Ion-exchangeable mixed alkali aluminosilicate glasses

BACKGROUND
Field

The present specification generally relates to glass compositions suitable for use as cover glass for electronic devices. More specifically, the present specification is directed to mixed alkali aluminosilicate glasses that may be formed into cover glass for electronic devices by fusion drawing.

Technical Background

The mobile nature of portable devices, such as smart phones, tablets, portable media players, personal computers, and cameras, makes these devices particularly vulnerable to accidental dropping on hard surfaces, such as the ground. These devices typically incorporate cover glasses, which may become damaged upon impact with hard surfaces. In many of these devices, the cover glasses function as display covers, and may incorporate touch functionality, such that use of the devices is negatively impacted when the cover glasses are damaged.

There are two major failure modes of cover glass when the associated portable device is dropped on a hard surface. One of the modes is flexure failure, which is caused by bending of the glass when the device is subjected to dynamic load from impact with the hard surface. The other mode is sharp contact failure, which is caused by introduction of damage to the glass surface. Impact of the glass with rough hard surfaces, such as asphalt, granite, etc., can result in sharp indentations in the glass surface. These indentations become failure sites in the glass surface from which cracks may develop and propagate.

Glass can be made more resistant to flexure failure by the ion-exchange technique, which involves inducing compressive stress in the glass surface. However, the ion-exchanged glass will still be vulnerable to dynamic sharp contact, owing to the high stress concentration caused by local indentations in the glass from the sharp contact.

It has been a continuous effort for glass makers and handheld device manufacturers to improve the resistance of handheld devices to sharp contact failure. Solutions range from coatings on the cover glass to bezels that prevent the cover glass from impacting the hard surface directly when the device drops on the hard surface. However, due to the constraints of aesthetic and functional requirements, it is very difficult to completely prevent the cover glass from impacting the hard surface.

It is also desirable that portable devices be as thin as possible. Accordingly, in addition to strength, it is also desired that glasses to be used as cover glass in portable devices be made as thin as possible. Thus, in addition to increasing the strength of the cover glass, it is also desirable for the glass to have mechanical characteristics that allow it to be formed by processes that are capable of making thin glass articles, such as thin glass sheets.

Accordingly, a need exists for glasses that can be strengthened, such as by ion exchange, and that have the mechanical properties that allow them to be formed as thin glass articles.

SUMMARY

According to a first embodiment, a glass composition comprises: from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol % SiO₂; from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O; from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, R₂O/Al₂O₃is greater than or equal to 1.06, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 8.0.

According to a second embodiment, a glass article comprises: a first surface; a second surface opposite the first surface, wherein a thickness (t) of the glass article is measured as a 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, wherein a central tension of the glass article is greater than or equal to 30 MPA, the compressive stress layer has a depth of compression that is from greater than or equal to 0.15t to less than or equal to 0.25t, and the glass article is formed from a glass comprising: from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol % SiO₂; from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, R₂O/Al₂O₃is greater than or equal to 1.06, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 8.0.

According to a third embodiment, a glass article comprises: a first surface; a second surface opposite the first surface, wherein a thickness (t) of the glass article is measured as a 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, wherein a central tension of the glass article is greater than or equal to 60 MPa, the compressive stress layer has a depth of compression that is from greater than or equal to 0.15t to less than or equal to 0.25t, and the glass article has a composition at a center depth of the glass article comprising: from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol % SiO₂; from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, R₂O/Al₂O₃is greater than or equal to 1.06, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 8.0.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to 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 character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into 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 operations of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically depicts a cross section of a glass having compressive stress layers on surfaces thereof according to embodiments disclosed and described herein;

FIG. 2A is a plan view of an exemplary electronic device incorporating any of the glass articles disclosed herein; and

FIG. 2B is a perspective view of the exemplary electronic device of FIG. 2A.

DETAILED DESCRIPTION

Reference will now be made in detail to alkali aluminosilicate glasses according to various embodiments. Alkali aluminosilicate glasses have good ion exchangeability, and chemical strengthening processes have been used to achieve high strength and high toughness properties in alkali aluminosilicate glasses. Sodium aluminosilicate glasses are highly ion exchangeable glasses with high glass formability and quality. The substitution of Al₂O₃into the silicate glass network increases the interdiffusivity of monovalent cations during ion exchange. By chemical strengthening in a molten salt bath (e.g., KNO₃and/or NaNO₃), glasses with high strength, high toughness, and high indentation cracking resistance can be achieved.

Therefore, alkali aluminosilicate glasses with good physical properties, chemical durability, and ion exchangeability have drawn attention for use as cover glass. In particular, lithium containing aluminosilicate glasses, which have lower annealing and softening temperatures, lower coefficient of thermal expansion (CTE) values, and fast ion exchangeability, are provided herein. Through different ion exchange processes, greater central tension (CT), depth of compression (DOC), and high compressive stress (CS) can be achieved. However, the addition of lithium in the alkali aluminosilicate glass may reduce the melting point, softening point, or liquidus viscosity of the glass.

Drawing processes for forming glass articles, such as, for example, glass sheets, are desirable because they allow a thin glass article to be formed with few defects. It was previously thought that glass compositions were required to have relatively high liquidus viscosities—such as a liquidus viscosity greater than 1000 kP, greater than 1100 kP, or greater than 1200 kP—to be formed by a drawing process, such as, for example, fusion drawing or slot drawing. However, developments in drawing processes allow glasses with lower liquidus viscosities to be used in drawing processes. Thus, glasses used in drawing processes may include more lithia than previously thought, and may include more glass network forming components, such as, for example, SiO₂, Al₂O₃, B₂O₃, and P₂O₅. Accordingly, a balance of the various glass components that allows the glass to realize the benefits of adding lithium and glass network formers to the glass composition, but that does not negatively impact the glass composition are provided herein.

In embodiments of glass compositions described herein, the concentration of constituent components (e.g., SiO₂, Al₂O₃, Li₂O, and the like) are given in mole percent (mol %) on an oxide basis, unless otherwise specified. Components of the alkali aluminosilicate glass composition according to embodiments are discussed individually below. It should be understood that any of the variously recited ranges of one component may be individually combined with any of the variously recited ranges for any other component.

In embodiments of the alkali aluminosilicate glass compositions disclosed herein, SiO₂is the largest constituent and, as such, SiO₂is the primary constituent of the glass network formed from the glass composition. Pure SiO₂has a relatively low CTE and is alkali free. However, pure SiO₂has a high melting point. Accordingly, if the concentration of SiO₂in the glass composition is too high, the formability of the glass composition may be diminished as higher concentrations of SiO₂increase the difficulty of melting the glass, which, in turn, adversely impacts the formability of the glass. In embodiments, the glass composition generally comprises SiO₂in an amount from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition comprises SiO₂in amounts greater than or equal to 58.0 mol %, such as greater than or equal to 60.0 mol %, greater than or equal to 62.0 mol %, greater than or equal to 64.0 mol %, greater than or equal to 66.0 mol %, greater than or equal to 68.0 mol %, or greater than or equal to 70.0 mol %. In embodiments, the glass composition comprises SiO₂in amounts less than or equal to 72.0 mol %, such as less than or equal to 70.0 mol %, less than or equal to 68.0 mol %, less than or equal to 66.0 mol %, less than or equal to 64.0 mol %, or less than or equal to 62.0 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises SiO₂in an amount from greater than or equal to 58.0 mol % to less than or equal to 70.0 mol %, such as from greater than or equal to 60.0 mol % to less than or equal to 68.0 mol %, or from greater than or equal to 62.0 mol % to less than or equal to 64.0 mol %, and all ranges and sub-ranges between the foregoing values.

The glass composition of embodiments may further comprise Al₂O₃. Al₂O₃may serve as a glass network former, similar to SiO₂. Al₂O₃may increase the viscosity of the glass composition due to its tetrahedral coordination in a glass melt formed from a glass composition, decreasing the formability of the glass composition when the amount of Al₂O₃is too high. However, when the concentration of Al₂O₃is balanced against the concentration of SiO₂and the concentration of alkali oxides in the glass composition, Al₂O₃can reduce the liquidus temperature of the glass melt, thereby enhancing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes, such as the fusion forming process. In embodiments, the glass composition generally comprises Al₂O₃in a concentration of from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition comprises Al₂O₃in amounts greater than or equal to 10.0 mol %, such as greater than or equal to 12.0 mol %, greater than or equal to 14.0 mol %, greater than or equal to 16.0 mol %, greater than or equal to 17.0 mol %, or greater than or equal to 19.0 mol %. In embodiments, the glass composition comprises Al₂O₃in amounts less than or equal to 19.0 mol %, such as less than or equal to 18.0 mol %, less than or equal to 17.0 mol %, less than or equal to 16.0 mol %, less than or equal to 15.0 mol %, less than or equal to 14.0 mol %, or less than or equal to 13.0 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises Al₂O₃in an amount from greater than or equal to 10.0 mol % to less than or equal to 18.0 mol %, such as from greater than or equal to 12.0 mol % to less than or equal to 16.0 mol %, or from greater than or equal to 15.0 mol % to less than or equal to 17.0 mol %, and all ranges and sub-ranges between the foregoing values.

Like SiO₂and Al₂O₃, P₂O₅may be added to the glass composition as a network former, thereby reducing the meltability and formability of the glass composition. Thus, P₂O₅may be added in amounts that do not overly decrease these properties. The addition of P₂O₅may also increase the diffusivity of ions in the glass composition during ion exchange treatment, thereby increasing the efficiency of these treatments. In embodiments, the glass composition may comprise P₂O₅in amounts from greater than or equal to 0.0 mol % to less than or equal to 8.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition may comprise P₂O₅in amounts greater than or equal to 0.5 mol %, greater than or equal to 1.0 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2.0 mol %, greater than or equal to 2.5 mol %, greater than or equal to 3.0 mol %, greater than or equal to 3.5 mol %, greater than or equal to 4.0 mol %, or greater than or equal to 4.5 mol %. In embodiments, the glass composition may comprise P₂O₅in an amount less than or equal to 7.5 mol %, less than or equal to 7.0 mol %, less than or equal to 6.5 mol %, less than or equal to 6.0 mol %, less than or equal to 5.5 mol %, less than or equal to 5.0 mol %, less than or equal to 4.5 mol %, less than or equal to 4.0 mol %, less than or equal to 3.5 mol %, less than or equal to 3.0 mol %, less than or equal to 2.5 mol %, less than or equal to 2.0 mol %, less than or equal to 1.5 mol %, less than or equal to 1.0 mol %, or less than or equal to 0.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition may comprise P₂O₅in amounts from greater than or equal to 0.5 mol % to less than or equal to 7.5 mol %, from greater than or equal to 1.0 mol % to less than or equal to 7.0 mol %, from greater than or equal to 1.5 mol % to less than or equal to 6.5 mol %, from greater than or equal to 2.0 mol % to less than or equal to 6.0 mol %, from greater than or equal to 2.5 mol % to less than or equal to 5.5 mol %, or from greater than or equal to 3.0 mol % to less than or equal to 5.0 mol %, and all ranges and sub-ranges between the foregoing values.

Like SiO₂, Al₂O₃, and P₂O₅, B₂O₃may be added to the glass composition as a network former, thereby reducing the meltability and formability of the glass composition. Thus, B₂O₃may be added in amounts that do not overly decrease these properties. In embodiments, the glass composition may comprise B₂O₃in amounts from greater than or equal to 0.0 mol % B₂O₃to less than or equal to 3.0 mol % B₂O₃, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition may comprise B₂O₃in amounts greater than or equal to 0.5 mol %, greater than or equal to 1.0 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2.0 mol %, or greater than or equal to 2.5 mol %. In embodiments, the glass composition may comprise B₂O₃in an amount less than or equal to 2.5 mol %, less than or equal to 2.0 mol %, less than or equal to 1.5 mol %, less than or equal to 1.0 mol %, or less than or equal to 0.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises B₂O₃in amounts from greater than or equal to 0.5 mol % to less than or equal to 2.5 mol %, or from greater than or equal to 1.0 mol % to less than or equal to 2.0 mol %, and all ranges and sub-ranges between the foregoing values.

In some embodiments, the glass composition comprises at least one of B₂O₃and P₂O₅as glass network forming elements. Accordingly, in embodiments B₂O₃+P₂O₅is greater than 0.0 mol %, such as greater than or equal to 0.5 mol %, greater than or equal to 1.0 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2.0 mol %, greater than or equal to 2.5 mol %, greater than or equal to 3.0 mol %, greater than or equal to 3.5 mol %, greater than or equal to 4.0 mol %, greater than or equal to 4.5 mol %, greater than or equal to 5.0 mol %, greater than or equal to 5.5 mol %, greater than or equal to 6.0 mol %, greater than or equal to 6.5 mol %, greater than or equal to 7.0 mol %, greater than or equal to 7.5 mol %, or greater than or equal to 8.0 mol %, and all ranges and sub-ranges between the foregoing values. In embodiments, B₂O₃+P₂O₅is less than or equal to 7.5 mol %, such as less than or equal to 7.0 mol %, less than or equal to 6.5 mol %, less than or equal to 6.0 mol %, less than or equal to 5.5 mol %, less than or equal to 5.0 mol %, less than or equal to 4.5 mol %, less than or equal to 4.0 mol %, less than or equal to 3.5 mol %, less than or equal to 3.0 mol %, less than or equal to 2.5 mol %, less than or equal to 2.0 mol %, less than or equal to 1.5 mol %, less than or equal to 1.0 mol %, or less than or equal to 0.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises B₂O₃+P₂O₅in amounts from greater than or equal to 0.5 mol % to less than or equal to 7.5 mol %, greater than or equal to 1.0 mol % to less than or equal to 7.0 mol %, greater than or equal to 1.5 mol % to less than or equal to 6.5 mol %, greater than or equal to 2.0 mol % to less than or equal to 6.0 mol %, greater than or equal to 2.5 mol % to less than or equal to 5.5 mol %, or greater than or equal to 3.0 mol % to less than or equal to 5.0 mol %, and all ranges and sub-ranges between the foregoing values.

