Ion-exchangeable mixed alkali aluminosilicate glass

Abstract

To provide a glass composition that can be strengthened, such as by ion exchange, and has mechanical properties that allow it to be formed into thin glass articles. [Solution] A glass composition containing 55.0 mol% to 75.0 mol% of SiO2, 13.0 mol% to 20.0 mol% of Al2O3, 3.0 mol% to 10.0 mol% of Li2O, 5.0 mol% to 15.0 mol% of Na2O, 1.5 mol% or less of K2O, and 0 mol% to 3.0 mol% of B2O3, wherein Al2O3 + Li2O is 23.0 mol% or more, R2O + RO is 18.0 mol% or more, where R2O is an alkali oxide present in the glass composition, and RO is a divalent cation oxide present in the glass composition, R2O / Al2O3 is 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 is 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 8.0 or more.

Description

Related applications

[0001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 62 / 591958, filed on 29 November 2017, on which its contents are based and which are incorporated herein by reference.

[0002] Furthermore, this application is a divisional application based on Japanese Patent Application No. 2021-87509, which was filed on May 25, 2021. [Technical Field]

[0003] This specification relates broadly to glass compositions suitable for use as cover glasses for electronic devices. More specifically, this specification relates to mixed alkali aluminosilicate glasses that can be formed into cover glasses for electronic devices by fusion drawing. [Background technology]

[0004] Due to their portable nature, portable devices such as smartphones, tablets, portable media players, personal computers, and cameras are particularly susceptible to being accidentally dropped onto hard surfaces such as the ground. These devices typically have a cover glass, which can be damaged when it comes into contact with a hard surface. In many of these devices, the cover glass functions as a display cover and may also provide touch functionality; therefore, damage to the cover glass can negatively impact the device's usability.

[0005] When a portable device is dropped onto a hard surface, there are two main modes of fracture of the cover glass. One mode is flexural fracture, which occurs when the glass is bent due to the dynamic load resulting from the device's impact with the hard surface. The other mode is sharp contact fracture, which occurs due to the introduction of damage to the glass surface. When glass collides with a rough, hard surface such as asphalt or granite, sharp indentations can be created on the glass surface. These indentations become fracture sites on the glass surface, from which cracks may develop and propagate.

[0006] Glass can be made resistant to flexural fracture by ion exchange techniques, which involve introducing compressive stress to the glass surface. However, ion-exchanged glass will still be subject to dynamic sharp contact due to high compressive concentration resulting from localized indentations in the glass from sharp contact.

[0007] Glass manufacturers and handheld device manufacturers have continuously strived to improve the resistance of handheld devices to sharp contact breakage. Solutions range from coatings on the cover glass to bezels that prevent the cover glass from directly impacting a hard surface when the device falls onto it. However, due to constraints of aesthetic and functional requirements, it is extremely difficult to completely prevent the cover glass from impacting a hard surface.

[0008] It is desirable that the handheld device be as thin as possible. Therefore, in addition to strength, it is also desirable that the glass to be used as a cover glass for the handheld device be made as thin as possible. Thus, in addition to increasing the strength of the cover glass, it is also desirable that the glass has mechanical properties that allow it to be formed by processes that enable the manufacture of thin glass articles such as thin glass sheets. [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] Therefore, there is a need for glass that can be strengthened by ion exchange or other means and possesses mechanical properties that allow it to be molded into thin glass articles. [Means for solving the problem]

[0010] According to the first embodiment, the glass composition contains 55.0 mol% to 75.0 mol% of SiO2, 8.0 mol% to 20.0 mol% of Al2O3, 3.0 mol% to 15.0 mol% of Li2O, 5.0 mol% to 15.0 mol% of Na2O, and 1.5 mol% or less of K2O, with Al2O3 + Li2O being greater than 22.5 mol%, R2O + RO being 18.0 mol% or more, R2O / Al2O3 being 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 being 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O being 8.0 or more.

[0011] According to the second embodiment, the glass article comprises a first surface; a second surface opposite to the first surface, the thickness (t) of the glass article being measured as the distance between the first and second surfaces; and a compressive stress layer extending from at least one of the first and second surfaces into the thickness (t) of the glass article, wherein the central tension of the glass article is 30 MPa or more, the compressive stress layer has a compression depth of 0.15t or more and 0.25t or less, and the glass article contains 55.0 mol% or more and 75.0 mol% or less of SiO2, and 8.0 mol% or more. It is formed from glass containing 20.0 mol% or less of Al2O3, 3.0 mol% to 15.0 mol% of Li2O, 5.0 mol% to 15.0 mol% of Na2O, and 1.5 mol% or less of K2O, where Al2O3 + Li2O is greater than 22.5 mol%, R2O + RO is 18.0 mol% or more, R2O / Al2O3 is 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 is 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 8.0 or more.

[0012] According to the third embodiment, the glass article includes a first surface; a second surface opposite to the first surface, where the thickness (t) of the glass article is measured as the distance between the first surface and the second surface; and a compressive stress layer extending from at least one of the first surface and the second surface into the thickness (t) of the glass article. The central tension of the glass article is 60 MPa or more, the compressive stress layer has a compressive depth of 0.15t or more and 0.25t or less, and the glass article has a composition at the center depth including 55.0 mol% or more and 75.0 mol% or less of SiO2, 8.0 mol% or more and 20.0 mol% or less of Al2O3, 3.0 mol% or more and 15.0 mol% or less of Li2O, 5.0 mol% or more and 15.0 mol% or less of Na2O, and 1.5 mol% or less of K2O, where Al2O3 + Li2O is more than 22.5 mol%, R2O + RO is 18.0 mol% or more, R2O / Al2O3 is 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 is 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 8.0 or more.

[0013] Additional features and advantages are described in the following detailed description, some of which will be readily apparent to those skilled in the art from that description or will be recognized by practicing the embodiments described herein, including the detailed description, the claims, and the accompanying drawings.

[0014] It will be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and characteristics of the subject matter of the claims. The accompanying drawings are included to provide a further understanding of the various embodiments and are incorporated herein and constitute a part of this specification. The drawings illustrate the various embodiments described herein and, together with the description, serve to explain the principles and operation of the subject matter of the claims.

Brief Description of the Drawings

[0015] [Figure 1] Cross-sectional view of glass having a compressive stress layer on its surface according to the embodiments disclosed and described herein [Figure 2A] Plan view of an exemplary electronic device including any of the glass articles disclosed herein [Figure 2B] Perspective view of the exemplary electronic device of FIG. 2A

Mode for Carrying Out the Invention

[0016] Here, an alkali aluminosilicate glass according to various embodiments will be specifically referred to. The alkali aluminosilicate glass has good ion-exchangeability, and a chemical strengthening process has been used to achieve high strength and high toughness in the alkali aluminosilicate glass. Sodium aluminosilicate glass is a highly ion-exchangeable glass with high glass formability and quality. Substituting Al2O3 in the network structure of the silicate glass increases the mutual diffusibility of monovalent cations during ion exchange. By chemical strengthening in a molten salt bath (e.g., KNO3 and / or NaNO3), a glass having high strength, high toughness, and high indentation crack formation resistance can be obtained.

[0017] Therefore, alkali aluminosilicate glasses having good physical properties, chemical durability, and ion-exchangeability have attracted attention for use as cover glasses. In particular, lithium-containing aluminosilicate glasses having a slow-cooling temperature and a softening temperature that are low, a low coefficient of thermal expansion (CTE) value, and a high ion-exchangeability are provided herein. Different ion-exchange processes can achieve a larger central tension (CT), a compression depth (DOC), and a high compressive stress (CS). However, adding lithium to the alkali aluminosilicate glass may lower the melting point, softening point, or liquid-phase viscosity of the glass.

[0018] For example, the stretching process for forming glass articles such as glass sheets is desirable because it allows for the formation of thin glass articles with fewer defects. Previously, it was thought that glass compositions needed to have relatively high liquid-phase viscosities, such as over 1000 kP, 1100 kP, or 1200 kP, in order to be formed by stretching processes such as fusion drawing or slot drawing. However, advancements in stretching processes have made it possible to use glasses with lower liquid-phase viscosities in the stretching process. Therefore, the glass used in the stretching process can contain more lithium than previously thought, and can contain more glass network structure-forming components such as SiO2, Al2O3, B2O3, and P2O5. Thus, a balance of various glass components is provided that allows the glass to realize the benefits of adding lithium and glass network structure-forming materials to the glass composition without adversely affecting the glass composition.

