Alkali-aluminosilicate glass

Abstract

The present disclosure relates to an alkali-aluminosilicate glass which contains between 47.5 and 55 wt.% SiO2, between 21 and 27.5% Al2O3; and between 12 and 16 wt.% Na2O. The molar ratio of Al2O3 and Na2O amounts to between 1:0.9 and 1:1.2. This glass is characterized by high hardness and high surface strengths after its chemical toughening, whereby the resulting extremely high scratch resistance favors its use as a display glass. A further preferred feature of this glass is its much lower viscosity for this group of glasses.

Claims

1. A glass, comprising between 47.5 and below 55 wt. % SiO2; between 21 and 27.5 wt. % Al2O3; and between 12 and 16 wt. % Na2O; and in that a molar ratio of Al2O3 to Na2O lies between 0.94:1 and 1.1:1; wherein the glass is free of CaO; wherein the glass includes between 4.5 and 6 wt. % MgO; wherein the glass contains between 1.5 and 2.5 wt. % K2O; wherein the glass contains between >0 and 1 wt. % SnO2; wherein the glass contains between >0 and 0.6 wt. % CeO2; wherein the glass contains between 1.8 and 3.5 wt. % ZrO2; and wherein the glass has a pre-hardening Vickers hardness of between 6400 and 6600 MPa.

2. The glass in accordance with claim 1, wherein the glass contains between 50 and below 55 wt. % SiO2.

3. The glass in accordance with claim 2, wherein the glass contains between 53 and below 55 wt. % SiO2.

4. The glass in accordance with claim 1, wherein the glass contains between 21 and 25 wt. % Al2O3.

5. The glass in accordance with claim 4, wherein the glass contains between 21.5 and 23.5 wt. % Al2O3.

6. The glass in accordance with claim 1, wherein the glass contains between 13 and 16 wt. % Na2O.

7. The glass in accordance with claim 6, wherein the glass contains between 13.8 and 15.6 wt. % Na2O.

8. The glass in accordance with claim 1, wherein a molar ratio of SiO2 to Al2O3 lies between 2.5:1 and 4.8:1.

9. The glass in accordance with claim 8, wherein the molar ratio of SiO2 to Al2O3 lies between 3.5:1 and 4.5:1.

10. The glass in accordance with claim 9, wherein the molar ratio of SiO2 to Al2O3 lies between 3.9:1 and 4.2:1.

11. The glass in accordance with claim 1, wherein the glass contains between >0 and 1 wt. % F.

12. The glass in accordance with claim 1, wherein the glass contains between >0.2 and 3.5 wt. % ZnO.

13. The glass in accordance with claim 1, wherein the glass comprises x wt. % Li2O, where 0<x≦1.5.

14. A glass article comprising: a glass comprising between 47.5 and below 55 wt. % SiO2; between 21 and 27.5 wt. % Al2O3; between 4.5 and 6 wt. % MgO; and between 12 and 16 wt. % Na2O; and wherein a molar ratio of Al2O3 to Na2O lies between 0.94:1 and 1.1:1, wherein the glass has a diffusion layer at least sectionally at its surface, wherein a K content of the glass is increased with respect to a base composition and a Li content and a Na content of the glass are lowered with respect to the base composition, wherein the glass is free of CaO, wherein the glass includes between 1.5 and 2.5 wt. % K2O, wherein the glass includes between >0 and 1 wt. % SnO2, wherein the glass includes between >0 and 0.6 wt. % CeO2, wherein the glass contains between 1.8 and 3.5 wt. % ZrO2, and wherein the glass has a pre-hardening Vickers hardness of between 6400 and 6600 MPa.

15. The glass article in accordance with claim 14, wherein the diffusion layer is between 10 μm and 60 mm thick.

16. The glass article in accordance with claim 14, wherein the glass article is a glass pane.

17. The glass article in accordance with claim 16, wherein the glass pane is shaped as a cover glass positioned and coupled as a display of electronic devices.