The effects of Li₂O in the glass composition are discussed above and discussed in further detail below. In part, the addition of lithium in the glass allows for better control of an ion exchange process and further reduces the softening point of the glass. In embodiments, the glass composition generally comprises Li₂O in an amount from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition comprises Li₂O in amounts greater than or equal to 3.5 mol %, greater than or equal to 4.0 mol %, greater than or equal to 4.5 mol %, greater than or equal to 5.0 mol %, greater than or equal to 5.5 mol %, greater than or equal to 6.0 mol %, greater than or equal to 6.5 mol %, greater than or equal to 7.0 mol %, greater than or equal to 7.5 mol %, greater than or equal to 8.0 mol %, greater than or equal to 8.5 mol %, greater than or equal to 9.0 mol %, greater than or equal to 9.5 mol %, greater than or equal to 10.0 mol %, greater than or equal to 10.5 mol %, greater than or equal to 11.0 mol %, greater than or equal to 11.5 mol %, greater than or equal to 12.0 mol %, greater than or equal to 12.5 mol %, greater than or equal to 13.0 mol %, greater than or equal to 13.5 mol %, greater than or equal to 14.0 mol %, or greater than or equal to 14.5 mol %. In some embodiments, the glass composition comprises Li₂O in amounts less than or equal to 14.5 mol %, less than or equal to 14.0 mol %, less than or equal to 13.5 mol %, less than or equal to 13.0 mol %, less than or equal to 12.5 mol %, less than or equal to 12.0 mol %, less than or equal to 11.5 mol %, less than or equal to 11.0 mol %, less than or equal to 10.5 mol %, less than or equal to 10.0 mol %, less than or equal to 9.5 mol %, less than or equal to 9.0 mol %, less than or equal to 8.5 mol %, less than or equal to 8.0 mol %, less than or equal to 7.5 mol %, less than or equal to 7.0 mol %, less than or equal to 6.5 mol %, less than or equal to 6.0 mol %, less than or equal to 5.5 mol %, less than or equal to 5.0 mol %, less than or equal to 4.5 mol %, less than or equal to 4.0 mol %, or less than or equal to 3.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises Li₂O in an amount from greater than or equal to 3.5 mol % to less than or equal to 14.5 mol %, such as from greater than or equal to 4.0 mol % to less than or equal to 14.0 mol %, from greater than or equal to 4.5 mol % to less than or equal to 13.5 mol %, from greater than or equal to 5.0 mol % to less than or equal to 13.0 mol %, from greater than or equal to 5.5 mol % to less than or equal to 12.5 mol %, from greater than or equal to 6.0 mol % to less than or equal to 12.0 mol %, from greater than or equal to 6.5 mol % to less than or equal to 11.5 mol %, or from greater than or equal to 7.0 mol % to less than or equal to 10.0 mol %, and all ranges and sub-ranges between the foregoing values.

In addition to being a glass network forming component, Al₂O₃also aids in increasing the ion exchangeability of the glass composition. Therefore, in embodiments, the amount of Al₂O₃and other components that may be ion exchanged may be relatively high. 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 %, such as greater than or equal to 23.0 mol %, greater than or equal to 23.5 mol %, greater than or equal to 24.0 mol %, greater than or equal to 24.5 mol %, greater than or equal to 25.0 mol %, greater than or equal to 25.5 mol %, or greater than or equal to 26.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the amount of Al₂O₃+Li₂O is less than or equal to 26.5 mol %, such as less than or equal to 26.0 mol %, less than or equal to 25.5 mol %, less than or equal to 25.0 mol %, less than or equal to 24.5 mol %, less than or equal to 24.0 mol %, less than or equal to 23.5 mol %, or less than or equal to 23.0 mol %, and all ranges and sub-ranges between the foregoing values. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the amount of Al₂O₃+Li₂O is from greater than or equal to 23.0 mol % to less than or equal to 26.5 mol %, from greater than or equal to 23.5 mol % to less than or equal to 26.0 mol %, from greater than or equal to 24.0 mol % to less than or equal to 25.5 mol %, or from greater than or equal to 24.5 mol % to less than or equal to 25.0 mol %, and all ranges and sub-ranges between the foregoing values.

According to embodiments, the glass composition may also comprise alkali metal oxides other than Li₂O, such as Na₂O. Na₂O aids in the ion exchangeability of the glass composition, and also increases the melting point of the glass composition and improves formability of the glass composition. 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 embodiments, the glass composition generally comprises Na₂O in an amount from greater than 5.0 mol % Na₂O to less than or equal to 15 mol % Na₂O, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition comprises Na₂O in amounts greater than or equal to 5.5 mol %, greater than or equal to 6.0 mol %, greater than or equal to 6.5 mol %, greater than or equal to 7.0 mol %, greater than or equal to 7.5 mol %, greater than or equal to 8.0 mol %, greater than or equal to 8.5 mol %, greater than or equal to 9.0 mol %, greater than or equal to 9.5 mol %, greater than or equal to 10.0 mol %, greater than or equal to 10.5 mol %, greater than or equal to 11.0 mol %, greater than or equal to 11.5 mol %, greater than or equal to 12.0 mol %, greater than or equal to 12.5 mol %, greater than or equal to 13.0 mol %, greater than or equal to 13.5 mol %, greater than or equal to 14.0 mol %, or greater than or equal to 14.5 mol %. In some embodiments, the glass composition comprises Na₂O in amounts less than or equal to 14.5 mol %, less than or equal to 14.0 mol %, less than or equal to 13.5 mol %, less than or equal to 13.0 mol %, less than or equal to 12.5 mol %, less than or equal to 12.0 mol %, less than or equal to 11.5 mol %, less than or equal to 11.0 mol %, less than or equal to 10.5 mol %, less than or equal to 10.0 mol %, less than or equal to 9.5 mol %, less than or equal to 9.0 mol %, less than or equal to 8.5 mol %, less than or equal to 8.0 mol %, less than or equal to 7.5 mol %, less than or equal to 7.0 mol %, less than or equal to 6.5 mol %, less than or equal to 6.0 mol %, less than or equal to 5.5 mol %, less than or equal to 5.0 mol %, or less than or equal to 4.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises Na₂O in an amount from greater than or equal to 5.5 mol % to less than or equal to 14.5 mol %, such as from greater than or equal to 6.0 mol % to less than or equal to 14.0 mol %, from greater than or equal to 6.5 mol % to less than or equal to 13.5 mol %, from greater than or equal to 7.0 mol % to less than or equal to 13.0 mol %, from greater than or equal to 7.5 mol % to less than or equal to 12.5 mol %, from greater than or equal to 8.0 mol % to less than or equal to 12.0 mol %, from greater than or equal to 8.5 mol % to less than or equal to 11.5 mol %, or from greater than or equal to 9.0 mol % to less than or equal to 10.0 mol %, and all ranges and sub-ranges between the foregoing values.

As noted above, Al₂O₃aids in increasing the ion exchangeability of the glass composition. Therefore, in embodiments, the amount of Al₂O₃and other components that may be ion exchanged may be relatively high. 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 %, such as greater than or equal to 25.5 mol %, greater than or equal to 26.0 mol %, greater than or equal to 26.5 mol %, greater than or equal to 27.0 mol %, greater than or equal to 27.5 mol %, greater than or equal to 28.0 mol %, greater than or equal to 28.5 mol %, greater than or equal to 29.0 mol %, or greater than or equal to 29.5 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the amount of Al₂O₃+Li₂O+Na₂O is less than or equal to 30.0 mol %, such as less than or equal to 29.5 mol %, less than or equal to 29.0 mol %, less than or equal to 28.5 mol %, less than or equal to 28.0 mol %, less than or equal to 27.5 mol %, less than or equal to 27.0 mol %, less than or equal to 26.5 mol %, less than or equal to 26.0 mol %, or less than or equal to 25.5 mol %, and all ranges and sub-ranges between the foregoing values. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the amount of Al₂O₃+Li₂O+Na₂O is from greater than or equal to 25.0 mol % to less than or equal to 30.0 mol %, from greater than or equal to 25.5 mol % to less than or equal to 29.5 mol %, from greater than or equal to 26.0 mol % to less than or equal to 29.0 mol %, from greater than or equal to 26.5 mol % to less than or equal to 28.5 mol %, or from greater than or equal to 27.0 mol % to less than or equal to 28.0 mol %, and all ranges and sub-ranges between the foregoing values.

Like Na₂O, K₂O also promotes ion exchange and increases the DOC of a compressive stress layer. However, adding K₂O may cause the CTE to be too low, and the melting point to be too high. In embodiments, the glass composition comprises less than or equal to 1.5 mol % K₂O, such as less than or equal to 1.0 mol %, or less than or equal to 0.5 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition is substantially free or free of potassium. As used herein, the term “substantially free” means that the component is not added as a component of the batch material even though the component may be present in the final glass in very small amounts as a contaminant, such as less than 0.01 mol %.

MgO lowers the viscosity of a glass, which enhances the formability, the strain point and the Young's modulus, and may improve the ion exchange ability. However, when too much MgO is added to the glass composition, the density and the CTE of the glass composition increase. In embodiments, the glass composition generally comprises MgO in a concentration of from greater than or equal to 0.0 mol % to less than or equal to 4.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition comprises MgO in amounts greater than or equal to 0.2 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1.0 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2.0 mol %, greater than or equal to 2.5 mol %, greater than or equal to 3.0 mol %, or greater than or equal to 3.5 mol %. In some embodiments, the glass composition comprises MgO in amounts less than or equal to 3.5 mol %, less than or equal to 3.0 mol %, less than or equal to 2.5 mol %, less than or equal to 2.0 mol %, less than or equal to 1.5 mol %, less than or equal to 1.0 mol %, less than or equal to 0.5 mol %, less than or equal to 0.4 mol %, or less than or equal to 0.2 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises MgO in an amount from greater than or equal to 0.2 mol % to less than or equal to 3.5 mol %, such as from greater than or equal to 0.5 mol % to less than or equal to 3.0 mol %, from greater than or equal to 1.0 mol % to less than or equal to 2.5 mol %, or from greater than or equal to 1.5 mol % to less than or equal to 2.0 mol %, and all ranges and sub-ranges between the foregoing values.

CaO lowers the viscosity of a glass, which enhances the formability, the strain point and the Young's modulus, and may improve the ion exchange ability. However, when too much CaO is added to the glass composition, the density and the CTE of the glass composition increase. In embodiments, the glass composition generally comprises CaO in a concentration of from greater than or equal to 0.0 mol % to less than or equal to 2.0 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition comprises CaO in amounts greater than or equal to 0.2 mol %, greater than or equal to 0.4 mol %, greater than or equal to 0.6 mol %, greater than or equal to 0.8 mol %, greater than or equal to 1.0 mol %, greater than or equal to 1.2 mol %, greater than or equal to 1.4 mol %, greater than or equal to 1.6 mol %, or greater than or equal to 1.8 mol %. In some embodiments, the glass composition comprises CaO in amounts less than or equal to 1.8 mol %, less than or equal to 1.6 mol %, less than or equal to 1.4 mol %, less than or equal to 1.2 mol %, less than or equal to 1.0 mol %, less than or equal to 0.8 mol %, less than or equal to 0.6 mol %, less than or equal to 0.4 mol %, or less than or equal to 0.2 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition comprises CaO in an amount from greater than or equal to 0.2 mol % to less than or equal to 1.8 mol %, such as from greater than or equal to 0.4 mol % to less than or equal to 1.6 mol %, from greater than or equal to 0.6 mol % to less than or equal to 1.4 mol %, or from greater than or equal to 0.8 mol % to less than or equal to 1.2 mol %, and all ranges and sub-ranges between the foregoing values.

In embodiments, the glass composition may optionally include one or more fining agents. In some embodiments, the fining agents may include, for example, SnO₂. In such embodiments, SnO₂may be present in the glass composition in an amount less than or equal to 0.2 mol %, such as from greater than or equal to 0.0 mol % to less than or equal to 0.1 mol %, and all ranges and sub-ranges between the foregoing values. In embodiments, SnO₂may be present in the glass composition in an amount from greater than or equal to 0.0 mol % to less than or equal to 0.2 mol %, or greater than or equal to 0.1 mol % to less than or equal to 0.2 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition may be substantially free or free of SnO₂.

ZnO enhances the ion exchange performance of a glass, such as by increasing the compressive stress of the glass. However, adding too much ZnO may increase density and cause phase separation. In embodiments, the glass composition may comprise ZnO in amounts from greater than or equal to 0.0 mol % to less than or equal to 2.5 mol %, such as from greater than or equal to 0.2 mol % to less than or equal to 2.0 mol %, or from greater than or equal to 0.5 mol % to less than or equal to 1.5 mol %, and all ranges and sub-ranges between the foregoing values. In some embodiments, the glass composition may comprise ZnO in amounts greater than or equal to 0.3 mol %, greater than or equal to 0.5 mol %, or greater than or equal to 0.8 mol %. In embodiments, the glass composition may comprise ZnO in amounts less than or equal to 2.0 mol %, such as less than or equal to 1.5 mol %, or less than or equal to 1.0 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range.

