras and large-size products such as POS machines, industrial control computers, all-in-one machines and game machines, particularly, Incell and OGS become mainstream of touch products, the requirement on corresponding cover glass is higher, and the glass needs to be thinnedAnd has high strength, scratch resistance and impact resistance. For ultra-thin glass with the thickness of less than 1mm, the chemical strengthening process is needed, and Na with smaller ion radius in the glass is obtained after ion exchange+K with large ionic radius in chemical tempering liquid+And (4) replacing to form a compressive stress layer on the surface of the glass, thereby playing a role in strengthening. Therefore, in the glass frit aspect, improvement of glass strength, scratch resistance and impact resistance is one of important issues.
Disclosure of Invention
The invention aims to solve the technical problems and provides a composition for glass, aluminosilicate glass, and a preparation method and application thereof. The aluminosilicate glass disclosed by the invention is easy to chemically strengthen, high in strength, scratch-resistant and scratch-resistant, and has excellent impact resistance.
In order to achieve the above object, the present invention provides, in a first aspect, a composition for glass containing 58 to 67 wt% of SiO in terms of oxide, based on the weight of the composition20.1-2 wt% of La2O312-16 wt% of Al2O38-15 wt% of Na2O, 0-2 wt% of Li2O, 2-5 wt% of MgO, 0.1-2 wt% of CaO, 0.5-2 wt% of SrO, 0.1-2 wt% of B2O30-1 wt% of TiO2And 0.01-2 wt% of ZrO2。
Preferably, the composition also contains a clarifying agent, and the clarifying agent is Na2SO4、NaNO3And CeO2The amount of the clarifying agent is 0.5-2 wt%, more preferably 0.8-1.5 wt% based on the weight of the composition;
preferably, Na2SO4、NaNO3And CeO2The weight ratio of (A) to (B) is 1.5-9:1:1-16, more preferably 1.6-5:1: 2.5-7.
Preferably, La is present in the composition in terms of oxides, based on the weight of the composition2O3The content of (B) is 0.5-1 wt%.
Preferably, B is calculated as the oxide based on the weight of the composition2O3The content of (B) is 1.3-1.6 wt%.
Preferably, ZrO is present in an oxide amount based on the weight of the composition2The content of (B) is 0.8-1 wt%.
Preferably, Li is calculated as an oxide based on the weight of the composition2The content of O is 0.8-1.2 wt%.
Preferably, the SiO is present in the composition in terms of oxide, based on the weight of the composition2The content of (B) is 60-64 wt%.
Preferably, Al is present in the composition as an oxide, based on the weight of the composition2O3The content of (B) is 14-16 wt%.
Preferably, Na is present in an oxide amount based on the weight of the composition2The content of O is 10-14 wt%.
Preferably, the MgO content is 3-4.6 wt% in terms of oxides, based on the weight of the composition.
Preferably, the CaO is present in an amount of 0.8 to 1.8 wt.% in terms of oxides, based on the weight of the composition.
Preferably, the SrO content is 0.7 to 1.2 wt% calculated as oxide based on the weight of the composition.
Preferably, the TiO is present in an oxide amount based on the weight of the composition2The content of (B) is 0.3-0.5 wt%.
In a second aspect, the present invention provides a method for producing an aluminosilicate glass, which comprises subjecting the composition for glass of the present invention to a melting treatment, a forming treatment, an annealing treatment and a machining treatment in this order.
Preferably, the method further comprises subjecting the product of the mechanical processing treatment to a chemical strengthening treatment.
In a third aspect, the present invention provides an aluminosilicate glass prepared by the above method.
Preferably, the aluminosilicate glass has an elastic modulus higher than 70GPa and a density lower than 2.45g/cm3A coefficient of thermal expansion in the range of 30-380 ℃ of less than 87 x 10-7/℃。
Preferably, the Vickers hardness of the aluminosilicate glass obtained by the chemical strengthening treatment is more than 870MPa, and the impact resistance is more than 4J.
Preferably, the aluminosilicate glass has a strain point above 550 ℃, an annealing point above 600 ℃, and a softening point above 820 ℃.
Preferably, the aluminosilicate glass has a viscosity of 104The corresponding temperature at dpa s is 1000-1150 ℃ and the viscosity is 102dpa s corresponds to a temperature of not more than 1620 ℃.
