CN112010552A - Aluminosilicate glass and strengthening method thereof - Google Patents
Aluminosilicate glass and strengthening method thereof Download PDFInfo
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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 aluminosilicate glass and a strengthening method thereof, wherein the components of the glass comprise SiO according to mass percentage2 54.2％～68％，Al2O3 9.5％～20.0％，Na2O 9.1％～20.0％，Li2O 3.0％～8.0％，ZrO2 0.1％～4.0％，ZnO 1.2％～3.6％，B2O3 3.2％～8.0％，La2O3 1.5％～2.5％，SnO20.1 to 1 percent. The preparation method comprises melting and clarifying raw materials, and forming into plate glass; then, carrying out chemical strengthening on the plate glass in a salt bath twice, wherein the first time temperature is 350-390 ℃, and the time is not more than 120 min; the second temperature is 380-410 ℃ and the time is not more than 40 min.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to aluminosilicate glass and a strengthening method thereof.
Background
Cover plate glass is one of the key raw materials widely used in the flat panel display industry, is usually a layer of glass with the outermost layer of a display device playing a protective role, and can also be used as a carrier material of a touch group, and is mainly applied to mobile terminal markets of electronic equipment, mobile electronic equipment and the like, such as mobile phones, watches, portable computers, notebook computers and digital cameras. Particularly, with the development of 5G communication and wireless charging technologies and the mass application of 3D cover plates and cover glass of vehicle-mounted glass, higher requirements are put on the performance of the cover glass, especially the strength, deformation resistance and impact resistance of the glass.
Generally, the strength is considered, and the deformation resistance of the cover glass is also important. With the development and demand of mobile devices, the cover glass protection screen and the touch screen require small deformability. When the entire device is dropped onto a hard surface, the cover glass may fail to bend, and the high deformation resistance may result in a small amount of bending so as to protect the electronic components inside the device from being lost, especially for thinner devices, which have a higher dimensional accuracy requirement for protecting the cover screen, so that the amount of deformation that occurs when subjected to external forces must be sufficiently small. The elastic modulus (E) of glass is directly related to the deformation resistance, and glass having high deformation resistance should have a large elastic modulus (E) but should fall within a suitable range. E is too large, the brittleness of the glass is larger, the glass becomes too hard and has small toughness, and the crack resistance expansibility is reduced; and E is too small, the glass has small deformation resistance, and large deformation can be caused under the action of pressure to cause damage to the electronic components on the inner layer of the cover plate protection screen. In addition, the glass should have a low Coefficient of Thermal Expansion (CTE), high thermal and chemical stability to ensure that the glass is not deformed, warped or bent during the manufacturing process, and stable in properties.
In addition, with the trend of light and thin electronic devices, portability is more and more important, and the density of the cover glass is a key issue in research. The glass with low density can reduce the weight of the equipment, increase the portability of the equipment and reduce the harm caused by the large gravity of the electronic product when the electronic product falls.
Therefore, there is a strong need for a cover glass with high strength and elastic modulus, small thermal expansion coefficient, low density, high thermal and chemical stability, and impact resistance, which is resistant to deformation, to meet the steady development of the display device industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides aluminosilicate glass and a strengthening method thereof, and the aluminosilicate glass and the strengthening method thereof can obtain the impact-resistant deformation-resistant cover glass with higher strength and elastic modulus, smaller thermal expansion coefficient, small density, higher thermal stability and chemical stability after chemical strengthening treatment.