[0019] In the embodiments of the glass compositions described herein, the concentrations of constituent components (e.g., SiO2, Al2O3, Li2O, etc.) are given in mole percent (mol%) based on oxides unless otherwise specified. The components of the alkali aluminosilicate glass compositions according to the embodiments are discussed individually below. It should be understood that any of the various listed ranges of one component can be individually combined with any of the various listed ranges of any other component.

[0020] In the embodiments of the alkali aluminosilicate glass compositions disclosed herein, SiO2 is the most abundant component and therefore the main component of the glass network structure formed from the glass composition. Pure SiO2 has a relatively low CTE and does not contain alkali. However, pure SiO2 has a high melting point. Therefore, if the concentration of SiO2 in the glass composition is too high, the difficulty of melting the glass increases as the concentration of SiO2 increases, which impairs the moldability of the glass composition, and this, in turn, adversely affects the moldability of the glass. In the embodiments, the glass composition generally contains SiO2 in an amount of 55.0 mol% or more and 75.0 mol% or less, as well as in all and partial ranges between the above values. In some embodiments, the glass composition contains SiO2 in an amount of 58.0 mol% or more, such as 60.0 mol% or more, 62.0 mol% or more, 64.0 mol% or more, 66.0 mol% or more, 68.0 mol% or more, or 70.0 mol% or more. In the embodiment, the glass composition contains SiO2 in an amount of 72.0 mol% or less, such as 70.0 mol% or less, 68.0 mol% or less, 66.0 mol% or less, 64.0 mol% or less, or 62.0 mol% or less. In the embodiment, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the glass composition contains SiO2 in an amount of 58.0 mol% or more and 70.0 mol% or less, such as 60.0 mol% or more and 68.0 mol% or less, or 62.0 mol% or more and 64.0 mol% or less, as well as in all and partial ranges between the above values.

[0021] The glass composition of the embodiment may further contain Al2O3. Al2O3 can act as a glass network structure-forming agent, similar to SiO2. Due to tetrahedral coordination in the glass melt formed from the glass composition, Al2O3 can increase the viscosity of the glass composition, and too much Al2O3 can reduce the moldability of the glass composition. However, when the concentration of Al2O3 is balanced with respect to the concentrations of SiO2 and alkali oxides in the glass composition, Al2O3 can lower the liquidus temperature of the glass melt, thereby increasing the liquidus viscosity and improving the compatibility of the glass composition with certain molding methods, such as fusion molding. In the embodiment, the glass composition generally contains Al2O3 at concentrations from 8.0 mol% to 20.0 mol%, and within the entire range and partial range between the above values. In some embodiments, the glass composition contains Al2O3 in an amount of 10.0 mol% or more, such as 12.0 mol% or more, 14.0 mol% or more, 16.0 mol% or more, 17.0 mol% or more, or 19.0 mol% or more. In embodiments, the glass composition contains Al2O3 in an amount of 19.0 mol% or less, such as 18.0 mol% or less, 17.0 mol% or less, 16.0 mol% or less, 15.0 mol% or less, 14.0 mol% or less, or 13.0 mol% or less. In embodiments, it should be understood that any of the above ranges may be combined with any other range. In embodiments, the glass composition contains Al2O3 in an amount of 10.0 mol% or more to 18.0 mol%, such as 12.0 mol% or more to 16.0 mol%, or 15.0 mol% or more to 17.0 mol%, as well as in all and partial ranges between the above values.

[0022] Like SiO2 and Al2O3, P2O5 can be added to a glass composition as a network structure-forming agent, which may reduce the meltability and moldability of the glass composition. Therefore, P2O5 will be added in an amount that does not excessively reduce these properties. The addition of P2O5 can also increase the diffusivity of ions in the glass composition during ion exchange treatment, thereby increasing the efficiency of these treatments. In some embodiments, the glass composition may contain P2O5 in amounts from 0.0 mol% to 8.0 mol%, as well as in all and partial ranges between the above values. In some embodiments, the glass composition may contain P2O5 in amounts of 0.5 mol% or more, 1.0 mol% or more, 1.5 mol% or more, 2.0 mol% or more, 2.5 mol% or more, 3.0 mol% or more, 3.5 mol% or more, 4.0 mol% or more, or 4.5 mol% or more. In the embodiments, the glass composition may contain P2O5 in amounts of 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, 6.0 mol% or less, 5.5 mol% or less, 5.0 mol% or less, 4.5 mol% or less, 4.0 mol% or less, 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.5 mol% or less, 1.0 mol% or less, or 0.5 mol% or less. In the embodiments, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the glass composition may contain P2O5 in amounts ranging from 0.5 mol% to 7.5 mol%, 1.0 mol% to 7.0 mol%, 1.5 mol% to 6.5 mol%, 2.0 mol% to 6.0 mol%, 2.5 mol% to 5.5 mol%, or 3.0 mol% to 5.0 mol%, as well as in amounts within all and partial ranges between the aforementioned values.

[0023] Like SiO2, Al2O3, and P2O5, B2O3 can be added to a glass composition as a network structure-forming material, which may reduce the meltability and moldability of the glass composition. Therefore, B2O3 should be added in an amount that does not excessively reduce these properties. In embodiments, the glass composition may contain B2O3 in amounts from 0.0 mol% to 3.0 mol%, and in all and partial ranges between the above values. In some embodiments, the glass composition may contain B2O3 in amounts of 0.5 mol% or more, 1.0 mol% or more, 1.5 mol% or more, 2.0 mol% or more, or 2.5 mol% or more. In embodiments, the glass composition may contain B2O3 in amounts of 2.5 mol% or less, 2.0 mol% or less, 1.5 mol% or less, 1.0 mol% or less, or 0.5 mol% or less. In embodiments, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the glass composition contains B2O3 in an amount ranging from 0.5 mol% to 2.5 mol%, or from 1.0 mol% to 2.0 mol%, as well as in amounts encompassing the entire range and partial range between the aforementioned values.

[0024] In some embodiments, the glass composition includes at least one of B2O3 and P2O5 as glass network structure forming elements. Therefore, in embodiments, B2O3 + P2O5 is in all and partial ranges between the above values, including greater than 0.0 mol%, such as 0.5 mol% or more, 1.0 mol% or more, 1.5 mol% or more, 2.0 mol% or more, 2.5 mol% or more, 3.0 mol% or more, 3.5 mol% or more, 4.0 mol% or more, 4.5 mol% or more, 5.0 mol% or more, 5.5 mol% or more, 6.0 mol% or more, 6.5 mol% or more, 7.0 mol% or more, 7.5 mol% or more, or 8.0 mol% or more. In the embodiment, the B2O3 + P2O5 is 7.5 mol% or less, 6.5 mol% or less, 6.0 mol% or less, 5.5 mol% or less, 5.0 mol% or less, 4.5 mol% or less, 4.0 mol% or less, 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.5 mol% or less, 1.0 mol% or less, or 0.5 mol% or less, and so on, up to 7.5 mol%. In the embodiment, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the glass composition contains B2O3 + P2O5 in amounts ranging from 0.5 mol% to 7.5 mol%, 1.0 mol% to 7.0 mol%, 1.5 mol% to 6.5 mol%, 2.0 mol% to 6.0 mol%, 2.5 mol% to 5.5 mol%, or 3.0 mol% to 5.0 mol%, as well as in amounts ranging from all to partial ranges between the aforementioned values.

