Yttrium-containing aluminosilicate glass with low liquidus temperature, preparation method and glass cover plate

Abstract

The invention belongs to the technical field of glass manufacturing and detection, and discloses yttrium-containing aluminosilicate glass with low liquidus temperature, a preparation method and a glass cover plate, the glass comprises SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3 and Y2O3, and the yttrium-containing aluminosilicate glass is obtained through melting treatment, coarse annealing and devitrification sample preparation. The glass has the elasticity modulus higher than 80 GPa and the transmittance higher than 90%, the liquidus temperature is effectively reduced by adjusting the proportion of part of materials, forming is promoted, the production requirements of a production line are met, and the prepared glass can be applied to the field of mobile phone cover plates and vehicle-mounted glass and has wide application prospects. And theoretical basis and reference value are provided for research and production of yttrium-containing aluminosilicate glass.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of glass manufacturing and detection, and relates to a yttrium-containing aluminosilicate glass with low liquidus temperature and a preparation method and a glass cover plate. BACKGROUND

[0002] With the rapid development of the flat panel display industry, especially the rapid popularization of mobile phones, tablet computers and other equipment, higher requirements are put forward for the performance of glass. Therefore, improving the elastic modulus of glass to improve the defects of brittleness and easy breakage has become one of the effective ways to improve the performance of glass materials.

[0003] By adding components with high field strength in the glass composition, the cross-linking density of the glass network can be effectively improved, and then the elastic modulus is improved. However, this structural strengthening effect will also cause a significant increase in the glass crystallization temperature (Tx). From the perspective of production process, too high crystallization temperature will cause the following problems: (1) when Tx is close to or exceeds the forming temperature, heterogeneous nucleation is easy to occur in the melt during the forming process, resulting in crystallization defects in the product; (2) crystallization deposition may occur on the production line, affecting the normal operation of the equipment. Therefore, in actual production, the crystallization temperature must be strictly controlled to ensure that Tx is always lower than the forming temperature, which is of key significance to ensure the stability of product quality and maintain the efficiency of continuous production. SUMMARY

[0004] The purpose of the application is to solve the problem that the existing glass system in the prior art is difficult to control the glass crystallization temperature while improving the elastic modulus, and to provide a yttrium-containing aluminosilicate glass with low liquidus temperature, a preparation method and a glass cover plate.

[0005] In order to achieve the above-mentioned purpose, the following technical solutions are adopted: The yttrium-containing aluminosilicate glass with low liquidus temperature according to the application comprises, in terms of mole percentage, 57% to 63% of SiO2, 12% to 17% of Al2O3, 2% to 4% of B2O3, 0% to 4% of Li2O, 10% to 15% of Na2O, 0% to 8% of MgO, 0% to 3% of P2O5, 0% to 2% of ZnO, 0% to 1% of TiO2, 0% to 0.1% of SnO2, 0% to 0.1% of Sb2O3, 0% to 2% of La2O3 and 2% to 4% of Y2O3.

[0006] Preferably, in the yttrium-containing aluminosilicate glass with low liquidus temperature, P2O5+TiO2 ranges from 0% to 3% in terms of mole percentage; La2O3+Y2O3 ranges from 3% to 5% in terms of mole percentage.

[0007] Preferably, the crystallization temperature T of the yttrium-containing aluminosilicate glass is less than 1250℃.

[0008] Preferably, the elastic modulus of the yttrium-containing aluminosilicate glass is greater than or equal to 80 GPa, and the elastic modulus is tested by a resonance method.

[0009] Preferably, the glass has a visible light transmittance greater than 90% and a haze less than 0.1%.

[0010] The present application provides a cover glass prepared from a yttrium-containing aluminosilicate glass with a low liquidus temperature.

[0011] The present application provides a preparation method of a yttrium-containing aluminosilicate glass with a low liquidus temperature, which comprises mixing raw materials according to the composition of the yttrium-containing aluminosilicate glass, and sequentially performing a melting treatment, a coarse annealing, and a sample preparation to obtain the yttrium-containing aluminosilicate glass with a low liquidus temperature.

[0012] Preferably, the yttrium-containing aluminosilicate glass comprises SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3, and Y2O3, and the proportions of the SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3, and Y2O3 are (57% ~ 63%): (12% ~ 17%): (2% ~ 4%): (0% ~ 4%): (10% ~ 15%): (0% ~ 8%): (0% ~ 3%): (0% ~ 2%): (0% ~ 1%): (0% ~ 0.1%): (0% ~ 0.1%): (0% ~ 2%): (2% ~ 4%) in terms of mole percentage.