The invention is realized by the following technical scheme:
the aluminosilicate glass comprises SiO in percentage by mass2 54.2％～68％，Al2O3 9.5％～20.0％，Na2O 9.1％～20.0％，Li2O 3.0％～8.0％，ZrO2 0.1％～4.0％，ZnO 1.2％～3.6％，B2O3 3.2％～8.0％，La2O3 1.5％～2.5％，SnO2 0.1％～1％。
Preferably, the ZrO2And Al2O3The mass percentage of (A) satisfies the following relationship:
0.005≤ZrO2/Al2O3≤0.3。
preferably, the Li2O、Na2O、ZrO2、B2O3And Al2O3The mass percentage of (A) satisfies the following relationship:
0≤(Na2O+Li2O-Al2O3-ZrO2)-B2O3≤0.8。
preferably, the La2O3、SiO2And Al2O3The mass percentage of (A) satisfies the following relationship:
0.02≤La2O3/(SiO2+Al2O3)≤0.04。
preferably, the ZrO2、ZnO、B2O3And Al2O3The mass percentage of (A) satisfies the following relationship: al of 0.14 or less2O3+ZrO2+B2O3+ZnO≤0.35。
Preferably, B is2O3And SiO2The mass percentage of (A) satisfies the following relationship:
0.05≤B2O3/SiO2≤0.15。
a method for preparing aluminosilicate glass comprises the following steps:
And 2, sequentially carrying out chemical strengthening twice on the flat glass in a salt bath to obtain chemically strengthened aluminosilicate glass, wherein:
during the first chemical strengthening, the molar percentage of potassium nitrate and sodium nitrate is (30-80%) (20-70%), the temperature is 350-390 ℃, and the time is not more than 120 min;
the molar percentage of potassium nitrate and sodium nitrate is (50-100%) (0-50%), the temperature is 380-410 deg.C, and the time is not more than 40 min.
Furthermore, the compression depth of the stress layer of the aluminosilicate glass in the step 2 is more than 100 μm, and the surface compressive stress is at least 800 MPa.
Still further, the aluminosilicate glass described in step 2 has the following thermal expansion coefficient, elastic modulus, vickers hardness and density:
7.0×10-7thermal expansion coefficient is more than or equal to K and less than or equal to 8.2 multiplied by 10-7K; the elastic modulus is more than or equal to 70GPa and less than or equal to 82 GPa; vickers hardness of greater than 580kg · f/mm2(ii) a The density is less than or equal to 2.35g/cm3。
An aluminosilicate glass obtained by the method for producing an aluminosilicate glass according to any one of the above.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to aluminosilicate glass, which is prepared from SiO2To form the skeleton structure of the glass, the mechanical strength and chemical stability of the glass can be improved when SiO is used2At a content of less than 54.2, the chemical resistance of the glass after forming is lowered; however, when the content exceeds 68%, the difficulty of melting is increased; 9.5 to 20 percent of Al2O3The crystallization tendency of the glass can be reduced, and the chemical stability, the thermal stability, the mechanical strength and the hardness of the glass can be improved, so that the elastic modulus of the glass can be improved; 3 to 8 mass percent of Li2O and 9.1 to 20 mass percent of Na2O bond, enabling [ SiO ]4]The formed network is relaxed and broken, the problem of difficult melting can be solved, the viscosity of the glass melt is greatly reduced, the exchange position is provided for the ion exchange during chemical strengthening, and Li with smaller ion radius2The addition of O can lead the glass to be subjected to secondary strengthening, and the number of layers of stress layers is increased, thereby increasing the bending strength and the impact strength of the glass; ZrO (ZrO)2Is intermediate oxide of glass, and ZrO 0.1-4.0% is added into glass2The object of (a) is to further improve the elastic modulus and chemical resistance of the glass and to facilitate the exchange process of chemically strengthening the glass, while at the same time being able to increase the viscosity, hardness, elasticity, refractive index and chemical stability of the glass and to reduce the coefficient of expansion. The addition of ZnO can properly improve the alkali resistance of the glass and make the silicon-oxygen tetrahedron [ SiO ]4]The formed network is relaxed and broken, thereby improving the ion exchange performance of the glass; b is2O3Added to glass as a network forming agent, the meltability and formability of the glass can be reduced, the high temperature viscosity and density can be reduced, and meanwhile, the thermal expansion property can be reduced, and the thermal shock resistance and chemical resistance can be increased; effect of lanthanum on glass Properties and Al2O3There is some similarity, introducing a small amount of La2O3The chemical stability of the glass can be properly improved, and the thermal expansion coefficient is reduced; SnO2The glass component is added as a clarifying agent, the addition amount of the clarifying agent is usually 0.1-1.5%, and bubbles in glass melt can be eliminated; can be finally processed by twiceThe cover glass with higher strength and elastic modulus, smaller thermal expansion coefficient, small density, higher thermal stability and chemical stability, higher deformation resistance and shock resistance is obtained by chemical strengthening and has wide application as a protective cover of mobile electronic equipment.