In addition to the above individual components, glass compositions according to embodiments disclosed herein may comprise divalent cation oxides (referred to herein as RO) in amounts from greater than or equal to 0.0 mol % to less than or equal to 5.0 mol %, and all ranges and sub-ranges between the foregoing values. As used herein, divalent cation oxides (RO) include, but are not limited to, MgO, CaO, SrO, BaO, FeO, and ZnO. In some embodiments, the glass composition may comprise RO in an amount greater than or equal to 0.2 mol %, such as greater than or equal to 0.5 mol %, greater than or equal to 1.0 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2.0 mol %, greater than or equal to 2.5 mol %, greater than or equal to 3.0 mol %, greater than or equal to 3.5 mol %, greater than or equal to 4.0 mol %, or greater than or equal to 4.5 mol %. In embodiments, the glass composition may comprise RO in an amount less than or equal to 4.5 mol %, such as less than or equal to 4.0 mol %, less than or equal to 3.5 mol %, less than or equal to 3.0 mol %, less than or equal to 2.5 mol %, less than or equal to 2.0 mol %, less than or equal to 1.5 mol %, less than or equal to 1.0 mol %, or less than or equal to 0.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition may comprise RO in amounts from greater than or equal to 0.2 mol % to less than or equal to 4.5 mol %, such as greater than or equal to 0.5 mol % to less than or equal to 4.0 mol %, greater than or equal to 1.0 mol % to less than or equal to 3.5 mol %, greater than or equal to 1.5 mol % to less than or equal to 3.0 mol %, or greater than or equal to 2.0 mol % to less than or equal to 2.5 mol %, and all ranges and sub-ranges between the foregoing values.

The amount of alkali metal oxides (also referred to herein as “R₂O”) and RO in the glass composition may have an effect on the viscosity of the glass composition, namely the softening point is decreased with increasing R₂O+RO content to enable easier 3 D forming processes. As utilized herein, R₂O includes Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, and Fr₂O. In embodiments, the sum of R₂O and RO (i.e., R₂O+RO) is greater than or equal to 18.0 mol %, such as greater than or equal to 18.5 mol %, greater than or equal to 19.0 mol %, greater than or equal to 19.5 mol %, greater than or equal to 20.0 mol %, greater than or equal to 20.5 mol %, greater than or equal to 21.0 mol %, greater than or equal to 21.5 mol %, greater than or equal to 22.0 mol %, greater than or equal to 22.5 mol %, or greater than or equal to 23.0 mol %. In embodiments, the sum of R₂O and RO is less than or equal to 22.5 mol %, such as less than or equal to 22.0 mol %, less than or equal to 21.5 mol %, less than or equal to 21.0 mol %, less than or equal to 20.5 mol %, less than or equal to 20.0 mol %, less than or equal to 19.5 mol %, less than or equal to 19.0 mol %, or less than or equal to 18.5 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the sum of R₂O and RO in the glass composition is from greater than or equal to 18.0 mol % to less than or equal to 23.0 mol %, such as from greater than or equal to 18.5 mol % to less than or equal to 22.5 mol %, from greater than or equal to 19.0 mol % to less than or equal to 22.0 mol %, from greater than or equal to 19.5 mol % to less than or equal to 21.5 mol %, or from greater than or equal to 20.0 mol % to less than or equal to 21.0 mol %, and all ranges and sub-ranges between the foregoing values.

In embodiments, a relationship, in mol %, of R₂O/Al₂O₃is greater than or equal to 1.06. Having a ratio of R₂O to Al₂O₃above 1.06 improves the meltability of the glass. One skilled in the art of glassmaking knows that R₂O in excess of Al₂O₃greatly improves the dissolution of SiO₂in a glass melt. This value is closely controlled in glass design to improve yields by reducing losses due to inclusions such as silica knots. In some embodiments, the molar ratio of R₂O/Al₂O₃is greater than or equal to 1.10, such as greater than or equal to 1.20, greater than or equal to 1.30, greater than or equal to 1.40, greater than or equal to 1.50, greater than or equal to 1.60, greater than or equal to 1.70, greater than or equal to 1.80, greater than or equal to 1.90, or greater than or equal to 2.00. However, if the R₂O/Al₂O₃ratio is too high, the glass may become susceptible to degradation. In embodiments, a molar ratio of R₂O/Al₂O₃is less than or equal to 2.10, such as less than or equal to 2.00, less than or equal to 1.90, less than or equal to 1.80, less than or equal to 1.70, less than or equal to 1.60, less than or equal to 1.50, less than or equal to 1.40, less than or equal to 1.30, less than or equal to 1.20, or less than or equal to 1.10. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the molar ratio of R₂O/Al₂O₃is from greater than or equal to 1.06 to less than or equal to 2.10, such as from greater than or equal to 1.10 to less than or equal to 1.90, from greater than or equal to 1.20 to less than or equal to 1.80, or from greater than or equal to 1.30 to less than or equal to 1.70, and all ranges and sub-ranges between the foregoing values.

In embodiments, the total amount of network forming components (e.g., Al₂O₃+SiO₂+B₂O₃+P₂O₅) is greater than or equal to 78.0 mol %, such as greater than or equal to 78.5 mol %, greater than or equal to 79.0 mol %, greater than or equal to 78.5 mol %, greater than or equal to 80.0 mol %, greater than or equal to 80.5 mol %, greater than or equal to 81.0 mol %, greater than or equal to 81.5 mol %, greater than or equal to 82.0 mol %, greater than or equal to 82.5 mol %, greater than or equal to 83.0 mol %, greater than or equal to 83.5 mol %, or greater than or equal to 84.0 mol %. Having a high amount of network forming components increases the connectivity and free volume of the glass, which makes it less brittle and improves the damage resistance. In embodiments, the total amount of network forming components is less than or equal to 85.0 mol %, such as less than or equal to 84.5 mol %, less than or equal to 84.0 mol %, less than or equal to 83.5 mol %, less than or equal to 83.0 mol %, less than or equal to 82.5 mol %, less than or equal to 82.0 mol %, less than or equal to 81.5 mol %, less than or equal to 81.0 mol %, less than or equal to 80.5 mol %, less than or equal to 80.0 mol %, less than or equal to 79.5 mol %, or less than or equal to 79.0 mol %. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the total amount of network forming components is from greater than or equal to 78.0 mol % to less than or equal to 85.0 mol %, such as greater than or equal to 78.0 mol % to less than or equal to 83.0 mol %, greater than or equal to 80.0 mol % to less than or equal to 82.0 mol %, or greater than or equal to 80.5 mol % to less than or equal to 81.5 mol %, and all ranges and sub-ranges between the foregoing values.

In one or more embodiments, the amount of glass network forming components, such as SiO₂, Al₂O₃, B₂O₃, and P₂O₅, may be balanced against the amount of Li₂O in the glass composition. Without being bound to any particular theory, it is believed that Li₂O decreases the free volume in the glass relative to other alkali ions, thus reducing the indentation crack resistance. Since Li₂O is needed for Na⁺ for Li⁺, ion-exchange, the free volume reducing Li₂O should be managed relative to the free volume increasing network formers, i.e. SiO₂, Al₂O₃, B₂O₃, and P₂O₅to retain suitable sharp contact damage resistance. Thus, in embodiments, the ratio, in mol %, of glass network formers to Li₂O (i.e., (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O) is greater than or equal to 8.0, such as greater than or equal to 8.5, greater than or equal to 9.0, greater than or equal to 9.5, greater than or equal to 10.0, greater than or equal to 10.5, greater than or equal to 11.0, greater than or equal to 11.5, greater than or equal to 12.0, greater than or equal to 12.5, greater than or equal to 13.0, greater than or equal to 13.5, greater than or equal to 14.0, greater than or equal to 14.5, greater than or equal to 15.0, greater than or equal to 15.5, greater than or equal to 16.0, or greater than or equal to 16.5. In other embodiments the ratio (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is less than or equal to 17.0, such as less than or equal to 16.5, less than or equal to 16.0, less than or equal to 15.5, less than or equal to 15.0, less than or equal to 14.5, less than or equal to 14.0, less than or equal to 13.5, less than or equal to 13.0, less than or equal to 12.5, less than or equal to 12.0, less than or equal to 11.5, less than or equal to 11.0, less than or equal to 10.5, less than or equal to 10.0, less than or equal to 9.5, less than or equal to 9.0, or less than or equal to 8.5. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the ratio (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is from greater than or equal to 8.0 to less than or equal to 17.0, such as from greater than or equal to 9.0 to less than or equal to 16.0, from greater than or equal to 10.0 to less than or equal to 15.0, from greater than or equal to 11.0 to less than or equal to 14.0, or from greater than or equal to 12.0 to less than or equal to 13.0, and all ranges and sub-ranges between the foregoing values.

The sum of Al₂O₃+Li₂O should be greater than or equal to 23.0 mol %, such as greater than or equal to 23.5 mol %, greater than or equal to 24.0 mol %, greater than or equal to 24.5 mol %, greater than or equal to 25.0 mol %, greater than or equal to 25.5 mol %, greater than or equal to 26.0 mol %, greater than or equal to 26.5 mol %, greater than or equal to 27.0 mol %, greater than or equal to 27.5 mol %, greater than or equal to 28.0 mol %, greater than or equal to 28.5 mol %, greater than or equal to 29.0 mol %, greater than or equal to 29.5 mol %, or greater than or equal to 30.0 mol %. The sum of Al₂O₃+Li₂O should be as high as possible to promote maximum compressive stress at a given depth for the tail of the ion-exchange profile.

In embodiments, the glass article may be substantially free of one or both of arsenic and antimony. In other embodiments, the glass article may be free of one or both of arsenic and antimony.

Physical properties of the alkali aluminosilicate glass compositions as disclosed above will now be discussed. These physical properties can be achieved by modifying the component amounts of the alkali aluminosilicate glass composition, as will be discussed in more detail with reference to the examples.

Glass compositions according to embodiments may have a density from greater than or equal to 2.20 g/cm³to less than or equal to 2.60 g/cm³, such as from greater than or equal to 2.25 g/cm³to less than or equal to 2.60 g/cm³, from greater than or equal to 2.30 g/cm³to less than or equal to 2.60 g/cm³, from greater than or equal to 2.35 g/cm³to less than or equal to 2.60 g/cm³, from greater than or equal to 2.40 g/cm³to less than or equal to 2.60 g/cm³, or from greater than or equal to 2.45 g/cm³to less than or equal to 2.60 g/cm³. In embodiments, the glass composition may have a density from greater than or equal to 2.20 g/cm³to less than or equal to 2.45 g/cm³, such as from greater than or equal to 2.20 g/cm³to less than or equal to 2.40 g/cm³, from greater than or equal to 2.20 g/cm³to less than or equal to 2.35 g/cm³, from greater than or equal to 2.20 g/cm³to less than or equal to 2.30 g/cm³, or from greater than or equal to 2.20 g/cm³to less than or equal to 2.25 g/cm³, and all ranges and sub-ranges between the foregoing values. Generally, as larger, denser alkali metal cations, such as Na⁺ or K⁺, are replaced with smaller alkali metal cations, such as Li⁺, in an alkali aluminosilicate glass composition, the density of the glass composition decreases. Accordingly, the higher the amount of lithium in the glass composition, the less dense the glass composition will be. The density values recited in this disclosure refer to a value as measured by the buoyancy method of ASTM C693-93(2013).

In embodiments, the liquidus viscosity of the glass composition is less than or equal to 1000 kP, such as less than or equal to 800 kP, less than or equal to 600 kP, less than or equal to 400 kP, less than or equal to 200 kP, less than or equal to 100 kP, less than or equal to 75 kP, less than or equal to 60 kP, less than or equal to 50 kP, less than or equal to 40 kP, or less than or equal to 30 kP. In embodiments, the liquidus viscosity of the glass composition is greater than or equal to 20 kP, such as greater than or equal to 40 kP, greater than or equal to 60 kP, greater than or equal to 80 kP, greater than or equal to 100 kP, greater than or equal to 120 kP, greater than or equal to 140 kP, or greater than or equal to 160 kP. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the liquidus viscosity of the glass composition is from greater than or equal to 20 kP to less than or equal to 1000 kP, such as greater than or equal to 40 kP to less than or equal to 900 kP, greater than or equal to 60 kP to less than or equal to 800 kP, or greater than or equal to 80 kP to less than or equal to 700 kP, and all ranges and sub-ranges between the foregoing values. The liquidus viscosity is determined by the following method. First, the liquidus temperature of the glass is measured in accordance with ASTM C829-81 (2015), titled “Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method”. Next, the viscosity of the glass at the liquidus temperature is measured in accordance with ASTM C965-96(2012), titled “Standard Practice for Measuring Viscosity of Glass Above the Softening Point”.