[0013] Preferably, the melting treatment is performed under the following conditions: a melting temperature of 1600℃ ~ 1650℃, a melting time of 12h ~ 24h, a coarse annealing temperature of 600℃ ~ 700℃, and an annealing time of 8h ~ 10h.

[0014] Preferably, the yttrium-containing aluminosilicate glass is prepared into a granular form for liquidus temperature testing, and the liquidus temperature testing method is a gradient furnace method, and the granular sample has a mesh size of 30 ~ 50.

[0015] Compared with the prior art, the present application has the following beneficial effects: The application provides a low liquidus temperature yttrium-containing aluminosilicate glass, and the glass composition comprises SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3 and Y2O3, and the content of SiO2 is 57 mol% to 63 mol%. SiO2 is the main component of the glass network skeleton, and if the content of SiO2 is low, it is difficult to obtain a glass with a high strain point and high durability; if the content of SiO2 is high, the glass viscosity increases, the melting temperature increases, and the liquidus temperature increases. 3+ Al2O3 is a network intermediate, and if the content of Al2O3 is low, the above effect cannot be achieved, but if the content of Al2O3 is high, the glass melting property is reduced and the liquidus temperature is increased. The content of B2O3 is 2 mol% to 4 mol%. B2O3 is a good fluxing agent, can reduce the high-temperature viscosity and increase the low-temperature viscosity. The content of Li2O is 0 mol% to 4 mol%, and the content of Na2O is 10 mol% to 15 mol%. Alkali metal oxides Li2O and Na2O are network outer bodies, can reduce the glass viscosity, and are good fluxing agents, but at the same time, the thermal stability and mechanical strength of the glass are reduced, so the amount of introduction should not be too much. The content of MgO is 0 mol% to 8 mol%. Alkaline earth metal oxides can reduce the overall viscosity of the glass, but if the content of MgO is too high, the crystallization tendency of the glass increases. The content of P2O5 is 0 mol% to 3 mol%. P2O5 can increase the strain point of the glass, but if the content of P2O5 is too high, the glass is prone to phase separation. The content of ZnO is 0 mol% to 2 mol%. ZnO can improve the melting property of the glass and reduce the liquidus temperature of the glass, but high content of ZnO promotes the formation of zinc spinel or zinc silicate, thereby increasing the liquidus temperature. The content of TiO2 is 0 mol% to 1 mol%. TiO2 often exists in silicate glass, is a network outer body ion, can generally reduce the thermal expansion coefficient of the glass and improve the acid resistance, but it also has coloring performance, and high content of TiO2 will cause the glass to be colored. 4+ The glass obtained based on the above materials has an elastic modulus higher than 80 GPa and a transmittance higher than 90%, the liquidus temperature is effectively reduced by adjusting the proportion of the materials, the forming is promoted, and the production line production demand is matched, and the prepared glass can be applied to the fields of mobile phone cover plates and vehicle-mounted glass, and provides a theoretical basis and reference value for the research and production of yttrium-containing aluminosilicate glass. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some of the embodiments of the present application, and therefore should not be regarded as a limitation to the scope. For those skilled in the art, other related drawings can also be obtained without creative labor.

[0017] Figure 1 Microscope crystal morphology of a crystallization sample of the embodiment glass of the present application. DETAILED DESCRIPTION

[0018] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the following will combine the drawings in the embodiments of the present application to make a clear and complete description of the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. The components of the embodiments of the present application described and shown in the drawings can be arranged and designed in various different configurations.

[0019] Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. All other embodiments obtained by those skilled in the art based on the embodiments in the present application without creative labor are within the scope of protection of the present application.

[0020] It should be noted that: similar reference numerals and letters represent similar items in the following drawings, and therefore, once an item is defined in one drawing, it does not need to be further defined and explained in the subsequent drawings.

[0021] The present application will be further described in detail below in combination with the drawings: The present application proposes a low liquidus temperature yttrium-containing aluminosilicate glass, which is a sodium aluminosilicate glass. The oxide composition used is as follows in terms of mole percentage: SiO2: 57% ~ 63%; Al2O3: 12% ~ 17%; B2O3: 2% ~ 4%; Li2O: 0% ~ 4%; Na2O: 10% ~ 15%; MgO: 0% ~ 8%; P2O5: 0% ~ 3%; ZnO: 0% ~ 2%; TiO2: 0% ~ 1%; SnO2: 0% ~ 0.1%; Sb2O3: 0% ~ 0.1%; La2O3: 0% ~ 2%; Y2O3: 2% ~ 4%.

[0022] The reasons for limiting the main components of the glass to the above ranges are as follows: SiO2 is the main component of the glass network skeleton, and a small amount of SiO2 is not conducive to obtaining high strain point and high durability glass; a high amount of SiO2 increases the viscosity of the glass and the melting temperature, and the liquidus temperature is also increased, preferably, the content of SiO2 is 57 mol% to 63 mol%.