Preferably, the compressive stress formed on the surface of the glass obtained by the chemical strengthening treatment is above 850MPa, and more preferably 870-920 MPa; the depth of the compressive stress layer is 55 μm or more, and more preferably 57 to 60 μm.
In a fourth aspect, the present invention provides a use of the composition for glass or the aluminosilicate glass of the present invention in preparing a touch screen display device, preferably a cover glass for a touch screen of a flat panel or flexible display product, and further preferably, the flat panel or flexible display product is at least one of a mobile phone, a handheld game console, a digital camera, an MP4, a liquid crystal display, a cash dispenser, a flat advertisement media machine, a multimedia information inquiry machine, a POS machine and an industrial control computer.
The glass composition of the invention is a glass frit with good chemical strengthening effect, belongs to an aluminosilicate glass system, and is suitable for various conventional glass manufacturing methods such as a float method, an overflow method, a downdraw method and the like to produce flat glass with the thickness of more than 0.1mm or flexible glass with the thickness of less than 0.1 mm. The prepared glass has high surface hardness, scratch resistance and excellent wear resistance and impact resistance after chemical strengthening, and can meet the performance requirements of the market on the cover plate glass of the touch screen.
According to a preferred embodiment of the present invention, the composition for glass contains a specific content of SiO2、La2O3、Al2O3、Na2O、Li2O、MgO、CaO、SrO、B2O3、TiO2、ZrO2、Na2SO4、NaNO3And CeO2By using the glassThe glass prepared from the glass composition has an elastic modulus higher than 70GPa and a density lower than 2.45g/cm3A coefficient of thermal expansion in the range of 30-380 ℃ of less than 87 x 10-7V, the Vickers hardness of the aluminosilicate glass obtained by chemical strengthening treatment is more than 870MPa, the impact resistance is more than 4J, the strain point is higher than 550 ℃, the annealing point is higher than 600 ℃, the softening point is higher than 820 ℃, and the viscosity is 104The corresponding temperature at dpa s is 1000-1150 ℃ and the viscosity is 102The corresponding temperature at dpa s is not more than 1620 ℃, and the compressive stress formed on the surface of the glass obtained by the chemical strengthening treatment is more than 850MPa (preferably 870-920 MPa); the depth of the compressive stress layer is 55 μm or more (preferably 57 to 60 μm).
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a composition for glass comprising 58 to 67 wt.% SiO calculated as oxide, based on the weight of the composition20.1-2 wt% of La2O312-16 wt% of Al2O38-15 wt% of Na2O, 0-2 wt% of Li2O, 2-5 wt% of MgO, 0.1-2 wt% of CaO, 0.5-2 wt% of SrO, 0.1-2 wt% of B2O30-1 wt% of TiO2And 0.01-2 wt% of ZrO2。
For glass of the present inventionThe composition preferably further comprises a clarifying agent which is Na2SO4、NaNO3And CeO2The amount of the clarifying agent is 0.5 to 2 wt%, more preferably 0.8 to 1.5 wt%, based on the weight of the composition.
Wherein the compound clarifying agent (Na) is adopted2SO4+NaNO3+CeO2) On the basis of clarification by sulfate and nitrate in the float process, cerium oxide is introduced, so that the clarification and defoaming effects are achieved, the quality and quality of glass can be greatly improved, the transparency of the glass is increased, and the strength and water resistance of the glass are improved.
Preferably, Na2SO4、NaNO3And CeO2The weight ratio of (A) to (B) is 1.5-9:1:1-16, more preferably 1.6-5:1: 2.5-7.
In the composition for glass of the present invention, 0.1 to 2 wt% of La is incorporated2O3The glass has the advantages of improving the strength and hardness of the glass, facilitating the clarification of the glass and improving the transparency of the glass. Preferably, La is present in the composition in terms of oxides, based on the weight of the composition2O3The content of (B) is 0.5-1 wt%.
In the composition for glass of the present invention, B is incorporated in an amount of 0.1 to 2 wt%2O3The fluxing agent has the fluxing function, can improve the chemical stability, and provides good conditions for subsequent chemical strengthening treatment. Preferably, B is calculated as the oxide based on the weight of the composition2O3The content of (B) is 1.3-1.6 wt%.
