CN107935378B - High-strength glass for display device and preparation method thereof - Google Patents
High-strength glass for display device and preparation method thereof Download PDFInfo
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- CN107935378B CN107935378B CN201711003895.4A CN201711003895A CN107935378B CN 107935378 B CN107935378 B CN 107935378B CN 201711003895 A CN201711003895 A CN 201711003895A CN 107935378 B CN107935378 B CN 107935378B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
The invention relates to a high-strength glass for a display device and a preparation method thereof, which improve the strength of the glass from two aspects of component design and strengthening method, wherein the components play a remarkable synergistic effect, and a new component CeO is introduced2And TiO2And defining the content relationship between the components, especially (Na)2O+K2O)/Al2O3、K2O/(Na2O+Li2O) is maintained in a certain range, the amount of ion exchange and the depth of ion exchange are increased, and TiO is limited2、ZrO2And CeO2The synergistic effect of the three improves the thermal stability of the glass and the performance of ion exchange. Finally, through two times of ion exchange, the mechanical property of the glass is greatly improved, so that the glass obtained by the invention has higher surface compressive stress, Vickers hardness, excellent strain point and thermal stability, and the performances of compression resistance, scratch resistance and scratch resistance, and can be widely applied to a protective cover plate of a display device.
Description
Technical Field
The invention relates to the technical field of glass manufacturing, in particular to high-strength glass for a display device and a preparation method thereof.
Background
In recent years, touch screen type electronic products such as smart phones, tablet computers, electronic reading devices and the like are developed rapidly, touch, friction and even scratch are generated inevitably in the using process, so that the generated scratches are accumulated to cause rough surface and low smoothness of a display screen, light scattering is increased, transmittance is reduced, and brightness, chromaticity, uniformity and resolution of the touch screen type electronic products are reduced, so that higher requirements on strength and wear resistance of a cover plate for a screen are provided.
In the development history of cover plates, organic materials have been used as protective cover plates for display devices, but organic materials have not been widely used due to limitations of materials such as easy aging and poor transmittance. Due to the limitation of organic materials, the industry has been going to research on commonly used glass as the cover plate material, wherein how to improve the strength of the cover plate material is the focus of research.
In the prior art, Chinese patent CN102351421A discloses chemical steel for protective cover plate of display deviceMelting glass; the glass consists of 54-65% of SiO by mass percent210-17% of Al2O38-16% of Na2O, 0-0.5% of Li2O, 0-6% of K2O, 0.01-3% of B2O30.1-5% of MgO, 0.1-5% of CaO, 0.01-2% of SrO and 0.01-1% of ZrO2And 0.01-1% SnO2Composition is carried out; and the surface hardness, the scratch resistance and the wear resistance of the glass are improved through specific chemical toughening treatment.
Chinese patent CN102320740A discloses a method for manufacturing a strengthened glass substrate, which comprises forming a layer containing 40-71% by mass of SiO23-21% of Al2O30-3.5% of Li2O, 7-20% of Na2O, 0-15% of K2O, melting the glass raw material, forming the glass into a sheet shape, and then performing an ion exchange treatment to form a compressive stress layer on the surface of the glass.
Chinese patent CN104692636A discloses a method for preparing composite strengthened glass, wherein a composite compressive stress strengthening layer is formed on the upper and lower surfaces of a glass body by preheating-ion exchange-preheating-ion exchange treatment, the composite compressive stress strengthening layer comprises at least two independent sub-strengthening layers, and the at least two independent sub-strengthening layers are arranged along the direction of the surface of the glass body extending inwards.
However, although the strength of the glass is improved to some extent by the above-mentioned methods of the prior art, there is still a gap in the expectation of glass for display devices having high strength and high abrasion resistance, and therefore, the research on methods for producing glass having higher strength is still an important research direction in the field of glass production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the high-strength glass for the display device and the preparation method thereof, the high-strength glass has high strength and good wear resistance, and can meet the use requirements of the industry.