The invention relates to a preparation method of aluminosilicate glass, which comprises the steps of preparing raw materials according to the components of the glass by mol percent, melting and clarifying the raw materials, forming the raw materials into flat glass, and performing secondary composite reinforcement, wherein the cover glass obtained by performing ion exchange reinforcement on the glass has higher deformation resistance and impact resistance, higher strength and elastic modulus, smaller thermal expansion coefficient, small density, higher thermal stability and chemical stability, and is widely applied to protective cover plates of mobile electronic equipment. The impact resistance of the glass is an important index for the use of cover glass, the impact resistance is represented by the resistance effect of stress depth of layer (DOL) and stress (CS) generated after ion exchange strengthening on the surface of a sample on impact energy generation, and the larger the CS and DOL are, the stronger the impact energy resistance and crack propagation resistance are. The sample with good impact resistance can keep the integrity of the glass under the action of large impact force without generating the situation of cracking. The deformation amount of the anti-deformation impact-resistant aluminosilicate glass is smaller under the action of external force, so that inner-layer electronic components can be protected from being damaged; meanwhile, by adopting a composite secondary strengthening process, potassium and sodium ions in the salt bath are exchanged with lithium and sodium ions in the glass, so that two compression stress layers are formed in the glass, and the mechanical strength of the glass is further enhanced. The falling ball impact resistance of the glass after ion exchange strengthening meets the high requirements of flat panel display industry on cover plate glass.
Drawings
Fig. 1 is a ball-drop point diagram of the ball-drop impact energy test according to the present invention.
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 system and composition of the glass are the main factors determining the strength of the glassHowever, the strength, deformation resistance and impact resistance of ordinary soda-lime glass are not as good as those of aluminosilicate glass, and parameters such as stress layer compression depth and surface compressive stress after chemical strengthening are not as good as those of aluminosilicate glass, so that an aluminosilicate glass system is selected and optimized on the basis of the parameters to improve the performance. Chemical strengthening can increase the strength of the glass by low temperature ion exchange, i.e. by subjecting the glass to a molten salt solution (potassium and sodium salts, e.g. KNO) at a temperature below the strain point of the glass3、NaNO3) In the method, small ions in the glass are replaced with large ions in the salt bath, so that the surface of the glass is in a compression state, compression stress is generated, and tensile stress compensation is generated in the center of the glass. On the basis of aluminosilicate glass, the strength of the aluminosilicate glass can be further improved through chemical strengthening, lithium element is added into the glass composition, the traditional primary strengthening can be converted into secondary composite strengthening, the primary strengthening mainly comprises the exchange of sodium ions in a salt bath and lithium ions in the glass to generate a first layer of compressive stress layer, and the secondary strengthening mainly comprises the exchange of potassium ions in the salt bath and sodium ions in the glass to generate a second layer of compressive stress layer, so that the number of layers and the depth of the stress layer of the glass can be increased through the secondary composite strengthening, and the product performance can be improved.
After the glass is chemically strengthened by ion exchange, the surface compressive stress CS and the compressive stress layer depth DOL generated on the surface of the glass can improve the impact resistance, the excellent impact resistance can improve the anti-falling performance of the product, and meanwhile, the service life of the cover plate glass is prolonged.