The addition of lithium to the glass composition also affects the Young's modulus, shear modulus, and Poisson's ratio of the glass composition. In embodiments, the Young's modulus of the glass composition may be from greater than or equal to 65 GPa to less than or equal to 85 GPa, such as from greater than or equal to 67 GPa to less than or equal to 82 GPa, from greater than or equal to 70 GPa to less than or equal to 80 GPa, from greater than or equal to 72 GPa to less than or equal to 78 GPa, or from greater than or equal to 74 GPa to less than or equal to 76 GPa, and all ranges and sub-ranges between the foregoing values. In other embodiments, the Young's modulus of the glass composition may be from greater than or equal to 66 GPa to less than or equal to 85 GPa, such as from greater than or equal to 68 GPa to less than or equal to 85 GPa, from greater than or equal to 70 GPa to less than or equal to 85 GPa, from greater than or equal to 72 GPa to less than or equal to 85 GPa, from greater than or equal to 74 GPa to less than or equal to 85 GPa, from greater than or equal to 76 GPa to less than or equal to 85 GPa, from greater than or equal to 78 GPa to less than or equal to 85 GPa, from greater than or equal to 80 GPa to less than or equal to 85 GPa, or from greater than or equal to 82 GPa to less than or equal to 85 GPa, and all ranges and sub-ranges between the foregoing values. In embodiments, the Young's modulus may be from greater than or equal to 65 GPa to less than or equal to 84 GPa, such as from greater than or equal to 65 GPa to less than or equal to 82 GPa, from greater than or equal to 65 GPa to less than or equal to 80 GPa, from greater than or equal to 65 GPa to less than or equal to 78 GPa, from greater than or equal to 65 GPa to less than or equal to 76 GPa, from greater than or equal to 65 GPa to less than or equal to 74 GPa, from greater than or equal to 65 GPa to less than or equal to 72 GPa, from greater than or equal to 65 GPa to less than or equal to 70 GPa, from greater than or equal to 65 GPa to less than or equal to 68 GPa, or from greater than or equal to 65 GPa to less than or equal to 10 GPa, and all ranges and sub-ranges between the foregoing values. The Young's modulus values recited in this disclosure refer to a value as measured by a resonant ultrasonic spectroscopy technique of the general type set forth in ASTM E2001-13, titled “Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts.”

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 may be from greater than or equal to 700° C. to less than or equal to 930° C., such as from greater than or equal to 705° C. to less than or equal to 925° C., from greater than or equal to 710° C. to less than or equal to 920° C., from greater than or equal to 715° C. to less than or equal to 915° C., from greater than or equal to 720° C. to less than or equal to 910° C., from greater than or equal to 725° C. to less than or equal to 905° C., from greater than or equal to 730° C. to less than or equal to 900° C., from greater than or equal to 735° C. to less than or equal to 895° C., from greater than or equal to 740° C. to less than or equal to 890° C., from greater than or equal to 745° C. to less than or equal to 885° C., from greater than or equal to 750° C. to less than or equal to 880° C., from greater than or equal to 755° C. to less than or equal to 875° C., from greater than or equal to 760° C. to less than or equal to 870° C., from greater than or equal to 765° C. to less than or equal to 865° C., from greater than or equal to 770° C. to less than or equal to 860° C., from greater than or equal to 775° C. to less than or equal to 855° C., from greater than or equal to 780° C. to less than or equal to 850° C., from greater than or equal to 785° C. to less than or equal to 845° C., from greater than or equal to 790° C. to less than or equal to 840° C., from greater than or equal to 795° C. to less than or equal to 835° C., from greater than or equal to 800° C. to less than or equal to 830° C., from greater than or equal to 805° C. to less than or equal to 825° C., or from greater than or equal to 810° C. to less than or equal to 820° C., and all ranges and sub-ranges between the foregoing values. The softening point was determined using the parallel plate viscosity method of ASTM C1351M-96(2012).

From the above, glass compositions according to embodiments may be formed by any suitable method, such as slot forming, float forming, rolling processes, fusion forming processes, etc.

The glass article may be characterized by the manner in which it is formed. For instance, the glass article may be characterized as float-formable (i.e., formed by a float process), down-drawable and, in particular, fusion-formable or slot-drawable (i.e., formed by a down draw process such as a fusion draw process or a slot draw process).

Some embodiments of the glass articles described herein may be formed by a down-draw process. Down-draw processes produce glass articles having a uniform thickness that possess relatively pristine surfaces. Because the average flexural strength of the glass article is controlled by the amount and size of surface flaws, a pristine surface that has had minimal contact has a higher initial strength. In addition, down drawn glass articles have a very flat, smooth surface that can be used in its final application without costly grinding and polishing.

Some embodiments of the glass articles may be described as fusion-formable (i.e., formable using a fusion draw process). The fusion process uses a drawing tank that has a channel for accepting molten glass raw material. The channel has weirs that are open at the top along the length of the channel on both sides of the channel. When the channel fills with molten material, the molten glass overflows the weirs. Due to gravity, the molten glass flows down the outside surfaces of the drawing tank as two flowing glass films. These outside surfaces of the drawing tank extend down and inwardly so that they join at an edge below the drawing tank. The two flowing glass films join at this edge to fuse and form a single flowing glass article. The fusion draw method offers the advantage that, because the two glass films flowing over the channel fuse together, neither of the outside surfaces of the resulting glass article comes in contact with any part of the apparatus. Thus, the surface properties of the fusion drawn glass article are not affected by such contact.

Some embodiments of the glass articles described herein may be formed by a slot draw process. The slot draw process is distinct from the fusion draw method. In slot draw processes, the molten raw material glass is provided to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle that extends the length of the slot. The molten glass flows through the slot/nozzle and is drawn downward as a continuous glass article and into an annealing region.

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, the glass articles exclude glass-ceramic materials in some embodiments.

As mentioned above, in embodiments, the alkali aluminosilicate glass compositions can be strengthened, such as by ion exchange, making a glass that is damage resistant for applications such as, but not limited to, glass for display covers. With reference to FIG. 1, the glass has a first region under compressive stress (e.g., first and second compressive layers 120, 122 in FIG. 1) extending from the surface to a depth of compression (DOC) of the glass and a second region (e.g., central region 130 in FIG. 1) under a tensile stress or central tension (CT) extending from the DOC into the central or interior region of the glass. As used herein, DOC refers to the depth at which the stress within the glass article changes from compressive to tensile. At the DOC, the stress crosses from a positive (compressive) stress to a negative (tensile) stress and thus exhibits a stress value of zero.

According to the convention normally used in the art, compression or compressive stress is expressed as a negative (<0) stress and tension or tensile stress is expressed as a positive (>0) stress. Throughout this description, however, CS is expressed as a positive or absolute value—i.e., as recited herein, CS=|CS|. The compressive stress (CS) has a maximum at or near the surface of the glass, and the CS varies with distance d from the surface according to a function. Referring again to FIG. 1, a first segment 120 extends from first surface 110 to a depth d₁and a second segment 122 extends from second surface 112 to a depth d₂. Together, these segments define a compression or CS of glass 100. Compressive stress (including surface CS) is measured by surface stress meter (FSM) using commercially available instruments such as the FSM-6000, manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC in turn is measured according to Procedure C (Glass Disc Method) described in ASTM standard C770-16, entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety.

In some embodiments, the CS is from greater than or equal to 450 MPa to less than or equal to 800 MPa, such as from greater than or equal to 475 MPa to less than or equal to 775 MPa, from greater than or equal to 500 MPa to less than or equal to 750 MPa, from greater than or equal to 525 MPa to less than or equal to 725 MPa, from greater than or equal to 550 MPa to less than or equal to 700 MPa, from greater than or equal to 575 MPa to less than or equal to 675 MPa, or from greater than or equal to 600 MPa to less than or equal to 650 MPa, and all ranges and sub-ranges between the foregoing values.

In one or more embodiments, Na⁺ and K⁺ ions are exchanged into the glass article and the Na⁺ ions diffuse to a deeper depth into the glass article than the K+ ions. The depth of penetration of K⁺ ions (“Potassium DOL”) is distinguished from DOC because it represents the depth of potassium penetration as a result of an ion exchange process. The Potassium DOL is typically less than the DOC for the articles described herein. Potassium DOL is measured using a surface stress meter such as the commercially available FSM-6000 surface stress meter, manufactured by Orihara Industrial Co., Ltd. (Japan), which relies on accurate measurement of the stress optical coefficient (SOC), as described above with reference to the CS measurement. The Potassium DOL of each of first and second compressive layers 120, 122 is from greater than or equal to 5 μm to less than or equal to 45 μm, such as from greater than or equal to 6 μm to less than or equal to 40 μm, from greater than or equal to 7 μm to less than or equal to 35 μm, from greater than or equal to 8 μm to less than or equal to 30 μm, or from greater than or equal to 9 μm to less than or equal to 25 μm, and all ranges and sub-rang es between the foregoing values. In embodiments, the Potassium DOL of each of the first and second compressive layers 120, 122 is from greater than or equal to 6 μm to less than or equal to 45 μm, from greater than or equal to 10 μm to less than or equal to 45 μm, from greater than or equal to 15 μm to less than or equal to 45 μm, from greater than or equal to 20 μm to less than or equal to 45 μm, or from greater than or equal to 25 μm to less than or equal to 45 μm, and all ranges and sub-ranges between the foregoing values. In embodiments, the Potassium DOL of each of the first and second compressive layers 120, 122 is from greater than or equal to 5 μm to less than or equal to 35 μm, from greater than or equal to 5 μm to less than or equal to 30 μm, from greater than or equal to 5 μm to less than or equal to 25 μm, or from greater than or equal to 5 μm to less than or equal to 15 μm, and all ranges and sub-ranges between the foregoing values.

The compressive stress of both major surfaces (110, 112 in FIG. 1) is balanced by stored tension in the central region (130) of the glass. The maximum central tension (CT) and DOC values are measured using a scattered light polariscope (SCALP) technique known in the art. The Refracted near-field (RNF) method or SCALP may be used to measure the stress profile. When the RNF method is utilized to measure the stress profile, the maximum CT value provided by SCALP is utilized in the RNF method. In particular, the stress profile measured by RNF is force balanced and calibrated to the maximum CT value provided by a SCALP measurement. The RNF method is described in U.S. Pat. No. 8,854,623, entitled “Systems and methods for measuring a profile characteristic of a glass sample”, which is incorporated herein by reference in its entirety. In particular, the RNF method includes placing the glass article adjacent to a reference block, generating a polarization-switched light beam that is switched between orthogonal polarizations at a rate of between 1 Hz and 50 Hz, measuring an amount of power in the polarization-switched light beam and generating a polarization-switched reference signal, wherein the measured amounts of power in each of the orthogonal polarizations are within 50% of each other. The method further includes transmitting the polarization-switched light beam through the glass sample and reference block for different depths into the glass sample, then relaying the transmitted polarization-switched light beam to a signal photodetector using a relay optical system, with the signal photodetector generating a polarization-switched detector signal. The method also includes dividing the detector signal by the reference signal to form a normalized detector signal and determining the profile characteristic of the glass sample from the normalized detector signal.

In embodiments, the glass composition may have a maximum CT greater than or equal to 30 MPa, such as greater than or equal to 35 MPa, greater than or equal to 40 MPa, greater than or equal to 45 MPa, greater than or equal to 50 MPa, greater than or equal to 55 MPa, greater than or equal to 60 MPa, greater than or equal to 65 MPa, greater than or equal to 70 MPa, greater than or equal to 75 MPa, greater than or equal to 80 MPa, or greater than or equal to 85 MPa. In embodiments, the glass composition may have a maximum CT less than or equal to 100 MPa, such as less than or equal to 95 MPa, less than or equal to 90 MPa, less than or equal to 85 MPa, less than or equal to 80 MPa, less than or equal to 75 MPa, less than or equal to 70 MPa, less than or equal to 65 MPa, less than or equal to 60 MPa, less than or equal to 55 MPa, less than or equal to 50 MPa, less than or equal to 45 MPa, or less than or equal to 40 MPa. It should be understood that, in embodiments, any of the above ranges may be combined with any other range. In embodiments, the glass composition may have a maximum CT from greater than or equal to 30 MPa to less than or equal to 100 MPa, such as from greater than or equal to 35 MPa to less than or equal to 95 MPa, from greater than or equal to 40 MPa to less than or equal to 90 MPa, from greater than or equal to 45 MPa to less than or equal to 85 MPa, from greater than or equal to 50 MPa to less than or equal to 80 MPa, from greater than or equal to 55 MPa to less than or equal to 75 MPa, or from greater than or equal to 60 MPa to less than or equal to 70 MPa, and all ranges and sub-ranges between the foregoing values.

As noted above, DOC is measured using a scattered light polariscope (SCALP) technique known in the art. The DOC is provided in some embodiments herein as a portion of the thickness (t) of the glass article. In embodiments, the glass compositions may have a depth of compression (DOC) from greater than or equal to 0.15t to less than or equal to 0.25t, such as from greater than or equal to 0.18t to less than or equal to 0.22t, or from greater than or equal to 0.19t to less than or equal to 0.21t, and all ranges and sub-ranges between the foregoing values. In embodiments, the glass composition may have a DOC from greater than or equal to 0.16t to less than or equal to 0.20t, such as from greater than or equal to 0.17t to less than or equal to 0.25t, from greater than or equal to 0.18t to less than or equal to 0.25t, from greater than or equal to 0.19t to less than or equal to 0.25t, from greater than or equal to 0.20t to less than or equal to 0.25t, from greater than or equal to 0.21t to less than or equal to 0.25t, from greater than or equal to 0.22t to less than or equal to 0.25t, from greater than or equal to 0.23 t to less than or equal to 0.25t, or from greater than or equal to 0.24t to less than or equal to 0.25t, and all ranges and sub-ranges between the foregoing values. In embodiments, the glass composition may have a DOC from greater than or equal to 0.15t to less than or equal to 0.24t, such as from greater than or equal to 0.15t to less than or equal to 0.23t, from greater than or equal to 0.15t to less than or equal to 0.22t, from greater than or equal to 0.15t to less than or equal to 0.21t, from greater than or equal to 0.15t to less than or equal to 0.20t, from greater than or equal to 0.15t to less than or equal to 0.19t, from greater than or equal to 0.15t to less than or equal to 0.18t, from greater than or equal to 0.15t to less than or equal to 0.17t, or from greater than or equal to 0.15t to less than or equal to 0.16t, and all ranges and sub-ranges between the foregoing values.