The invention is realized by the following technical scheme:
a method for preparing high-strength glass for a display device comprises the following steps,
1) accurately weighing the following raw materials in percentage by mass:
54-65% of SiO210-17% of Al2O30-0.7% of Li2O, 12-16% of Na2O, 0.2-6% of K2O, 0.01-3% of B2O30.1-5% of MgO, 0.1-5% of CaO, 0.01-3% of SrO and 0.01-1.2% of ZrO20.01-1% of CeO20.01-1% of SnO2And 0.01-0.8% TiO2；
And the mass percentages of the components also satisfy the following relations:
(Na2O+K2O)/Al2O31.1-1.4;
K2O/(Na2O+Li2o) is 0.01 to 0.5;
ZrO2/CeO20.5 to 2;
TiO2/(ZrO2+CeO2) 0.01-5;
2) fully and uniformly mixing the raw materials in the step 1) and then melting to form molten glass;
3) preparing glass liquid into plate-shaped glass and annealing;
4) cutting, grinding and polishing the annealed glass plate, cleaning the surface of the glass plate, heating to 330-380 ℃, preserving the heat for 1-4h, and then placing the glass plate in molten potassium nitrate solution at the temperature of 430-500 ℃ for preserving the heat for 4-10 h to perform primary ion exchange;
5) taking out the glass plate after the primary ion exchange, cooling to 330-plus 380 ℃, preserving heat for 1-4h, then continuing cooling to room temperature, then heating to 340-plus 390 ℃, preserving heat for 2-6h, and then placing in molten rubidium nitrate liquid at 430-plus 500 ℃ for preserving heat for 2-6h for secondary ion exchange; cooling to room temperature after secondary ion exchange; and cleaning the surface of the glass plate again to obtain the high-strength glass for the display device.
Preferably, the specific step of the step 2) is that the raw materials in the step 1) are fully and uniformly mixed, then the temperature is raised to T1, the glass liquid is obtained after the reaction is carried out for 5 to 10 hours, and then the temperature is lowered to T2 and the temperature is kept for 60 to 120 minutes; wherein, T1 is 1550-.
Preferably, the step 3) comprises the specific steps of pouring the molten glass into a template to be cooled into plate-shaped glass, and annealing the plate-shaped glass at the temperature of 500-600 ℃ for 4-6 hours.
Preferably, step 1) (Na)2O+K2O)/Al2O3Is 1.1-1.3 or 1.2-1.3.
Preferably, K in step 1)2O/(Na2O+Li2O) is 0.01 to 0.2 or 0.02 to 0.1.
Preferably, ZrO in step 1)2/CeO20.8-1.5 or 1.
Preferably, TiO in step 1)2/(ZrO2+CeO2) 0.02-4 or 0.2-0.8.
The high-strength glass for the display device is prepared by the preparation method, and the direction extending from the surface of the glass to the inside comprises a rubidium ion exchange layer at the outer layer, a glass inner body at the inner part and a potassium ion exchange layer at the rubidium ion exchange layer and the glass inner body.
Preferably, the rubidium ion exchange layer is 10-20 μm deep, the potassium ion exchange layer is 80-100 μm thick, and the total ion exchange layer is greater than 95 μm deep.
Preferably, the surface compressive stress of the high-strength glass is 800-850MPa, and the Vickers hardness is 660-680 kilograms/mm2The size change of the obtained glass after heat treatment at 500 ℃ for 5min is 15-30ppm, and the strain point temperature is 570-590 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention improves the strength of the glass from two aspects of component design and strengthening method, wherein the components play a remarkable synergistic effect, and a new component CeO is introduced2And TiO2And the content relationship among the components is defined, especially the ZrO is defined2/CeO2And TiO2/(ZrO2+CeO2In the range of (A), (B) and (C) at the same time2O+K2O)/Al2O3、K2O/(Na2O+Li2O) is maintained in a certain range, the amount of ion exchange and the depth of ion exchange are increased, and TiO is limited2、ZrO2And CeO2The synergistic effect of the three improves the thermal stability of the glass and the performance of ion exchange. Finally, through two times of ion exchange, the mechanical property of the glass is greatly improved, so that the glass obtained by the invention has higher surface compressive stress, Vickers hardness, excellent strain point and thermal stability, and the performances of compression resistance, scratch resistance and scratch resistance, and can be widely applied to a protective cover plate of a display device.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of high-strength glass for a display device, which comprises the following steps:
1) accurately weighing the following raw materials in percentage by mass:
54-65% of SiO210-17% of Al2O30-0.7% of Li2O, 12-16% of Na2O, 0.2-6% of K2O, 0.01-3% of B2O30.1-5% of MgO, 0.1-5% of CaO, 0.01-3% of SrO and 0.01-1.2% of ZrO20.01-1% of CeO20.01-1% of SnO2And 0.01-0.8% TiO2；
And the relationship between the components also satisfies:
(Na2O+K2O)/Al2O31.1-1.4; can be preferably selected in the range of 1.1-1.3 and 1.2-1.3;
K2O/(Na2O+Li2o) is 0.01 to 0.5; can be preferably selected in the ranges of 0.01-0.2 and 0.02-0.1;
ZrO2/CeO20.5 to 2; the ranges 0.8-1.5 and 1 can be preferably selected;
TiO2/(ZrO2+CeO20.01-5; can be preferredThe ranges are selected from 0.02-4 and 0.2-0.8.