[0025] The effects of Li2O in glass compositions have been described above and are described in more detail below. In some cases, the addition of lithium to glass allows for better control of the ion exchange process and further lowers the softening point of the glass. In embodiments, the glass composition generally contains Li2O in amounts ranging from 3.0 mol% to 15.0 mol%, and within the entire range and partial range between the above values. In some embodiments, the glass composition contains Li2O in amounts of 3.5 mol% or more, 4.0 mol% or more, 4.5 mol% or more, 5.0 mol% or more, 5.5 mol% or more, 6.0 mol% or more, 6.5 mol% or more, 7.0 mol% or more, 7.5 mol% or more, 8.0 mol% or more, 8.5 mol% or more, 9.0 mol% or more, 9.5 mol% or more, 10.0 mol% or more, 10.5 mol% or more, 11.0 mol% or more, 11.5 mol% or more, 12.0 mol% or more, 12.5 mol% or more, 13.0 mol% or more, 13.5 mol% or more, 14.0 mol% or more, or 14.5 mol% or more. In some embodiments, the glass composition contains Li2O in amounts of 14.5 mol% or less, 14.0 mol% or less, 13.5 mol% or less, 13.0 mol% or less, 12.5 mol% or less, 12.0 mol% or less, 11.5 mol% or less, 11.0 mol% or less, 10.5 mol% or less, 10.0 mol% or less, 9.5 mol% or less, 9.0 mol% or less, 8.5 mol% or less, 8.0 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, 6.0 mol% or less, 5.5 mol% or less, 5.0 mol% or less, 4.5 mol% or less, 4.0 mol% or less, or 3.5 mol% or less. It should be understood that in embodiments, any of the above ranges may be combined with any other range. In the embodiment, the glass composition contains Li2O in amounts ranging from 3.5 mol% to 14.5 mol%, as well as in amounts within the entire range and partial range between the aforementioned values, such as 4.0 mol% to 14.0 mol%, 4.5 mol% to 13.5 mol%, 5.0 mol% to 13.0 mol%, 5.5 mol% to 12.5 mol%, 6.0 mol% to 12.0 mol%, 6.5 mol% to 11.5 mol%, or 7.0 mol% to 10.0 mol%, etc.

[0026] In addition to being a component that forms the glass network structure, Al2O3 also helps to increase the ion exchangeability of the glass composition. Therefore, in some embodiments, the amounts of Al2O3 and other components that may be ion-exchangeable may be relatively large. For example, Li2O is an ion-exchangeable component. In some embodiments, the amount of Al2O3 + Li2O in the glass composition may be greater than 22.5 mol%, as well as all and partial ranges between the above values, such as 23.0 mol% or more, 23.5 mol% or more, 24.0 mol% or more, 24.5 mol% or more, 25.0 mol% or more, 25.5 mol% or more, or 26.0 mol% or more. In some embodiments, the amount of Al2O3 + Li2O is 26.0 mol% or less, 25.5 mol% or less, 25.0 mol% or less, 24.5 mol% or less, 24.0 mol% or less, 23.5 mol% or less, 23.0 mol% or less, and all and partial ranges between the above values. In embodiments, it should be understood that any of the above ranges may be combined with any other range. In embodiments, the amount of Al2O3 + Li2O is 23.0 mol% or more to 26.5 mol% or less, 23.5 mol% or more to 26.0 mol% or less, 24.0 mol% or more to 25.5 mol% or less, and all and partial ranges between the above values.

[0027] In some embodiments, the glass composition may also contain alkali metal oxides other than Li2O, such as Na2O. Na2O contributes to the ion exchangeability of the glass composition, increases its melting point, and improves its moldability. However, if too much Na2O is added to the glass composition, the CTE may be too low and the melting point may be too high. In some embodiments, the glass composition generally contains Na2O in amounts ranging from 5.0 mol% to 15.0 mol%, and in all and partial ranges between these values. In some embodiments, the glass composition contains Na2O in amounts of 5.5 mol% or more, 6.0 mol% or more, 6.5 mol% or more, 7.0 mol% or more, 7.5 mol% or more, 8.0 mol% or more, 8.5 mol% or more, 9.0 mol% or more, 9.5 mol% or more, 10.0 mol% or more, 10.5 mol% or more, 11.0 mol% or more, 11.5 mol% or more, 12.0 mol% or more, 12.5 mol% or more, 13.0 mol% or more, 13.5 mol% or more, 14.0 mol% or more, or 14.5 mol% or more. In some embodiments, the glass composition contains Na2O in amounts of 14.5 mol% or less, 14.0 mol% or less, 13.5 mol% or less, 13.0 mol% or less, 12.5 mol% or less, 12.0 mol% or less, 11.5 mol% or less, 11.0 mol% or less, 10.5 mol% or less, 10.0 mol% or less, 9.5 mol% or less, 9.0 mol% or less, 8.5 mol% or less, 8.0 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, 6.0 mol% or less, 5.5 mol% or less, 5.0 mol% or less, or 4.5 mol% or less. It should be understood that in embodiments, any of the above ranges may be combined with any other range. In the embodiment, the glass composition contains Na2O in amounts ranging from 5.5 mol% to 14.5 mol%, as well as in amounts within the entire range and partial range between the aforementioned values, such as 6.0 mol% to 14.0 mol%, 6.5 mol% to 13.5 mol%, 7.0 mol% to 13.0 mol%, 7.5 mol% to 12.5 mol%, 8.0 mol% to 12.0 mol%, 8.5 mol% to 11.5 mol%, or 9.0 mol% to 10.0 mol%, etc.

[0028] As mentioned above, Al2O3 contributes to the ion exchangeability of the glass composition. Therefore, in some embodiments, the amounts of Al2O3 and other components that may be ion-exchangeable may be relatively large. For example, Li2O and Na2O are ion-exchangeable components. In some embodiments, the amount of Al2O3 + Li2O + Na2O in the glass composition may be greater than 25.0 mol%, as well as all and partial ranges between the aforementioned values, such as 25.5 mol% or more, 26.0 mol% or more, 26.5 mol% or more, 27.0 mol% or more, 27.5 mol% or more, 28.0 mol% or more, 28.5 mol% or more, 29.0 mol% or more, or 29.5 mol% or more. In some embodiments, the amount of Al2O3+Li2O+Na2O is within the range of 29.5 mol% or less, 29.0 mol% or less, 28.5 mol% or less, 28.0 mol% or less, 27.5 mol% or less, 27.0 mol% or less, 26.5 mol% or less, 26.0 mol% or less, or 25.5 mol% or less, up to 30.0 mol%, as well as all and partial ranges between the aforementioned values. In embodiments, it should be understood that any of the above ranges may be combined with any other range. In embodiments, the amount of Al2O3+Li2O+Na2O is within the range of 25.0 mol% or more to 30.0 mol%, 25.5 mol% or more to 29.5 mol%, 26.0 mol% or more to 29.0 mol%, 26.5 mol% or more to 28.5 mol%, or 27.0 mol% or more to 28.0 mol%, as well as all and partial ranges between the aforementioned values.

[0029] Like Na2O, K2O also promotes ion exchange and increases the DOC of the compressive stress layer. However, the addition of K2O can result in a CTE that is too low and a melting point that is too high. In some embodiments, the glass composition contains K2O in amounts of 1.0 mol% or less, or 0.5 mol% or less, and in all and partial ranges between the aforementioned values. In some embodiments, the glass composition is substantially potassium-free or potassium-free. As used herein, the term “substantially potassium-free” means that the component is not added as a component of the batch material, even if it is present in the final glass in very small amounts as a contaminant, such as less than 0.01 mol%.

[0030] MgO reduces the viscosity of glass, which can improve moldability, strain point and Young's modulus, and ion exchange capacity. However, too much MgO added to the glass composition increases the density and CTE of the glass composition. In some embodiments, the glass composition generally contains MgO at concentrations between 0.0 mol% and 4.0 mol%, and within the entire and partial ranges between these values. In some embodiments, the glass composition contains MgO in amounts of 0.2 mol% or more, 0.5 mol% or more, 1.0 mol% or more, 1.5 mol% or more, 2.0 mol% or more, 2.5 mol% or more, 3.0 mol% or more, or 3.5 mol% or more. In some embodiments, the glass composition contains MgO in amounts of 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.5 mol% or less, 1.0 mol% or less, 0.5 mol% or less, 0.4 mol% or less, or 0.2 mol% or less. In the embodiments, it should be understood that any of the above-described ranges may be combined with any other range. In the embodiments, the glass composition contains MgO in amounts from 0.2 mol% to 3.5 mol%, such as 0.5 mol% to 3.0 mol%, 1.0 mol% to 2.5 mol%, or 1.5 mol% to 2.0 mol%, as well as in amounts within all and partial ranges between the above values.