Compressive stress layers may be formed in the glass by exposing the glass to an ion exchange solution. In embodiments, the ion exchange solution may be molten nitrate salt. In embodiments, the ion exchange solution may be molten KNO₃, molten NaNO₃, or combinations thereof. In embodiments, the ion exchange solution may comprise about 80% molten KNO₃, about 75% molten KNO₃, about 70% molten KNO₃, about 65% molten KNO₃, or about 60% molten KNO₃. In embodiments, the ion exchange solution may comprise about 20% molten NaNO₃, about 25% molten NaNO₃, about 30% molten NaNO₃, about 35% molten NaNO₃, or about 40% molten NaNO₃. In embodiments, the ion exchange solution may comprise about 80% molten KNO₃and about 20% molten NaNO₃, about 75% molten KNO₃and about 25% molten NaNO₃, about 70% molten KNO₃and about 30% molten NaNO₃, about 65% molten KNO₃and about 35% molten NaNO₃, or about 60% molten KNO₃and about 40% molten NaNO₃, and all ranges and sub-ranges between the foregoing values. In embodiments, other sodium and potassium salts may be used in the ion exchange solution, such as, for example sodium or potassium nitrites, phosphates, or sulfates. In some embodiments, the ion exchange solution may include lithium salts, such as LiNO₃.

The glass composition may be exposed to the ion exchange solution by dipping a glass article made from the glass composition into a bath of the ion exchange solution, spraying the ion exchange solution onto a glass article made from the glass composition, or otherwise physically applying the ion exchange solution to a glass article made from the glass composition. Upon exposure to the glass composition, the ion exchange solution may, according to embodiments, be at a temperature from greater than or equal to 400° C. to less than or equal to 500° C., such as from greater than or equal to 410° C. to less than or equal to 490° C., from greater than or equal to 420° C. to less than or equal to 480° C., from greater than or equal to 430° C. to less than or equal to 470° C., or from greater than or equal to 440° C. to less than or equal to 460° C., and all ranges and sub-ranges between the foregoing values. In embodiments, the glass composition may be exposed to the ion exchange solution for a duration from greater than or equal to 4 hours to less than or equal to 48 hours, such as from greater than or equal to 8 hours to less than or equal to 44 hours, from greater than or equal to 12 hours to less than or equal to 40 hours, from greater than or equal to 16 hours to less than or equal to 36 hours, from greater than or equal to 20 hours to less than or equal to 32 hours, or from greater than or equal to 24 hours to less than or equal to 28 hours, and all ranges and sub-ranges between the foregoing values.

The ion exchange process may be performed in an ion exchange solution under processing conditions that provide an improved compressive stress profile as disclosed, for example, in U.S. Patent Application Publication No. 2016/0102011, which is incorporated herein by reference in its entirety.

After an ion exchange process is performed, it should be understood that a composition at the surface of a glass article may be different than the composition of the as-formed glass article (i.e., the glass article before it undergoes an ion exchange process). This results from one type of alkali metal ion in the as-formed glass, such as, for example Li⁺or Na⁺, being replaced with larger alkali metal ions, such as, for example Na⁺or K⁺, respectively. However, the glass composition at or near the center of the depth of the glass article will, in embodiments, still have the composition of the as-formed (non-ion exchanged) glass utilized to form the glass article.

The glass articles disclosed herein may be incorporated into another article such as an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automobiles, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof. An exemplary article incorporating any of the glass articles disclosed herein is shown in FIGS. 2A and 2B. Specifically, FIGS. 2A and 2B show a consumer electronic device 200 including a housing 202 having front 204, back 206, and side surfaces 208; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that it is over the display. In some embodiments, a portion of the cover substrate 212 and/or a portion of housing 202 may include any of the glass articles disclosed herein.

A first clause comprises a glass composition comprising: from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol % SiO₂; from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, R₂O/Al₂O₃is greater than or equal to 1.06, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 8.0.

A second clause comprises a glass composition according to the first clause, wherein Al₂O₃+Li₂O is greater than or equal to 23.0 mol %.

A third clause comprises a glass composition according to any one of the first and second clauses, wherein Al₂O₃+Li₂O is from greater than or equal to 23.0 mol % to less than or equal to 26.5 mol %.

A fourth clause comprises a glass composition according to any one of the first to third clauses, wherein R₂O+RO is from greater than or equal to 18.0 mol % to less than or equal to 23.0 mol %.

A fifth clause comprises a glass composition according to any one of the first to fourth clauses, wherein R₂O+RO is from greater than or equal to 19.0 mol % to less than or equal to 22.0 mol %.

A sixth clause comprises a glass composition according to any one of the first to fifth clauses, wherein R₂O/Al₂O₃is from greater than or equal to 1.06 to less than or equal to 2.10.

A seventh clause comprises a glass composition according to any one of the first to sixth clauses, wherein R₂O/Al₂O₃is from greater than or equal to 1.10 to less than or equal to 1.90.

An eighth clause comprises a glass composition according to any one of the first to seventh clauses, wherein SiO₂+Al₂O₃+B₂O₃+P₂O₅is from greater than or equal to 78.0 mol % to less than or equal to 85.0 mol %.

A ninth clause comprises a glass composition according to any one of the first to eighth clauses, wherein SiO₂+Al₂O₃+B₂O₃+P₂O₅is from greater than or equal to 78.0 mol % to less than or equal to 83.0 mol %.

A tenth clause comprises a glass composition according to any one of the first to ninth clauses, wherein (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is from greater than or equal to 8.0 to less than or equal to 17.0.

An eleventh clause comprises a glass composition according to any one of the first to tenth clauses, wherein (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is from greater than or equal to 10.0 to less than or equal to 15.0.

A twelfth clause comprises a glass composition according to any one of the first to eleventh clauses, wherein B₂O₃+P₂O₅is greater than 0.0 mol %.

A thirteenth clause comprises a glass article comprising: a first surface; a second surface opposite the first surface, wherein a thickness (t) of the glass article is measured as a 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, wherein a central tension of the glass article is greater than or equal to 30 MPa, the compressive stress layer has a depth of compression that is from greater than or equal to 0.15t to less than or equal to 0.25t, and the glass article is formed from a glass comprising: from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol % SiO₂; from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O; from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, R₂O/Al₂O₃is greater than or equal to 1.06, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 8.0.

A fourteenth clause comprises a glass article according to the thirteenth clause, wherein the central tension of the glass article is greater than or equal to 50 MPa.

A fifteenth clause comprises a glass article of any one of the thirteenth and fourteenth clauses, wherein the central tension of the glass article is greater than or equal to 80 MPa.

A sixteenth clause comprises a glass article according to any one of the thirteenth to fifteenth clauses, wherein a potassium depth of layer of the compressive stress layer into the thickness of the glass article is from greater than 5 μm to less than or equal to 45 μm.

A seventeenth clause comprises a glass article according to any one of the thirteenth to sixteenth clauses, wherein the glass has a liquidus viscosity from greater than or equal to 20 kP to less than 1000 kP.

An eighteenth clause comprises a glass article according to any one of the thirteenth to seventeenth clauses, wherein a surface compressive stress of the compressive stress layer is greater than or equal to 450 MPa to less than or equal to 800 MPa.

A nineteenth clause comprises a consumer electronic product, comprising: a housing comprising a front surface, a back surface and side surfaces; electrical components at least partially within the housing, the electrical components comprising at least a controller, a memory, and a display, the display at or adjacent the front surface of the housing; and a cover substrate disposed over the display, wherein at least a portion of at least one of the housing and the cover substrate comprises the a glass article according to any one of the thirteenth through eighteenth clauses.

A twentieth clause comprises a glass article comprising: a first surface; a second surface opposite the first surface, wherein a thickness (t) of the glass article is measured as a 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, wherein a central tension of the glass article is greater than or equal to 60 MPa, the compressive stress layer has a depth of compression that is from greater than or equal to 0.15t to less than or equal to 0.25t, and the glass article has a composition at a center depth of the glass article comprising: from greater than or equal to 55.0 mol % to less than or equal to 75.0 mol % SiO₂; from greater than or equal to 8.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O; from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, R₂O/Al₂O₃is greater than or equal to 1.06, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 8.0.

A twenty first clause comprises a glass composition comprising: from greater than or equal to 55.0 mol % to less than or equal to 70.0 mol % SiO₂; from greater than or equal to 10.0 mol % to less than or equal to 20.0 mol % Al₂O₃; from greater than or equal to 3.0 mol % to less than or equal to 15.0 mol % Li₂O from greater than or equal to 5.0 mol % to less than or equal to 15.0 mol % Na₂O; and less than or equal to 1.5 mol % K₂O, wherein Al₂O₃+Li₂O is greater than 22.5 mol %, R₂O+RO is greater than or equal to 18.0 mol %, SiO₂+Al₂O₃+B₂O₃+P₂O₅is greater than or equal to 78.0 mol %, and (SiO₂+Al₂O₃+B₂O₃+P₂O₅)/Li₂O is greater than or equal to 10.50.

A twenty second clause comprises a glass article comprising: a first surface; a second surface opposite the first surface, wherein a thickness (t) of the glass article is measured as a 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, wherein a central tension of the glass article is greater than or equal to 30 MPa, the compressive stress layer has a depth of compression that is from greater than or equal to 0.15t to less than or equal to 0.25t, and the glass article is formed from a glass according to the twenty first clause.

A twenty third clause comprises the glass article of the twenty second clause, wherein the central tension of the glass article is greater than or equal to 50 MPa.

A twenty fourth clause comprises the glass article of any one of the twenty second and twenty third clauses, wherein the central tension of the glass article is greater than or equal to 80 MPa.

A twenty fifth clause comprises the glass article of any one of the twenty second to twenty fourth clauses, wherein a potassium depth of layer of the compressive stress layer into the thickness of the glass article is from greater than 5 μm to less than or equal to 45 μm.

A twenty sixth clause comprises the glass article of any one of the twenty second to twenty fifth, wherein the glass has a liquidus viscosity from greater than or equal to 20 kP to less than 1000 kP.

A twenty seventh clause comprises the glass article of any one of the twenty second to twenty sixth clauses, wherein a surface compressive stress of the compressive stress layer is greater than or equal to 450 MPa to less than or equal to 800 MPa.

A twenty eighth clause comprises a consumer electronic product, comprising: a housing comprising a front surface, a back surface and side surfaces; electrical components at least partially within the housing, the electrical components comprising at least a controller, a memory, and a display, the display at or adjacent the front surface of the housing; and a cover substrate disposed over the display, wherein at least a portion of at least one of the housing and the cover substrate comprises the glass article of anyone of the twenty second to twenty seventh clauses.

EXAMPLES

Embodiments will be further clarified by the following examples. It should be understood that these examples are not limiting to the embodiments described above.

Glass compositions having components listed in Table 1 below were prepared by conventional glass forming methods. In Table 1, all components are in mol %, and various properties of the glass compositions were measured according to the methods disclosed in this specification.

TABLE 1

Sample
1
2
3
4
5
6
7
8
9
10

SiO₂
64.35
63.38
62.28
61.30
60.28
59.35
64.52
63.36
62.47
61.40

Al₂O₃
16.33
16.26
16.30
16.32
16.36
16.34
16.16
16.32
16.21
16.30

P₂O₅
0.00
0.96
1.94
2.93
3.91
4.86
0.00
0.98
1.91
2.93

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
7.19
7.27
7.35
7.39
7.39
7.39
7.53
7.71
7.79
7.83

Na₂O
12.05
12.05
12.05
11.99
11.97
11.99
11.70
11.53
11.54
11.46

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
23.52
23.53
23.65
23.71
23.75
23.72
23.69
24.04
24.00
24.13

R₂O
19.25
19.33
19.41
19.39
19.37
19.39
19.25
19.26
19.34
19.30

R₂O + RO
19.27
19.35
19.43
19.40
19.40
19.41
19.27
19.28
19.36
19.32

Li₂O/Na₂O
0.60
0.60
0.61
0.62
0.62
0.62
0.64
0.67
0.67
0.68

SiO₂+ Al₂O₃
80.68
79.64
78.58
77.62
76.64
75.68
80.68
79.69
78.68
77.70

R₂O/Al₂O₃
1.18
1.19
1.19
1.19
1.18
1.19
1.19
1.18
1.19
1.18

SiO₂+ Al₂O₃+
80.68
80.60
80.52
80.55
80.55
80.54
80.68
80.67
80.59
80.63

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
11.22
11.09
10.96
10.90
10.90
10.90
10.71
10.46
10.35
10.29

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.438
2.433
2.428
2.423
2.419
2.414
2.439
2.432
2.427
2.423

Strain Pt. (° C.)
542
555
564
565
561
548
538
555
564
566

Anneal Pt. (° C.)
591
605
614
615
611
598
586
605
615
616

Softening Pt. (° C.)
836.2
848.6
854.7
858.6
854
849.3
826.2
845.1
854.7
854.2

10¹¹Poise
674
689
697
699
694
683
667
688
699
699

Temperature (° C.)