2) The raw materials are fully and uniformly mixed and then placed in a platinum-rhodium alloy crucible, and then placed in a container built by refractory materials, the temperature in the container is raised to T1 by using a silicon-molybdenum rod, and after the reaction is carried out for 5 to 10 hours, the temperature in the container is lowered to T2 and is kept for 60 to 120 minutes; wherein, T1 is 1550-;
3) quickly pouring the glass liquid in the crucible into a preheated metal mold plate to be cooled into a plate shape, and then placing the plate-shaped glass in a high-temperature furnace at 500-600 ℃ to anneal for 4-6 hours;
4) cutting, grinding and polishing the annealed glass plate, cleaning the surface of the glass plate for 3-5 times by using deionized water, heating to the temperature of 330-;
5) taking out the glass plate, cooling to 330-plus 380 ℃, keeping the temperature for 1-4h, then continuing cooling to room temperature, then heating to 340-plus 390 ℃, preserving the temperature for 2-6h, and then placing the glass plate in molten rubidium nitrate liquid at 500 ℃ and 430-plus for preserving the temperature for 2-6 h; cooling to room temperature; and cleaning the surface of the glass plate for 3-5 times again to obtain the high-strength glass for the display device.
The invention relates to high-strength glass for a display device, which is prepared by the method, and comprises a rubidium ion exchange layer at the outer layer, a potassium ion exchange layer at the rubidium ion exchange layer and a glass inner body in the direction extending from the surface of the glass to the inside, wherein the depth of the rubidium ion exchange layer is 10-20 mu m, the thickness of the potassium ion exchange layer is 80-100 mu m, and the depth of the total ion exchange layer is more than 95 mu m; the surface compressive stress of the glass for the high-strength display device is 800-850MPa, and the Vickers hardness is 660-680 kilograms/mm2The size change of the obtained glass after heat treatment at 500 ℃ for 5min is 15-30ppm, and the strain point temperature is 570-590 ℃.
In the present invention, SiO2The mass percentage content is 54-65%. SiO 22The increase in the content as a main component for forming the glass contributes to the weight reduction of the glass, the improvement of chemical resistance, and other properties of the glass will be improved. But with SiO2Increase in content the high-temperature viscosity will riseThis is disadvantageous for production, so SiO2The content is 54-65%, preferably 58-64%.
Al2O3The content of (B) is 10-17% by mass. High content of Al2O3Is favorable for improving the strain point and the bending strength of the glass, has strong promoting effect on the improvement of the strength of the glass after chemical tempering, and is because non-bridge oxygen and Al are introduced into alkali metal in the alkali aluminosilicate glass3+Form alundum tetrahedron (AlO)4]The aluminoxy tetrahedron is a siloxy tetrahedron [ SiO4]The volume is larger, larger gaps can be generated in the glass structure, ion exchange is facilitated, and a product with better chemical toughening effect is finally obtained. However, Al2O3Too high makes the glass easy to crystallize, and at the same time, increases the difficulty of melting the glass.
Na2O is an essential component of the process for realizing chemical toughening, wherein the component is replaced by potassium ions with larger volume in the process of carrying out chemical toughening (ion exchange) on the glass. Meanwhile, the glass is used as a network outer body, which plays a role in breaking the network in the glass structure and can reduce the viscosity of the glass. Too much causes deterioration of a series of properties of the glass, such as chemical resistance, mechanical properties, etc., and too low causes deterioration of chemical tempering effect of the glass, and the tendency of the glass to devitrify increases, and the Na of the present invention2The content of O in percentage by mass is controlled to be 12-16%.
Introduction of K2The O is mainly used for promoting the glass melting by utilizing the mixed alkali effect of the O and Na, and meanwhile, the introduction of a certain amount of K has a certain promotion effect on the improvement of the performance effect after chemical tempering. K in the invention2The content of O in percentage by mass is controlled to be 0.2-6%, preferably 1-5%;
in the present invention, (Na) is in the glass2O+K2O)/Al2O31.1-1.4; the research of the invention discovers that (Na)2O+K2O)/Al2O3To influence the important parameters of the chemically enhanced ion exchange depth, a higher (Na) is maintained2O+K2O)/Al2O3The ratio will increase the amount and rate of subsequent ion exchange, (Na)2O+K2O)/Al2O3Preferably 1.1 to 1.3, and more preferably 1.2 to 1.3.