[0031] CaO reduces the viscosity of glass, which can improve moldability, strain point, and Young's modulus, and may also improve ion exchange capacity. However, too much CaO added to the glass composition increases the density and CTE of the glass composition. In embodiments, the glass composition generally contains CaO at concentrations between 0.0 mol% and 2.0 mol%, and within the entire and partial ranges between these values. In some embodiments, the glass composition contains CaO in amounts of 0.2 mol% or more, 0.4 mol% or more, 0.6 mol% or more, 0.8 mol% or more, 1.0 mol% or more, 1.2 mol% or more, 1.4 mol% or more, 1.6 mol% or more, or 1.8 mol% or more. In some embodiments, the glass composition contains CaO in amounts of 1.8 mol% or less, 1.6 mol% or less, 1.4 mol% or less, 1.2 mol% or less, 1.0 mol% or less, 0.8 mol% or less, 0.6 mol% or less, 0.4 mol% or less, or 0.2 mol% or less. In embodiments, it should be understood that any of the above ranges may be combined with any other range. In embodiments, the glass composition contains CaO in amounts of 0.2 mol% or more and 1.8 mol% or less, such as 0.4 mol% or more and 1.6 mol% or less, 0.6 mol% or more and 1.4 mol% or less, or 0.8 mol% or more and 1.2 mol% or less, as well as all and partial ranges between the above values.

[0032] In some embodiments, the glass composition may contain one or more clarifying agents as needed. In some embodiments, an example of such clarifying agent is SnO2. In such embodiments, SnO2 may be present in the glass composition in amounts of 0.2 mol% or more, such as 0.0 mol% or more and 0.1 mol% or less, and in all and partial ranges between the above values. In some embodiments, SnO2 may be present in the glass composition in amounts of 0.0 mol% or more and 0.2 mol% or less, or 0.1 mol% or more and 0.2 mol% or less, and in all and partial ranges between the above values. In some embodiments, the glass composition may be substantially free of SnO2 or may not contain any SnO2 at all.

[0033] ZnO improves the ion exchange performance of glass by increasing its compressive stress, among other things. However, adding too much ZnO can increase density and cause phase separation. In some embodiments, the glass composition may contain ZnO in amounts ranging from 0.2 mol% to 2.0 mol%, or from 0.5 mol% to 1.5 mol%, and in all and partial ranges between these values. In some embodiments, the glass composition may contain ZnO in amounts ranging from 0.3 mol% to 0.5 mol%, or 0.8 mol%. In some embodiments, the glass composition may contain ZnO in amounts ranging from 2.0 mol%, or from 1.5 mol%, or 1.0 mol%, or less. In some embodiments, it should be understood that any of the above ranges may be combined with any other range.

[0034] The glass compositions according to the embodiments disclosed herein may contain, in addition to the individual components described herein, divalent cation oxides (hereinafter referred to as RO) in amounts ranging from 0.0 mol% to 5.0 mol%, and in all and partial ranges between the aforementioned values. Examples of divalent cation oxides (RO) as used herein include, but are not limited to, MgO, CaO, SrO, BaO, FeO, and ZnO. In some embodiments, the glass composition may contain RO in amounts of 0.2 mol% or more, such as 0.5 mol% or more, 1.0 mol% or more, 1.5 mol% or more, 2.0 mol% or more, 2.5 mol% or more, 3.0 mol% or more, 3.5 mol% or more, 4.0 mol% or more, or 4.5 mol% or more. In the embodiments, the glass composition may contain RO in amounts of 4.5 mol% or less, such as 4.0 mol% or less, 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.5 mol% or less, 1.0 mol% or less, or 0.5 mol% or less. In the embodiments, it should be understood that any of the above ranges may be combined with any other range. In the embodiments, the glass composition may contain RO in amounts of 0.2 mol% or more to 4.5 mol%, such as 0.5 mol% or more to 4.0 mol%, 1.0 mol% or more to 3.5 mol%, 1.5 mol% or more to 3.0 mol%, or 2.0 mol% or more to 2.5 mol%, as well as all and partial ranges between the above values.

[0035] The amount of alkali metal oxide (also referred to here as "R2O") and RO in the glass composition may affect the viscosity of the glass composition; that is, increasing the R2O+RO content to facilitate 3D molding lowers the softening point. Examples of R2O used here include Li2O, Na2O, K2O, Rb2O, Cs2O, and Fr2O. In the embodiment, the total of R2O and RO (i.e., R2O+RO) is 18.0 mol% or more, such as 18.5 mol% or more, 19.0 mol% or more, 19.5 mol% or more, 20.0 mol% or more, 20.5 mol% or more, 21.0 mol% or more, 21.5 mol% or more, 22.0 mol% or more, 22.5 mol% or more, or 23.0 mol% or more. In the embodiment, the total of R2O and RO is 22.5 mol% or less, such as 22.0 mol% or less, 21.5 mol% or less, 21.0 mol% or less, 20.5 mol% or less, 20.0 mol% or less, 19.5 mol% or less, 19.0 mol% or less, or 18.5 mol% or less. In the embodiment, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the total of R2O and RO is 18.0 mol% or more to 23.0 mol%, such as 18.5 mol% or more to 22.5 mol%, 19.0 mol% or more to 22.0 mol%, 19.5 mol% or more to 21.5 mol%, or 20.0 mol% or more to 21.0 mol%, as well as all and partial ranges between the above values.

[0036] In some embodiments, the relationship expressed as mol% for R2O / Al2O3 is 1.06 or higher. A ratio of R2O to Al2O3 greater than 1.06 improves the meltability of the glass. Those skilled in glassmaking know that R2O exceeding Al2O3 significantly improves the dissolution of SiO2 in the glass molten material. This value is strictly controlled in glass design to improve yield by reducing losses due to inclusions such as silica knots. In some embodiments, the molal ratio of R2O / Al2O3 is 1.10 or higher, such as 1.20 or higher, 1.30 or higher, 1.40 or higher, 1.50 or higher, 1.60 or higher, 1.70 or higher, 1.80 or higher, 1.90 or higher, or 2.00 or higher. If the R2O / Al2O3 ratio is too high, the glass will be more susceptible to degradation. In the embodiment, the molar ratio of R2O / Al2O3 is 2.10 or less, such as 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, 1.60 or less, 1.50 or less, 1.40 or less, 1.30 or less, 1.20 or less, or 1.10 or less. In the embodiment, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the molar ratio of R2O / Al2O3 is in the range from 1.06 or more to 2.10 or less, such as 1.10 or more to 1.90 or less, 1.20 or more to 1.80 or less, or 1.30 or more to 1.70 or less, as well as all and partial ranges between the above values.

[0037] In the embodiment, the total amount of the network structure-forming component (e.g., Al2O3 + SiO2 + B2O3 + P2O5) is 78.0 mol% or more, 79.0 mol% or more, 78.5 mol% or more, 80.0 mol% or more, 80.5 mol% or more, 81.0 mol% or more, 81.5 mol% or more, 82.0 mol% or more, 82.5 mol% or more, 83.0 mol% or more, 83.5 mol% or more, or 84.0 mol% or more, etc., and is 78.0 mol% or more. Having a large amount of network structure-forming component increases the connectivity and free volume of the glass, which makes the glass less brittle and improves its resistance to damage. In the embodiments, the total amount of the network structure-forming component is 85.0 mol% or less, such as 84.5 mol% or less, 84.0 mol% or less, 83.5 mol% or less, 83.0 mol% or less, 82.5 mol% or less, 82.0 mol% or less, 81.5 mol% or less, 81.0 mol% or less, 80.5 mol% or less, 80.0 mol% or less, 79.5 mol% or less, or 79.0 mol% or less. In the embodiments, it should be understood that any of the above ranges may be combined with any other range. In the embodiments, the total amount of the network structure-forming component is 78.0 mol% or more to 83.0 mol%, 80.0 mol% or more to 82.0 mol%, or 80.5 mol% or more to 81.5 mol%, such as 78.0 mol% or more to 85.0 mol%, as well as all and partial ranges between the above values.