CTE * 10⁻⁷
84.8
85.7
86.5
86
86.5
86.2
84.3
85
84.6
85

(1/° C.)

Fulchers A
−3.789
−3.451
−3.171
−3.43
−2.873
−3.055
−3.478
−3.497
−3.161
−3.083

Fulchers B
10641.6
9417.5
8603.9
9096
7750.1
8143.9
9775.3
9535.6
8556.3
8276.4

Fulchers To
−124.5
−21.8
44.9
18.3
107.4
78.2
−75.3
−28
45.1
71.1

200 P Temperature
1623
1615
1617
1605
1605
1599
1616
1617
1612
1608

(° C.)

35000 P Temperature
1153
1156
1160
1159
1152
1150
1143
1158
1156
1156

(° C.)

200000 P Temperature
1046
1054
1060
1060
1056
1053
1038
1056
1056
1058

(° C.)

Liquidus Viscosity
575
526
957
1067
1020
2190
452
328
458
540

(kiloPoise)

SOC (nm/mm/MPa)
2.88
2.908
2.92
2.917
2.959
2.927
2.882
2.883
2.91
2.911

Refractive Index
1.5114
1.5094
1.5073
1.5055
1.5036
1.5029
1.5119
1.5098
1.5077
1.506

Young's Modulus
79.6
78.2
77.4
76.1
74.6
73.7
80.2
78.9
77.3
76.3

(GPa)

Sample
11
12
13
14
15
16
17
18
19
20

SiO₂
60.29
59.46
64.31
63.32
62.48
61.36
60.29
59.43
59.89
60.39

Al₂O₃
16.31
16.25
16.19
16.30
16.19
16.33
16.36
16.32
16.31
16.26

P₂O₅
3.93
4.84
0.00
0.97
1.99
2.92
3.97
4.91
4.91
4.90

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
7.92
7.95
8.12
8.21
8.21
8.31
8.33
8.33
8.35
8.42

Na₂O
11.48
11.42
11.30
11.12
11.05
11.00
10.97
10.94
10.46
9.95

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
24.22
24.20
24.31
24.51
24.40
24.64
24.69
24.65
24.65
24.69

R₂O
19.40
19.37
19.42
19.34
19.26
19.31
19.31
19.28
18.82
18.38

R₂O + RO
19.42
19.39
19.44
19.36
19.28
19.33
19.33
19.30
18.84
18.40

Li₂O/Na₂O
0.69
0.70
0.72
0.74
0.74
0.76
0.76
0.76
0.80
0.85

SiO₂+ Al₂O₃
76.60
75.71
80.51
79.62
78.68
77.69
76.65
75.75
76.20
76.66

R₂O/Al₂O₃
1.19
1.19
1.20
1.19
1.19
1.18
1.18
1.18
1.15
1.13

SiO₂+ Al₂O₃+
80.53
80.56
80.51
80.59
80.67
80.62
80.62
80.65
81.11
81.55

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
10.17
10.13
9.92
9.81
9.83
9.70
9.68
9.68
9.72
9.68

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.418
2.414
2.437
2.429
2.425
2.42
2.417
2.413
2.409
2.404

Strain Pt. (° C.)
561
555
531
554
560
565
561
552
553
557

Anneal Pt. (° C.)
610
605
579
602
610
614
611
602
602
607

Softening Pt. (° C.)
851.5
849.5
815.1
842.5
846.5
855
850.6
843.3
847
853

10¹¹Poise
692
689
660
683
692
696
694
685
685
691

Temperature (° C.)

CTE * 10⁻⁷
86
85.8
84.3
84.1
84.2
84.9
85.4
85.1
82.7
81.4

(1/° C.)

Fulchers A
−3.564
−3.164
−3.476
−3.824
−3.254
−2.999
−3.349
−3.189
−2.854
−3.191

Fulchers B
9520.9
8372.3
9779.2
10717.7
8803.7
8062.7
8831
8366.6
7673
8433.7

Fulchers To
−45.9
58
−93.3
−150.9
7.6
83.2
27.2
57.3
105.4
67.4

200 P Temperature
1577
1590
1599
1599
1592
1604
1590
1581
1594
1603

(° C.)

35000 P Temperature
1128
1144
1126
1130
1137
1152
1146
1139
1143
1158

(° C.)

200000 P Temperature
1028
1047
1021
1024
1037
1055
1048
1043
1046
1061

(° C.)

Liquidus Viscosity
424
1312
223
179
206
405
536
756
474
512

(kiloPoise)

SOC (nm/mm/MPa)
2.906
2.919
2.865
2.892
2.912
2.922
2.931
2.941
2.935
2.966

Refractive Index
1.5041
1.5026
1.5126
1.5101
1.5081
1.5063
1.5048
1.5033
1.5028
1.5021

Young's Modulus
75.1
74.1
80.4
79.2
78.1
76.7
75.8
74.6
74.0
74.6

(GPa)

Sample
21
22
23
24
25
26
27
28
29
30

SiO₂
59.90
60.19
59.84
60.10
61.40
61.36
61.32
61.37
61.39
61.45

Al₂O₃
16.31
16.38
16.40
16.45
16.25
16.30
16.33
16.29
16.25
16.29

P₂O₅
4.91
4.94
4.95
4.99
2.91
2.92
2.91
2.92
2.92
2.89

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
8.84
8.95
9.24
9.37
8.38
8.41
8.37
8.34
8.39
8.38

Na₂O
9.95
9.46
9.49
9.00
9.99
9.99
10.07
9.02
9.05
9.00

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.02
0.02
0.02
0.02
1.01
0.02
0.49
2.00
0.02
1.00

ZnO
0.00
0.00
0.00
0.00
0.00
0.94
0.46
0.00
1.92
0.93

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
25.15
25.34
25.63
25.82
24.63
24.71
24.69
24.64
24.64
24.66

R₂O
18.80
18.42
18.73
18.38
18.38
18.41
18.44
17.37
17.45
17.39

R₂O + RO
18.82
18.44
18.75
18.40
19.39
19.36
19.39
19.37
19.39
19.32

Li₂O/Na₂O
0.89
0.95
0.97
1.04
0.84
0.84
0.83
0.93
0.93
0.93

SiO₂+ Al₂O₃
76.21
76.57
76.24
76.55
77.65
77.67
77.65
77.66
77.64
77.74

R₂O/Al₂O₃
1.15
1.12
1.14
1.12
1.13
1.13
1.13
1.07
1.07
1.07

SiO₂+ Al₂O₃+
81.13
8151
81.19
81.55
80.56
80.59
80.56
80.58
80.56
80.63

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
9.18
9.11
8.79
8.70
9.61
9.58
9.63
9.66
8.60
9.63

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.407
2.403
2.406
2.401
2.421
2.435
2.425
2.422
2.448
2.436

Strain Pt. (° C.)
557
558
554
560
566
562
565
573
561
565

Anneal Pt. (° C.)
606
608
604
609
615
611
614
621
611
614

Softening Pt. (° C.)
843
852
843
853
856.4
854
854.8
861.8
853.9
855.8

10¹¹Poise
688
692
687
692
697
693
696
702
694
696

Temperature (° C.)

CTE * 10⁻⁷
82.9
80.5
81.9
79.8
81
80.1
80.6
77.6
76.3
76.4

(1/° C.)

Fulchers A
−3.407
−3.083
−3.065
−3.373
−3.386
−3.514
−3.437
−3.416
−3.416
−3.247

Fulchers B
8891.5
8247.5
8041.1
8793.4
8767.4
9029.1
8904.5
8684
8789
8225.7

Fulchers To
25.7
63.2
83.9
47.6
46
28.7
34.7
62.8
42.7
97.3

200 P Temperature
1583
1595
1582
1597
1588
1581
1587
1582
1580
1580

(° C.)

35000 P Temperature
1144
1145
1141
1158
1152
1149
1150
1154
1147
1153

(° C.)

200000 P Temperature
1047
1047
1045
1061
1055
1053
1054
1059
1051
1060

(° C.)

Liquidus Viscosity
229
229
164
116
201
212
215
132
95
82

(kiloPoise)

SOC (nm/mm/MPa)
2.949
2.963
2.932
2.956
2.924
2.949
2.956
2.932
2.99
2.966

Refractive Index
1.5034
1.5027
1.5038
1.5031
1.507
1.5084
1.5074
1.5081
1.5103
1.5091

Young's Modulus
74.8
74.7
75.1
75.2
77.8
77.4
77.6
78.5
78.2
78.5

(GPa)

Sample
31
32
33
34
35
36
37
38
39
40

SiO₂
61.36
61.41
61.50
61.36
61.27
61.51
70.21
68.19
66.26
72.19

Al₂O₃
16.33
16.23
16.14
16.29
16.20
16.27
9.83
11.85
13.81
9.94

P₂O₅
2.97
3.47
2.99
2.95
2.97
2.97
0.00
0.00
0.05
0.00

B₂O₃
0.00
0.00
0.00
0.00
0.98
1.91
0.00
0.00
0.00
0.00

Li₂O
8.35
8.35
8.37
8.39
8.37
8.34
6.01
6.01
6.01
6.01

Na₂O
10.45
10.46
10.42
10.48
9.90
8.91
13.89
13.89
13.86
11.80

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.02
0.02
0.49
0.24
0.01
0.01
0.00
0.00
0.00
0.00

ZnO
0.46
0.02
0.02
0.23
0.23
0.00
0.00
0.00
0.00
0.00

SnO₂
0.06
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.00
0.05

Al₂O₃+ Li₂O
24.68
24.57
24.51
24.67
24.58
24.62
15.84
17.86
19.82
15.95

R₂O
18.81
18.81
18.80
18.87
18.28
17.26
19.91
19.91
19.88
17.82

R₂O + RO
19.28
18.85
19.31
19.35
18.53
17.28
19.91
19.91
19.88
17.82

Li₂O/Na₂O
0.80
0.80
0.80
0.80
0.85
0.94
0.43
0.43
0.43
0.51

SiO₂+ Al₂O₃
77.69
77.63
77.64
77.64
77.47
77.78
80.04
80.04
80.07
82.13

R₂O/Al₂O₃
1.15
1.16
1.16
1.16
1.13
1.06
2.02
1.68
1.44
1.79

SiO₂+ Al₂O₃+
80.66
81.10
80.63
80.60
81.42
82.67
80.04
80.04
80.12
82.13

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
9.66
9.72
9.63
9.61
9.72
9.91
13.32
13.32
13.33
13.67

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.428
2.414
2.42
2.424
2.409
2.396
2.425
2.433
2.440
2.408

Strain Pt. (° C.)
561
568
565
562
552
546
458
475
499
470

Anneal Pt. (° C.)
611
618
614
612
604
598
499
517
542
513

Softening Pt. (° C.)
850.4
861.2
854.4
853.3
847.5
847.1
705
731
769
735

10¹¹Poise
694
701
696
695
689
684
568
589
616
587

Temperature (° C.)

CTE * 10⁻⁷
82
82.7
82.7
82.2
81.1
76.9
87.1
87.7
88.2
80.3

(1/° C.)

Fulchers A
−3.507
−3.68
−3.151
−3.428
−3.51
−3.293
−1.855
−2.373
−2.668
−1.950

Fulchers B
9164.8
9566
8306
8922.5
9133.7
8482.9
6336.7
7638.0
8386.1
6900.0

Fulchers To
13.3
−0.4
68.6
30.2
15.2
59.6
18.9
−55.9
−76.3
−3.6

200 P Temperature
1591
1599
1592
1588
1587
1576
1544
1578
1611
1620

(° C.)

35000 P Temperature
1152
1163
1148
1149
1149
1142
1009
1048
1086
1059

(° C.)

200000 P Temperature
1054
1065
1051
1052
1052
1047
904
939
976
948

(° C.)