In the composition for glass of the present invention, ZrO is incorporated in an amount of 0.01 to 2 wt%2Can increase the strength and wear resistance of the glass, and Al2O3、ZrO2And when the glass is used together, the exchange speed and the exchange depth of sodium and potassium ions can be improved, and the strengthening effect of the glass is enhanced. Preferably, ZrO is present in an oxide amount based on the weight of the composition2The content of (B) is 0.8-1 wt%.
In the composition for glass of the present invention, 0 to 2 wt% of Li is incorporated2O, Na having a smaller ionic radius in the glass can be accelerated+K with larger ionic radius in chemical tempering liquid+The displacement of (3) enhances the compressive stress of the compressive stress layer on the glass surface, and improves the scratch resistance. Preferably, Li is calculated as an oxide based on the weight of the composition2The content of O is 0.8-1.2 wt%.
In the composition for glass of the present invention, SiO is preferably contained in an oxide amount based on the weight of the composition2The content of (B) is 60-64 wt%.
In the composition for glass of the present invention, it is preferable that Al is contained in oxide in the composition by weight2O3The content of (B) is 14-16 wt%.
In the composition for glass of the present invention, Na is preferably contained in an oxide amount based on the weight of the composition2The content of O is 10-14 wt%.
In the composition for glass of the present invention, the content of MgO is preferably 3 to 4.6% by weight in terms of oxide based on the weight of the composition.
In the composition for glass of the present invention, the content of CaO is preferably 0.8 to 1.8 wt% in terms of oxide based on the weight of the composition.
In the composition for glass of the present invention, it is preferable that the content of SrO is 0.7 to 1.2% by weight in terms of oxide based on the weight of the composition
In the composition for glass of the present invention, TiO is preferably present in an oxide amount based on the weight of the composition2The content of (B) is 0.3-0.5 wt%.
It will be understood by those skilled in the art that in the composition for glass of the present invention, the composition contains SiO2、La2O3、Al2O3、Na2O、Li2O、MgO、CaO、SrO、B2O3、TiO2、ZrO2And CeO2The term "means that the composition contains a Si-containing compound, a La-containing compound, an Al-containing compound, a Na-containing compound, a Li-containing compound, a Mg-containing compound, a Ca-containing compound, a Sr-containing compound, a B-containing compound, and a Ti-containing compoundThe Zr-containing compound and the Ce-containing compound, such as carbonate, nitrate, sulfate, oxide and the like containing the elements, and the content of each component mentioned above is calculated by the oxide of each element, and the selection of the carbonate, nitrate, sulfate and oxide of each element is well known by the person skilled in the art and is not described in detail herein.
The composition for glass of the present invention, when used for preparing aluminosilicate glass, enables the glass to have excellent overall properties mainly due to the coordination of the components in the composition, especially SiO2、La2O3、Al2O3、Na2O、Li2O、MgO、CaO、SrO、B2O3、TiO2、ZrO2、Na2SO4、NaNO3And CeO2And more particularly, the specific amounts of the components mentioned above.
In a second aspect, the present invention provides an aluminosilicate glass comprising 58 to 67 wt% SiO, based on the weight of the glass20.1-2 wt% of La2O312-16 wt% of Al2O38-15 wt% of Na2O, 0-2 wt% of Li2O, 2-5 wt% of MgO, 0.1-2 wt% of CaO, 0.5-2 wt% of SrO, 0.1-2 wt% of B2O30-1 wt% of TiO2And 0.01-2 wt% of ZrO2。
Preferably, the aluminosilicate glass also contains a clarifying agent, and the clarifying agent is Na2SO4、NaNO3And CeO2The amount of the refining agent is 0.5 to 2 wt%, more preferably 0.8 to 1.5 wt%, based on the weight of the glass.
Further preferably, Na2SO4、NaNO3And CeO2The weight ratio of (A) to (B) is 1.5-9:1:1-16, more preferably 1.6-5:1: 2.5-7.
Preferably, the aluminosilicate glass has La based on the weight of the glass2O3The content of (B) is 0.5-1 wt%.
Preferably, in the aluminosilicate glass, B is based on the weight of the glass2O3The content of (B) is 1.3-1.6 wt%.
Preferably, the aluminosilicate glass has ZrO based on the weight of the glass2The content of (B) is 0.8-1 wt%.
Preferably, the aluminosilicate glass has Li, based on the weight of the glass2The content of O is 0.8-1.2 wt%.
Preferably, the aluminosilicate glass has SiO in the glass based on the weight of the glass2The content of (B) is 60-64 wt%.