In the present invention, K2O/(Na2O+Li2O) is also an important parameter affecting ion exchange, if K2O/(Na2O+Li2O) is higher, the first ion exchange (K for Na) is not favored, if K is higher2O/(Na2O+Li2O) is low, the second ion exchange (Ru exchanges K) is not favored, so the invention creatively researches and discovers that the K can be maintained2O/(Na2O+Li2O) 0.01 to 0.5, K) having an unexpected ion exchange effect2O/(Na2O+Li2O) is preferably 0.01 to 0.2, more preferably 0.02 to 0.1, most preferably 0.05, in which case the effect of the two ion exchanges is the best. It should be noted that the ion exchange is carried out twice in sequence, the first time of the ion exchange is Na by using K, the second time of the ion exchange is K by using Ru, the sequence of the two ion exchanges cannot be changed, and the large-size K ions replace the small-size Na ions on the surface of the glass body during the first exchange, so that the concentration of the K ions on the surface of the glass body is improved, and the exchangeable K ions are provided for the subsequent second time of Ru exchange with larger size. If only K is exchanged, higher surface compressive stress cannot be obtained, and if only Ru is exchanged, a satisfactory amount of exchange cannot be obtained because of a large difference in size between Ru and Na. The inventive study of the present invention thus found that (Na) is defined in step one of the present invention2O+K2O)/Al2O3And K2O/(Na2O+Li2O), and obvious strength performance can be obtained only by sequentially replacing Na with K and replacing K with Ru.
B2O3Has special effect, can independently generate glass, and can be melted at high temperature under the condition of B2O3Difficult to form [ BO4]Can reduce the viscosity at high temperature, and B can deprive free oxygen to form [ BO ] at low temperature4]The trend of (2) makes the structure tend to be compact, improves the low-temperature viscosity of the glass, and prevents the occurrence of crystallization. The invention introduces a certain amount of B2O3Mainly promoteThe glass is melted, and the mass percentage content is controlled between 0.01 and 3 percent, and more preferably between 1 and 2.5 percent.
MgO, CaO, SrO and BaO belong to alkaline earth metal oxides and are network exosomes, and a certain amount of MgO, CaO, SrO and BaO can be introduced to promote the melting of glass. Only in the absence of Al2O3、B2O3When oxides are formed, Mg enters the network to form MgO4]Are present. Excessive MgO introduction can lead to glass porosity, reduced density, and reduced hardness. MgO also reduces the tendency and rate of crystallization and improves the chemical stability and mechanical strength of the glass. But should not be present in too great an amount that would cause the glass to devitrify easily and have too high an expansion coefficient. The MgO content of the present invention is 0.1 to 5%, preferably 1 to 3%.
CaO and MgO act similarly, Ca acting on the glass structure. CaO can be adjusted to reduce the high temperature viscosity and significantly improve the melting behavior of the glass without reducing the strain point of the glass, and excess CaO can reduce the chemical resistance of the glass. Here, the content of CaO is selected from the range of 0.1 to 5% by mass, more preferably 0.5 to 2% by mass.
Both SrO and BaO have the functions of increasing the chemical resistance of the glass and improving the devitrification resistance of the glass. However, large amounts of SrO and BaO result in increased glass density and expansion coefficient. Both SrO and BaO are components having particularly improved chemical resistance of the glass, and the total content of these components must exceed 0.2% or more. The contents of SrO and BaO are desirably as high as possible in terms of the requirement for improving chemical resistance, but are desirably as low as possible in terms of glass density and coefficient of expansion, and therefore, it is necessary to control the contents of SrO and BaO within a certain range. Meanwhile, based on Ba which is considered as a heavy metal with certain toxicity, the invention does not contain BaO basically, and the content of SrO in percentage by mass is controlled to be 0.01-3%, preferably 0.5-2%, and optimally 0.8-1.5%. In the present invention, the meaning of substantially not containing BaO means that BaO is not separately introduced except for BaO in an unavoidable impurity state.