Liquidus Viscosity
195
296
308
314
253
127

(kiloPoise)

SOC (nm/mm/MPa)
2.936
2.939
2.933
2.925
2.978
3.047
2.851
2.848
2.862
2.925

Refractive Index
1.5074
1.5052
1.5064
1.5071
1.5055
1.5046
1.5054
1.5073
1.5089
1.5028

Young's Modulus
77.4
76.1
77.2
76.7
76.5
75.3
76.1
77.2
77.6
76.3

(GPa)

Sample
41
42
43
44
45
46
47
48
49
50

SiO₂
70.06
68.13
67.46
66.33
65.30
64.26
63.28
61.85
64.37
63.47

Al₂O₃
11.72
13.77
14.72
15.76
16.56
16.85
16.41
16.67
16.86
16.75

P₂O₅
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
6.01
6.01
5.71
5.67
5.69
5.83
5.61
5.76
5.81
5.70

Na₂O
12.15
12.03
12.03
12.16
12.37
11.94
12.37
12.38
11.87
11.96

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.00
0.00
0.02
0.02
0.02
1.07
2.28
3.29
1.03
2.07

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
17.73
19.78
20.43
21.43
22.25
22.68
22.02
22.43
22.67
22.44

R₂O
18.17
18.05
17.75
17.84
18.07
17.77
17.98
18.15
17.69
17.67

R₂O + RO
18.17
18.05
17.77
17.86
18.09
18.85
20.26
21.44
18.72
19.73

Li₂O/Na₂O
0.49
0.50
0.47
0.47
0.46
0.49
0.45
0.47
0.49
0.48

SiO₂+ Al₂O₃
81.78
81.90
82.19
82.09
81.86
81.11
79.69
78.51
81.23
80.22

R₂O/Al₂O₃
1.55
1.31
1.20
1.13
1.09
1.05
1.10
1.09
1.05
1.05

SiO₂+ Al₂O₃+
81.78
81.90
82.19
82.09
81.86
81.11
79.69
78.51
81.23
80.22

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
13.61
13.63
14.41
14.47
14.39
13.91
14.21
13.63
13.98
14.08

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.418
2.424
2.425
2.429
2.431
2.438
2.448
2.456
2.438
2.448

Strain Pt. (° C.)
486
517
540
565
586
593
575
573
593
575

Anneal Pt. (° C.)
530
563
590
616
638
645
625
622
645
625

Softening Pt. (° C.)
758
812
843.8
877.9
906.7
905
875.3
860.8
905
875

10¹¹Poise
606
643
675
703
727
733
710
704
733
710

Temperature (° C.)

CTE * 10⁻⁷
81.7
81.9
81.9
82.7
83.7
82.1
82.2
82.4
82.10
82.20

(1/° C.)

Fulchers A
−2.355
−3.091
−4.529
−4.374
−3.951
−3.276
−3.592
−3.062
−3.276
−3.592

Fulchers B
7943.7
9648.4
13672.9
12400.8
10724.5
8698.3
9477.4
8016.7
8698.3
9477.4

Fulchers To
−60
−105.5
−318.2
−178.6
−35.9
93.6
10.3
98.2
93.6
10.3

200 P Temperature
1646
1684
1684
1679
1679
1653
1619
1593
1653
1619

(° C.)

35000 P Temperature
1091
1158
1189
1212
1227
1206
1175
1152
1206
1175

(° C.)

200000 P Temperature
978
1044
1073
1103
1123
1108
1076
1057
1108
1076

(° C.)

Liquidus Viscosity

1472

3182
1853
1519
387
1853
1519

(kiloPoise)

SOC (nm/mm/MPa)
2.909
2.930
2.944
2.944
2.938
2.918
2.873
2.858
2.918
2.873

Refractive Index
1.5049
1.5066
1.5068
1.5073
1.5078
1.5100
1.5115
1.5136
1.5100
1.5115

Young's Modulus
76.9
77.9
78.2
78.0
78.3
79.7
79.9
80.5
79.7
79.9

(GPa)

Sample
51
52
53
54
55
56
57
58
59
60

SiO₂
63.29
63.35
63.24
63.24
63.40
62.05
62.24
62.94
61.72
62.18

Al₂O₃
17.46
17.86
17.09
17.47
16.16
16.43
16.30
16.36
16.52
17.02

P₂O₅
0.00
0.00
0.00
0.00
0.00
1.10
1.09
0.00
1.10
1.10

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
5.72
5.73
6.00
6.22
6.73
6.20
7.03
6.54
6.92
6.92

Na₂O
11.93
11.93
12.00
11.97
13.64
13.08
13.27
12.93
12.60
12.71

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
1.54
1.07
1.62
1.05
0.02
1.08
0.02
1.18
1.10
0.02

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.04
0.05
0.04
0.04

Al₂O₃+ Li₂O
23.18
23.59
23.09
23.69
22.89
22.63
23.33
22.89
23.44
23.94

R₂O
17.66
17.67
18.01
18.19
20.37
19.29
20.31
19.48
19.53
19.63

R₂O + RO
19.20
18.74
19.62
19.24
20.39
20.38
20.33
20.65
20.62
19.66

Li₂O/Na₂O
0.48
0.48
0.50
0.52
0.49
0.47
0.53
0.51
0.55
0.54

SiO₂+ Al₂O₃
80.75
81.21
80.33
80.71
79.56
78.48
78.54
79.30
78.24
79.20

R₂O/Al₂O₃
1.01
0.99
1.05
1.04
1.26
1.17
1.25
1.19
1.18
1.15

SiO₂+ Al₂O₃+
80.75
81.21
80.33
80.71
79.56
79.58
79.63
79.30
79.33
80.30

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
14.12
14.17
13.39
12.98
11.83
12.83
11.32
12.13
11.47
11.61

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.443
2.440
2.444
2.442
2.400
2.400
2.400
2.400
2.400
2.400

Strain Pt. (° C.)
601
615
584
592
524
564
545
546
559
573

Anneal Pt. (° C.)
654
670
637
644
571
614
593
594
608
624

Softening Pt. (° C.)
908
926
889
898
800
857
828
834
846
869

10¹¹Poise
742
760
724
731
649
697
673
675
690
709

Temperature (° C.)

CTE * 10⁻⁷
81.00
80.90
82.20
82.30
88.6
86.6
88.5
87.2
85.9
87.2

(1/° C.)

Fulchers A
−3.607
−3.554
−3.468
−3.723
−3.311
−2.657
−3.409
−3.487
−3.067
−3.525

Fulchers B
9163.8
8892.3
8990.5
9397
9487.1
7241.1
9457.1
9503.6
8245.3
9417.5

Fulchers To
76.5
118.3
64.2
59.4
−89.7
149.4
−55.3
−43.1
61.3
3.3

200 P Temperature
1628
1637
1623
1619
1601
1610
1601
1599
1597
1620

(° C.)

35000 P Temperature
1201
1216
1186
1196
1118
1155
1134
1140
1145
1170

(° C.)

200000 P Temperature
1105
1123
1089
1101
1012
1059
1030
1038
1047
1070

(° C.)

Liquidus Viscosity
1275
1401
1378
1147
207
1299
805
283
906
839

(kiloPoise)

SOC (nm/mm/MPa)
2.918

2.895
2.908
2.814
2.888
2.864
2.852
2.864
2.888

Refractive Index
1.5111

1.5115
1.5114
1.5121
1.5088
1.5097
1.5122
1.5102
1.5093

Young's Modulus
80.0

80.0
80.2
79.4
78.0
77.9
79.6
78.8
78.3

(GPa)

Sample
61
62
63
64
65
66
67
68
69
70

SiO₂
62.34
62.24
62.32
62.25
62.24
62.26
61.38
60.52
59.63
58.66

Al₂O₃
17.25
17.22
17.22
17.23
17.24
17.25
16.32
16.41
16.48
16.48

P₂O₅
1.09
1.06
1.04
1.05
1.06
1.05
0.93
1.93
2.91
3.93

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
7.14
7.56
7.70
7.30
7.57
7.80
7.00
7.08
7.17
7.13

Na₂O
12.11
11.84
11.64
11.70
11.42
11.18
12.71
12.47
12.27
12.26

K₂O
0.01
0.01
0.01
0.40
0.40
0.40
0.52
0.50
0.49
0.49

MgO
0.02
0.02
0.02
0.02
0.03
0.02
1.09
1.04
1.01
1.00

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.04
0.04
0.05
0.04
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
24.39
24.78
24.93
24.54
24.82
25.05
23.32
23.48
23.65
23.61

R₂O
19.26
19.41
19.35
19.40
19.39
19.38
20.23
20.05
19.93
19.88

R₂O + RO
19.28
19.44
19.37
19.42
19.41
19.40
21.33
21.09
20.94
20.89

Li₂O/Na₂O
0.59
0.64
0.66
0.62
0.66
0.70
0.55
0.57
0.58
0.58

SiO₂+ Al₂O₃
79.59
79.46
79.54
79.48
79.48
79.51
77.70
76.93
76.11
75.14

R₂O/Al₂O₃
1.12
1.13
1.12
1.10
1.10
1.10
1.21
1.19
1.18
1.18

SiO₂+ Al₂O₃+
80.68
80.51
80.59
80.53
80.54
80.55
78.63
78.86
79.02
79.07

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
11.29
10.65
10.46
11.03
10.64
10.33
11.23
11.15
11.02
11.09

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.434
2.433
2.432
2.434
2.433
2.433
2.449
2.440
2.436
2.433

Strain Pt. (° C.)
585
584
590
584
584
582
538
555
566
565

Anneal Pt. (° C.)
636
636
641
635
635
634
586
601
609
607

Softening Pt. (° C.)
883.1
878.9
878.6
879.5
879.9
879.3
817.4
836.8
846.9
844.2

10¹¹Poise
721
721
724
720
720
720
666
680
685
682

Temperature (° C.)

CTE * 10⁻⁷(1/° C.)
85.6
85.9
84.8
86.6
85.4
86.1
90.10
90.10
90.20
90.60

Fulchers A
−3.325
−3.869
−3.268
−3.432
−3.955
−3.373

−3.493
−3.199
−3.556

Fulchers B
8741
10051.8
8568.8
9057.8
10392.1
8843.4

9216.9
8403.2
9085.3

Fulchers To
67.1
−17.3
75.5
45.5
−42.4
57.3

−17.4
49.2
10.1

200 P Temperature
1621
1612
1614
1625
1619
1616

1573
1577
1561

(° C.)

35000 P Temperature
1178
1177
1172
1181
1180
1174

1129
1134
1132

(° C.)

200000 P Temperature
1080
1079
1075
1083
1080
1077

1031
1038
1036

(° C.)

Liquidus Viscosity
788
482
512
587
604
381

1530
1519
1638

(kiloPoise)

SOC (nm/mm/MPa)
2.930
2.923
2.922
2.906
2.903
2.897
2.823
2.877
2.880
2.880

Refractive Index
1.5093
1.5096
1.5098
1.5093
1.5096
1.5100
1.5113
1.5085
1.5069
1.5052

Young's Modulus
78.5
78.9
78.7
78.4
78.9
78.9
79.4
78.0
77.0
75.6

(GPa)

Sample
71
72
73
74
75
76
77
78
79
80

SiO₂
57.73
56.66
64.38
63.28
62.39
61.36
60.45
59.40
64.30
63.25

Al₂O₃
16.49
16.46
16.17
16.28
16.25
16.31
16.30
16.27
16.15
16.26

P₂O₅
4.92
5.91
0.00
0.94
1.90
2.94
3.93
5.02
0.00
0.97

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
7.11
7.20
8.65
8.74
8.77
8.81
8.83
8.81
9.25
9.29

Na₂O
12.21
12.21
10.72
10.68
10.61
10.48
10.45
10.47
10.22
10.14

K₂O
0.49
0.49
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
1.00
1.01
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.00
0.01
0.05
0.05

Al₂O₃+ Li₂O
23.60
23.66
24.82
25.01
25.02
25.13
25.13
25.07
25.40
25.55

R₂O
19.81
19.91
19.38
19.43
19.39
19.31
19.29
19.29
19.48
19.44

R₂O + RO
20.81
20.92
19.40
19.45
19.41
19.33
19.31
19.31
19.50
19.46

Li₂O/Na₂O
0.58
0.59
0.81
0.82
0.83
0.84
0.85
0.84
0.90
0.92

SiO₂+ Al₂O₃
74.22
73.12
80.55
79.56
78.64
77.68
76.75
75.67
80.45
79.52

R₂O/Al₂O₃
1.17
1.18
1.20
1.19
1.19
1.18
1.18
1.19
1.21
1.19

SiO₂+ Al₂O₃+
79.14
79.03
80.55
8050
80.54
80.62
80.68
80.69
80.45
80.49

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
11.13
10.97
9.31
9.22
9.18
9.15
9.13
9.16
8.70
8.66

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.428
2.425
2.434
2.429
2.424
2.419
2.415
2.411
2.433
2.426

Strain Pt. (° C.)
563
545
535
553
563
562
560
551
535
552

Anneal Pt. (° C.)
608
591
582
600
612
611
609
601
581
600

Softening Pt. (° C.)
837.6
827.1
818.1
837.4
849.8
849.2
849.8
840.8
810

10¹¹Poise
685
670
661
679
693
692
690
683
658

Temperature (° C.)

CTE * 10⁻⁷
90.00
90.30
83.6
83.8
83.6
84.6
84.1
84.2
82.7
82.5

(1/° C.)

Fulchers A
−3.161
−3.588
−3.826
−3.63
−2.79
−3.512
−3.12
−3.28
−2.877
−3.537

Fulchers B
8180.3
9097.4
10478.8
9677.6
7575.6
9191.9
8193.7
8569.4
8126.3
9491.6

Fulchers To
66.5
3.9
−115.5
−39.6
110.2
5.7
74.7
43.8
31
−34.9

200 P Temperature
1564
1549
1595
1592
1598
1587
1586
1579
1600
1591

(° C.)

35000 P Temperature
1128
1123
1136
1144
1143
1147
1144
1139
1126
1140

(° C.)

200000 P Temperature
1033
1027
1033
1044
1046
1049
1048
1042
1025
1039

(° C.)