The invention relates to aluminosilicate glass, which comprises the following components in percentage by mass: SiO 22 54.2％～68％，Al2O3 9.5％～20.0％，Na2O 9.1％～20.0％，Li2O 3.0％～8.0％，ZrO2 0.1％～4.0％，ZnO 1.2％～3.6％，B2O3 3.2％～8.0％，La2O3 1.5％～2.5％，SnO2 0.1％～1％。
Further, the corresponding numerical range is narrowed, and Al is more than or equal to 0.142O3+ZrO2+B2O3+ZnO≤0.35；0.005≤ZrO2/Al2O3≤0.3；0.05≤B2O3/SiO2≤0.15；0≤(Na2O+Li2O-Al2O3-ZrO2)-B2O3≤0.8；0.02≤La2O3/(SiO2+Al2O3) Less than or equal to 0.04, and the corresponding effects are specifically analyzed below.
SiO2Is an important glass-forming oxide, forms the framework of the glass, can improve the mechanical strength and chemical stability of the glass, but excessive SiO2Increase of glass transition temperature and melting temperature, so that SiO2The content has its optimum value. In the deformation-resistant high-strength glass, if the content is less than 54.2 wt%, the chemical resistance of the glass after forming is lowered, and if it is more than 68 wt%, the difficulty of melting is increased, and SiO2When the content of (A) is in the range of 54.2 to 68 wt%, the thermal expansion coefficient of the glass can be effectively reduced, so that SiO2The mass percentage is 54.2-68%.
Al2O3The oxide is an intermediate oxide, participates in the action of a network formation body, can reduce the crystallization tendency of glass, improves the chemical stability, the thermal stability, the mechanical strength and the hardness of the glass, and can improve the elastic modulus of the glass. At the same time, Al in the glass3+Tends to form [ AlO4]Tetrahedral network, this ratio [ SiO4]The tetrahedron has large volume, so that larger pores in a glass system are used as ion diffusion channels, and Na can be promoted during chemical strengthening+→K+And (4) ion exchange. However, if the content is too large, the softening temperature of the glass rises, and it is difficult to obtain a long glass, and it is difficult to perform a float glass forming operation, and the glass is devitrified, and the thermal expansion coefficient becomes too small to be consistent with the surrounding material. Thus Al2O3The mass percentage of the component (A) is 9.5-20.0%.
Na2O and Li2O is a network exo-oxide which mainly plays a role of breaking a network and enables the [ SiO ] to be introduced4]The formed network is loosened and broken, the problem of difficult melting can be solved, the viscosity of the glass melt is greatly reduced, and the method has the same effect as the methodProvides an exchange site for ion exchange during chemical strengthening. Li having a small ionic radius2The addition of O can lead the glass to be subjected to secondary strengthening, and the number of layers of stress layers is increased, thereby increasing the bending strength and the impact strength of the glass.
ZrO2Is a glass intermediate oxide, and the addition of the glass intermediate oxide can further improve the elastic modulus and chemical resistance of the glass, promote the exchange process of chemical strengthening examples, and simultaneously improve the viscosity, hardness, elasticity, refractive index and chemical stability of the glass and reduce the expansion coefficient. But excess ZrO2The tendency to devitrify increases with increasing difficulty of melting. ZrO (ZrO)20.1 to 4.0 percent by mass.
Further, only Al is contained2O3The glass of (2) is more brittle and more likely to be broken, and ZrO is added2Replacing part of Al2O3The microstructure of the glass can be changed. Further control of ZrO2/Al2O3Can increase the strength and elastic modulus of the glass, ZrO2/Al2O3The mass percentage ratio of the component (A) is 0.005-0.3.
The addition of ZnO can properly improve the alkali resistance of the glass and make the silicon-oxygen tetrahedron [ SiO ]4]The formed network is relaxed and broken, thereby improving the ion exchange performance of the glass. But adding too much ZnO may increase the density and cause phase separation. The mass percent of ZnO is 1.2-3.6%.
Experiments prove that when Al is more than or equal to 0.142O3+ZrO2+B2O3When the + ZnO is less than or equal to 0.35, the strength of the glass can be improved, and the chemical strengthening ion exchange is facilitated.