Preferably, the aluminosilicate glass has Al in it based on the weight of the glass2O3The content of (B) is 14-16 wt%.
Preferably, the aluminosilicate glass contains Na based on the weight of the glass2The content of O is 10-14 wt%.
Preferably, the aluminosilicate glass has a MgO content of 3 to 4.6 wt% based on the weight of the glass.
Preferably, the aluminosilicate glass has a CaO content of 0.8 to 1.8 wt.% based on the weight of the glass.
Preferably, the aluminosilicate glass has a SrO content of 0.7-1.2 wt%, based on the weight of the glass.
Preferably, the TiO in the aluminosilicate glass is based on the weight of the glass2The content of (B) is 0.3-0.5 wt%.
In a third aspect, the present invention provides a method for producing an aluminosilicate glass, which comprises subjecting the composition for glass of the present invention to a melting treatment, a forming treatment, an annealing treatment and a machining treatment in this order.
In the method of the present invention, for the specific definition of the composition for glass, reference is made to the corresponding description above, and details are not repeated here.
In the method of the present invention, the conditions for the melting treatment preferably include: the temperature is 1580-1650 ℃, and the time is 8-12 h. In addition, the specific melting temperature and melting time can be determined by those skilled in the art according to actual conditions, which are well known to those skilled in the art and will not be described herein again.
In the method of the present invention, the annealing conditions preferably include: the temperature is 600 ℃ and 620 ℃, and the time is more than 0.5 h. In addition, the specific annealing temperature and annealing time can be determined by those skilled in the art according to practical situations, which are well known to those skilled in the art and will not be described herein again.
In the method of the present invention, the machining treatment is not particularly limited, and various machining methods common in the art may be used, and for example, the product obtained by the annealing treatment may be cut, ground, polished, and the like.
In order to further improve the overall properties of the glass, the method preferably further comprises chemically strengthening the product of the mechanical treatment. Further preferably, the method of chemical strengthening treatment comprises: the product obtained by mechanical processing is placed in molten KNO at 400-460 DEG C3For at least 0.1h (e.g., 3-8 h). The temperature and time of the chemical strengthening treatment can be determined by those skilled in the art according to the actual situation, which is well known to those skilled in the art and will not be described herein. After the chemical strengthening treatment, the surface stress of the glass can reach at least 850MPa in a short time, the ion exchange depth is more than 55 microns, and a pressure stress layer is formed on the surface of the glass and endows the glass with higher strength and surface scratch resistance.
In a fourth aspect, the present invention provides an aluminosilicate glass prepared by the above method.
Preferably, the aluminosilicate glass has an elastic modulus of greater than 70GPa and a density of less than 2.45g/cm3A coefficient of thermal expansion in the range of 30-380 ℃ of less than 87 x 10-7/℃。
Preferably, the aluminosilicate glass obtained by the chemical strengthening treatment has a Vickers hardness of more than 870MPa and an impact resistance of more than 4J.
Preferably, the aluminosilicate glass has a strain point above 550 ℃, an annealing point above 600 ℃, and a softening point above 820 ℃.
Preferably, the aluminosilicate glass is stickyDegree of 104The corresponding temperature at dpa s is 1000-1150 ℃ and the viscosity is 102dpa s corresponds to a temperature of not more than 1620 ℃.
Preferably, the compressive stress formed on the surface of the glass obtained by the chemical strengthening treatment is 850MPa or more, more preferably 870-920 MPa; the depth of the compressive stress layer is 55 μm or more, and more preferably 57 to 60 μm.
In a fifth aspect, the present invention provides a use of the composition for glass or the aluminosilicate glass of the present invention in preparing a touch screen display device, preferably a cover glass for a touch screen of a flat panel or flexible display product, and further preferably, the flat panel or flexible display product is at least one of a mobile phone, a handheld game console, a digital camera, an MP4, a liquid crystal display, a cash dispenser, a flat advertisement media machine, a multimedia information inquiry machine, a POS machine and an industrial control computer.
Examples
The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.
In the following examples and comparative examples, the glass density was measured in g/cm with reference to ASTM C-6933。
Determination of the coefficient of thermal expansion alpha of the glass at 30-380 ℃ by means of a horizontal dilatometer with reference to ASTM E-22830/380Expressed as the average coefficient of expansion, the unit is 10-7/℃。
The Young's modulus of glass was measured in GPa using a mechanical testing machine in accordance with ASTM C-623.