Liquidus Viscosity
2331
5458
123
148
127
215
233
388
81
124

(kiloPoise)

SOC (nm/mm/MPa)
2.889
2.882

2.878
2.900
2.915
2.914
2.926

2.882

Refractive Index
1.5040
1.5023

1.5111
1.5089
1.5070
1.5055
1.5036

1.5112

Young's Modulus
74.7
73.1

79.7
78.5
77.2
75.8
74.7

79.8

(GPa)

Sample
81
82
83
84
85
86
87
88
89
90

SiO₂
62.53
61.40
60.37
59.50
64.10
63.35
62.25
61.33
60.37
59.47

Al₂O₃
16.28
16.30
16.27
16.22
16.31
16.22
16.33
16.30
16.28
16.22

P₂O₅
1.94
2.91
3.93
4.87
0.00
0.94
1.95
2.88
3.89
4.85

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
9.11
9.27
9.31
9.34
9.83
9.76
9.86
9.91
9.86
9.90

Na₂O
10.06
10.03
10.03
9.99
9.68
9.64
9.55
9.49
9.52
9.48

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02

ZnO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
25.39
25.57
25.58
25.56
26.14
25.99
26.18
26.21
26.14
26.11

R₂O
19.17
19.31
19.34
19.34
19.52
19.41
19.41
19.41
19.39
19.38

R₂O + RO
19.20
19.33
19.37
19.36
19.54
19.43
19.44
19.43
19.41
19.41

Li₂O/Na₂O
0.91
0.92
0.93
0.94
1.02
1.01
1.03
1.04
1.04
1.04

SiO₂+ Al₂O₃
78.81
77.70
76.65
75.73
80.41
79.58
78.57
77.64
76.65
75.69

R₂O/Al₂O₃
1.18
1.18
1.19
1.19
1.20
1.20
1.19
1.19
1.19
1.19

SiO₂+ Al₂O₃+
80.75
80.62
80.58
80.59
80.41
80.52
80.52
80.52
80.54
80.54

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
8.87
8.69
8.66
8.63
8.18
8.25
8.17
8.13
8.17
8.14

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.422
2.418
2.414
2.410
2.431
2.425
2.420
2.416
2.412
2.408

Strain Pt. (° C.)
560
563
556
547
537
550
559
561
556
547

Anneal Pt. (° C.)
609
612
606
596
584
599
608
610
605
597

Softening Pt. (° C.)
844.9
849.7
845.3
836.2

841.4
845
841.7
835.3

10¹¹Poise
690
693
688
677

689
691
686
679

Temperature (° C.)

CTE * 10⁻⁷
82.8
83.6
83.5
84
81.7
81.9
82.6
82.5
83.3
83.2

(1/° C.)

Fulchers A
−3.174
−3.318
−2.859
−3.164
−2.948
−3.471
−3.167
−2.681
−3.336
−3.133

Fulchers B
8419.1
8713
7568.2
8218.3
8181
9289.7
8361.2
7083.5
8632.9
8110.1

Fulchers To
56.7
38.3
114.3
68.4
32.2
−23.8
54.2
163.2
36.4
71.8

200 P Temperature
1594
1589
1581
1572
1591
1586
1583
1585
1568
1564

(° C.)

35000 P Temperature
1148
1147
1137
1135
1124
1135
1139
1144
1132
1128

(° C.)

200000 P Temperature
1050
1049
1042
1039
1024
1035
1042
1051
1036
1033

(° C.)

Liquidus Viscosity
113
122
170
218
48
68
62
92
86
74

(kiloPoise)

SOC (nm/mm/MPa)
2.882
2.907
2.915
2.917

2.879
2.895
2.899
2.904
2.924

Refractive Index
1.5090
1.5072
1.5057
1.5042

1.5119
1.5100
1.5082
1.5064
1.5048

Young's Modulus
78.3
77.4
76.2
75.1

80.1
78.8
77.6
76.5
75.3

(GPa)

Sample
91
92
93
94
95
96
97
98
99
100

SiO₂
60.33
60.44
60.38
60.32
60.45
60.35
61.46
61.49
61.41
61.38

Al₂O₃
16.31
16.26
16.28
16.26
16.27
16.23
16.26
16.26
16.23
16.25

P₂O₅
3.92
3.88
3.95
4.00
3.91
4.02
2.92
2.90
2.95
2.97

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

Li₂O
8.38
8.43
8.37
8.33
8.45
8.39
7.80
7.85
7.87
7.85

Na₂O
10.00
9.98
9.97
9.04
8.97
9.00
10.49
10.50
10.51
9.48

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
1.01
0.02
0.50
1.99
0.02
1.01
1.02
0.02
0.51
2.01

ZnO
0.00
0.94
0.49
0.00
1.87
0.95
0.00
0.93
0.47
0.00

SnO₂
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
24.69
24.68
24.65
24.59
24.72
24.62
24.06
24.11
24.10
24.10

R₂O
18.38
18.42
18.35
17.38
17.43
17.40
18.30
18.35
18.39
17.34

R₂O + RO
19.39
19.37
19.34
19.37
19.32
19.36
19.32
19.31
19.37
19.36

Li₂O/Na₂O
0.84
0.84
0.84
0.92
0.94
0.93
0.74
0.75
0.75
0.83

SiO₂+ Al₂O₃
76.64
76.70
76.66
76.58
76.73
76.57
77.71
77.74
77.64
77.62

R₂O/Al₂O₃
1.13
1.13
1.13
1.07
1.07
1.07
1.13
1.13
1.13
1.07

SiO₂+ Al₂O₃+
80.56
80.58
80.61
80.58
80.63
80.59
80.63
80.65
80.59
80.59

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
9.62
9.56
9.63
9.67
9.54
9.60
10.33
10.28
10.24
10.26

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.418
2.430
2.423
2.418
2.444
2.430
2.422
2.436
2.428
2.423

Strain Pt. (° C.)
563
555
558
568
555
560
570
564
566
575

Anneal Pt. (° C.)
611
606
607.0
616
605
610
620
615
616
624

Softening Pt. (° C.)
854.9
850.1
850.4
857.2
851.8
852.1
860.4
858.1
859.7
865.6

10¹¹Poise
695
688
689
698
688
691
701
697
699
706

Temperature (° C.)

CTE * 10⁻⁷
82.3
80.6
80.5
77.3
76.2
76.4
80.8
81.2
81
78.1

(1/° C.)

Fulchers A
−3.335
−3.361
−3.421
−3.467
−3.405
−3.44
−3.108
−3.484
−3.386
−2.992

Fulchers B
8633.5
8739.7
8866.5
8755.7
8753.7
8798.6
8110.4
9086.5
8788.5
7780.3

Fulchers To
55
39
35.9
54.3
42.8
42.9
99.8
27.8
50.7
115.7

200 P Temperature
1587
1583
1585
1572
1577
1575
1599
1598
1596
1586

(° C.)

35000 P Temperature
1151
1145
1149
1147
1144
1145
1160
1160
1159
1148

(° C.)

200000 P Temperature
1055
1048
1052
1053
1048
1049
1064
1062
1062
1054

(° C.)

Liquidus Viscosity
243
192
257
142
108
134
367
281
314
216

(kiloPoise)

SOC (nm/mm/MPa)
2.932
2.966
2.932
2.934
2.988
2.961
2.92
2.962
2.925
2.929

Refractive Index
1.5055
1.5067
1.5059
1.5060
1.5086
1.5069
1.5062
1.5075
1.5070
1.5074

Young's Modulus
76.2
76.1
76.3
77.2
77.1
77.2
77.0
77.3
77.2
78.2

(GPa)

Sample
101
102
103
104
105
106
107
108

SiO₂
61.27
61.34
61.36
61.41
61.50
61.36
61.27
61.51

Al₂O₃
16.24
16.34
16.33
16.23
16.14
16.29
16.20
16.27

P₂O₅
2.98
2.96
2.97
3.47
2.99
2.95
2.97
2.97

B₂O₃
0.00
0.00
0.00
0.00
0.00
0.00
0.98
1.91

Li₂O
7.98
7.85
8.35
8.35
8.37
8.39
8.37
8.34

Na₂O
9.50
9.53
10.45
10.46
10.42
10.48
9.90
8.91

K₂O
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

MgO
0.03
1.00
0.02
0.02
0.49
0.24
0.01
0.01

ZnO
1.94
0.93
0.46
0.02
0.02
0.23
0.23
0.00

SnO₂
0.05
0.05
0.06
0.05
0.05
0.05
0.05
0.05

Al₂O₃+ Li₂O
24.22
24.19
24.68
24.57
24.51
24.67
24.58
24.62

R₂O
17.49
17.39
18.81
18.81
18.80
18.87
18.28
17.26

R₂O + RO
19.45
19.31
19.28
18.85
19.31
19.35
18.53
17.28

Li₂O/Na₂O
0.84
0.82
0.80
0.80
0.80
0.80
0.85
0.94

SiO₂+ Al₂O₃
77.51
77.67
77.69
77.63
77.64
77.64
77.47
77.78

R₂O/Al₂O₃
1.08
1.06
1.15
1.16
1.16
1.16
1.13
1.06

SiO₂+ Al₂O₃+
80.49
80.64
80.66
81.10
80.63
80.60
81.42
82.67

B₂O₃+ P₂O₅

(SiO₂+ Al₂O₃+
10.09
10.27
9.66
9.72
9.63
9.61
9.72
9.91

B₂O₃+ P₂O₅)/Li₂O

Density (g/cm³)
2.449
2.437
2.428
2.414
2.42
2.424
2.409
2.396

Strain Pt. (° C.)
563
565
561
568
565
562
552
546

Anneal Pt. (° C.)
614
615
611
618
614
612
604
598

Softening Pt. (° C.)
859.2
860.8
850.4
861.2
854.4
853.3
847.5
847.1

10¹¹Poise
698
699
694
701
696
695
689
684

Temperature (° C.)

CTE * 10⁻⁷
77
76.7
82
82.7
82.7
82.2
81.1
76.9

(1/° C.)

Fulchers A
−3.613
−3.506
−3.507
−3.68
−3.151
−3.428
−3.51
−3.293

Fulchers B
9324.8
8964.3
9164.8
9566
8306
8922.5
9133.7
8482.9

Fulchers To
1.6
39.9
13.3
−0.4
68.6
30.2
15.2
59.6

200 P Temperature
1578
1584
1591
1599
1592
1588
1587
1576

(° C.)

35000 P Temperature
1145
1153
1152
1163
1148
1149
1149
1142

(° C.)

200000 P Temperature
1048
1058
1054
1065
1051
1052
1052
1047

(° C.)

Liquidus Viscosity
143
157
195
296
308
314
253
127

(kiloPoise)

SOC (nm/nm/MPa)
2.987
2.963
2.936
2.939
2.933
2.925
2.978
3.047

Refractive Index
1.5096
1.5090
1.5074
1.5052
1.5064
1.5071
1.5055
1.5046

Young's Modulus
77.9
78.1
77.4
76.1
77.2
76.7
76.5
75.3

(GPa)

All compositional components, relationships, and ratios described in this specification are provided in mol % unless otherwise stated. All ranges disclosed in this specification include any and all ranges and subranges encompassed by the broadly disclosed ranges whether or not explicitly stated before or after a range is disclosed.

It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.

As used herein, a trailing 0 in a number is intended to represent a significant digit for that number. For example, the number “1.0” includes two significant digits, and the number “1.00” includes three significant digits.

Number	Name	Date	Kind
3433611	Kubichan	Mar 1969	A
5674790	Araujo	Oct 1997	A
8518545	Akiba	Aug 2013	B2
8652979	Murata	Feb 2014	B2
9593042	Hu	Mar 2017	B2
10065880	Gross	Sep 2018	B2
10633279	Gross	Apr 2020	B2
10906834	Gross	Feb 2021	B2
20030109370	Ikenishi	Jun 2003	A1
20110111160	Kawai	May 2011	A1
20120052271	Gomez	Mar 2012	A1
20120183812	Kajita	Jul 2012	A1
20120321898	Meinhardt	Dec 2012	A1
20130040169	Ikenishi et al.	Feb 2013	A1
20130288001	Murata	Oct 2013	A1
20140023865	Comte	Jan 2014	A1
20140308526	Chapman	Oct 2014	A1
20140364298	Ohara	Dec 2014	A1
20160010201	Hu	Apr 2016	A1
20160102011	Hu et al.	Apr 2016	A1
20160376186	Gross	Dec 2016	A1
20170197869	Beall	Jul 2017	A1
20170295657	Gross	Oct 2017	A1
20170341973	Gross	Nov 2017	A1
20180118615	Fukada	May 2018	A1
20190161386	Gross et al.	May 2019	A1

Number	Date	Country
101522584	Sep 2009	CN
102363567	Feb 2012	CN
102795766	Nov 2012	CN
103068759	Apr 2013	CN
104703937	Jun 2015	CN
105753314	Jul 2016	CN
107265884	Oct 2017	CN
03-144830	Jun 1991	JP
3144830	Mar 2001	JP
2014-141363	Aug 2014	JP
2014141363	Aug 2014	JP
2018-520082	Jul 2018	JP
201710204	Mar 2017	TW
201733946	Oct 2017	TW
201736300	Oct 2017	TW
2016210244	Dec 2016	WO
2017120424	Jul 2017	WO

	Number	Date	Country
Parent	16202767	Nov 2018	US
Child	17164060		US

Ion-exchangeable mixed alkali aluminosilicate glasses

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

CPC

Field of Search

CPC

International Classifications

Disclaimer

Term Extension

Abstract

Description

Claims

RELATED APPLICATIONS

US Referenced Citations (26)

Foreign Referenced Citations (17)

Non-Patent Literature Citations (6)

Related Publications (1)

Provisional Applications (1)

Continuations (1)

Entry
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