B2O3Added to glass as a network former can reduce the meltability and formability of the glass, reduce high temperature viscosity and density, while reducing thermal expansion, increasing thermal shock resistance and chemical resistance. But adding an excess of B2O3Will form compact [ BO4]The network, the migration of ions in the glass is hindered, which seriously affects the chemical strengthening effect, so that a proper amount is required.
Addition of B2O3To replace part of SiO2The network structure of the glass can be changed, and CS and DOL are improved. [ SiO ]4]Tetrahedron and [ BO3]The planar triangle does not require a compensating charge, so an open network structure is formed, which leads to easier densification of the glass, suitable B2O3/SiO2The ratio can reduce the thermal expansion coefficient, density and brittleness of the glass and improve the crack propagation resistance of the glass. B is2O3/SiO2The ratio of (A) to (B) is in the range of 0.05-0.15.
The number of non-bridging oxygen atoms NBO is approximated by the equation NBO ═ R2O+R′O-Al2O3-ZrO2-B2O3Is calculated wherein R is2O is an alkali metal oxide and R' O is an alkaline earth metal oxide, but the alkaline earth metal oxide is not referred to in the present invention. The presence of larger NBO generally lowers the melting temperature of the glass, thereby promoting melting, but larger NBO can result in a glass with greater hardness and lower toughness, resulting in higher brittleness, which is detrimental to the use of the glass. The reasonable control of the NBO amount can improve the performance of the glass, when the NBO value is near zero, the toughness of the glass reaches the maximum, B2O3The hardness of the glass is also reduced, which, when combined with a higher toughness, results in a desired minimization of brittleness, and a mechanically durable glass is produced which is resistant to damage and edge chipping, so that the value of NBO is 0 ≦ NBO ═ Na (Na)2O+Li2O-Al2O3-ZrO2))-B2O3≤0.8。
La belongs to rare earth oxide, and lanthanum in glass is generally La3+Status. Due to La3+Large radius and high coordination number, so that lanthanum oxide is not a glass former, cannot enter a network and is positioned in network gaps, and La is contained2O3The glass structure of (2) is relatively compact. Effect of lanthanum on glass Properties and Al2O3There is some similarity, introducing a small amount of La2O3Can properly improve the chemical stability of the glass and reduce the thermal expansion coefficient.
Controlling La2O3/(SiO2+Al2O3) Can further improve the scratch resistance of the glass.
SnO2Added as a fining agent to the glass component of the present invention, usually in an amount of 0.1% to 1.0%, to eliminate bubbles in the glass melt, when SnO is used2When the mass percent of the gas is 0.2-0.5%, the effect of completely removing bubbles can be achieved while saving raw materials. The glass is a zirconium aluminosilicate glass system, and the viscosity and the surface tension of the glass liquid are increased due to the fact that the components contain more aluminum oxide and zirconium oxide, and melting and clarification of the glass liquid are difficult.
The invention relates to a production process of high-deformation-resistance impact-resistant aluminosilicate glass, which comprises the following steps of:
firstly, selecting glass raw materials and a glass clarifying agent, preparing, uniformly mixing, and melting in a glass melting furnace, wherein the melting mode can be an all-electric melting furnace mode, the melting temperature is 1650 ℃, the glass is formed by a float method to obtain flat glass with the thickness of 0.7mm, and the cutting size is 146 multiplied by 70 mm. The glass thickness is generally in the range of 0.3mm to 3.0 mm. The formation may be by, for example, an overflow downdraw process or a float process.
Then, carrying out composite secondary chemical strengthening on the glass product, wherein the steps are as follows: firstly, performing primary strengthening, namely putting glass into a mixed molten salt bath of potassium salt and sodium salt at the temperature of 350-390 ℃ for keeping for not more than 120min, wherein the mass percent of the potassium salt and the sodium salt in the salt bath is (30-80%): (20-70%); then performing secondary strengthening, and putting the glass into a mixed molten salt bath of potassium salt and sodium salt at the temperature of 380-410 ℃ for not more than 40min, wherein the mass percent of the potassium salt and the sodium salt in the salt bath is (50-100%): (0% to 50%).