[0023] Al2O3 is a network intermediate, Al 3+ Al2O3 can capture non-bridge oxygen to form aluminum oxygen tetrahedron into the silicon oxygen network, and if the content of Al2O3 is low, the above effect cannot be achieved, but if the content of Al2O3 is high, the melting property of the glass is reduced and the liquidus temperature is increased, preferably, the content of Al2O3 is 12 mol% to 17 mol%.

[0024] B2O3 is a good fluxing agent that can reduce the high-temperature viscosity and increase the low-temperature viscosity, preferably, the content of B2O3 is 2 mol% to 4 mol%.

[0025] Alkali metal oxides Li2O and Na2O are glass network exoskeletons, which can reduce the viscosity of the glass and are good fluxing agents, but at the same time, they can reduce the thermal stability and mechanical strength of the glass, so the amount introduced should not be too much, preferably, the content of Li2O is 0 mol% to 4 mol%, and the content of Na2O is 10 mol% to 15 mol%.

[0026] Alkaline earth metal oxides can reduce the overall viscosity of the glass, but a high content of alkaline earth metal oxides can increase the crystallization tendency of the glass, preferably, the content of MgO is 0 mol% to 8 mol%.

[0027] P2O5 can increase the strain point of the glass, but a high content of P2O5 can cause the glass to phase separate, preferably, the content of P2O5 is 0 mol% to 3 mol%.

[0028] ZnO can improve the melting property of the glass and reduce the liquidus temperature of the glass, but a high content of ZnO promotes the formation of zinc spinel or zinc silicate, which increases the liquidus temperature, preferably, the content of ZnO is 0 mol% to 2 mol%.

[0029] TiO2 often exists in silicate glass as Ti 4+ , which is an octahedral network exoskeleton ion that can generally reduce the thermal expansion coefficient of the glass and improve the acid resistance, but it also has coloring properties, and a high content of TiO2 will cause the glass to be colored, preferably, the content of TiO2 is 0 mol% to 1 mol%.

[0030] SnO2 and Sb2O3 exist in the glass as fining agents, preferably, the content of SnO2+Sb2O3 is 0 mol% to 0.1 mol%.

[0031] La2O3 and Y2O3 are high dissociation energy oxides, which can increase the elastic modulus of the glass in silicate glass, but also can increase the crystallization temperature, preferably, the content of La2O3+Y2O3 is 3 mol% ~5 mol%.

[0032] A preparation method of a low liquidus temperature yttrium-containing aluminosilicate glass, raw materials are mixed according to the composition of the yttrium-containing aluminosilicate glass, and then sequentially subjected to melting treatment, rough annealing and crystallization sample preparation to obtain a low liquidus temperature yttrium-containing aluminosilicate glass.

[0033] The yttrium-containing aluminosilicate glass comprises SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3 and Y2O3; the proportions of the SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3 and Y2O3 are (57% ~ 63%): (12% ~ 17%): (2% ~ 4%): (0% ~ 4%): (10% ~ 15%): (0% ~ 8%): (0% ~ 3%): (0% ~ 2%): (0% ~ 1%): (0% ~ 0.1%): (0% ~ 0.1%): (0% ~ 2%): (2% ~ 4%) in terms of mole percentage.

[0034] A liquidus temperature testing method of a low liquidus temperature yttrium-containing aluminosilicate glass, raw materials are mixed according to the composition of the yttrium-containing aluminosilicate glass, and the method comprises the steps of: preparing a mixture, melting and forming, rough annealing, preparing a crystallization sample, and testing in a gradient temperature furnace.

[0035] Glass melting: after the above raw materials are mixed, they are placed in a melting furnace, the melting temperature is 1600℃ ~ 1650℃, the melting time is 12h ~ 24h, the annealing temperature is 600℃ ~ 700℃, and the annealing time is 8h ~ 10h.

[0036] Glass forming is formed by casting method, the visible light transmittance of the glass is > 90%, and the haze is < 0.1%.

[0037] The crystallization temperature of the yttrium-containing aluminosilicate glass is < 1250℃.

[0038] The elastic modulus of the yttrium-containing aluminosilicate glass is 80GPa or more, the elastic modulus of the glass is detected by resonance method, and the test sample is a block sample.

[0039] The liquidus temperature of the glass is detected by the gradient temperature furnace method, and the holding time is 24h.

[0040] The sample for the gradient furnace test is prepared by casting the glass sample, and then processing it into a granular sample with a particle size of 30-50 mesh. The sample is cleaned of impurities by ultrasonic cleaning for 30 min, and then dried in an oven at 120°C for standby use.