18. The glass article in accordance with claim 14, wherein the glass comprises x wt. % Li2O, where 0<x≦1.5.

Description

BRIEF DESCRIPTION OF THE FIGURE

(1) FIG. 1 shows measured viscosity curves of glasses in accordance with the present disclosure in comparison with glasses from the prior art in the temperature range between 1200° C. and 1550° C.

DETAILED DESCRIPTION

(2) Embodiment 1

(3) A batch of suitable starting materials was melted, homogenized, fined and left to stand in a glass furnace to obtain a glass having the following composition: 53.8 wt. % SiO2; 21.9 wt. % Al2O3; 5.7 wt. % MgO; 14 wt. % Na2O; 1.9 wt. % K2O; 2.2 wt. % ZrO2; 0.4 wt. % SnO2; and 0.1 wt. % CeO2.

(4) A block was subsequently cast and fine annealed. In a further sequence, panes of the glass in accordance with the present disclosure, which is called Glass 1 in the following, were produced from this block by cutting, grinding and polishing.

(5) Embodiment 2

(6) A batch of suitable starting materials was melted, homogenized, fined and left to stand in a glass furnace to obtain a glass having the following composition 53.8 wt. % SiO2; 22.9 wt. % Al2O3; 4.7 wt. % MgO; 14 wt. % Na2O; 1.9 wt. % K2O; 2.2 wt. % ZrO2; 0.4 wt. % SnO2; and 0.1 wt. % CeO2.

(7) A block was subsequently cast and fine annealed. In a further sequence, panes of the glass in accordance with the present disclosure, which is called Glass 2 in the following, were produced from this block by cutting, grinding and polishing.

(8) With respect to embodiment 1, the portion of Al2O was therefore increased by 1 wt. % and the portion of MgO was decreased by 1 wt. % in the glass composition.

(9) Embodiment 3

(10) The glasses 1 and 2 were chemically hardened by dipping in a salt bath of molten KNO3 at 430° C. for 4 h. In this respect, a diffusion of Na ions from the glass into the salt melt and of K ions from the salt melt into the glass took place. A 20 μm thick diffusion layer formed at the surface of the panes in this respect.

(11) The following Table 1 contains measured property values of the glasses 1 and 2 and the corresponding properties of the “Gorilla” brand glass from the manufacturer Corning which is used as a cover glass for displays of the iPhone, for example.

(12) TABLE-US-00001 TABLE 1 Property Glass 1 Glass 2 Gorilla Refractive index 1.522 1.509 Density [g/cm.sup.3] 2.52 2.44 Coeff. of linear thermal expansion (20 to 300° C. [10−6/ 8.67 8.27 K] Fixed viscosity points [° C.] Transformation temperature [° C.] 668 619 Viscosity value [° C.] for log η = 6.6 (η in Pa .Math. s) 891 843 Viscosity value [° C.] for log η = 3.0 (η in Pa .Math. s) 1210 1260 1275 Viscosity value [° C.] for log η = 2.0 (η in Pa .Math. s) 1390 1450 1500 Viscosity value [° C.] for log η = 1.0 (η in Pa .Math. s) 1615 1680 1730 Liquidus temperature [° C.] 1260 1220 Vickers hardness (DIN 50 133-2) [MPa] Before chem. hardening 6465 6550 5915 After chem. hardening 7112 7200 6330 Mechanical values (before chem. hardening) Transverse contraction number 0.2 0.2 Shear modulus [GPa] 32 30 Compression modulus [GPa] 43 39 Young's modulus [GPa] 77 72 Strength values (after chem. hardening) [MPa] Surface strength as per the double ring method 1246 1260 950 (430° C./4 h) Surface strength (CS), optically measured (440° C./4 h) 1156 900 Surface strength (SC) (mathematical model) 1216 878 Chemical resistance (before chem. hardening) Hydrolytic resistance as per DIN ISO 719 [μg] 70 43 42

(13) With respect to the viscosity properties and the crystallization properties, it can be seen from the measured values that the temperatures for the fixed viscosity points in the melting and processing range for the glasses in accordance with the present disclosure lie at significantly lower temperatures in comparison with the Gorilla glass.