The thermal expansion coefficient of the aluminosilicate glass strengthened by the composite ion exchange is 7.0 multiplied by 10-7/K≤CTE≤8.2×10-7K; the elastic modulus E is more than or equal to 70GPa and less than or equal to 82 GPa; density ≦ 2.35g/cm3(ii) a The glass is provided with a compression layer extending from the surface to the depth of layer DOL, and the compression depth DOL of the stress layer reaches more than 100 mu m; the surface compressive stress CS is at least 800 MPa.
The surface impact energy of the aluminosilicate glass passes the ball drop impact test five points once, as shown in fig. 1. Placing glass in a grinding tool, wherein the falling point position is 10mm away from each edge and the central point is five points, 64g of steel ball is used once, the initial height is 30cm, the steel ball is lifted by 10cm each time to carry out limit test, observing whether a sample generates cracks or is cracked to carry out limit test, and testing and calculating the falling ball impact energy E of the glass to be mFalling ballgh, the ball impact energy E ═ mFalling ballghHeight of fall≥0.56J。
The chemically strengthened glass product can be applied to mobile terminal markets such as electronic equipment and mobile electronic equipment.
The relevant parameters for examples 1 to 7 are tabulated below.
Table 1 relevant parameters for examples 1 to 7
Table 1 is an exemplary embodiment within the preferred compositional ranges, and the above components and their corresponding compositional ranges are reasonably expanded based on these data, and corresponding experimental validation is also performed. Wherein, IOX1Denotes the first ion exchange, mainly Li in glass+With Na in the salt bath+Exchange, thereby increasing the stress layer depth; IOX2Indicating a second ion exchange, mainly Na in the glass+Exchange with K + in the salt bath, thereby increasing the compressive stress of the glass surface; a is potassium nitrate and B is sodium nitrate, and the sample size is 0.7X 146X 70 mm. Surface compressive stress of glass(CS) and depth of stress layer compression (DOL) were tested jointly with FSM-6000LE and SLP. The modulus of elasticity of the glass was measured by a universal tester model CMT6503, supplied by Meits Industrial systems Ltd. The glass has a thermal expansion coefficient and a transition temperature measured by a relaxation resistance dilatometer (relaxation resistance DIL402 PC). The hardness of the glass was measured by HXD-1000 Vickers hardness tester.
Table 2 properties of the high deformation resistance impact resistant aluminosilicate glasses of examples 1 to 7, sample sizes were 0.7 × 146 × 70 mm.
Table 3 falling ball impact test of samples having dimensions of 0.7X 146X 70 mm.