ZrO2Can effectively improve the chemical stability of the glass, reduce the expansion coefficient of the glass and obviously improve the elastic modulus, ZrO of the glass2It is also beneficial to improve the acid resistance, elasticity and bending strength of the glassPerformance in terms of thermal expansion. However, since the glass has low solubility in water, the high-temperature viscosity of the glass is increased and the liquidus temperature of the glass is increased, thereby increasing the tendency of the glass to devitrify. The content of the zirconium oxide in percentage by mass is controlled between 0.01 and 1.2 percent, or the zirconium oxide is not basically contained.
CeO2The glass liquid clarifying agent and the glass liquid decoloring agent can be used for making the glass smooth and transparent and can not change color under the irradiation of strong radiation. However, the price is expensive, and the introduction amount is determined to be 0.01 to 1%, preferably 0.01 to 0.2%.
The invention discovers that certain CeO is added2Will be mixed with ZrO2The synergistic effect is generated, the chemical stability is improved, the expansion coefficient is reduced, and the stable Ce-Zr solid solution is probably formed, so that the glass performance is improved. The proportional relationship between the two needs to maintain a certain area, otherwise, the synergistic effect is difficult to achieve. In the present invention, ZrO2/CeO2Is 0.5-2, preferably 0.8-1.5, most preferably 1, and the effect is most preferable.
SnO2Is a fining agent used in the present invention, and is substantially free of arsenic and antimony, SnO2The content of (A) is 0.01-1%; by substantially free of arsenic and antimony is meant that the arsenic and antimony are not introduced separately, except in the unavoidable impurity state.
TiO2Has the effects of improving the ion exchange performance of the glass and improving the mechanical strength of the glass substrate. When TiO is present2When the content exceeds 1%, the glass tends to have poor resistance to devitrification. Therefore, the content thereof is limited to 0.01 to 0.8%, preferably 0.01 to 0.2%.
The present invention has surprisingly found that ZrO is maintained2/CeO2In a certain range, ZrO2And CeO2The chemical stability of the glass is obviously improved due to the interaction between the CeO and the glass2At the same time as a fining agent, with SnO2The compound also obtains obvious clarification effect, and balances to a certain extent due to the introduction of TiO2Resulting in a technical problem of deterioration of resistance to devitrification. In the present invention, TiO is used2/(ZrO2+CeO2) Is 0.01 to 5, preferably 0.02 to 4, and more preferably 0.2 to 0.8.
Specifically, the preparation steps of the embodiments 1 to 3 of the present invention are:
1) mixing the materials according to the mass percentage shown in the table 1, wherein the mass percentage of each material is 100 percent, and the weight of each material is 1000 g;
2) the raw materials are fully and uniformly mixed and then are placed in a platinum-rhodium alloy crucible, and then are placed in a container built by refractory materials, the temperature in the container is raised to 1550-; and keeping the difference between the temperature rise temperature and the temperature drop temperature between 50 and 100 ℃;
3) after the heat preservation is finished, the glass liquid in the crucible is quickly poured into a preheated metal template to be cooled into a plate shape (about 100mm multiplied by 200mm multiplied by 10mm), and then the plate is placed in a high-temperature furnace at 500-600 ℃ for annealing treatment, generally for 4-6 hours;
4) cutting, grinding and polishing the annealed sample into a thin glass plate with the thickness of 50 multiplied by 1mm, fully cleaning the surface of the glass plate for 3-5 times, and then preserving heat for 1-4 hours at the temperature of 330-; then placing the mixture in molten potassium nitrate solution with the temperature of 430-500 ℃ for heat preservation for 4-10 hours;
5) taking out the glass plate, cooling to 330-plus 380 ℃, keeping the temperature for 1-4h, then continuing cooling to room temperature, then heating to 340-plus 390 ℃, preserving the temperature for 2-6h, and then placing the glass plate in molten rubidium nitrate liquid at 500 ℃ and 430-plus for preserving the temperature for 2-6 h; cooling to room temperature; and cleaning the surface of the glass plate for 3-5 times again to obtain the glass product.
And (3) performing related tests on the glass product, wherein the transmittance is more than 90% after chemical toughening. The test results are shown in table 1.
Table 1 compares the data for specific examples 1-3 of the present invention and comparative examples.
As can be seen from table 1, in comparison with comparative example 1, in examples 1 to 3 of the present invention, by adding new components Ce and Ti, and performing component optimization and twice ion exchange, the resulting glass product achieves significant technical effects, and all the aspects of vickers hardness, surface compressive stress, thermal stability parameters, strain point, etc. are significantly improved compared with the prior art.
Specific examples 4 to 7 of the present invention are shown in Table 2.
Table 2 shows data for examples 4 to 7 of the present invention.