(14) It must be stated for the optimum fining range with viscosities of log η=1 to 2 that the glass 1 reaches a viscosity of log η=1 at a temperature which is 115 K lower than with Gorilla glass. For log η=2, the temperature difference amounts to 110 K. With glass 2, the values are 50 K (log η=1 and 2) lower than with Gorilla glass. Overall, the glasses in accordance with the present disclosure therefore have a log η of 2 [Pa.Math.s] at a temperature of ≦1450° C. A mean fining temperature lowering with respect to the comparison glass of 50 to 100 K in the viscosity range between 10 and 100 Pa.Math.s is therefore generally to be assumed.

(15) There is therefore a temperature reserve in the manufacture which can be utilized in different manners. Examples for the utilization of the temperature reserve comprise a utilization for energy saving, a utilization for lowering the strain of the refractory material, a utilization for improving the quality and yield, or a utilization for increasing the specific melting performance.

(16) In the FIGURE, measured viscosity curves of the glasses 1 and 2 in accordance with the present disclosure compared with the Gorilla glass and of the brand glass “Xensation” of Schott AG, which is used as a cover glass for displays of smart phones, are shown. The temperature range shown lies between 1200° C. and 1550° C. As can be seen from the FIGURE, the viscosity of the glasses in accordance with the present disclosure is much lower in the total temperature range than that of the glasses of the prior art.

(17) Glasses 1 and 2 are furthermore suitable for an application in float processing. As can be seen from Table 1, in particular the liquidus temperature of glass 2 (1220° C.) is below the temperatures which characterize the floating processing range between 400 Pa.Math.s and 800 Pa.Math.s (log η is 2.6 to 2.9). A safety interval of more than 50° C. is given here in the case of glass 2. Glass 1 does not have a safety interval, but no crystallization was able to be found in the temperature range in question as part of the prior examinations of fine annealed, cast blocks.

(18) As regards the mechanical properties, it can be recognized from the table that the glasses in accordance with the present disclosure already have an approximately 10% higher Vickers hardness in the chemically non-hardened state than the comparison glass. This difference additionally becomes noticeable on the hardening under comparable diffusion depths of (20 μm for glasses 1 and 2; 30 μm for the Gorilla glass) since the value on the chemical toughening for the glasses in accordance with the present disclosure increases by around 10%, while the relative hardness increase, and also the absolute hardness increase, is lower in the comparison glass.

(19) In addition, the glasses in accordance with the present disclosure have a higher surface strength. It was determined in the double ring measurement in accordance with DIN 1288-5 that the surface strength of the hardened glasses is 30% higher than that of the Gorilla glass. In order also to take account of the lower diffusion depth for the glasses in accordance with the present disclosure with respect to the Gorilla glass in the comparison (20 μm for glasses 1 and 2; 30 μm for the Gorilla glass), optical measurements were thereupon made using the refractive index method with comparable thicknesses of the diffusion layers. For this purpose, glass 1 in an alternative embodiment was chemically hardened by dipping into a salt bath of liquid KNO3 at 440° C. for 4 h. In this respect, a diffusion layer having a thickness of 30 μm resulted. The numerical values listed accordingly in the table here also confirm the considerably higher surface strength.

(20) This means that even at lower diffusion depths and thus lower, and so more economic, dwell times in the salt bath no disadvantages are to be expected in the scratch resistance with respect to known glasses.

(21) As noted herein, a system may comprise an electronic device, such as a cell phone or computer, the device having a screen acting as a display for the device, with one or more of an LCD and/or plasma matrix positioned behind the screen. The screen may be rectangularly shaped, curved, flat, and/or combinations thereof. The screen may be a glass article, such as a glass article consisting of a glass comprising between 47.5 and 55 wt. % SiO2; between 21 and 27.5 wt. % Al2O3; and between 12 and 16 wt. % Na2O; and in that the a molar ratio of Al2O3 to Na2O lies between 0.9:1 and 1.2:1, wherein the glass has a diffusion layer at least sectionally at its surface, wherein a K content of the glass is increased with respect to a base composition and the Li content and Na content of the glass are lowered with respect to the base composition.