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Mass of steel ball/g | 64 | 64 | 64 | 64 | 64 | 64 | 64 |
| Ultimate height/m | 0.9 | 1 | 0.9 | 1.1 | 1 | 0.9 | 1.1 |
| Impact energy/J | 0.56 | 0.62 | 0.56 | 0.69 | 0.62 | 0.56 | 0.69 |
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. An aluminosilicate glass characterized byThe components of the glass comprise SiO in percentage by mass2 54.2％～68％，Al2O3 9.5％～20.0％，Na2O 9.1％～20.0％，Li2O 3.0％～8.0％，ZrO2 0.1％～4.0％，ZnO 1.2％～3.6％，B2O3 3.2％～8.0％，La2O31.5％～2.5％，SnO2 0.1％～1％。
2. The aluminosilicate glass of claim 1, wherein the ZrO 22And Al2O3The mass percentage of (A) satisfies the following relationship:
0.005≤ZrO2/Al2O3≤0.3。
3. the aluminosilicate glass of claim 1, wherein the Li is2O、Na2O、ZrO2、B2O3And Al2O3The mass percentage of (A) satisfies the following relationship:
0≤(Na2O+Li2O-Al2O3-ZrO2)-B2O3≤0.8。
4. the aluminosilicate glass of claim 1, wherein the La is2O3、SiO2And Al2O3The mass percentage of (A) satisfies the following relationship:
0.02≤La2O3/(SiO2+Al2O3)≤0.04。
5. the aluminosilicate glass of claim 1, wherein the ZrO 22、ZnO、B2O3And Al2O3The mass percentage of (A) satisfies the following relationship: al of 0.14 or less2O3+ZrO2+B2O3+ZnO≤0.35。
6. According to claimThe aluminosilicate glass according to claim 1, wherein B is2O3And SiO2The mass percentage of (A) satisfies the following relationship:
0.05≤B2O3/SiO2≤0.15。
7. a method for preparing aluminosilicate glass is characterized by comprising the following steps:
step 1, preparing raw materials according to the components of the glass by mass percent, melting and clarifying the raw materials, and forming the raw materials into plate glass; the glass comprises the following components in percentage by mass, SiO254.2％～68％，Al2O3 9.5％～20.0％，Na2O 9.1％～20.0％，Li2O 3.0％～8.0％，ZrO2 0.1％～4.0％，ZnO 1.2％～3.6％，B2O33.2％～8.0％，La2O3 1.5％～2.5％，SnO2 0.1％～1％；
And 2, sequentially carrying out chemical strengthening twice on the flat glass in a salt bath to obtain chemically strengthened aluminosilicate glass, wherein:
during the first chemical strengthening, the molar percentage of potassium nitrate and sodium nitrate is (30-80%) (20-70%), the temperature is 350-390 ℃, and the time is not more than 120 min;
the molar percentage of potassium nitrate and sodium nitrate is (50-100%) (0-50%), the temperature is 380-410 deg.C, and the time is not more than 40 min.
8. The method according to claim 7, wherein the aluminosilicate glass of step 2 has a stress layer compression depth of 100 μm or more and a surface compressive stress of at least 800 MPa.
9. The method for producing an aluminosilicate glass according to claim 7, wherein the aluminosilicate glass of step 2 has a thermal expansion coefficient, an elastic modulus, a Vickers hardness, and a density as follows:
7.0×10-7thermal expansion coefficient is more than or equal to K and less than or equal to 8.2 multiplied by 10-7K; the elastic modulus is more than or equal to 70GPa and less than or equal to 82 GPa; vickers hardness of greater than 580kg · f/mm2(ii) a The density is less than or equal to 2.35g/cm3。
10. An aluminosilicate glass obtained by the method for producing an aluminosilicate glass according to any one of claims 7 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113582558A (en) * | 2021-08-24 | 2021-11-02 | Oppo广东移动通信有限公司 | Glass strengthening method, glass, case assembly, and electronic device |
| CN114835397A (en) * | 2022-06-14 | 2022-08-02 | 北京工业大学 | Batch for preparing lithium-containing high-zirconium-aluminum-silicon glass by using spodumene and zirconite and method |
| CN115818956A (en) * | 2022-10-26 | 2023-03-21 | 彩虹集团（邵阳）特种玻璃有限公司 | High-alumina-silica glass and preparation method and application thereof |
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| CN113582558A (en) * | 2021-08-24 | 2021-11-02 | Oppo广东移动通信有限公司 | Glass strengthening method, glass, case assembly, and electronic device |
| CN114835397A (en) * | 2022-06-14 | 2022-08-02 | 北京工业大学 | Batch for preparing lithium-containing high-zirconium-aluminum-silicon glass by using spodumene and zirconite and method |
| CN114835397B (en) * | 2022-06-14 | 2024-01-05 | 北京工业大学 | Batch and method for preparing lithium-containing high-zirconium aluminum silicate glass by using spodumene and zirconite |
| CN115818956A (en) * | 2022-10-26 | 2023-03-21 | 彩虹集团（邵阳）特种玻璃有限公司 | High-alumina-silica glass and preparation method and application thereof |
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