[0038] In one or more embodiments, the amounts of glass network structure-forming components such as SiO2, Al2O3, B2O3, and P2O5 may be balanced with the amount of Li2O in the glass composition. Although not bound by any particular theory, Li2O is thought to reduce the free volume in the glass compared to other alkali ions, and therefore reduce the resistance to intrusion cracks. Li2O is Li + Na +Since Li2O is necessary for ion exchange with the glass, reducing its free volume should be controlled in relation to the network-forming materials, namely SiO2, Al2O3, B2O3, and P2O5, which increase the free volume, in order to maintain appropriate sharp contact damage resistance. Therefore, in the embodiment, the molar ratio of the glass network-forming material to Li2O (i.e., (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O) is 8.0 or higher, 9.0 or higher, 9.5 or higher, 10.0 or higher, 10.5 or higher, 11.0 or higher, 11.5 or higher, 12.0 or higher, 12.5 or higher, 1.30 or higher, 13.5 or higher, 14.0 or higher, 14.5 or higher, 15.0 or higher, 15.5 or higher, 16.0 or higher, or 16.5 or higher, etc. In other embodiments, the ratio (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 17.0 or less, such as 16.5 or less, 16.0 or less, 15.5 or less, 15.0 or less, 14.5 or less, 14.0 or less, 13.5 or less, 13.0 or less, 12.5 or less, 12.0 or less, 11.5 or less, 11.0 or less, 10.5 or less, 10.0 or less, 9.5 or less, 9.0 or less, or 8.5 or less. It should be understood that in embodiments, any of the above ranges may be combined with any other range. In the embodiment, the ratio (SiO2+Al2O3+B2O3+P2O5) / Li2O is in the range of 8.0 to 17.0, as well as all and partial ranges between the aforementioned values, such as 9.0 to 16.0, 10.0 to 15.0, 11.0 to 14.0, or 12.0 to 13.0.

[0039] The total amount of Al2O3 + Li2O should be 23.0 mol% or more, such as 23.5 mol% or more, 24.0 mol% or more, 24.5 mol% or more, 25.0 mol% or more, 25.5 mol% or more, 26.0 mol% or more, 26.5 mol% or more, 27.0 mol% or more, 27.5 mol% or more, 28.0 mol% or more, 28.5 mol% or more, 29.0 mol% or more, 29.5 mol% or more, or 30.0 mol% or more. The total amount of Al2O3 + Li2O should be as high as possible to increase the maximum compressive stress at a given depth at the end of the ion exchange profile.

[0040] In an embodiment, the glass article may substantially not contain one or both of arsenic and antimony. In other embodiments, the glass article may not contain one or both of arsenic and antimony.

[0041] The physical properties of the alkali aluminosilicate glass composition as disclosed above are discussed herein. These physical properties can be achieved by varying the amounts of the components of the alkali aluminosilicate glass composition, as will be discussed in more detail with respect to the examples.

[0042] The glass composition according to an embodiment has a density of from 2.25 g / cm 3 to 2.60 g / cm 3 or from 2.30 g / cm 3 to 2.60 g / cm 3 or from 2.35 g / cm 3 to 2.60 g / cm 3 or from 2.40 g / cm 3 to 2.60 g / cm 3 or from 2.45 g / cm 3 to 2.60 g / cm 3 or from 2.20 g / cm 3 to 2.60 g / cm 3 or the glass composition may have a density within other ranges, such as from 2.20 g / cm 3 to 2.40 g / cm 3 or from 2.20 g / cm 3 to 2.35 g / cm 3 or from 2.20 g / cm 3 to 2.30 g / cm 3 or from 2.20 g / cm 3 to 2.25 g / cm 3 or from 2.20 g / cm 3 to 2.45 g / cm 3 or the glass composition may have a density within all ranges and sub-ranges between the previous values. Generally, in an alkali aluminosilicate glass composition, Na + or K +Larger, more dense alkali metal cations such as Li + The density of the glass composition decreases as it is replaced by smaller alkali metal cations such as . Therefore, the higher the amount of lithium in the glass composition, the less dense the glass composition becomes. The density values ​​given herein refer to values ​​such as those measured by the buoyancy method of ASTM C693-93 (2013).

[0043] In the embodiment, the liquid-phase viscosity of the glass composition is 1000 kP or less, such as 800 kP or less, 600 kP or less, 400 kP or less, 200 kP or less, 100 kP or less, 75 kP or less, 60 kP or less, 50 kP or less, 40 kP or less, or 30 kP or less. In the embodiment, the liquid-phase viscosity of the glass composition is 20 kP or more, such as 40 kP or more, 60 kP or more, 80 kP or more, 100 kP or more, 120 kP or more, 140 kP or more, or 160 kP or more. In the embodiment, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the liquidus viscosity of the glass composition is in the range of 20 kP to 1000 kP, as well as all and partial ranges between the above values, such as 40 kP to 900 kP, 60 kP to 800 kP, or 80 kP to 700 kP. The liquidus viscosity is determined by the following method: First, the liquidus temperature of the glass is measured according to ASTM C829-81 (2015), entitled "Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method". Next, the viscosity of the glass at that liquidus temperature is measured according to ASTM C965-96 (2012), entitled "Standard Practice for Measuring Viscosity of Glass Above the Softening Point".

[0044] Adding lithium to the glass composition affects the Young's modulus, shear modulus, and Poisson's ratio of the glass composition. In the embodiment, the Young's modulus of the glass composition may be in the range of 65 GPa to 85 GPa, as well as all and partial ranges between the aforementioned values, such as 67 GPa or more and 82 GPa or less, 70 GPa or more and 80 GPa or less, 72 GPa or more and 78 GPa or less, or 74 GPa or more and 76 GPa or less. In the embodiment, the Young's modulus of the glass composition may be in the range of 66 GPa or more and 85 GPa, as well as all and partial ranges between the aforementioned values, such as 68 GPa or more and 85 GPa or less, 70 GPa or more and 85 GPa or less, 72 GPa or more and 85 GPa or less, 74 GPa or more and 85 GPa or less, 76 GPa or more and 85 GPa or less, 78 GPa or more and 85 GPa or less, 80 GPa or more and 85 GPa or less, or 82 GPa or more and 85 GPa or less. In embodiments, the Young's modulus may be between 65 GPa and 84 GPa, as well as all and partial ranges between the aforementioned values, such as 65 GPa to 82 GPa, 65 GPa to 80 GPa, 65 GPa to 78 GPa, 65 GPa to 76 GPa, 65 GPa to 74 GPa, 65 GPa to 72 GPa, 65 GPa to 70 GPa, 65 GPa to 68 GPa, or 65 GPa to 10 GPa, etc. The Young's modulus values ​​listed herein refer to values ​​measured by general resonant ultrasonic spectroscopy techniques as described in ASTM E2001-13, entitled "Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts".

[0045] The softening point of the glass composition is affected by the addition of lithium to the glass composition. According to one or more embodiments, the softening point of the glass composition is 705°C to 925°C, 710°C to 920°C, 715°C to 915°C, 720°C to 910°C, 725°C to 905°C, 730°C to 900°C, 735°C to 895°C, 740°C to 890°C, 745°C to 885°C, 750°C to 880°C, 755°C to 875°C, and 760°C to 87 The softening point can be below 0°C, between 765°C and 865°C, between 770°C and 860°C, between 775°C and 855°C, between 780°C and 850°C, between 785°C and 845°C, between 790°C and 840°C, between 795°C and 835°C, between 800°C and 830°C, between 805°C and 825°C, or between 810°C and 820°C, as well as between 700°C and 930°C, and all and partial ranges between the aforementioned values. The softening point was determined using the parallel plate viscosity method of ASTM C1351M-96 (2012).

[0046] From the above, the glass composition according to the embodiment may be formed by any suitable method, such as slot molding, float molding, rolling, or fusion molding.

[0047] The glass articles may be characterized by the manner in which they are formed. For example, the glass articles may be characterized as float-formable (i.e., formed by the float method), down-drawable, and in particular as fusion-formable or slot-formable (i.e., formed by down-draw methods such as the fusion-draw method or the slot-draw method).