[0041] After the gradient furnace test, the sample is observed by polarized light microscopy to determine the upper crystallization temperature.

[0042] The glass sample with a thickness of 0.7 mm is used for optical performance testing, wherein the transmittance is measured at a characteristic wavelength of 550 nm, and the haze value of the sample is also determined at this thickness.

[0043] The following examples are used to illustrate the present application in detail. It should be noted that the following examples are only examples, and the present application is not limited by any of the following examples.

[0044] Table 1

[0045] As can be seen from the test results of Examples 1-7 in Table 1, the elastic modulus of the aluminosilicate glass prepared according to the glass formula of the present application is 82-89 GPa.

[0046] As can be seen from the test results of Examples 1-7 in Table 1, the liquidus temperature of the aluminosilicate glass prepared according to the glass formula of the present application is 1175-1245°C.

[0047] As can be seen from the test results of Examples 1-7 in Table 1, the transmittance of the aluminosilicate glass prepared according to the glass formula of the present application is 90.6-91.5%, and the haze is 0.02-0.08%.

[0048] The above results show that the glass of the present application is suitable for use as a cover plate for a mobile phone and a vehicle-mounted display screen.

[0049] The above is only a preferred embodiment of the present application and is not intended to limit the present application. Various modifications and changes can be made by those skilled in the art without departing from the spirit and principles of the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A low liquidus temperature yttrium-containing aluminosilicate glass, characterized in that, The yttrium-containing aluminosilicate glass comprises, in terms of mole percentage, 57% to 63% of SiO2, 12% to 17% of Al2O3, 2% to 4% of B2O3, 0% to 4% of Li2O, 10% to 15% of Na2O, 0% to 8% of MgO, 0% to 3% of P2O5, 0% to 2% of ZnO, 0% to 1% of TiO2, 0% to 0.1% of SnO2, 0% to 0.1% of Sb2O3, 0% to 2% of La2O3 and 2% to 4% of Y2O3.

2. The low liquidus temperature yttrium-containing aluminosilicate glass of claim 1, wherein, In the yttrium-containing aluminosilicate glass with low liquidus temperature, P2O5+TiO2 ranges from 0% to 3% in terms of mole percentage; La2O3+Y2O3 ranges from 3% to 5% in terms of mole percentage.

3. The low liquidus temperature yttrium-containing aluminosilicate glass of claim 1, wherein, The crystallization temperature of the yttrium-containing aluminosilicate glass is less than 1250℃.

4. The low liquidus temperature yttrium-containing aluminosilicate glass of claim 1, wherein, The elastic modulus of the yttrium-containing aluminosilicate glass is greater than or equal to 80 GPa, and the elastic modulus is tested by a resonance method.

5. The low liquidus temperature yttrium-containing aluminosilicate glass of claim 1, wherein, The glass has a visible light transmittance greater than 90% and a haze less than 0.1%.

6. A cover glass, characterized by The yttrium-containing aluminosilicate glass with low liquidus temperature is prepared by any one of claims 1 to 5.

7. The method for preparing yttrium aluminum silicate glass with a low liquidus temperature according to any one of claims 1 to 5, characterized in that, Raw materials are mixed according to the composition of the yttrium-containing aluminosilicate glass, and then melt treatment, rough annealing and crystallization sample preparation are sequentially performed to obtain the yttrium-containing aluminosilicate glass with low liquidus temperature.

8. The method of making a low liquidus temperature yttrium-containing aluminosilicate glass according to claim 7, wherein, The yttrium-containing aluminosilicate glass comprises SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3 and Y2O3; the proportions of the SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, P2O5, ZnO, TiO2, SnO2, Sb2O3, La2O3 and Y2O3 are (57% to 63%):(12% to 17%):(2% to 4%):(0% to 4%):(10% to 15%):(0% to 8%):(0% to 3%):(0% to 2%):(0% to 1%):(0% to 0.1%):(0% to 0.1%):(0% to 2%):(2% to 4%) in terms of mole percentage.

9. The method of making a low liquidus temperature yttrium-containing aluminosilicate glass according to claim 7, wherein, The melt treatment conditions include a melt temperature of 1600℃ to 1650℃ and a melt time of 12h to 24h; the rough annealing temperature is 600℃ to 700℃, and the annealing time is 8h to 10h.

10. The method of making a low liquidus temperature yttrium-containing aluminosilicate glass according to claim 7, wherein, The yttrium-containing aluminosilicate glass is prepared into a granular form for liquidus temperature testing, and the liquidus temperature testing method is a gradient furnace method, and the granular sample is between 30 meshes and 50 meshes.

Images