Specific examples 8 to 10 of the present invention are shown in Table 3, and any of the methods of examples 1 to 7 can be used for the production thereof.
Table 3 shows the raw material ratios of the embodiments 8 to 10 of the present invention.
Claims (10)
1. A method for preparing high-strength glass for a display device is characterized by comprising the following steps,
1) accurately weighing the following raw materials in percentage by mass:
54-65% of SiO210-17% of Al2O30-0.7% of Li2O, 12-16% of Na2O, 0.2-6% of K2O, 0.01-3% of B2O30.1-5% of MgO, 0.1-5% of CaO, 0.01-3% of SrO and 0.01-1.2% of ZrO20.01-1% of CeO20.01-1% of SnO2And 0.01-0.8% TiO2；
And the mass percentages of the components also satisfy the following relations:
(Na2O+K2O)/Al2O31.1-1.4;
K2O/(Na2O+Li2o) is 0.01 to 0.5;
ZrO2/CeO20.5 to 2;
TiO2/(ZrO2+CeO2) 0.01-5;
2) fully and uniformly mixing the raw materials in the step 1) and then melting to form molten glass;
3) preparing glass liquid into plate-shaped glass and annealing;
4) cutting, grinding and polishing the annealed glass plate, cleaning the surface of the glass plate, heating to 330-380 ℃, preserving the heat for 1-4h, and then placing the glass plate in molten potassium nitrate solution at the temperature of 430-500 ℃ for preserving the heat for 4-10 h to perform primary ion exchange;
5) taking out the glass plate after the primary ion exchange, cooling to 330-plus 380 ℃, preserving heat for 1-4h, then continuing cooling to room temperature, then heating to 340-plus 390 ℃, preserving heat for 2-6h, and then placing in molten rubidium nitrate liquid at 430-plus 500 ℃ for preserving heat for 2-6h for secondary ion exchange; cooling to room temperature after secondary ion exchange; cleaning the surface of the glass plate again to obtain the high-strength glass for the display device, wherein the added CeO2And ZrO2The synergistic effect is generated, and a stable Ce-Zr solid solution is formed.
2. The method for preparing high-strength glass for a display device according to claim 1, wherein the step 2) comprises the specific steps of mixing the raw materials in the step 1) thoroughly, heating to T1, reacting for 5-10 hours to obtain molten glass, cooling to T2, and keeping the temperature for 60-120 minutes; wherein, T1 is 1550-.
3. The method as claimed in claim 1 or 2, wherein the step 3) comprises the steps of pouring the molten glass into a mold, cooling the molten glass into plate-shaped glass, and annealing the plate-shaped glass at 600 ℃ for 4-6 hours.
4. The method of claim 1 or 2, wherein in step 1) (Na)2O+K2O)/Al2O3Is 1.1-1.3 or 1.2-1.3.
5. The method of claim 1 or 2, wherein K is in step 1)2O/(Na2O+Li2O) is 0.01 to 0.2 or 0.02 to 0.1.
6. The method of claim 1 or 2, wherein ZrO in the step 1) is added to the glass for display device2/CeO20.8-1.5 or 1.
7. The method of claim 1 or 2, wherein the TiO in the step 1) is used for preparing a high strength glass for a display device2/(ZrO2+CeO2) 0.02-4 or 0.2-0.8.
8. A high-strength glass for a display device, which is produced by the production method according to any one of claims 1 to 7, characterized in that the direction extending from the surface of the glass to the inside comprises a rubidium ion exchange layer at the outer layer and a glass inner body at the inside, and a potassium ion exchange layer at the rubidium ion exchange layer and the glass inner body.
9. The high strength glass for display device of claim 8, wherein the rubidium ion exchange layer has a depth of 10-20 μm, the potassium ion exchange layer has a thickness of 80-100 μm, and the total ion exchange layer has a depth of greater than 95 μm.
10. The high-strength glass for display devices as claimed in claim 8 or 9, wherein the high-strength glass has a surface compressive stress of 800-2The size change of the obtained glass after heat treatment at 500 ℃ for 5min is 15-30ppm, and the strain point temperature is 570-590 ℃.
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Application publication date: 20180420 Assignee: Hunan Shaohong special glass Co.,Ltd. Assignor: CAIHONG GROUP (SHAOYANG) SPECIAL GLASS Co.,Ltd. Contract record no.: X2023980041911 Denomination of invention: A high-strength glass for display devices and its preparation method Granted publication date: 20201020 License type: Common License Record date: 20230915 |