[0048] Some embodiments of the glass articles described herein may be formed by the down-draw method. The down-draw method produces glass articles with a uniform thickness and a relatively clean surface. The average bending strength of the glass article is controlled by the amount and size of surface imperfections, so a clean surface with minimal contact has higher initial strength. Furthermore, glass articles produced by the down-draw method have a very flat and smooth surface that can be used for end-use without costly grinding and polishing.

[0049] Some embodiments of the glass articles can be described as fusion-formable (i.e., formable using the fusion drawing method). The fusion method uses a stretching tank having a passage for receiving molten glass raw material. The passage has weirs on both sides of the passage that open at the top along the length of the passage. When the passage is filled with molten material, the molten glass overflows from the weirs. Due to gravity, the molten glass flows down the outer surface of the stretching tank as two flowing glass films. These outer surfaces of the stretching tank extend downward and inward so that they join at the lower edge of the stretching tank. The two flowing glass films join and fuse at this edge to form a single flowing glass article. This fusion drawing method has the advantage that, because the two glass films flowing across the passage fuse with each other, the outer surfaces of the resulting glass articles do not come into contact with any part of the apparatus. Therefore, the surface properties of glass articles formed by the fusion drawing method are unaffected by such contact.

[0050] Some embodiments of the glass articles described herein can be formed by the slot-draw method, which differs from the fusion-draw method. In the slot-draw method, molten raw glass is supplied to a stretching tank. At the bottom of the stretching tank is a slot with a nozzle extending along the length of the slot. The molten glass flows through the slot / nozzle and is stretched downward into a annealing region as a continuous glass article.

[0051] In one or more embodiments, the glass articles described herein may exhibit an amorphous microstructure and may be substantially free of crystals or crystallites. In other words, in some embodiments, the glass articles may be free of glass-ceramic materials.

[0052] As previously stated, in the embodiment, the alkali aluminosilicate glass composition can be strengthened by ion exchange or the like to produce damage-resistant glass for applications such as display covers, but is not limited to the following. Referring to Figure 1, the glass has a first region under compressive stress extending from the surface of the glass to the depth of compression (DOC) (e.g., the first and second compression layers 120, 122 in Figure 1) and a second region under tensile stress or central tension (CT) extending from the DOC of the glass to the center or internal region (e.g., the central region 130 in Figure 1). As used herein, DOC refers to the depth at which the stress in the glass article changes from compression to tension. At DOC, the stress crosses from positive (compressive) stress to negative (tensile) stress, and therefore exhibits a stress value of zero.

[0053] Following the conventions commonly used in this technical field, compressive stress is expressed as a negative (<0) stress, and tensile stress is expressed as a positive (>0) stress. However, throughout this description, CS is expressed as a positive or absolute value—that is, CS = |CS|, as stated herein. Compressive stress (CS) has its maximum value at or near the surface of the glass, and the CS value varies with distance d from the surface according to some function. Referring again to Figure 1, the first area 120 extends from the first surface 110 to a depth d1, and the second area 122 extends from the second surface 112 to a depth d2. These areas together define the compression or CS of the glass 100. Compressive stress (including surface CS) is measured by a surface stress measuring instrument (FSM) using commercially available instruments such as the FSM-6000 manufactured by Orihara Corporation (Japan). Surface stress measurement relies on the precise measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. Next, SOC is measured as described in procedure C (glass disk method) of ASTM standard C770-16, titled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the full content of which is quoted here.

[0054] In some embodiments, CS is in the range of 450 MPa to 800 MPa, as well as all and partial ranges between the aforementioned values, such as 475 MPa to 775 MPa, 500 MPa to 750 MPa, 525 MPa to 725 MPa, 550 MPa to 700 MPa, 575 MPa to 675 MPa, or 600 MPa to 650 MPa.

[0055] In one or more embodiments, Na + and K + The ions are exchanged in the glass article, and the Na + Ions are K + It diffuses to a greater depth in the glass article than ions do. +The ion penetration depth ("potassium DOL") is distinct from DOC as it represents the potassium penetration depth as a result of the ion exchange process. Potassium DOL is typically smaller than the DOC of the articles described herein. Potassium DOL is measured using a surface stress measuring instrument, such as the commercially available FSM-6000 surface stress measuring instrument manufactured by Orihara Corporation (Japan), which relies on precise measurement of the stress optical coefficient (SOC), as previously described for CS measurement. The potassium DOL of the first and second compression layers 120 and 122, respectively, is in the range of 5 μm to 45 μm, as well as all and partial ranges between the aforementioned values, such as 6 μm to 40 μm, 7 μm to 35 μm, 8 μm to 30 μm, or 9 μm to 25 μm. In the embodiment, the potassium DOL in each of the first and second compression layers 120 and 122 is in the range of 6 μm to 45 μm, 10 μm to 45 μm, 15 μm to 45 μm, 20 μm to 45 μm, or 25 μm to 45 μm, as well as all and partial ranges between the above values. In the embodiment, the potassium DOL in each of the first and second compression layers 120 and 122 is in the range of 5 μm to 35 μm, 5 μm to 30 μm, 5 μm to 25 μm, or 5 μm to 15 μm, as well as all and partial ranges between the above values.

[0056] The compressive stresses on both principal surfaces (110 and 112 in Figure 1) are balanced by the tension stored in the central region (130) of the glass. The values ​​of the maximum central tension (CT) and DOC are measured using a scattered light polarizer (SCALP) technique known in the art. The stress profile may be measured using the refractive near-field (RNF) method or SCALP. When the RNF method is used to measure the stress profile, the maximum CT value given by SCALP is used in the RNF method. More specifically, the stress profile measured by RNF is force-equipped and calibrated against the maximum CT value given by the SCALP measurement. This RNF method is described in U.S. Patent No. 8,854,623, entitled "Systems and methods for measuring a profile characteristic of a glass sample," which is cited herein by all. More specifically, the RNF method includes the steps of: placing a glass article adjacent to a reference block; generating a polarization-switching ray that switches between orthogonal polarization at a rate between 1 Hz and 50 Hz; measuring the output amount of the polarization-switching ray; and generating a polarization-switching reference signal, wherein the measured output amounts of each orthogonal polarization are within 50% of each other. The method further includes transmitting the polarization-switching ray through the glass article and the reference block at different depths in the glass article, and then relaying the transmitted polarization-switching ray to a signal photodetector using a relay optical system, the signal photodetector generating a polarization-switching detector signal. The method also includes the steps of dividing the detector signal by a reference signal to form a normalized detector signal, and determining the profile characteristics of the glass article from the normalized detector signal.

[0057] In the embodiments, the glass composition may have a maximum CT of 30 MPa or more, such as 35 MPa or more, 40 MPa or more, 45 MPa or more, 50 MPa or more, 55 MPa or more, 60 MPa or more, 65 MPa or more, 70 MPa or more, 75 MPa or more, 80 MPa or more, or 85 MPa or more. In the embodiments, the glass composition may have a maximum CT of 100 MPa or less, such as 95 MPa or less, 90 MPa or less, 85 MPa or less, 80 MPa or less, 75 MPa or less, 70 MPa or less, 65 MPa or less, 60 MPa or less, 55 MPa or less, 50 MPa or less, 45 MPa or less, or 40 MPa or less. In the embodiments, it should be understood that any of the above ranges may be combined with any other range. In the embodiment, the glass composition may have a maximum CT of 30 MPa to 100 MPa, as well as all and partial ranges between the aforementioned values, such as 35 MPa to 95 MPa, 40 MPa to 90 MPa, 45 MPa to 85 MPa, 50 MPa to 80 MPa, 55 MPa to 75 MPa, or 60 MPa to 70 MPa.

[0058] As described above, the DOC is measured using a scattered light polarizer (SCALP) technique known in the art. In some embodiments herein, the DOC is given as part of the thickness (t) of the glass article. In embodiments, the glass composition may have a compression depth (DOC) of 0.15t to 0.25t, such as 0.18t to 0.22t or 0.19t to 0.21t, as well as all and partial ranges between the aforementioned values. In the embodiment, the glass composition may have DOC values ​​ranging from 0.17t to 0.25t, 0.18t to 0.25t, 0.19t to 0.25t, 0.20t to 0.25t, 0.21t to 0.25t, 0.22t to 0.25t, 0.23t to 0.25t, or 0.24t to 0.25t, as well as from 0.16t to 0.20t, and all and partial ranges between the aforementioned values. In the embodiment, the glass composition may have a DOC of 0.15t or more to 0.23t or less, 0.15t or more to 0.22t or less, 0.15t or more to 0.21t or less, 0.15t or more to 0.20t or less, 0.15t or more to 0.19t or less, 0.15t or more to 0.18t or less, 0.15t or more to 0.17t or less, or 0.15t or more to 0.16t or less, as well as a DOC of 0.15t or more to 0.24t or less, and all and partial ranges between the aforementioned values.