The Vickers hardness of glass is measured in MPa using a Vickers hardness tester in accordance with ASTM E-384.
The annealing point of the glass (viscosity 10) was determined using a glass annealing point and strain point tester with reference to ASTM C-33613Temperature at dpa s) and strain point (viscosity of 10)14.5Temperature at dpa s) in degrees centigrade.
Determination of softness of glass Using glass softening Point tester with reference to ASTM C-338Melting point (viscosity 10)7.6Temperature at dpa s) in degrees centigrade.
The viscosity was calculated from Fulcher (also called VFT formula) as 10 on the high temperature viscometric curve of the glass measured using a rotary high temperature viscometer of the cylindrical type with reference to ASTM C-9654Temperature corresponding to dpa s (i.e. operating temperature T)w) And a viscosity of 102Temperature corresponding to dpa s (i.e. melting point T)m) In units of ℃.
The compressive stress (in MPa) and the depth of the compressive stress layer (in μm) were measured on the glass surface using a FSM-6000LE surface stress meter.
The impact energy (in J) of the glass was determined according to the standard ASTM D1709 using a falling ball tester with an impact ball weight of 227 g.
Examples 1 to 8
The components were weighed according to the glass composition shown in table 1, mixed well, and the mixture was poured into a platinum crucible, and then heated in a high temperature furnace at 1620 ℃ for 10 hours, and stirred using a platinum rod to discharge bubbles. Pouring the molten glass into a stainless steel cast iron grinding tool to form a specified block-shaped glass product, then annealing the glass product in an annealing furnace at 610 ℃ for 1 hour, and turning off a power supply to cool the glass product to 25 ℃ along with the furnace. Cutting, grinding and polishing the glass product, cleaning the surface of the glass product with the thickness of 50 multiplied by 1mm obtained by polishing with deionized water, and then putting the glass product into molten KNO3And (4) treating for a certain time, then taking out and cooling to 25 ℃, cleaning with deionized water and drying to obtain a glass finished product. The various properties of each finished glass were measured and the results are shown in Table 1.
TABLE 1
Examples 9 to 11, comparative examples 1 to 5
The procedure of example 5 was followed except that the composition of the batch (corresponding to the glass composition) and the results of the measurement of the properties of the obtained product were as shown in Table 2.
TABLE 2
As can be seen by comparing the data of example 5 in Table 1 with those of comparative examples 1 to 4 in Table 2, the glass batch contained La in a specific amount2O3、B2O3、ZrO2、Li2When O is used, the glass can be further improved in hardness, chemical strengthening properties, impact resistance, and the like.
Comparing the data of example 5 in table 1 with the data of comparative example 5 in table 2, it can be seen that the glass prepared from the glass batch with specific composition and content according to the present invention has significantly higher hardness, more excellent chemical strengthening property and impact resistance, and the like, and is more suitable for the performance requirements of the market on the touch screen cover plate glass.
As can be seen by comparing the data in tables 1-2, the process of the present invention utilizes a composition containing a specific amount of SiO2、La2O3、Al2O3、Na2O、Li2O、MgO、CaO、SrO、B2O3、TiO2、ZrO2、Na2SO4、NaNO3And CeO2The glass prepared by the composition for glass has an elastic modulus higher than 70GPa and a density lower than 2.45g/cm3A coefficient of thermal expansion in the range of 30-380 ℃ of less than 87 x 10-7V, the Vickers hardness of the glass obtained by chemical strengthening treatment is more than 870MPa, the impact resistance is more than 4J, the strain point is more than 550 ℃, the annealing point is more than 600 ℃, the softening point is more than 820 ℃, and the viscosity is 104The corresponding temperature at dpa s is 1000-1150 ℃ and the viscosity is 102dpa s at a temperature of not more than 1620 ℃, formed on the surface of the glass obtained by chemical strengthening treatmentThe compressive stress is above 850MPa (preferably 870-920 MPa); the depth of the compressive stress layer is more than 55 μm (preferably 57-60 μm), which can endow the glass with higher hardness and effectively prevent the impact and scratch damage of the glass surface of the display product. The glass prepared by the glass composition designed based on the combination principle of the expansion coefficients of oxides of all components, the combination principle of refractory oxides and the ion exchange occupying technology has excellent physical and chemical properties, and can be used for preparing the cover plate glass of the touch screen.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.