[0059] A compressive stress layer can be formed in glass by exposing the glass to an ion exchange solution. In some embodiments, the ion exchange solution may be a molten nitrate. In some embodiments, the ion exchange solution may be molten KNO3, molten NaNO3, or a combination thereof. In some embodiments, the ion exchange solution may contain about 80% molten KNO3, about 75% molten KNO3, about 70% molten KNO3, about 65% molten KNO3, or about 60% molten KNO3. In some embodiments, the ion exchange solution may contain about 20% molten NaNO3, about 25% molten NaNO3, about 30% molten NaNO3, about 35% molten NaNO3, or about 40% molten NaNO3. In some embodiments, the ion exchange solution may include approximately 80% molten KNO3 and approximately 20% molten NaNO3, approximately 75% molten KNO3 and approximately 25% molten NaNO3, approximately 70% molten KNO3 and approximately 30% molten NaNO3, approximately 65% ​​molten KNO3 and approximately 35% molten NaNO3, or approximately 60% molten KNO3 and approximately 40% molten NaNO3, as well as all and partial ranges between the aforementioned values. In some embodiments, other sodium and potassium salts, such as sodium or potassium nitrates, phosphates, or sulfates, may be used in the ion exchange solution. In some embodiments, the ion exchange solution may include lithium salts such as LiNO3.

[0060] The glass composition can be exposed to an ion exchange solution by immersing a glass article made from the glass composition in a bath of the ion exchange solution, by spraying the ion exchange solution onto a glass article made from the glass composition, or by physically applying the ion exchange solution to the glass article made from the glass composition in another manner. When the glass composition is exposed to the ion exchange solution, according to the embodiment, the temperature of the ion exchange solution may be between 400°C and 500°C, as well as all and partial ranges between the above values, such as 410°C to 490°C, 420°C to 480°C, 430°C to 470°C, or 440°C to 460°C. In the embodiment, the glass composition may be exposed to an ion exchange solution for a period of time ranging from 4 to 48 hours, including periods of 8 to 44 hours, 12 to 40 hours, 16 to 36 hours, 20 to 32 hours, or 24 to 28 hours, as well as all and partial ranges between the aforementioned values.

[0061] The ion exchange process can be carried out in an ion exchange solution under process conditions that give an improved compressive stress profile, for example, as disclosed in U.S. Patent Application Publication No. 2016 / 0102011, which is cited herein by reference.

[0062] It should be understood that after the ion exchange process, the composition on the surface of the glass article will differ from the composition of the glass article as it was formed (i.e., the glass article before the ion exchange process). This is because, for example, Li + or Na + Certain types of alkali metal ions in the as-formed glass, such as Na, are each, for example, Na + or K + This is caused by exchange with larger alkali metal ions. However, the glass composition at or near the center of the depth of the glass article still has the composition of the as-formed (un-ion-exchanged) glass used to form the glass article in the embodiment.

[0063] The glass articles disclosed herein may be incorporated into other articles such as articles having a display (or display article) (e.g., consumer electronics including mobile phones, tablets, computers, navigation systems, etc.), building articles, transport articles (e.g., automobiles, trains, aircraft, ships, etc.), electrical appliances, or any article requiring a certain degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles containing any of the glass articles disclosed herein are shown in Figures 2A and 2B. More specifically, Figures 2A and 2B show a home electronic device 200 comprising a housing 202 having a front 204, a rear 206, and a side 208; electrical components (not shown) at least partially inside or entirely inside the housing, including at least a control unit, memory, and an electrical component on or near the front of the housing, the display 210; and a cover substrate 212 on or covering the front of the housing as being on the display. In some embodiments, part of the cover substrate 212 and / or part of the housing 202 may include any of the glass articles disclosed herein.

[0064] The first embodiment includes a glass composition comprising 55.0 mol% to 75.0 mol% of SiO2, 8.0 mol% to 20.0 mol% of Al2O3, 3.0 mol% to 15.0 mol% of Li2O, 5.0 mol% to 15.0 mol% of Na2O, and 1.5 mol% or less of K2O, wherein Al2O3 + Li2O is greater than 22.5 mol%, R2O + RO is 18.0 mol% or more, R2O / Al2O3 is 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 is 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 8.0 or more.

[0065] The second embodiment includes a glass composition according to the first embodiment, wherein Al2O3 + Li2O is 23.0 mol% or more.

[0066] The third embodiment includes a glass composition according to either the first or second embodiment, wherein the amount of Al2O3 + Li2O is between 23.0 mol% and 26.5 mol%.

[0067] The fourth embodiment includes a glass composition according to any one of the first to third embodiments, wherein the R2O+RO content is between 18.0 mol% and 23.0 mol%.

[0068] The fifth embodiment includes a glass composition according to any one of the first to fourth embodiments, wherein the R2O+RO content is between 19.0 mol% and 22.0 mol%.

[0069] The sixth embodiment includes a glass composition according to any one of the first to fifth embodiments, wherein the R2O / Al2O3 ratio is between 1.06 and 2.10.

[0070] The seventh embodiment includes a glass composition according to any one of the first to sixth embodiments, wherein the R2O / Al2O3 ratio is between 1.10 and 1.90.

[0071] The eighth aspect includes a glass composition according to any one of the first to seventh aspects, wherein the amount of SiO2 + Al2O3 + B2O3 + P2O5 is between 78.0 mol% and 85.0 mol%.

[0072] The ninth embodiment includes a glass composition according to any one of the first to eighth embodiments, wherein the amount of SiO2 + Al2O3 + B2O3 + P2O5 is between 78.0 mol% and 83.0 mol%.

[0073] The tenth embodiment includes a glass composition according to any one of the first to ninth embodiments, wherein the (SiO2+Al2O3+B2O3+P2O5) / Li2O ratio is between 8.0 and 17.0.

[0074] The eleventh embodiment includes a glass composition according to any one of the first to tenth embodiments, wherein the (SiO2+Al2O3+B2O3+P2O5) / Li2O ratio is between 10.0 and 15.0.

[0075] The twelfth embodiment includes a glass composition according to any one of the first to eleventh embodiments, wherein the amount of B2O3 + P2O5 is greater than 0.0 mol%.

[0076] The 13th embodiment is a glass article comprising: a first surface; a second surface opposite to the first surface, the thickness (t) of the glass article being measured as the distance between the first and second surfaces; and a compressive stress layer extending from at least one of the first and second surfaces into the thickness (t) of the glass article, wherein the central tension of the glass article is 30 MPa or more, the compressive stress layer has a compression depth of 0.15t or more and 0.25t or less, and the glass article contains 55.0 mol% or more and 75.0 mol% or less of SiO2, and 8.0 mol% or more. The invention includes glass articles formed from glass containing 20.0 mol% or less of Al2O3, 3.0 mol% to 15.0 mol% of Li2O, 5.0 mol% to 15.0 mol% of Na2O, and 1.5 mol% or less of K2O, wherein Al2O3 + Li2O is greater than 22.5 mol%, R2O + RO is 18.0 mol% or more, R2O / Al2O3 is 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 is 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 8.0 or more.

[0077] The 14th embodiment includes a glass article according to the 13th embodiment, wherein the central tension of the glass article is 50 MPa or more.

[0078] The 15th embodiment includes a glass article of either the 13th or 14th embodiment, wherein the central tension of the glass article is 80 MPa or more.

[0079] The 16th embodiment includes a glass article according to any one of the 13th to 15 embodiments, wherein the depth of the potassium layer in the compressive stress layer within the thickness of the glass article is greater than 5 μm and less than or equal to 45 μm.

[0080] The 17th embodiment includes a glass article according to any one of the 13th to 16th embodiments, wherein the glass has a liquid phase viscosity of 20 kP or more and less than 1000 kP.

[0081] The 18th embodiment includes a glass article according to any one of the 13th to 17th embodiments, wherein the surface compressive stress of the compressive stress layer is between 450 MPa and 800 MPa.

[0082] The 19th embodiment includes a home appliance comprising a housing having a front, rear, and side; electrical components at least partially located inside the housing, including at least a control device, memory, and electrical components including a display on or near the front of the housing; and a cover substrate disposed on the display, wherein at least a portion of at least one of the housing and the cover substrate includes a glass article according to any one of the 13th to 18th embodiments.

[0083] The 20th embodiment is a glass article comprising: a first surface; a second surface opposite to the first surface, the thickness (t) of the glass article being measured as the distance between the first and second surfaces; and a compressive stress layer extending from at least one of the first and second surfaces into the thickness (t) of the glass article, wherein the central tension of the glass article is 60 MPa or more, the compressive stress layer has a compression depth of 0.15t or more and 0.25t or less, and the glass article contains 55.0 mol% or more and 75.0 mol% or less of SiO2, and 8.0 mol% or more and 20. The glass article contains a composition at the center depth of the glass article that includes 0 mol% or less of Al2O3, 3.0 mol% or more and 15.0 mol% or less of Li2O, 5.0 mol% or more and 15.0 mol% or less of Na2O, and 1.5 mol% or less of K2O, with Al2O3 + Li2O being greater than 22.5 mol%, R2O + RO being 18.0 mol% or more, R2O / Al2O3 being 1.06 or more, SiO2 + Al2O3 + B2O3 + P2O5 being 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O being 8.0 or more.

[0084] The 21st embodiment includes a glass composition comprising 55.0 mol% to 70.0 mol% of SiO2, 10.0 mol% to 20.0 mol% of Al2O3, 3.0 mol% to 15.0 mol% of Li2O, 5.0 mol% to 15.0 mol% of Na2O, and 1.5 mol% or less of K2O, wherein Al2O3 + Li2O is greater than 22.5 mol%, R2O + RO is 18.0 mol% or more, SiO2 + Al2O3 + B2O3 + P2O5 is 78.0 mol% or more, and (SiO2 + Al2O3 + B2O3 + P2O5) / Li2O is 10.50 or more.

[0085] The 22nd embodiment includes a glass article comprising: a first surface; a second surface opposite to the first surface, the thickness (t) of the glass article being measured as the distance between the first and second surfaces; and a compressive stress layer extending from at least one of the first and second surfaces into the thickness (t) of the glass article, wherein the central tension of the glass article is 30 MPa or more, the compressive stress layer has a compression depth of 0.15t or more and 0.25t or less, and the glass article is formed from a glass composition according to the 21st embodiment.

[0086] The 23rd embodiment includes a glass article of the 22nd embodiment, wherein the central tension of the glass article is 50 MPa or more.

[0087] The 24th embodiment includes a glass article of either the 22nd or 23rd embodiment, wherein the central tension of the glass article is 80 MPa or more.

[0088] The 25th embodiment includes any one of the 22nd to 24th embodiments, wherein the depth of the potassium layer in the compressive stress layer within the thickness of the glass article is greater than 5 μm and less than or equal to 45 μm.

[0089] The 26th embodiment includes a glass article of any one of the 22nd to 25th embodiments, wherein the glass composition has a liquid phase viscosity of 20 kP or more and less than 1000 kP.

[0090] The 27th embodiment includes a glass article of any one of the 22nd to 26th embodiments, wherein the surface compressive stress of the compressive stress layer is between 450 MPa and 800 MPa.

[0091] The 28th embodiment includes a home appliance comprising a housing having a front, rear, and side; electrical components at least partially located inside the housing, including at least a control device, memory, and electrical components including a display on or near the front of the housing; and a cover substrate disposed on the display, wherein at least a portion of at least one of the housing and the cover substrate includes a glass article of any one of the 22nd to 27th embodiments. [Examples]

[0092] The following examples further illustrate the embodiments. It should be understood that these examples are not limitations to the embodiments described above.

[0093] Glass compositions having the components listed in Table 1 below were prepared by conventional glassmaking methods. In Table 1, all components are expressed in mole percent, and various properties of the glass compositions were measured according to the methods disclosed herein.

[0094] [Table 1-1]

[0095] [Table 1-2]

[0096] [Table 1-3]

[0097] [Table 1-4]

[0098] [Table 1-5]

[0099] [Table 1-6]

[0100] [Table 1-7]

[0101] [Table 1-8]

[0102] [Table 1-9]

[0103] [Table 1-10]

[0104] [Table 1-11]

[0105] All compositional components, relationships, and ratios described herein are given in mole percent unless otherwise specified. All scopes disclosed herein include any and all scopes and partial scopes encompassed by the broadly disclosed scope, whether explicitly stated before or after the disclosure of the scope.

[0106] It will be apparent to those skilled in the art that various modifications and alterations can be made to the embodiments described herein without departing from the spirit and scope of the subject matter of the claims. Therefore, this specification is intended to encompass such modifications and alterations to the various embodiments described herein, provided that such modifications and alterations fall within the scope of the accompanying claims and their equivalents.

[0107] As used here, the zeros following a number are intended to indicate the number of significant digits. For example, the number "1.0" has two significant digits, and the number "1.00" has three significant digits. [Explanation of Symbols]

[0108] 100 Glass 120 First Compression Layer 122 Second Compression Layer 130 Central area 200 Consumer Electronics 202 enclosures 204 Front 206 Back 208 Side view 210 displays 212 Cover board

Claims

1. SiO2 between 55.0 mol% and 70.0 mol% ２ , Al 13.0 mol% or more and 19.0 mol% or less ２ O ３ , Li between 3.0 mol% and 10.0 mol% ２ O, Na 5.0 mol% or more and 15.0 mol% or less ２ O, P between 0.5 mol% and 8.0 mol% ２ O ５ , and K 1.5 mol% or less ２ O A glass composition containing, Al ２ O ３ + Li ２ O is 24.0 mol% or more, R ２ O + RO is 18.0 mol% or more, where R ２ O is an alkali metal oxide present in the glass composition, and RO is a divalent cation oxide present in the glass composition. SiO ２ +Al ２ O ３ +B ２ O ３ +P ２ O ５ It is 78.0 mol% or more. (SiO ２ +Al ２ O ３ +B ２ O ３ +P ２ O ５ ) / Li ２ O is 9.0 or higher. A glass composition.

2. Li ２ O is between 3.0 mol% and 9.0 mol%, R ２ The glass composition according to claim 1, wherein the O+RO content is between 18.0 mol% and 23.0 mol%.

3. B ２ O ３ However, it is between 0.0 mol% and 3.0 mol%, (SiO ２ +Al ２ O ３ +B ２ O ３ +P ２ O ５ ) / Li ２ The glass composition according to claim 1 or 2, wherein O is 10.50 or higher.

4. Al ２ O ３ The amount is between 15.0 mol% and 19.0 mol%, Li ２ The glass composition according to claim 1 or 2, wherein the amount of O is between 4.0 mol% and 9.0 mol%.

5. In glass articles, Front page; A second surface opposite to the first surface, the thickness (t) of the glass article being measured as the distance between the first surface and the second surface; and A compressive stress layer extending from at least one of the first surface and the second surface into the thickness (t) of the glass article; A glass article equipped with, The central tension of the glass article is 30 MPa or more. The aforementioned compressive stress layer has a compression depth of 0.15t or more and 0.25t or less. The aforementioned glass article is A glass article formed from the glass composition according to claim 1 or 2.

6. The glass article according to claim 5, wherein the central tension of the glass article is 50 MPa or more.

7. The glass article according to claim 5, wherein the depth of the potassium layer in the compressive stress layer within the thickness of the glass article is greater than 5 μm and less than or equal to 45 μm.

8. The glass article according to claim 5, wherein the glass article has a liquid phase viscosity of 20 kP or more and less than 1000 kP.

9. The glass article according to claim 5, wherein the surface compressive stress of the compressive stress layer is 450 MPa or more and 800 MPa or less.

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